WO2020254494A1 - Fungicidal oxadiazoles - Google Patents

Fungicidal oxadiazoles Download PDF

Info

Publication number
WO2020254494A1
WO2020254494A1 PCT/EP2020/066947 EP2020066947W WO2020254494A1 WO 2020254494 A1 WO2020254494 A1 WO 2020254494A1 EP 2020066947 W EP2020066947 W EP 2020066947W WO 2020254494 A1 WO2020254494 A1 WO 2020254494A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
oxadiazol
haloalkyl
methyl
amine
Prior art date
Application number
PCT/EP2020/066947
Other languages
French (fr)
Inventor
Anne-Sophie Rebstock
Philippe Desbordes
Jeremy Dufour
Pierre-Yves Coqueron
Pierre Genix
Vincent Thomas
Sophie DUCERF
Andreas GÖRTZ
Christoph Andreas Braun
Aurelie MALLINGER
Jacopo NEGRONI
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to BR112021025300A priority Critical patent/BR112021025300A2/en
Priority to EP20734340.1A priority patent/EP3986889A1/en
Publication of WO2020254494A1 publication Critical patent/WO2020254494A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to heterocyclylaminophenyloxadiazole and derivatives thereof that may be used as fungicides.
  • Oxadiazole derivatives are known to be useful as crop protection agents to combat or prevent microorganisms’ infestations.
  • WO2017/1 10862 and WO2018/187553 discloses oxadiazole derivatives that may be used as fungicides.
  • fungicidal agents Numerous fungicidal agents have been developed until now. However, the need remains for the development of new fungicidal compounds as such, so as to provide compounds being effective against a broad spectrum of fungi, having lower toxicity, higher selectivity, being used at lower dosage rate to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control. It may also be desired to have new compounds to prevent the emergence of fungicides resistances.
  • the present invention provides new fungicidal compounds which have advantages over known compounds and compositions in at least some of these aspects.
  • the present invention relates to the use of compounds of the formula (I) for controlling phytopathogenic fungi on plants, in particular fungi causing rust diseases in crop protection:
  • the present invention also relates to compounds of the formula (G) as defined herein.
  • the present invention relates to a composition
  • a composition comprising at least one compound of formula (G) as defined herein and at least one agriculturally suitable auxiliary.
  • the present invention relates to a method for controlling phytopathogenic fungi which comprises the step of applying at least one compound of formula (I) as defined herein or a composition as defined herein to the plants, plant parts, seeds, fruits or to the soil in which the plants grow.
  • alkyl as used herein in the context of alkyl or alkylsulfonyl, alkylsulfinyl, alkylthio, alkylamino, for example, is to be understood as preferably meaning branched and unbranched alkyl, meaning e.g. methyl, ethyl, n-propyl, /so-propyl, n-butyl, /so-butyl, fe/ -butyl, sec-butyl, pentyl, /so-pentyl, hexyl, heptyl, octyl, nonyl and decyl and the isomers thereof.
  • haloalkyl as used herein is to be understood as preferably meaning branched and unbranched alkyl, as defined supra, in which one or more of the hydrogen substituents is replaced in the same way or differently with halogen.
  • said haloalkyl is, e.g. chloromethyl, fluoropropyl, fluoromethyl, difluoromethyl, trichloromethyl, 2,2 ,2-trifluoroethyl , pentafluoroethyl, bromobutyl, trifluoromethyl, iodoethyl, and isomers thereof.
  • alkoxy as used herein is to be understood as preferably meaning branched and unbranched alkoxy, meaning e.g. methoxy, ethoxy, propyloxy, /so-propyloxy, butyloxy, /so-butyloxy, fe/ -butyloxy, sec-butyloxy, pentyloxy, /so-pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy and dodecyloxy and the isomers thereof.
  • haloalkoxy as used herein is to be understood as preferably meaning branched and unbranched alkoxy, as defined supra, in which one or more of the hydrogen substituents is replaced in the same way or differently with halogen, e.g. chloromethoxy, fluoromethoxy, pentafluoroethoxy, fluoropropyloxy, difluoromethyloxy, trichloromethoxy, 2,2,2-trifluoroethoxy, bromobutyloxy, trifluoromethoxy, iodoethoxy, and isomers thereof.
  • halogen e.g. chloromethoxy, fluoromethoxy, pentafluoroethoxy, fluoropropyloxy, difluoromethyloxy, trichloromethoxy, 2,2,2-trifluoroethoxy, bromobutyloxy, trifluoromethoxy, iodoethoxy, and isomers thereof.
  • carbocyclyl refers to a non-aromatic mono- or polycyclic (fused, spiro or bridged) carbon containing ring, which may be saturated or partially unsaturated, having 3 to 10 ring carbon atoms.
  • carbocyclyl include cycloalkyl and cycloalkenyl groups.
  • saturated cycloalkyl include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl group.
  • Examples of partially unsaturated carbocyclyl group include but are not limited to cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, or cyclodecenyl group, wherein the linkage of said cyclolaklyl group to the rest of the molecule can be provided to the double or single bond.
  • heterocyclyl refers to three- to ten-membered, preferably three- to nine- membered, saturated or partially unsaturated heterocycles (including mono-, bi- or tricyclic heterocycles) containing one to four heteroatoms independently selected from the group of oxygen, nitrogen and sulphur. If the ring contains more than one oxygen atom, they are not directly adjacent.
  • heterocyclyl group examples include but are not limited to oxiranyl, aziridinyl, 2-tetrahydrofuranyl, 3- tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl,
  • halogen or“Hal” as used herein is to be understood as meaning fluorine, chlorine, bromine or iodine.
  • alkenyl as used herein is to be understood as preferably meaning branched and unbranched alkenyl, e.g. a vinyl, propen-1 -yl, propen-2-yl, but-1 -en-1 -yl, but-1 -en-2-yl, but-2-en-1 -yl, but-2-en-2-yl, but-1 -en-3-yl, 2-methyl-prop-2-en-1 -yl, or 2-methyl-prop-1 -en-1 -yl group.
  • alkynyl as used herein is to be understood as preferably meaning branched and unbranched alkynyl, e.g. an ethynyl, prop-1 -yn-1 -yl, but-1 -yn-1 -yl, but-2-yn-1 -yl,or but-3-yn-1 -yl group.
  • aryl refers to an aromatic, hydrocarbon, ring system, comprising from 6 to 15, or from 6 to 12 carbon atoms, preferably from 6 to 10 carbon atoms.
  • the ring system may be monocyclic or fused polycyclic (e.g. bicyclic or tricyclic) aromatic ring system.
  • Examples of aryl include but are not limited to phenyl, azulenyl, naphthyl and fluorenyl. It is further understood that when said aryl group is substituted with one or more substituents, said substituent(s) may be at any positions on said aryl ring(s).
  • aryl being a phenyl group
  • said substituent(s) may occupy one or both ortho positions, one or both meta positions, or the para position, or any combination of these positions.
  • This definition also applies to aryl as part of a composite substituent (e.g. aryloxy).
  • heteroaryl refers to an aromatic ring system containing from 5 to 15 member atoms, or from 5 to 12 member atoms, of which carbons and one or more heteroatoms which may be identical or different selected from O, N and S. If the ring contains more than one oxygen atom, they are not directly adjacent. Heteroaryl may be monocyclic or polycyclic (e.g. bicyclic or tricyclic). A monocyclic heteroaryl may have 1 to 4 heteroatoms in the ring, while a polycyclic heteroaryl ring may have 1 to 10 heteroatoms. Bicyclic heteroaryl rings may contain from 8 to 15, or from 8 to 12 member atoms (carbon and heteroatoms).
  • Monocyclic heteroaryl may contain from 5 to 8 member atoms.
  • heteroaryl include but are not limited to thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl etc., and benzo derivatives thereof, such as, e.g., benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl, etc. ⁇ , or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and benzo derivatives thereof, such as, for example, quinolinyl, isoquinol
  • heteroaryl being a pyridyl group
  • said substituent(s) may occupy any one or more of positions 2, 3, 4, 5, and/or 6 with respect to the nitrogen atom in the pyridine ring.
  • This definition also applies to heteroaryl as part of a composite substituent (e.g. heteroaryloxy).
  • the term“C1-C6”, e.g. in the context of the definition of“Ci-C6-alkyl”, or“Ci-C6-alkoxy”, is to be understood as meaning a group having a finite number of carbon atoms of 1 to 6, i.e. 1 , 2, 3, 4, 5, or 6 carbon atoms.
  • acyclic radicals as used herein in the expressions “wherein acyclic radicals may be substituted” designate any of the acyclic groups recited in the paragraph before said expressions, or any acyclic moiety of a composite group (e.g. the Ci-Cs-alkyl moiety of aryl-Ci-Cs-alkyl).
  • cyclic radicals as used herein in the expressions“wherein cyclic radicals may be substituted” designate any of the cyclic groups, be it alicyclic or aromatic, recited in the paragraph before said expressions, or any cyclic moiety of a composite group (e.g. the aryl moiety of aryl-Ci-C6-alkyl).
  • each of these moieties may be substituted independently of each other.
  • the term“leaving group” as used herein is to be understood as meaning a group which is displaced from a compound in a substitution or an elimination reaction, for example a halogen atom, a trifluoromethanesulphonate (“triflate”) group, alkoxy, methanesulphonate, p-toluenesulphonate, etc..
  • the present invention relates to the use of compounds of formula (I) for controlling phytopathogenic fungi on plants (in particular fungi causing rust diseases in crop protection):
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, cyano, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-Cs-haloalkynyl, C3-C7- carbocyclyl, aryl, 3- to 10-membered-heterocyclyl, heteroaryl, aryl-Ci-Cs-alkyl, 3- to 10- membered-heterocyclyl-Ci-C8-alkyl, heteroaryl-Ci-Cs-alkyl and C3-C7-carbocyclyl-Ci-C8-alkyl, wherein said acyclic R1 and R2 may be substituted with, respectively one or more R 1a and R 2a substituents and said cyclic R1 and R2 may be substituted with, respectively one or more R 1b and R
  • R1 , R2 may form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl or a 3- to 10-membered heterocyclyl, wherein said C3-C7-carbocyclyl or 3- to 10-membered heterocyclyl may be substituted with one or more R 1b substituents;
  • Cy is C3-Cio-carbocyclyl, 3- to 10-membered heterocyclyl, aryl or heteroaryl;
  • n 0, 1 , 2, 3 or 4;
  • R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-
  • acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine
  • R 1a , R 2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbon
  • R 1b , R 2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci
  • aryl aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
  • the compound of formula (I) is not: (a) N-[1-(pyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
  • the invention encompasses pure stereoisomers of the compound of formula (I) respectively (G) and any mixture of these isomers.
  • the compound of formula (I) respectively (G) may be present in the form of different stereoisomers. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the invention encompasses both pure stereoisomers and any mixture of these isomers. Where a compound can be present in two or more tautomer forms in equilibrium, reference to the compound by means of one tautomeric description is to be considered to include all tautomer forms.
  • the compound of formula (I) respectively (G) can suitably be in its free form, salt form, N-oxide form or solvate form (e.g. hydrate).
  • the compound of formula (I) respectively (G) may be present in the form of the free compound and/or a salt thereof, such as an agrochemically active salt.
  • Agrochemically active salts include acid addition salts of inorganic and organic acids well as salts of customary bases.
  • inorganic acids are hydrohalic acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid, and acidic salts, such as sodium bisulfate and potassium bisulfate.
  • Useful organic acids include, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated or mono- or diunsaturated fatty acids having 6 to 20 carbon atoms, alkylsulfuric monoesters, alkylsulfonic acids (sulfonic acids having straight- chain or branched alkyl radicals having 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl, which bear one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic
  • Solvates of the compounds of formula (I) respectively (G) or their salts are stoichiometric compositions of the compounds with solvents.
  • the compounds of formula (I) respectively (G) may exist in multiple crystalline and/or amorphous forms. Crystalline forms include unsolvated crystalline forms, solvates and hydrates.
  • R1 and R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl (preferably C3-C7-cycloalkyl), or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (preferably C3-C7-cycloalkyl and C3-C7-cycloalkenyl) or a 3- to 10-membered heterocyclyl.
  • R1 and R2 may be substituted as described herein.
  • R1 and R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl (e.g. cyclopropyl).
  • R1 and R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl (preferably phenyl), or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl ring.
  • R1 and R2 may be substituted as described herein.
  • R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl, and halogen.
  • R1 and R2 are independently selected from the group consisting of hydrogen, methyl and phenyl, or R1 and R2 form, together with the carbon atom to which they are linked, a cyclopropyl or cyclobutyl ring, wherein the cyclopropyl and cyclobutyl ring may be substituted with one or more substituents selected from hydroxy, methyl and fluorine.
  • Cy is phenyl or 5- or 6-membered heteroaryl, preferably selected from the group consisting of phenyl, furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl.
  • Cy is selected from the group consisting of phenyl, thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl and pyrazinyl. Cy may be substituted as described herein. In some embodiments, in the above formula (I), Cy is phenyl.
  • Cy is a 5-membered heteroaryl selected from the group consisting of furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl and tetrazolyl.
  • Cy is selected from the group consisting of thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl and triazolyl.
  • Cy is 6-membered heteroaryl selected from the group consisting of pyridinyl, pyridazinyl, pyrimidinyl or pyrazinyl. In some of these embodiments, Cy is selected from the group consisting of pyridinyl, pyrimidinyl and pyrazinyl.
  • Cy is pyridinyl
  • Cy is naphthyl or a fused bicyclic partially unsaturated Cg-Cio-carbocyclyl.
  • Cy is A84, A91 or A1 14:
  • Cy is bicyclic 8-, 9- or 10-membered heteroaryl or a fused bicyclic 8-, 9- or 10-membered partially unsaturated heterocyclyl.
  • Non-limiting examples of Cy include the followings:
  • Cy is a benzofused 9- or 10-membered heteroaryl.
  • benzofused 9-membered heteroaryl include indol-1 -yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-1 -yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5- yl, indazol-1 -yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, 1 - benzofuran-2-yl, 1 -benzofuran-3-yl, 1 -benzofuran-4-yl
  • Examples of benzofused 10-membered heteroaryl include quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl and isoquinolin-8-yl.
  • Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10-membered heteroaryl.
  • Cy is selected from the group consisting of cyclopropyl, phenyl, thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl, pyrazinyl and quinolin-2-yl.
  • Cy is selected from pyridinyl and phenyl.
  • n 0, 1 or 2.
  • n is 1 , 2, 3 or 4.
  • n 1 or 2.
  • R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, carboxyl, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci- C6-haloalkylsulfanyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci-C6-hydroxy alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, Ci-Cs-alkyl, Ci-Cs-alkyl,
  • R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy.
  • R3 is independently selected from the group consisting of halogen, in particular fluorine.
  • R4 is hydrogen
  • R5 is hydrogen
  • X is fluorine
  • X is chlorine
  • R1 , R2, R3, R4, R5, Cy and n can be combined in various manners to provide sub-classes of compounds according to the invention.
  • Non-limiting examples of sub-classes of compounds include the sub-classes described herein below.
  • the compounds used according to the present invention are compounds of formula (I)
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl, or
  • R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (e.g.
  • R1 and R2 may be substituted as described herein;
  • Cy is aryl, preferably phenyl
  • n is O, 1 , 2, 3 or 4;
  • R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-halo
  • acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine
  • R 1a , R 2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- C8-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbon
  • R 1 b , R 2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl,
  • phenyl aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy. provided that the compound of formula (I) is not:
  • Cy is phenyl
  • the compounds used according to the present invention are compounds of formula (I)
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl, or
  • R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (e.g.
  • R1 and R2 may be substituted as described herein;
  • Cy is a 5- or 6-membered heteroaryl (e.g. pyridinyl);
  • n 0, 1 , 2, 3 or 4;
  • R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-
  • acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine
  • R 1a , R 2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbon
  • R 1 b , R 2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl,
  • aryl aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy; provided that the compound of formula (I) is not:
  • Cy (5- or 6-membered heteroaryl) is as described herein.
  • Cy is selected from the group consisting of furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl.
  • Cy is selected from the group consisting of thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl and pyrazinyl.
  • Cy is pyridinyl
  • the compounds used according to the present invention are compounds of formula (I)
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl, or
  • R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (e.g.
  • R1 and R2 may be substituted as described herein;
  • Cy is a C3-Cio-carbocyclyl (e.g. cyclopropyl);
  • n 0, 1 , 2, 3 or 4;
  • R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-
  • acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine
  • R 1a , R 2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbon
  • R 1b , R 2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci
  • phenyl aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy.
  • Cy (C3-Ci 0 -carbocyclyl) is as described herein.
  • the compounds used according to the present invention are compounds of formula (I)
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl, or
  • R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (e.g.
  • R1 and R2 may be substituted as described herein;
  • Cy is a 3- to 10-membered-heterocyclyl
  • n 0, 1 , 2, 3 or 4;
  • R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-
  • R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine
  • R 1a , R 2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- Cyhalocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl
  • R 1b , R 2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci
  • phenyl aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy.
  • Cy 3- to 10-membered-heterocyclyl
  • R1 and R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl.
  • R1 and R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl (preferably phenyl), or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl ring.
  • R1 and R2 may be substituted as described herein. In particular, R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl, and halogen.
  • R1 and R2 are independently selected from the group consisting of hydrogen, methyl and phenyl, or R1 and R2 form, together with the carbon atom to which they are linked, a cyclopropyl or cyclobutyl ring, wherein the cyclopropyl and cyclobutyl ring may be substituted with one or more substituents selected from hydroxy, methyl and fluorine.
  • n is 0, 1 or 2.
  • n is 1 , 2, 3 or 4.
  • n is 1 or 2.
  • R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, carboxyl, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy- Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci- C6-hydroxy alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6
  • R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy. In some of these embodiments, R3 is independently selected from the group consisting of fluorine, chlorine, bromine, methyl, tert-butyl, trifluoromethyl, 2,2,2-trifluoroethoxy and methoxy.
  • R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl and Ci-C6-haloalkyl.
  • R3 is independently selected from the group consisting of halogen, in particular fluorine.
  • R4 is hydrogen
  • R5 is hydrogen
  • X is fluorine
  • X is chlorine
  • the compounds used according to the present invention are compounds of formula (I)
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl
  • R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
  • R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen; Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
  • n 0, 1 or 2;
  • R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine, preferably hydrogen; provided that the compound of formula (I) is not:
  • the compounds used according to the present invention are compounds of formula (I)
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl
  • R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
  • R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen;
  • Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
  • n 1 or 2;
  • R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine, preferably hydrogen.
  • Cy is phenyl or 5- or 6- membered heteroaryl, preferably selected from the group consisting of phenyl, furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl.
  • Cy is selected from the group consisting of phenyl, thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl and pyrazinyl.
  • Cy is phenyl or pyridinyl.
  • R5 is hydrogen
  • R1 , R2 are independently selected from the group consisting of hydrogen, methyl and phenyl, or R1 and R2 form, together with the carbon atom to which they are linked, a cyclopropyl or cyclobutyl ring, wherein the cyclopropyl and cyclobutyl ring may be substituted with one or more substituents selected from hydroxy, methyl and fluorine;
  • R3 is independently selected from the group consisting of fluorine, chlorine, bromine, methyl, tert-butyl, trifluoromethyl, 2,2,2-trifluoroethoxy and methoxy;
  • R4 is selected from the group consisting of hydrogen, hydroxy, methoxy and 2-chloro-2,2-difluoroacetyl, preferably R4 is hydrogen;
  • R5 is hydrogen
  • n 1 or 2.
  • X is fluorine
  • X is chlorine
  • R3 is halogen, in particular fluorine.
  • R1 , R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl (e.g. cyclopropyl),
  • R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl and Ci-C6-haloalkyl, preferably halogen;
  • the present invention also relates to the use of any compounds of formula (I) disclosed in Table 1 for controlling phytopathogenic fungi on plants (in particular fungi causing rust diseases in crop protection). Accordingly, the present invention also relates to the use of compounds of the formula (I) selected from the group consisting of
  • the present invention also relates to compounds of formula (G):
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, cyano, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-Cs-haloalkynyl, C3-C7- carbocyclyl, aryl, 3- to 10-membered-heterocyclyl, heteroaryl, aryl-Ci-Cs-alkyl, 3- to 10- membered-heterocyclyl-Ci-C8-alkyl, heteroaryl-Ci-Cs-alkyl and C3-C7-carbocyclyl-Ci-C8-alkyl, wherein said acyclic R1 and R2 may be substituted with, respectively one or more R 1a and R 2a substituents and said cyclic R1 and R2 may be substituted with, respectively one or more R 1b and R
  • R1 , R2 may form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl or a 3- to 10-membered heterocyclyl, wherein said C3-C7-carbocyclyl or 3- to 10-membered heterocyclyl may be substituted with one or more R 1 b substituents;
  • Cy is C3-Cio-carbocyclyl, 3- to 10-membered heterocyclyl, aryl or heteroaryl;
  • n 0, 1 , 2, 3 or 4;
  • R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-
  • acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine
  • R 1a , R 2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- C8-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbon
  • R i b p2 b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl
  • aryl aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
  • compounds are excluded in which X is fluorine, Cy is phenyl or 6-membered heteroaryl and R1 , R2 and R4 are each independently selected from hydrogen and Ci-C3-alkyl.
  • n 1 or 2
  • R1 and R2 are not both hydrogen
  • R1 , R2, R3, R4, Cy and n are defined according to embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f), and X is chlorine.
  • R1 , R2, R3, R4, X and n are as defined in embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f), and Cy is an unsubstituted or substituted 5-membered heteroaryl.
  • R3, R4, Cy, X and n are as defined in embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f), and R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl, wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen.
  • R1 , R2, R3, R4, Cy and X are as defined in embodiment (I’a), (I’b), (I’c), (I’d) or (I’e) and n is 1 or 2.
  • R1 , R2, R3, R4, Cy and X are defined according to embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f),
  • n 1 or 2
  • R1 and R2 are not both hydrogen
  • R1 , R2, R3, n, Cy and X are as defined in embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f), and R4 is hydrogen.
  • the present invention also relates to the compounds of formula (I’)
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl
  • R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
  • R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen;
  • Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
  • n 0, 1 or 2;
  • R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine, preferably hydrogen; wherein when X is fluorine and R4 is hydrogen or Ci-C6-alkyl, R1 and R2 are not both hydrogen; wherein compounds are excluded in which X is fluorine, Cy is phenyl or 6-membered heteroaryl, n is 0 and R1 , R2 and R4 are each independently selected from hydrogen and Ci-C3-alkyl; and
  • R1 , R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl (e.g. cyclopropyl),
  • R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl and Ci-C6-haloalkyl; Cy is phenyl or 5- or 6-membered heteroaryl;
  • R5 is hydrogen
  • the present invention also relates to the compounds of formula (G)
  • X is fluorine or chlorine
  • R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl
  • R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
  • R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen;
  • Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
  • n 1 or 2;
  • R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
  • R5 is hydrogen or fluorine, preferably hydrogen
  • embodiment I’j In some embodiments in accordance with embodiment (I’i) (referred herein as embodiment I’j),
  • R1 , R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl (e.g. cyclopropyl), R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl and Ci-C6-haloalkyl; Cy is phenyl or 5- or 6-membered heteroaryl;
  • R5 is hydrogen
  • X is chlorine
  • Cy is an unsubstituted or substituted 5-membered heteroaryl.
  • Cy is an unsubstituted or substituted 6-membered heteroaryl.
  • Cy is unsubstituted or substituted phenyl.
  • R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl, wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen.
  • R3 is selected from halogen and Ci-C6-haloalkyl, preferably halogen, more preferably fluorine.
  • compounds are excluded in which X is fluorine, Cy is phenyl or 6-membered heteroaryl and R1 , R2 and R4 are each independently selected from hydrogen and Ci-C3-alkyl.
  • n 1 or 2
  • R1 and R2 are not both hydrogen
  • the present invention also relates to processes for the preparation of compounds of formula (I) respectively (I’).
  • the radicals R1 , R2, R3, R4, R5 and X have the meanings given above for the compounds of formula (I) respectively (I’). These definitions apply not only to the end products of the formula (I) respectively (I’) but likewise to all intermediates.
  • Amidoximes of formulae (II) and (II’) can be prepared according to known procedures (see for examples WO2013080120), as shown in process P2 by treating nitriles of formula (III) respectively (III’) with hydroxylamine (or its hydrochloride salt) in the presence of a base such as triethylamine in a solvent such as ethanol.
  • compounds of formulae (I) and (G) can be prepared, according to process P4, from a compound of formula (V) respectively (V’), wherein LG2 is a leaving group by nucleophilic substitution with a compound of formula (VI) respectively (VI’) (as described for example in European Journal of Medicinal Chemistry, 135, 531 -543; 2017 or Bioorganic & Medicinal Chemistry, 25(17), 4553-4559; 2017) optionally in presence of a base (like for example triethylamine) or an acid (like for example p- toluenesulfonic acid or (1 S)-(+)-10-camphorsulfonic acid) in a solvent such as for example dichloromethane or dioxane. It may be necessary to activate the leaving group for example by oxidation with 3-chloroperbenzoic acid when LG2 is SMe.
  • a base like for example triethylamine
  • an acid like for example p- toluenesulfonic acid
  • compounds of formulae (I) and (G) can be prepared, according to process P5, from a compound of formula (VII’) with a compound of formula (VIM’) wherein LG3 is a leaving group such as chlorine by nucleophilic substitution (as described for example in European Journal of Medicinal Chemistry, 135, 531 -543; 2017 or Bioorganic & Medicinal Chemistry, 25(17), 4553-4559; 2017) optionally in presence of a base (like for example triethylamine) or an acid (like for example p- toluenesulfonic acid or (1 S)-(+)-10-Camphorsulfonic acid) in a solvent such as for example dichloromethane or dioxane.
  • a base like for example triethylamine
  • an acid like for example p- toluenesulfonic acid or (1 S)-(+)-10-Camphorsulfonic acid
  • solvent such as for example dichloromethane or dioxan
  • Compounds of formulae (VIII) and (VIII’) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
  • compounds of formulae (I) and (G) can be prepared, according to process P6, from a compound of formula (IX) respectively (IX’) with a compound of formula (X) respectively (X’), wherein LG4 is a leaving group, by nucleophilic substitution (as described for example in Medicinal Chemistry Research, 22(1 1), 5267-5273; 2013 or W02013080120) optionally in presence of a base (like for example triethylamine), optionally in presence of a solvent such as for example dichloromethane.
  • a base like for example triethylamine
  • processes P1 to P7 can be performed if appropriate in the presence of a solvent and if appropriate in the presence of a base.
  • Suitable solvents for carrying out processes P1 to P7 according to the invention are customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2- diethoxyethane or anisole ; nitriles, such as
  • Suitable bases for carrying out processes P1 to P7 according to the invention are inorganic and organic bases which are customary for such reactions.
  • alkaline earth metal alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide
  • alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate
  • alkali metal or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, A/,A/-dimethylaniline, pyridine, /V-methylpiperidine, A/,A/-dimethylaminopyridine, 1
  • reaction temperature can independently be varied within a relatively wide range.
  • processes according to the invention are carried out at temperatures between -20°C and 160°C.
  • Processes P1 to P7 according to the invention are generally independently carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.
  • reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can be freed by customary methods, such as chromatography or recrystallization, from any impurities that can still be present.
  • compositions and formulations are provided.
  • the present invention further relates to a composition, in particular a composition for controlling unwanted microorganisms, comprising one or more compounds of formula (I) or (I’).
  • the composition is preferably is a fungicidal composition.
  • composition typically comprises one or more compounds of formula (I) or (I’) and one or more acceptable carriers, in particular one or more agriculturally acceptable carriers.
  • a carrier is a solid or liquid, natural or synthetic, organic or inorganic substance that is generally inert.
  • the carrier generally improves the application of the compounds, for instance, to plants, plants parts or seeds.
  • suitable solid carriers include, but are not limited to, ammonium salts, natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates.
  • typically useful solid carriers for preparing granules include, but are not limited to crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks.
  • suitable liquid carriers include, but are not limited to, water, organic solvents and combinations thereof.
  • suitable solvents include polar and nonpolar organic chemical liquids, for example from the classes of aromatic and nonaromatic hydrocarbons (such as cyclohexane, paraffins, alkylbenzenes, xylene, toluene alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride), alcohols and polyols (which may optionally also be substituted, etherified and/or esterified, such as butanol or glycol), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides (such as dimethylformamide), lactams (such as N- alkylpyrrolidones) and lactones, sulf
  • the carrier may also be a liquefied gaseous extender, i.e. liquid which is gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, butane, propane, nitrogen and carbon dioxide.
  • the amount of carrier typically ranges from 1 to 99.99%, preferably from 5 to 99.9%, more preferably from 10 to 99.5%, and most preferably from 20 to 99 % by weight of the composition.
  • composition may further comprise one or more acceptable auxiliaries which are customary for formulating compositions (e.g. agrochemical compositions), such as one or more surfactants.
  • acceptable auxiliaries which are customary for formulating compositions (e.g. agrochemical compositions), such as one or more surfactants.
  • the surfactant can be an ionic (cationic or anionic) or non-ionic surfactant, such as ionic or non-ionic emulsifier(s), foam former(s), dispersant(s), wetting agent(s) and any mixtures thereof.
  • surfactants include, but are not limited to, salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene and/or propylene oxide with fatty alcohols, fatty acids or fatty amines (polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols and derivatives of compounds containing sulfates, sulfonates, phosphates (for example, alkylsulfonates, alkyl sulfates, arylsulfonates) and protein hydroly
  • auxiliaries which are customary for formulating agrochemical compositions include water repellents, siccatives, binders (adhesive, tackifier, fixing agent, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids such as cephalins and lecithins and synthetic phospholipids, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose), thickeners, stabilizers (e.g.
  • dyes or pigments such as inorganic pigments, e.g. iron oxide, titanium oxide and Prussian Blue ; organic dyes, e.g. alizarin, azo and metal phthalocyanine dyes), antifoams (e.g. silicone antifoams and magnesium stearate), preservatives (e.g.
  • dichlorophene and benzyl alcohol hemiformal secondary thickeners (cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica), stickers, gibberellins and processing auxiliaries, mineral and vegetable oils, perfumes, waxes, nutrients (including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc), protective colloids, thixotropic substances, penetrants, sequestering agents and complex formers.
  • secondary thickeners cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica
  • stickers gibberellins and processing auxiliaries
  • mineral and vegetable oils perfumes
  • waxes including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc
  • protective colloids including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molyb
  • auxiliaries are related to the intended mode of application of the compound of the formula (I) respectively (G) and/or on the physical properties. Furthermore, the auxiliaries may be chosen to impart particular properties (technical, physical and/or biological properties) to the compositions or use forms prepared therefrom. The choice of auxiliaries may allow customizing the compositions to specific needs.
  • the composition may be in any customary form, such as solutions (e.g.
  • the compound of formula (I) respectively (G) may be present in a suspended, emulsified or dissolved form.
  • compositions may be provided to the end user as ready-for-use formulation, i.e. the compositions may be directly applied to the plants or seeds by a suitable device, such as a spraying or dusting device.
  • a suitable device such as a spraying or dusting device.
  • the composition may be provided to the end user in the form of concentrates which have to be diluted, preferably with water, prior to use.
  • composition can be prepared in conventional manners, for example by mixing the compound formula (I) respectively (I’) with one or more suitable auxiliaries, such as disclosed herein above.
  • the composition contains generally from 0.01 to 99% by weight, from 0.05 to 98% by weight, preferably from 0.1 to 95% by weight, more preferably from 0.5 to 90% by weight, most preferably from 1 to 80 % by weight of the compound of formula (I) respectively (I’).
  • the compound(s) and composition(s) comprising thereof can be mixed with other active ingredients like fungicides, bactericides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners or semiochemicals. This may allow to broaden the activity spectrum or to prevent development of resistance. Examples of known fungicides, insecticides, acaricides, nematicides and bactericides are disclosed in the Pesticide Manual, 17th Edition.
  • fungicides which could be mixed with the compound(s) of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and the composition of the invention are:
  • Inhibitors of the ergosterol biosynthesis for example (1 .001) cyproconazole, (1 .002) difenoconazole, (1 .003) epoxiconazole, (1 .004) fenhexamid, (1 .005) fenpropidin, (1 .006) fenpropimorph, (1 .007) fenpyrazamine, (1 .008) fluquinconazole, (1 .009) flutriafol, (1 .010) imazalil, (1 .01 1) imazalil sulfate, (1 .012) ipconazole, (1 .013) metconazole, (1 .014) myclobutanil, (1 .015) paclobutrazol, (1 .016) prochloraz, (1 .017) propiconazole, (1 .018) prothioconazole, (1 .019) pyrisoxazole, (1 .020) spiroxamine, (1 .021) te
  • Inhibitors of the respiratory chain at complex I or II for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) Isofetamid, (2.010) isopyrazam (anti-epimeric enantiomer 1 R,4S,9S), (2.01 1) isopyrazam (anti-epimeric enantiomer 1 S,4R,9R), (2.012) isopyrazam (anti-epimeric racemate 1 RS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate 1 RS,4SR,9RS and anti-epimeric racemate 1 RS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enantiomer 1 R,
  • Inhibitors of the respiratory chain at complex III for example (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.01 1) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2- ⁇ 2-[( ⁇ [(1 E)-1 -(3- ⁇ [(3-
  • Inhibitors of the mitosis and cell division for example (4.001) carbendazim, (4.002) diethofencarb,
  • Inhibitors of the amino acid and/or protein biosynthesis for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1 -yl)quinoline.
  • Inhibitors of the ATP production for example (8.001) silthiofam.
  • Inhibitors of the cell wall synthesis for example (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1 -(morpholin-4-yl)prop-2-en-1 -one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1 -(morpholin-4-yl)prop-2-en-1 -one.
  • Inhibitors of the lipid and membrane synthesis for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
  • Inhibitors of the melanin biosynthesis for example (1 1 .001) tricyclazole, (1 1 .002) tolprocarb.
  • Inhibitors of the nucleic acid synthesis for example (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).
  • Inhibitors of the signal transduction for example (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.
  • fungicides selected from the group consisting of (15.001 ) abscisic acid, (15.002) benthiazole, (15.003) bethoxazin, (15.004) capsimycin, (15.005) carvone, (15.006) chinomethionat, (15.007) cufraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.01 1) flutianil, (15.012) fosetyl-aluminium, (15.013) fosetyl-calcium, (15.014) fosetyl-sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyldithiocarbamate, (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiprolin,
  • the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof may be combined with one or more biological control agents.
  • biological control agents which may be combined with the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof are:
  • Antibacterial agents selected from the group of:
  • (A1) bacteria such as (A1 .1) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 and described in U.S. Patent No. 6,060,051);
  • amyloliquefaciens strain FZB24 (available as Taegro® from Novozymes, US); (A1.5) a Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129 and described in International Patent Publication No. WO 2016/154297; and
  • (A2) fungi such as (A2.1) Aureobasidium pullulans, in particular blastospores of strain DSM14940; (A2.2) Aureobasidium pullulans blastospores of strain DSM 14941 ; (A2.3) Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM14941 ;
  • (B1) bacteria for example (B1.1) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 and described in U.S. Patent No. 6,060,051); (B1 .2) Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B- 30087 and described in U.S. Patent No.
  • Bacillus pumilus in particular strain GB34 (available as Yield Shield® from Bayer AG, DE); (B1 .4) Bacillus pumilus, in particular strain BU F-33 (having NRRL Accession No. 50185); (B1.5) Bacillus amyloliquefaciens, in particular strain D747 (available as Double NickelTM from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); (B1.6) Bacillus subtilis Y1336 (available as BIOBAC ® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.
  • Bacillus amyloliquefaciens strain MBI 600 (available as SUBTILEX from BASF SE); (B1 .8) Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE); (B1 .9) Bacillus subtilis var. amyloliquefaciens strain FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as the fungicide TAEGRO ® or TAEGRO ® ECO (EPA Registration No.
  • Bacillus mycoides, isolate J available as BmJ TGAI or WG from Certis USA
  • Bacillus licheniformis in particular strain SB3086 (available as EcoGuard TM Biofungicide and Green Releaf from Novozymes)
  • Bacillus licheniformis in particular strain SB3086 (available as EcoGuard TM Biofungicide and Green Releaf from Novozymes)
  • B1 .12 a Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129 and described in International Patent Publication No. WO 2016/154297.
  • the biological control agent is a Bacillus subtilis or Bacillus amyloliquefaciens strain that produces a fengycin or plipastatin-type compound, an iturin-type compound, and/or a surfactin-type compound.
  • Bacillus subtilis or Bacillus amyloliquefaciens strain that produces a fengycin or plipastatin-type compound, an iturin-type compound, and/or a surfactin-type compound.
  • Bacillus strains capable of producing lipopeptides include Bacillus subtilis QST713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 and described in U.S. Patent No. 6,060,051), Bacillus amyloliquefaciens strain D747 (available as Double NickelTM from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); Bacillus subtilis MBI600 (available as SUBTILEX ® from Becker Underwood, US EPA Reg. No.
  • Bacillus subtilis Y1336 (available as BIOBAC ® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277); Bacillus amyloliquefaciens, in particular strain FZB42 (available as RHIZOVITAL ® from ABiTEP, DE); and Bacillus subtilis var. amyloliquefaciens FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as the fungicide TAEGRO ® or TAEGRO ® ECO (EPA Registration No. 70127-5); and
  • (B2) fungi for example: (B2.1) Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM-9660; e.g. Contans ® from Bayer); (B2.2) Metschnikowia fructicola, in particular strain NRRL Y- 30752 (e.g. Shemer®); (B2.3) Microsphaeropsis ochracea (e.g. Microx® from Prophyta); (B2.5) Trichoderma spp., including Trichoderma atroviride, strain SC1 described in International Application No.
  • Trichoderma atroviride from Kumiai Chemical Industry
  • Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR);
  • Trichoderma atroviride strain no. V08/002387;
  • B2.40 Trichoderma atroviride, strain NMI no. V08/002388;
  • B2.41 Trichoderma atroviride, strain NMI no. V08/002389;
  • B2.42 Trichoderma atroviride, strain NMI no. V08/002390;
  • Trichoderma atroviride strain LC52 (e.g.
  • Trichoderma atroviride strain ATCC 20476 (IMI 206040); (B2.45) Trichoderma atroviride, strain T11 (IMI352941 / CECT20498); (B2.46) Trichoderma harmatum ; (B2.47) Trichoderma harzianum ; (B2.48) Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US); (B2.49) Trichoderma harzianum, in particular, strain KD (e.g.
  • Trichoplus from Biological Control Products, SA (acquired by Becker Underwood)); (B2.50) Trichoderma harzianum, strain ITEM 908 (e.g. Trianum-P from Koppert); (B2.51) Trichoderma harzianum, strain TH35 (e.g. Root-Pro by Mycontrol); (B2.52) Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (e.g. SoilGard 12G by Certis, US); (B2.53) Trichoderma viride, strain TV1 (e.g. Trianum-P by Koppert); (B2.54) Ampelomyces quisqualis, in particular strain AQ 10 (e.g.
  • Botector® by bio-ferm, CH (B2.64) Cladosporium cladosporioides, strain H39 (by Stichting Divichting Diviching Diviching Diviching Diviching Diviching Divichoek); (B2.69) Gliocladium catenulatum (Synonym: Clonostachys rosea f catenuiate) strain J1446 (e.g. Prestop ® by AgBio Inc. and also e.g. Primastop® by Kemira Agro Oy); (B2.70) Lecanicillium lecanii (formerly known as Verticillium lecanii ) conidia of strain KV01 (e.g.
  • Vertalec® by Koppert/Arysta (B2.71) PeniciIHum vermiculatum ⁇ , (B2.72) Pichia anomala, strain WRL-076 (NRRL Y-30842); (B2.75) Trichoderma atroviride, strain SKT-1 (FERM P-16510); (B2.76) Trichoderma atroviride, strain SKT-2 (FERM P-16511); (B2.77) Trichoderma atroviride, strain SKT-3 (FERM P-17021); (B2.78) Trichoderma gamsii (formerly T. viride), strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A.
  • strain WCS850 CBS 276.92; e.g. Dutch Trig by Tree Care Innovations
  • Verticillium chlamydosporium Verticillium chlamydosporium
  • mixtures of Trichoderma asperellum strain ICC 012 and Trichoderma gamsii strain ICC 080 product known as e.g. BIO-TAMTMfrom Bayer CropScience LP, US).
  • biological control agents which may be combined with the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof are:
  • Bacillus cereus in particular B. cereus strain CNCM I- 1562 and Bacillus ftrmus, strain 1-1582 (Accession number CNCM 1-1582), Bacillus subtilis strain OST 30002 (Accession No. NRRL B-50421), Bacillus thuringiensis, in particular B. thuringiensis subspecies israelensis (serotype H-14), strain AM65-52 (Accession No. ATCC 1276), B. thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372), B. thuringiensis subsp. kurstaki strain HD-1 , B. thuringiensis subsp.
  • viruses selected from the group consisting of Adoxophyes orana (summer fruit tortrix) granulosis virus (GV), Cydia pomonella (codling moth) granulosis virus (GV), Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, and Spodoptera littoralis (African cotton leafworm) NPV.
  • Adoxophyes orana sumr fruit tortrix
  • GV Cydia pomonella (codling moth) granulosis virus
  • NPV nuclear polyhedrosis virus
  • Spodoptera exigua beet armyworm
  • Spodoptera frugiperda fall armyworm
  • mNPV Spodoptera littoralis
  • bacteria and fungi which can be added as 'inoculant' to plants or plant parts or plant organs and which, by virtue of their particular properties, promote plant growth and plant health.
  • Examples are: Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp., or Gigaspora monosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suill
  • plant extracts and products formed by microorganisms including proteins and secondary metabolites which can be used as biological control agents such as Allium sativum, Artemisia absinthium, azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, chitin, Armour-Zen, Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Fungastop, Heads Up ( ' Chenopodium quinoa saponin extract), Pyrethrum/Pyrethrins, Quassia amara, Quercus, Quillaja, Regalia, "Requiem TM Insecticide", rotenone, ryanial ryanodine, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassica
  • insecticides examples include insecticides, acaricides and nematicides, respectively, which could be mixed with the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof are:
  • Acetylcholinesterase (AChE) inhibitors such as, for example, carbamates, for example alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or organophosphates, for example acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifo
  • GABA-gated chloride channel blockers such as, for example, cyclodiene-organochlorines, for example chlordane and endosulfan or phenylpyrazoles (fiproles), for example ethiprole and fipronil.
  • Sodium channel modulators such as, for example, pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(I R)-trans-isomer], deltamethrin, empenthrin [(EZ)-(1 R)-i
  • Nicotinic acetylcholine receptor (nAChR) competitive modulators such as, for example, neonicotinoids, e.g. acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.
  • Nicotinic acetylcholine receptor (nAChR) allosteric modulators such as, for example, spinosyns, e.g. spinetoram and spinosad.
  • Glutamate-gated chloride channel (GluCI) allosteric modulators such as, for example, avermectins/milbemycins, for example abamectin, emamectin benzoate, lepimectin and milbemectin.
  • Juvenile hormone mimics such as, for example, juvenile hormone analogues, e.g. hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen.
  • Miscellaneous non-specific (multi-site) inhibitors such as, for example, alkyl halides, e.g. methyl bromide and other alkyl halides; or chloropicrine or sulfuryl fluoride or borax or tartar emetic or methyl isocyanate generators, e.g. diazomet and metam.
  • alkyl halides e.g. methyl bromide and other alkyl halides
  • chloropicrine or sulfuryl fluoride or borax or tartar emetic or methyl isocyanate generators e.g. diazomet and metam.
  • Mite growth inhibitors such as, for example clofentezine, hexythiazox and diflovidazin or etoxazole.
  • Microbial disruptors of the insect gut membrane such as, for example Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and B.t. plant proteins: CrylAb, CrylAc, Cryl Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1/35Ab1 .
  • Inhibitors of mitochondrial ATP synthase such as, ATP disruptors such as, for example, diafenthiuron or organotin compounds, for example azocyclotin, cyhexatin and fenbutatin oxide or propargite or tetradifon.
  • ATP disruptors such as, for example, diafenthiuron or organotin compounds, for example azocyclotin, cyhexatin and fenbutatin oxide or propargite or tetradifon.
  • Nicotinic acetylcholine receptor channel blockers such as, for example, bensultap, cartap hydrochloride, thiocylam, and thiosultap-sodium.
  • Inhibitors of chitin biosynthesis type 0, such as, for example, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.
  • Inhibitors of chitin biosynthesis type 1 , for example buprofezin.
  • Moulting disruptor in particular for Diptera, i.e. dipterans, such as, for example, cyromazine.
  • Ecdysone receptor agonists such as, for example, chromafenozide, halofenozide, methoxyfenozide and tebufenozide.
  • Octopamine receptor agonists such as, for example, amitraz.
  • Mitochondrial complex III electron transport inhibitors such as, for example, hydramethylnone or acequinocyl or fluacrypyrim.
  • Mitochondrial complex I electron transport inhibitors such as, for example from the group of the METI acaricides, e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).
  • METI acaricides e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).
  • Voltage-dependent sodium channel blockers such as, for example indoxacarb or metaflumizone.
  • Inhibitors of acetyl CoA carboxylase such as, for example, tetronic and tetramic acid derivatives, e.g. spirodiclofen, spiromesifen and spirotetramat.
  • Mitochondrial complex IV electron transport inhibitors such as, for example, phosphines, e.g. aluminium phosphide, calcium phosphide, phosphine and zinc phosphide or cyanides, e.g. calcium cyanide, potassium cyanide and sodium cyanide.
  • Mitochondrial complex II electron transport inhibitors such as, for example, befa-ketonitrile derivatives, e.g. cyenopyrafen and cyflumetofen and carboxanilides, such as, for example, pyflubumide.
  • Ryanodine receptor modulators such as, for example, diamides, e.g.
  • chlorantraniliprole, cyantraniliprole and flubendiamide further active compounds such as, for example, Afidopyropen, Afoxolaner, Azadirachtin, Benclothiaz, Benzoximate, Bifenazate, Broflanilide, Bromopropylate, Chinomethionat, Chloroprallethrin, Cryolite, Cyclaniliprole, Cycloxaprid, Cyhalodiamide, Dicloromezotiaz, Dicofol, epsilon-Metofluthrin, epsilon- Momfluthrin, Flometoquin, Fluazaindolizine, Fluensulfone, Flufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon, Fluopyram, Fluralaner, Fluxametamide, Fufenozide, Guadipyr, Heptafluthrin, Imid
  • WO 2011/085575 A1 (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-dichloro-2-propen-1-yl)oxy] phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN 101337940 A) (CAS 1108184-52-6); (2 £)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-A/-[4-
  • Examples of safeners which could be mixed with the compounds of formula (I) used according to the invention, the compound(s) of formula (I’) according to the invention and compositions comprising thereof are, for example, benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole (-ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-( ⁇ 4-[(methylcarbamoyl)amino]phenyl ⁇ - sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526- 07-3), 2,2,5
  • herbicides which could be mixed with the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof are:
  • plant growth regulators are:
  • the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and the compositions comprising thereof have potent microbicidal activity. They can be used for controlling unwanted microorganisms, such as unwanted fungi and bacteria. They can be particularly useful in crop protection (they control microorganisms that cause plants diseases) or for protecting materials (e.g. industrial materials, timber, storage goods) as described in more details herein below. More specifically, the compounds of formula (I) used according to the invention, the compounds of formula (G) according to the invention and the compositions comprising thereof can be used to protect seeds, germinating seeds, emerged seedlings, plants, plant parts, fruits, harvest goods and/or the soil in which the plants grow from unwanted microorganisms.
  • Control or controlling as used herein encompasses protective, curative and eradicative treatment of unwanted microorganisms.
  • Unwanted microorganisms may be pathogenic bacteria, pathogenic virus, pathogenic oomycetes or pathogenic fungi, more specifically phytopathogenic bacteria phytopathogenic virus, phytopathogenic oomycetes or phytopathogenic fungi. As detailed herein below, these phytopathogenic microorganims are the causal agents of a broad spectrum of plants diseases.
  • the compounds of formula (I) used according to the invention, the compounds of formula (G) according to the invention and compositions comprising thereof can be used as fungicides.
  • the term“fungicide” refers to a compound or composition that can be used in crop protection for the control of unwanted fungi, such as Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes and/or for the control of Oomycetes, more preferably for the control of Basidiomycetes (causing rust diseases).
  • the present invention also relates to a method for controlling unwanted microorganisms, such as phytopathogenic fungi, oomycetes and bacteria, comprising the step of applying at least one compound of formula (I) or at least one composition comprising thereof to the microorganisms and/or their habitat (to the plants, plant parts, seeds, fruits or to the soil in which the plants grow).
  • unwanted microorganisms such as phytopathogenic fungi, oomycetes and bacteria
  • Suitable substrates that may be used for cultivating plants include inorganic based substrates, such as mineral wool, in particular stone wool, perlite, sand or gravel; organic substrates, such as peat, pine bark or sawdust; and petroleum based substrates such as polymeric foams or plastic beads.
  • Effective and plant-compatible amount means an amount that is sufficient to control or destroy the fungi present or liable to appear on the cropland and that does not entail any appreciable symptom of phytotoxicity for said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the crop growth stage, the climatic conditions and the respective compound or composition of the invention used. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.
  • the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof may be applied to any plants or plant parts.
  • Plants mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the genetically modified plants (GMO or transgenic plants) and the plant cultivars which are protectable and non-protectable by plant breeders’ rights.
  • Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples of which include leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes.
  • the plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
  • Plants which may be treated in accordance with the methods of the invention include the following: cotton, flax, grapevine, fruit, vegetables, such as Rosaceae sp. (for example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp.
  • Rosaceae sp. for example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries
  • Rosaceae sp. for example pome fruits such as apples and pears, but also
  • Rubiaceae sp. for example coffee
  • Theaceae sp. Sterculiceae sp.
  • Rutaceae sp. for example lemons, oranges and grapefruit
  • Solanaceae sp. for example tomatoes
  • Liliaceae sp. for example lettuce
  • Umbelliferae sp. for example lettuce
  • Alliaceae sp. for example leek, onion
  • peas for example peas
  • major crop plants such as Gramineae sp. (for example maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (for example sunflower), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, and oilseed rape, mustard, horseradish and cress), Fabacae sp. (for example bean, peanuts), Papilionaceae sp. (for example soya bean), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example sugar beet, fodder beet, swiss chard, beetroot); useful plants and ornamental plants for gardens and wooded areas; and genetically modified varieties of each of these plants.
  • wild plant species and plant cultivars or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated in accordance with the methods of the invention.
  • transgenic plants and plant cultivars obtained by genetic engineering methods if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated in accordance with the methods of the invention. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention.
  • Plant cultivars are understood to mean plants which have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
  • GMOs genetically modified organisms
  • Genetically modified plants are plants of which a heterologous gene has been stably integrated into 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 down regulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microRNA - miRNA - 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.
  • Plants and plant cultivars which can be treated by the above disclosed methods 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 can be treated by the above disclosed methods include plants and plant cultivars which 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 can be treated by the above disclosed methods include those plants which are resistant to one or more abiotic stresses.
  • Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
  • Plants and plant cultivars which can be treated by the above disclosed methods include 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 and composition for example cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
  • Plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars which are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering
  • plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars which 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.
  • Plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars which 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. Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars which 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.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which can be treated by the above disclosed methods include plants and plant cultivars which show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which can be treated by the above disclosed methods include plants and plant cultivars, 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.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering
  • plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered oil profile characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which can be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which can be treated by the above disclosed methods include plants and plant cultivars, such as Tobacco plants, with altered post-translational protein modification patterns.
  • the methods disclosed above can be used to control microorganisms, in particular phytopathogenic microorganisms such as phytopathogenic fungi, causing diseases, such as: diseases caused by powdery mildew pathogens, such as Blumeria species (e.g. Blumeria graminis), Podosphaera species (e.g. Podosphaera leucotricha), Sphaerotheca species (e.g. Sphaerotheca fuliginea), Uncinula species (e.g. Uncinula necator);
  • diseases caused by powdery mildew pathogens such as Blumeria species (e.g. Blumeria graminis), Podosphaera species (e.g. Podosphaera leucotricha), Sphaerotheca species (e.g. Sphaerotheca fuliginea), Uncinula species (e.g. Uncinula necator);
  • Gymnosporangium species e.g. Gymnosporangium sabinae
  • Hemileia species e.g. Hemileia vastatrix
  • Phakopsora species e.g. Phakopsora pachyrhizi or Phakopsora meibomiae
  • Puccinia species e.g. Puccinia recondita, Puccinia graminis or Puccinia striiformis
  • Uromyces species e.g. Uromyces appendiculatus
  • Albugo species e.g. Albugo Candida
  • Bremia species e.g. Bremia lactucae
  • Peronospora species e.g. Peronospora pisi or P. brassicae
  • Phytophthora species e.g. Phytophthora infestans
  • Plasmopara species e.g. Plasmopara viticola
  • Pseudoperonospora species e.g. Pseudoperonospora humuli or Pseudoperonospora cubensis
  • Pythium species e.g. Pythium ultimum
  • Pythium species e.g. Pythium ultimum
  • leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species (e.g. Alternaria solani), Cercospora species (e.g. Cercospora beticola), Cladiosporium species (e.g. Cladiosporium cucumerinum), Cochliobolus species (e.g. Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium) or Cochliobolus miyabeanus), Colletotrichum species (e.g. Colletotrichum lindemuthanium), Cycloconium species (e.g. Cycloconium oleaginum), Diaporthe species (e.g.
  • Diaporthe citri Elsinoe species (e.g. Elsinoe fawcettii), Gloeosporium species (e.g. Gloeosporium laeticolor), Glomerella species (e.g. Glomerella cingulate), Guignardia species (e.g. Guignardia bidwelli), Leptosphaeria species (e.g. Leptosphaeria maculans), Magnaporthe species (e.g. Magnaporthe grisea), Microdochium species (e.g. Microdochium nivale), Mycosphaerella species (e.g.
  • Phaeosphaeria species e.g. Phaeosphaeria nodorum
  • Corticium species e.g. Corticium graminearum
  • Fusarium species e.g. Fusarium oxysporum
  • Gaeumannomyces species e.g. Gaeumannomyces graminis
  • Plasmodiophora species e.g. Plasmodiophora brassicae
  • Rhizoctonia species e.g. Rhizoctonia solani
  • Sarocladium species e.g. Sarocladium oryzae
  • Sclerotium species e.g. Sclerotium oryzae
  • Tapesia species e.g. Tapesia acuformis
  • Thielaviopsis species e.g. Thielaviopsis basicola
  • Thielaviopsis species e.g. Thielaviopsis basicola
  • ear and panicle diseases caused, for example, by Alternaria species, (e.g. Alternaria spp.), Aspergillus species (e.g. Aspergillus flavus), Cladosporium species (e.g. Cladosporium cladosporioides, Claviceps species (e.g. Claviceps purpurea), Fusarium species, (e.g. Fusarium culmorum), Gibberella species (e.g. Gibberella zeae), Monographella species, (e.g. Monographella nivalis), Stagnospora species, (e.g. Stagnospora nodorum);
  • Alternaria species e.g. Alternaria spp.
  • Aspergillus species e.g. Aspergillus flavus
  • Cladosporium species e.g. Cladosporium cladosporioides
  • Claviceps species e.g. Clavic
  • Sphacelotheca species e.g. Sphacelotheca reiliana
  • Tilletia species e.g. Tilletia caries or Tilletia controversa
  • Urocystis species e.g. Urocystis occulta
  • Ustilago species e.g. Ustilago nuda
  • fruit rot caused, for example, by Aspergillus species (e.g. Aspergillus flavus), Botrytis species (e.g. Botrytis cinerea), Penicillium species (e.g. Penicillium expansum or Penicillium purpurogenum), Rhizopus species (e.g. Rhizopus stolonifer), Sclerotinia species (e.g. Sclerotinia sclerotiorum), Verticilium species (e.g. Verticilium alboatrum) ; seed- and soil-borne rot and wilt diseases, and also diseases of seedlings, caused, for example, by Alternaria species (e.g.
  • Alternaria brassicicola Aphanomyces species (e.g. Aphanomyces euteiches), Ascochyta species (e.g. Ascochyta lentis), Aspergillus species (e.g. Aspergillus flavus), Cladosporium species (e.g. Cladosporium herbarum), Cochliobolus species (e.g. Cochliobolus sativus (conidial form: Drechslera, Bipolaris Syn: Helminthosporium)), Colletotrichum species (e.g. Colletotrichum coccodes), Fusarium species (e.g. Fusarium culmorum), Gibberella species (e.g.
  • Macrophomina species e.g. Macrophomina phaseolina
  • Microdochium species e.g. Microdochium nivale
  • Monographella species e.g. Monographella nivalis
  • Penicillium species e.g. Penicillium expansum
  • Phoma species e.g. Phoma lingam
  • Phomopsis species e.g. Phomopsis sojae
  • Phytophthora species e.g. Phytophthora cactorum
  • Pyrenophora species e.g. Pyrenophora graminea
  • Pyricularia species e.g. Pyricularia oryzae
  • Pythium species e.g.
  • Rhizoctonia species e.g. Rhizoctonia solani
  • Rhizopus species e.g. Rhizopus oryzae
  • Sclerotium species e.g. Sclerotium rolfsii
  • Septoria species e.g. Septoria nodorum
  • Typhula species e.g. Typhula incarnate
  • Verticillium species e.g. Verticillium dahlia
  • Nectria species e.g. Nectria galligena
  • Monilinia species e.g. Monilinia laxa
  • Exobasidium species e.g. Exobasidium vexans
  • Taphrina species e.g. Taphrina deformans
  • degenerative diseases in woody plants caused, for example, by Esca species (e.g. Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranea), Ganoderma species (e.g. Ganoderma boninense);
  • Esca species e.g. Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranea
  • Ganoderma species e.g. Ganoderma boninense
  • Botrytis species e.g. Botrytis cinerea
  • Rhizoctonia species e.g. Rhizoctonia solani
  • Helminthosporium species e.g. Helminthosporium solani
  • Xanthomonas species e.g. Xanthomonas campestris pv. Oryzae
  • Pseudomonas species e.g. Pseudomonas syringae pv. Lachrymans
  • Erwinia species e.g. Erwinia amylovora
  • the compounds of formula (I) used according to the invention, the compounds of formula (G) according to the invention and compositions comprising thereof are efficient in controlling pythopathogenic fungi causing rust diseases.
  • the method for controlling unwanted microorganisms may be used to protect seeds from phytopathogenic microorganisms, such as fungi.
  • seed(s) include dormant seed, primed seed, pregerminated seed and seed with emerged roots and leaves.
  • the present invention also relates to a method for protecting seeds and/or crops from unwanted microorganisms, such as bacteria or fungi, which comprises the step of treating the seeds with one or more compounds of formula (I) or a composition comprising thereof.
  • the treatment of seeds with the compound(s) of formula (I) or or a composition comprising thereof not only protects the seeds from phytopathogenic microorganisms, but also the germinating plants, the emerged seedlings and the plants after emergence.
  • the seeds treatment may be performed prior to sowing, at the time of sowing or shortly thereafter.
  • the seeds treatment may be performed as follows: the seeds may be placed into a mixer with a desired amount of compound(s) of formula (I) or a composition comprising thereof (either as such or after dilution), the seeds and the compound(s) of formula (I) or the composition comprising thereof are mixed until a homogeneous distribution on seeds is achieved. If appropriate, the seeds may then be dried.
  • the invention also relates to seeds treated with one or more compounds of formula (I) or a composition comprising thereof.
  • treated seeds allows not only protecting the seeds before and after sowing from unwanted microorganisms, such as phytopathogenic fungi, but also allows protecting the germinating plants and young seedlings emerging from said treated seeds.
  • a large part of the damage to crop plants caused by harmful organisms is triggered by the infection of the seeds before sowing or after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even small damage may result in the death of the plant.
  • the present invention also relates to a method for protecting seeds, germinating plants and emerged seedlings, more generally to a method for protecting crop from phytopathogenic microorganisms, which comprises the step of using seeds treated by one or more compounds of formula (I) or a composition comprising thereof.
  • the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment.
  • seeds can be treated at any time between harvest and shortly after sowing. It is customary to use seeds which have been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seeds which have been harvested, cleaned and dried down to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seeds which, after drying, for example, have been treated with water and then dried again, or seeds just after priming, or seeds stored in primed conditions or pre-germinated seeds, or seeds sown on nursery trays, tapes or paper.
  • the amount of compound(s) of formula (I) or composition comprising thereof applied to the seed is typically such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This must be ensured particularly in case the active ingredients would exhibit phytotoxic effects at certain application rates.
  • the intrinsic phenotypes of transgenic plants should also be taken into consideration when determining the amount of compound(s) of formula (I) or composition comprising thereof to be applied to the seed in order to achieve optimum seed and germinating plant protection with a minimum amount of compound(s) of formula (I) or composition comprising thereof being employed.
  • the compounds of the formula (I) can be applied, as such, directly to the seeds, i.e.
  • compositions are applied to the seed in any suitable form.
  • suitable formulations include solutions, emulsions, suspensions, powders, foams, slurries or combined with other coating compositions for seed, such as film forming materials, pelleting materials, fine iron or other metal powders, granules, coating material for inactivated seeds, and also ULV formulations.
  • the formulations may be ready-to-use formulations or may be concentrates that need to be diluted prior to use.
  • formulations are prepared in a known manner, for instance by mixing the active ingredient or mixture thereof with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • customary additives for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • formulations are prepared in a known manner, by mixing the active ingredients or active ingredient combinations with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • customary additives for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • Useful dyes which may be present in the seed dressing formulations are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.l. Pigment Red 112 and C.l. Solvent Red 1 .
  • Useful wetting agents which may be present in the seed dressing formulations are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients. Usable with preference are alkylnaphthalenesulfonates, such as diisopropyl- or diisobutylnaphthalenesulfonates.
  • Useful dispersants and/or emulsifiers which may be present in the seed dressing formulations are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Usable with preference are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Useful nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sulfated derivatives thereof.
  • Suitable anionic dispersants are especially lignosulfonates, polyacrylic acid salts and arylsulfonate/formaldehyde condensates.
  • Antifoams which may be present in the seed dressing formulations are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.
  • Preservatives which may be present in the seed dressing formulations are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.
  • Secondary thickeners which may be present in the seed dressing formulations are all substances usable for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
  • Adhesives which may be present in the seed dressing formulations are all customary binders usable in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
  • the compounds of the formula (I) and the compositions comprising thereof are suitable for protecting seeds of any plant variety which is used in agriculture, in greenhouses, in forests or in horticulture. More particularly, the seed is that of cereals (such as wheat, barley, rye, millet, triticale, and oats), oilseed rape, maize, cotton, soybean, rice, potatoes, sunflower, beans, coffee, peas, beet (e.g. sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onions and lettuce), lawns and ornamental plants. Of particular significance is the treatment of the seed of wheat, soybean, oilseed rape, maize and rice.
  • the compounds of formula (I) or the compositions comprising thereof can be used for treating transgenic seeds, in particular seeds of plants capable of expressing a protein which acts against pests, herbicidal damage or abiotic stress, thereby increasing the protective effect. Synergistic effects may also occur in interaction with the substances formed by expression.
  • the compound of formula (I) can be applied as such, or for example in the form of as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with the compound of formula (I), synthetic substances impregnated with the compound of formula (I), fertilizers or microencapsulations in polymeric substances.
  • Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading-on and the like. It is also possible to deploy the compound of formula (I) by the ultra-low volume method, via a drip irrigation system or drench application, to apply it infurrow or to inject it into the soil stem or trunk. It is further possible to apply the compound of formula (I) by means of a wound seal, paint or other wound dressing.
  • the effective and plant-compatible amount of the compound of formula (I) which is applied to the plants, plant parts, fruits, seeds or soil will depend on various factors, such as the compound/composition employed, the subject of the treatment (plant, plant part, fruit, seed or soil), the type of treatment (dusting, spraying, seed dressing), the purpose of the treatment (curative and protective), the type of microorganisms, the development stage of the microorganisms, the sensitivity of the microorganisms, the crop growth stage and the environmental conditions.
  • the application rates can vary within a relatively wide range, depending on the kind of application.
  • the application rate may range from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more preferably from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used).
  • the application rate may range from 0.1 to 200 g per 100 kg of seeds, preferably from 1 to 150 g per 100 kg of seeds, more preferably from 2.5 to 25 g per 100 kg of seeds, even more preferably from 2.5 to 12.5 g per 100 kg of seeds.
  • the application rate may range from 0.1 to 10 000 g/ha, preferably from 1 to 5000 g/ha.
  • the compound and the composition of the invention may also be used in the protection of materials, especially for the protection of industrial materials against attack and destruction by unwanted microorganisms.
  • the compound and the composition of the invention may be used as antifouling compositions, alone or in combinations with other active ingredients.
  • Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry.
  • industrial materials which are to be protected from microbial alteration or destruction may be adhesives, glues, paper, wallpaper and board/cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms.
  • Parts of production plants and buildings, for example cooling-water circuits, cooling and heating systems and ventilation and air-conditioning units, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected.
  • Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood.
  • the compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • the compound and the composition of the invention may also be used against fungal diseases liable to grow on or inside timber.
  • 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 compound and the composition of the invention may be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signaling systems, from fouling.
  • Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired.
  • Storage goods of vegetable origin for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, may be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting.
  • Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture.
  • Storage goods of animal origin are, for example, hides, leather, furs and hairs.
  • the compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • Microorganisms capable of degrading or altering industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms.
  • the compound and the composition of the invention preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi ( Ascomycetes , Basidiomycetes, Deuteromycetes and Zygomycetes), and against slime organisms and algae.
  • microorganisms of the following genera Alternaria, such as Altemaria tenuis Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana Lentinus, such as Lentinus tigrinus ; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans ; Sclerophoma, such as Sclerophoma pityophila ; Trichoderma, such as Trichoderma viride Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Poria
  • LogP value is determined by measurement of LC-UV, in an acidic range, with 0.1 % formic acid in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
  • [bl LogP value is determined by measurement of LC-UV, in a neutral range, with 0.001 molar ammonium acetate solution in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
  • [cl LogP value is determined by measurement of LC-UV, in an acidic range, with 0.1 % phosphoric acid and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
  • 1 H-NMR data of selected examples are written in form of 1 H-NMR-peak lists. To each signal peak are listed the d-value in ppm and the signal intensity in round brackets. Between the 5-value - signal intensity pairs are semicolons as delimiters.
  • the peak list of an example has therefore the form: di (intensityi); 82 (intensityz); . ; 5, (intensity,); ; 5n (intensityn)
  • Intensity of sharp signals correlates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectrum can be shown.
  • tetramethylsilane For calibrating chemical shift for 1 H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilane peak can occur but not necessarily.
  • the 1 H-NMR peak lists are similar to classical 1 H-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation.
  • the peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).
  • Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore their peaks can help to recognize the reproduction of our preparation process via“side-products-fingerprints”.
  • An expert who calculates the peaks of the target compounds with known methods (MestreC, ACD- simulation, but also with empirically evaluated expectation values) can isolate the peaks of the target compounds as needed optionally using additional intensity filters. This isolation would be similar to relevant peak picking at classical 1 H-NMR interpretation.
  • Emulsifier 1 mI of Tween ® 80 per mg of active ingredient
  • the active ingredients were made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of wheat were treated by spraying the active ingredient prepared as described above.
  • Control plants were treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween ® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores.
  • the contaminated wheat plants were incubated for 24 hours at 20°C and at 100% relative humidity and then for 9 days at 20°C and at 70-80% relative humidity.
  • the test was evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
  • Emulsifier 1 pi of Tween ® 80 per mg of active ingredient
  • the active ingredients were made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of soybean were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Phakospora pachyrhizi spores.
  • the contaminated soybean plants were incubated for 24 hours at 24°C and at 100% relative humidity and then for 10 days at 24°C and at 70-80% relative humidity.
  • the test was evaluated 1 1 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
  • Culture medium 14.6g anhydrous D-glucose (VWR), 7.1 g Mycological Peptone (Oxoid), 1 .4g granulated Yeast Extract (Merck), QSP 1 liter
  • Inoculum mycelial suspension
  • Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations.
  • the final concentration of DMSO used in the assay was ⁇ D1 %.
  • Inoculum was prepared from a pre-culture of R. solani grown in liquid medium by homogenization using a blender. The concentration of ground mycelium in the inoculum was estimated and adjusted to the desired optical density (OD).
  • Fungicides were evaluated for their ability to inhibit mycelium growth in liquid culture assay.
  • the compounds were added in the desired concentrations to culture medium containing the mycelial suspension. After 5 days of incubation, the fungicidal efficacy of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
  • Culture medium 14.6g anhydrous D-glucose (VWR), 7.1 g Mycological Peptone (Oxoid), 1 .4g granulated Yeast Extract (Merck), QSP 1 liter
  • Inoculum spores suspension
  • Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations.
  • the final concentration of DMSO used in the assay was ⁇ D1 %.
  • a spore suspension of C. lindemuthianum was prepared and diluted to the desired spore density.
  • Fungicides were evaluated for their ability to inhibit spores germination and mycelium growth in liquid culture assay.
  • the compounds were added in the desired concentration to the culture medium with spores. After 6 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
  • Emulsifier 1 part by weight of polyoxyethylene sorbitan monooleate
  • the plants remained in the incubation cabinet at approximately 24°C and a relative atmospheric humidity of approximately 80 % and a day / night interval of 12h.
  • Emulsifier 1 part by weight of polyoxyethylene sorbitan monooleate
  • the plants remained in the incubation cabinet at approximately 24°C and a relative atmospheric humidity of approximately 80 % and a day / night interval of 12h.
  • Emulsifier 1 part by weight of polyoxyethylene sorbitan monooleate To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.

Abstract

The present invention relates to heterocyclylaminophenyloxadiazole and derivatives thereof that may be used as fungicides.

Description

FUNGICIDAL OXADIAZOLES
TECHNICAL FIELD
The present invention relates to heterocyclylaminophenyloxadiazole and derivatives thereof that may be used as fungicides.
BACKGROUND
Oxadiazole derivatives are known to be useful as crop protection agents to combat or prevent microorganisms’ infestations. For instance, WO2017/1 10862 and WO2018/187553 discloses oxadiazole derivatives that may be used as fungicides.
Numerous fungicidal agents have been developed until now. However, the need remains for the development of new fungicidal compounds as such, so as to provide compounds being effective against a broad spectrum of fungi, having lower toxicity, higher selectivity, being used at lower dosage rate to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control. It may also be desired to have new compounds to prevent the emergence of fungicides resistances.
The present invention provides new fungicidal compounds which have advantages over known compounds and compositions in at least some of these aspects.
SUMMARY
The present invention relates to the use of compounds of the formula (I) for controlling phytopathogenic fungi on plants, in particular fungi causing rust diseases in crop protection:
Figure imgf000002_0001
wherein Cy, X, R1 , R2, R3, R4, R5 and n are described herein.
The present invention also relates to compounds of the formula (G) as defined herein.
The present invention relates to a composition comprising at least one compound of formula (G) as defined herein and at least one agriculturally suitable auxiliary.
The present invention relates to a method for controlling phytopathogenic fungi which comprises the step of applying at least one compound of formula (I) as defined herein or a composition as defined herein to the plants, plant parts, seeds, fruits or to the soil in which the plants grow. DEFINITIONS
The term“alkyl” as used herein in the context of alkyl or alkylsulfonyl, alkylsulfinyl, alkylthio, alkylamino, for example, is to be understood as preferably meaning branched and unbranched alkyl, meaning e.g. methyl, ethyl, n-propyl, /so-propyl, n-butyl, /so-butyl, fe/ -butyl, sec-butyl, pentyl, /so-pentyl, hexyl, heptyl, octyl, nonyl and decyl and the isomers thereof.
The term “haloalkyl” as used herein is to be understood as preferably meaning branched and unbranched alkyl, as defined supra, in which one or more of the hydrogen substituents is replaced in the same way or differently with halogen. Particularly preferably, said haloalkyl is, e.g. chloromethyl, fluoropropyl, fluoromethyl, difluoromethyl, trichloromethyl, 2,2 ,2-trifluoroethyl , pentafluoroethyl, bromobutyl, trifluoromethyl, iodoethyl, and isomers thereof.
The term“alkoxy” as used herein is to be understood as preferably meaning branched and unbranched alkoxy, meaning e.g. methoxy, ethoxy, propyloxy, /so-propyloxy, butyloxy, /so-butyloxy, fe/ -butyloxy, sec-butyloxy, pentyloxy, /so-pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy and dodecyloxy and the isomers thereof.
The term “haloalkoxy” as used herein is to be understood as preferably meaning branched and unbranched alkoxy, as defined supra, in which one or more of the hydrogen substituents is replaced in the same way or differently with halogen, e.g. chloromethoxy, fluoromethoxy, pentafluoroethoxy, fluoropropyloxy, difluoromethyloxy, trichloromethoxy, 2,2,2-trifluoroethoxy, bromobutyloxy, trifluoromethoxy, iodoethoxy, and isomers thereof.
The term“carbocyclyl” as used herein refers to a non-aromatic mono- or polycyclic (fused, spiro or bridged) carbon containing ring, which may be saturated or partially unsaturated, having 3 to 10 ring carbon atoms. Examples of carbocyclyl include cycloalkyl and cycloalkenyl groups. Examples of saturated cycloalkyl include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl group. Examples of partially unsaturated carbocyclyl group include but are not limited to cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, or cyclodecenyl group, wherein the linkage of said cyclolaklyl group to the rest of the molecule can be provided to the double or single bond.
The term“heterocyclyl” as used herein refers to three- to ten-membered, preferably three- to nine- membered, saturated or partially unsaturated heterocycles (including mono-, bi- or tricyclic heterocycles) containing one to four heteroatoms independently selected from the group of oxygen, nitrogen and sulphur. If the ring contains more than one oxygen atom, they are not directly adjacent. Examples of heterocyclyl group include but are not limited to oxiranyl, aziridinyl, 2-tetrahydrofuranyl, 3- tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl,
4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4- pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl,
5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin-5-yl, 1 ,2,4- thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3-yl, 1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4- thiadiazolidin-2-yl, 1 ,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4- dihydrofur-3-yl, 2,3-dihyd rothien-2-yl, 2,3-dihyd rothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl,
2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4- isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3- isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3- dihydropyrazol-1 -yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3- dihydropyrazol-5-yl, 3,4-dihydropyrazol-l -yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4- dihydropyrazol-5-yl, 4,5-dihydropyrazol-l -yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5- dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3- dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4- dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl,
3-piperidinyl, 4-piperidinyl, 1 ,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5- hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl, 1 ,2,4-hexahydrotriazin-3-yl, indol-1 -yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-1 -yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-1 -yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, 1 -benzofuran-2-yl, 1 -benzofuran-3-yl, 1 -benzofuran-4-yl, 1 -benzofuran-5-yl, 1 - benzofuran-6-yl, 1 -benzofuran-7-yl, 1 -benzothiophen-2-yl, 1 -benzothiophen-3-yl, 1 -benzothiophen-4-yl, 1 -benzothiophen-5-yl, 1 -benzothiophen-6-yl, 1 -benzothiophen-7-yl, 1 ,3-benzothiazol-2-yl, 1 ,3- benzothiazol-4-yl, 1 ,3-benzothiazol-5-yl, 1 ,3-benzothiazol-6-yl, 1 ,3-benzothiazol-7-yl, 1 ,3-benzoxazol-2- yl, 1 ,3-benzoxazol-4-yl, 1 ,3-benzoxazol-5-yl, 1 ,3-benzoxazol-6-yl and 1 ,3-benzoxazol-7-yl, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1 -yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl and isoquinolin-8-yl. This definition also applies to heterocyclyl as part of a composite substituent, for example heterocyclylalkyl etc., unless defined elsewhere.
The term“halogen” or“Hal” as used herein is to be understood as meaning fluorine, chlorine, bromine or iodine.
The term“alkenyl” as used herein is to be understood as preferably meaning branched and unbranched alkenyl, e.g. a vinyl, propen-1 -yl, propen-2-yl, but-1 -en-1 -yl, but-1 -en-2-yl, but-2-en-1 -yl, but-2-en-2-yl, but-1 -en-3-yl, 2-methyl-prop-2-en-1 -yl, or 2-methyl-prop-1 -en-1 -yl group.
The term“alkynyl” as used herein is to be understood as preferably meaning branched and unbranched alkynyl, e.g. an ethynyl, prop-1 -yn-1 -yl, but-1 -yn-1 -yl, but-2-yn-1 -yl,or but-3-yn-1 -yl group.
The term“aryl” as used herein refers to an aromatic, hydrocarbon, ring system, comprising from 6 to 15, or from 6 to 12 carbon atoms, preferably from 6 to 10 carbon atoms. The ring system may be monocyclic or fused polycyclic (e.g. bicyclic or tricyclic) aromatic ring system. Examples of aryl include but are not limited to phenyl, azulenyl, naphthyl and fluorenyl. It is further understood that when said aryl group is substituted with one or more substituents, said substituent(s) may be at any positions on said aryl ring(s). Particularly, in the case of aryl being a phenyl group, said substituent(s) may occupy one or both ortho positions, one or both meta positions, or the para position, or any combination of these positions. This definition also applies to aryl as part of a composite substituent (e.g. aryloxy).
The term“heteroaryl” as used herein refers to an aromatic ring system containing from 5 to 15 member atoms, or from 5 to 12 member atoms, of which carbons and one or more heteroatoms which may be identical or different selected from O, N and S. If the ring contains more than one oxygen atom, they are not directly adjacent. Heteroaryl may be monocyclic or polycyclic (e.g. bicyclic or tricyclic). A monocyclic heteroaryl may have 1 to 4 heteroatoms in the ring, while a polycyclic heteroaryl ring may have 1 to 10 heteroatoms. Bicyclic heteroaryl rings may contain from 8 to 15, or from 8 to 12 member atoms (carbon and heteroatoms). Monocyclic heteroaryl may contain from 5 to 8 member atoms. Examples of heteroaryl include but are not limited to thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl etc., and benzo derivatives thereof, such as, e.g., benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl, etc.·, or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and benzo derivatives thereof, such as, for example, quinolinyl, isoquinolinyl, etc. ·, or azocinyl, indolizinyl, purinyl, etc., and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthpyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, xanthenyl, or oxepinyl, etc. It is further understood that in the case in which said heteroaryl group is substituted with one or more substituents, said substituent(s) may occupy any one or more positions on said heteroaryl ring(s). Particularly, in the case of heteroaryl being a pyridyl group, for example, said substituent(s) may occupy any one or more of positions 2, 3, 4, 5, and/or 6 with respect to the nitrogen atom in the pyridine ring. This definition also applies to heteroaryl as part of a composite substituent (e.g. heteroaryloxy).
As used herein, the term“C1-C6”, e.g. in the context of the definition of“Ci-C6-alkyl”, or“Ci-C6-alkoxy”, is to be understood as meaning a group having a finite number of carbon atoms of 1 to 6, i.e. 1 , 2, 3, 4, 5, or 6 carbon atoms.
The terms “acyclic radicals” as used herein in the expressions “wherein acyclic radicals may be substituted” designate any of the acyclic groups recited in the paragraph before said expressions, or any acyclic moiety of a composite group (e.g. the Ci-Cs-alkyl moiety of aryl-Ci-Cs-alkyl).
The term“cyclic radicals” as used herein in the expressions“wherein cyclic radicals may be substituted” designate any of the cyclic groups, be it alicyclic or aromatic, recited in the paragraph before said expressions, or any cyclic moiety of a composite group (e.g. the aryl moiety of aryl-Ci-C6-alkyl).
In a group containing an acyclic moiety and a cyclic moiety (e.g. aryl-Ci-C6-alkyl), each of these moieties may be substituted independently of each other. The term“leaving group” as used herein is to be understood as meaning a group which is displaced from a compound in a substitution or an elimination reaction, for example a halogen atom, a trifluoromethanesulphonate (“triflate”) group, alkoxy, methanesulphonate, p-toluenesulphonate, etc..
DETAILED DESCRIPTION
ACTIVE INGREDIENTS
The present invention relates to the use of compounds of formula (I) for controlling phytopathogenic fungi on plants (in particular fungi causing rust diseases in crop protection):
Figure imgf000006_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, cyano, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-Cs-haloalkynyl, C3-C7- carbocyclyl, aryl, 3- to 10-membered-heterocyclyl, heteroaryl, aryl-Ci-Cs-alkyl, 3- to 10- membered-heterocyclyl-Ci-C8-alkyl, heteroaryl-Ci-Cs-alkyl and C3-C7-carbocyclyl-Ci-C8-alkyl, wherein said acyclic R1 and R2 may be substituted with, respectively one or more R1a and R2a substituents and said cyclic R1 and R2 may be substituted with, respectively one or more R1b and R2b substituents, or
R1 , R2 may form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl or a 3- to 10-membered heterocyclyl, wherein said C3-C7-carbocyclyl or 3- to 10-membered heterocyclyl may be substituted with one or more R1b substituents;
Cy is C3-Cio-carbocyclyl, 3- to 10-membered heterocyclyl, aryl or heteroaryl;
n is 0, 1 , 2, 3 or 4;
R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci-C6-hydroxyalkyl, C1-C6- alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, C1-C6- haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs- alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-C6-haloalkylsulfonylamino, sulfamoyl, Ci-C8-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl-Ci-C6-alkyl and heteroaryl,
wherein said acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, formyl, Ci-C6-alkyl, C1-C6- haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -C(=0)-Ci-C6- alkyl, -C(=0)-Ci-C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=S)-Ci-C6-haloalkyl, -C(=0)-0-Ci-C6- alkyl, -C(=0)-0-Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, C1-C6- haloalkylsulfonyl, phenylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl (phenyl), heteroaryl, C3-Cio-carbocyclyl-Ci-C6-alkyl, C3-Cio-carbocyclyl-Ci-C6-haloalkyl, aryl- Ci-C6-alkyl, aryl-Ci-C6-haloalkyl, heteroaryl-Ci-C6-alkyl and heteroaryl-Ci-C6-haloalkyl, wherein said acyclic and cyclic R4 may be substituted with one or more substituents selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R5 is hydrogen or fluorine;
R1a, R2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, Ci-Ce-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Ce-haloalkylsulfonyl, Ci-Cs-alkylsulfonylamino, Ci-Cs-haloalkylsulfonylamino, sulfamoyl, Ci-Ce-alkylsulfamoyl and di-Ci-Cs-alkylsulfamoyl;
R1b, R2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, Ci-C6-alkyl-C(=0)-NH-, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, hydroxy- Ci-C6-alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, C1-C6- alkoxycarbonyl, Ci-C6-haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci-Cs-haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, C1-C6- haloalkylsulfonylamino, sulfamoyl, Ci-Cs-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
provided that the compound of formula (I) is not: (a) N-[1-(pyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(b) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-[1-(pyridin-2-yl)cyclobutyl]pyrimidin-2-amine;
(c) N-(1 -phenylcyclopropyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(d) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-(1-phenylcyclopropyl)pyrimidin-2-amine.
Compounds (a), (b), (c) and (d) are disclosed in WO2019/122323.
The invention encompasses pure stereoisomers of the compound of formula (I) respectively (G) and any mixture of these isomers.
Not encompassed herein are compounds resulting from combinations which are against natural laws and which the person skilled in the art would therefore exclude based on his/her expert knowledge. For instance, ring structures having three or more adjacent oxygen atoms are excluded.
Depending on the nature of the substituents, the compound of formula (I) respectively (G) may be present in the form of different stereoisomers. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the invention encompasses both pure stereoisomers and any mixture of these isomers. Where a compound can be present in two or more tautomer forms in equilibrium, reference to the compound by means of one tautomeric description is to be considered to include all tautomer forms.
Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound. Geometric isomers by nature of substituents about a double bond or a ring may be present in cis (= Z-) or trans (= E-) form. The invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions.
The compound of formula (I) respectively (G) can suitably be in its free form, salt form, N-oxide form or solvate form (e.g. hydrate).
Depending on the nature of the substituents, the compound of formula (I) respectively (G) may be present in the form of the free compound and/or a salt thereof, such as an agrochemically active salt. Agrochemically active salts include acid addition salts of inorganic and organic acids well as salts of customary bases. Examples of inorganic acids are hydrohalic acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid, and acidic salts, such as sodium bisulfate and potassium bisulfate. Useful organic acids include, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated or mono- or diunsaturated fatty acids having 6 to 20 carbon atoms, alkylsulfuric monoesters, alkylsulfonic acids (sulfonic acids having straight- chain or branched alkyl radicals having 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl, which bear one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which bear one or two phosphonic acid radicals), where the alkyl and aryl radicals may bear further substituents, for example p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2- phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.
Solvates of the compounds of formula (I) respectively (G) or their salts are stoichiometric compositions of the compounds with solvents.
The compounds of formula (I) respectively (G) may exist in multiple crystalline and/or amorphous forms. Crystalline forms include unsolvated crystalline forms, solvates and hydrates.
Compounds of formula (I) respectively (G) are referred herein as“active ingredients”.
In some embodiments, in the above formula (I), R1 and R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl (preferably C3-C7-cycloalkyl), or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (preferably C3-C7-cycloalkyl and C3-C7-cycloalkenyl) or a 3- to 10-membered heterocyclyl. R1 and R2 may be substituted as described herein.
In some embodiments, in the above formula (I), R1 and R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl (e.g. cyclopropyl).
In some embodiments, in the above formula (I), R1 and R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl (preferably phenyl), or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl ring. R1 and R2 may be substituted as described herein. In particular, R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl, and halogen.
In some preferred embodiments, in the above formula (I), R1 and R2 are independently selected from the group consisting of hydrogen, methyl and phenyl, or R1 and R2 form, together with the carbon atom to which they are linked, a cyclopropyl or cyclobutyl ring, wherein the cyclopropyl and cyclobutyl ring may be substituted with one or more substituents selected from hydroxy, methyl and fluorine.
In some embodiments, in the above formula (I), Cy is phenyl or 5- or 6-membered heteroaryl, preferably selected from the group consisting of phenyl, furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl. In some of these embodiments, Cy is selected from the group consisting of phenyl, thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl and pyrazinyl. Cy may be substituted as described herein. In some embodiments, in the above formula (I), Cy is phenyl.
In some embodiments, in the above formula (I), Cy is a 5-membered heteroaryl selected from the group consisting of furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl and tetrazolyl. In some of these embodiments, Cy is selected from the group consisting of thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl and triazolyl.
In some embodiments, in the above formula (I), Cy is 6-membered heteroaryl selected from the group consisting of pyridinyl, pyridazinyl, pyrimidinyl or pyrazinyl. In some of these embodiments, Cy is selected from the group consisting of pyridinyl, pyrimidinyl and pyrazinyl.
In some embodiments, in the above formula (I), Cy is pyridinyl.
In some embodiments, in the above formula (I), Cy is naphthyl or a fused bicyclic partially unsaturated Cg-Cio-carbocyclyl.
In some embodiments, in the above formula (I), Cy is A84, A91 or A1 14:
Figure imgf000010_0001
A84 A91 A1 14
In some embodiments, in the above formula (I), Cy is bicyclic 8-, 9- or 10-membered heteroaryl or a fused bicyclic 8-, 9- or 10-membered partially unsaturated heterocyclyl.
Non-limiting examples of Cy include the followings:
Figure imgf000010_0002
Figure imgf000011_0001
Figure imgf000012_0001
A146 A147 A148
In some embodiments, in the above formula (I), Cy is a benzofused 9- or 10-membered heteroaryl. Examples of benzofused 9-membered heteroaryl include indol-1 -yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-1 -yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5- yl, indazol-1 -yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, 1 - benzofuran-2-yl, 1 -benzofuran-3-yl, 1 -benzofuran-4-yl, 1 -benzofuran-5-yl, 1 -benzofuran-6-yl, 1 - benzofuran-7-yl, 1 -benzothiophen-2-yl, 1 -benzothiophen-3-yl, 1 -benzothiophen-4-yl, 1 -benzothiophen-5- yl, 1 -benzothiophen-6-yl, 1 -benzothiophen-7-yl, 1 ,3-benzothiazol-2-yl, 1 ,3-benzothiazol-4-yl, 1 ,3- benzothiazol-5-yl, 1 ,3-benzothiazol-6-yl, 1 ,3-benzothiazol-7-yl, 1 ,3-benzoxazol-2-yl, 1 ,3-benzoxazol-4-yl, 1 ,3-benzoxazol-5-yl, 1 ,3-benzoxazol-6-yl and 1 ,3-benzoxazol-7-yl. Examples of benzofused 10-membered heteroaryl include quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl and isoquinolin-8-yl.
In some embodiments, in the above formula (I), Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10-membered heteroaryl. In some of these embodiments, Cy is selected from the group consisting of cyclopropyl, phenyl, thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl, pyrazinyl and quinolin-2-yl.
In some preferred embodiments, in the above formula (I), Cy is selected from pyridinyl and phenyl.
In some embodiments, in the above formula (I), n is 0, 1 or 2.
In some embodiments, in the above formula (I), n is 1 , 2, 3 or 4.
In some embodiments, in the above formula (I), n is 1 or 2.
In some embodiments, in the above formula (I), R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, carboxyl, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci- C6-haloalkylsulfanyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci-C6-hydroxy alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-Cs-alkylsulfamoylaryl (e.g. phenyl) and heteroaryl. Acyclic and cyclic R3 may be substituted as described herein.
In some embodiments, in the above formula (I), R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy.
In some embodiments, in the above formula (I), R3 is independently selected from the group consisting of halogen, in particular fluorine.
In some embodiments, in the above formula (I), R4 is selected from the group consisting of hydrogen, hydroxy, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, -C(=0)-Ci-C6-alkyl, -C(=0)-Ci-C6- haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=0)-0-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, C3-Cio-carbocyclyl-Ci-C6-alkyl, aryl-Ci-C6-alkyl and heteroaryl-Ci-C6-alkyl. Acyclic and cyclic R4 may be substituted as described herein.
In some embodiments, in the above formula (I), R4 is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, -C(=0)-Ci-C6-alkyl, -C(=0)-Ci-C6-haloalkyl, - C(=S)-Ci-C6-alkyl, -C(=0)-0-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, C3-C10- carbocyclyl, 3- to 10-membered-heterocyclyl, C3-Cio-carbocyclyl-Ci-C6-alkyl, aryl-Ci-C6-alkyl and heteroaryl-Ci-C6-alkyl. Acyclic and cyclic R4 may be substituted as described herein. In some embodiments, in the above formula (I), R4 is selected from the group consisting of hydrogen, hydroxy, Ci-C6-alkyl, Ci-C6-haloalkyl, -C(=0)-Ci-C6-alkyl, -C(=0)-Ci-C6-haloalkyl, -C(=S)-Ci-C6-alkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy
In some embodiments, in the above formula (I), R4 is selected from the group consisting of hydrogen, hydroxy, C(=0)-Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
In some embodiments, in the above formula (I), R4 is selected from the group consisting of hydrogen, C(=0)-Ci-C6-alkyl and -C(=0)-Ci-C6-haloalkyl.
In some embodiments, in the above formula (I), R4 is hydrogen.
In some embodiments, in the above formula (I), R5 is hydrogen.
In some embodiments, in the above formula (I), X is fluorine.
In some embodiments, in the above formula (I), X is chlorine.
The above specified definitions of R1 , R2, R3, R4, R5, Cy and n can be combined in various manners to provide sub-classes of compounds according to the invention.
Non-limiting examples of sub-classes of compounds include the sub-classes described herein below.
In some embodiments (referred herein as embodiment la), the compounds used according to the present invention are compounds of formula (I)
Figure imgf000016_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl, or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (e.g.
cyclopropyl) or a 3- to 10-membered heterocyclyl,
wherein R1 and R2 may be substituted as described herein;
Cy is aryl, preferably phenyl;
n is O, 1 , 2, 3 or 4; R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci-C6-hydroxyalkyl, C1-C6- alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, C1-C6- haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs- alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-C6-haloalkylsulfonylamino, sulfamoyl, Ci-C8-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl-Ci-C6-alkyl and heteroaryl,
wherein said acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, formyl, Ci-C6-alkyl, C1-C6- haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -C(=0)-Ci-C6- alkyl, -C(=0)-Ci-C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=S)-Ci-C6-haloalkyl, -C(=0)-0-Ci-C6- alkyl, -C(=0)-0-Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, C1-C6- haloalkylsulfonyl, phenylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl (phenyl), heteroaryl, C3-Cio-carbocyclyl-Ci-C6-alkyl, C3-Cio-carbocyclyl-Ci-C6-haloalkyl, aryl- Ci-C6-alkyl, aryl-Ci-C6-haloalkyl, heteroaryl-Ci-C6-alkyl and heteroaryl-Ci-C6-haloalkyl, wherein said acyclic and cyclic R4 may be substituted with one or more substituents selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R5 is hydrogen or fluorine;
R1a, R2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- C8-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-C8-haloalkylsulfonyl, Ci-Cs-alkylsulfonylamino, Ci-Cs-haloalkylsulfonylamino, sulfamoyl, Ci-C8-alkylsulfamoyl and di-Ci-Cs-alkylsulfamoyl;
R1 b, R2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, Ci-C6-alkyl-C(=0)-NH-, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, hydroxy- Ci-C6-alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, C1-C6- alkoxycarbonyl, Ci-C6-haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci-Cs-haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, C1-C6- haloalkylsulfonylamino, sulfamoyl, Ci-Cs-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy. provided that the compound of formula (I) is not:
(c) N-(1 -phenylcyclopropyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(d) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-(1-phenylcyclopropyl)pyrimidin-2-amine.
In some preferred embodiments in accordance with embodiment (la), Cy is phenyl.
In some embodiments (referred herein as embodiment lb), the compounds used according to the present invention are compounds of formula (I)
Figure imgf000018_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl, or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (e.g.
cyclopropyl) or a 3- to 10-membered heterocyclyl,
wherein R1 and R2 may be substituted as described herein;
Cy is a 5- or 6-membered heteroaryl (e.g. pyridinyl);
n is 0, 1 , 2, 3 or 4;
R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci-C6-hydroxyalkyl, Ci-Ce- alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, C1-C6- haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs- alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-C6-haloalkylsulfonylamino, sulfamoyl, Ci-C8-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl-Ci-C6-alkyl and heteroaryl,
wherein said acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, formyl, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -C(=0)-Ci-C6-alkyl, -C(=0)-Ci- C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=S)-Ci-C6-haloalkyl, -C(=0)-0-Ci-C6-alkyl, -C(=0)-0-Ci- C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl (phenyl), heteroaryl, C3-Cio-carbocyclyl-Ci-C6-alkyl, C3-Cio-carbocyclyl-Ci-C6-haloalkyl, aryl-Ci-C6-alkyl, aryl-Ci- C6-haloalkyl, heteroaryl-Ci-C6-alkyl and heteroaryl-Ci-C6-haloalkyl, wherein said acyclic and cyclic R4 may be substituted with one or more substituents selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
R5 is hydrogen or fluorine;
R1a, R2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, Ci-Ce-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Ce-haloalkylsulfonyl, Ci-Cs-alkylsulfonylamino, Ci-Cs-haloalkylsulfonylamino, sulfamoyl, Ci-C8-alkylsulfamoyl and di-Ci-Cs-alkylsulfamoyl;
R1 b, R2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, Ci-C6-alkyl-C(=0)-NH-, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, hydroxy- Ci-C6-alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, C1-C6- alkoxycarbonyl, Ci-C6-haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci-Cs-haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, C1-C6- haloalkylsulfonylamino, sulfamoyl, Ci-Cs-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy; provided that the compound of formula (I) is not:
(a) N-[1-(pyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(b) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-[1-(pyridin-2-yl)cyclobutyl]pyrimidin-2-amine.
In embodiment (l-b), Cy (5- or 6-membered heteroaryl) is as described herein.
In some preferred embodiments in accordance with embodiments l-b, Cy is selected from the group consisting of furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl. In some of these embodiments, Cy is selected from the group consisting of thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl and pyrazinyl.
In some even more preferred embodiments in accordance with embodiments l-b, Cy is pyridinyl.
In some embodiments (referred herein as embodiment lc), the compounds used according to the present invention are compounds of formula (I)
Figure imgf000020_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl, or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (e.g.
cyclopropyl) or a 3- to 10-membered heterocyclyl,
wherein R1 and R2 may be substituted as described herein;
Cy is a C3-Cio-carbocyclyl (e.g. cyclopropyl);
n is 0, 1 , 2, 3 or 4;
R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci-C6-hydroxyalkyl, C1-C6- alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, C1-C6- haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs- alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-C6-haloalkylsulfonylamino, sulfamoyl, Ci-C8-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl-Ci-C6-alkyl and heteroaryl,
wherein said acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, formyl, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -C(=0)-Ci-C6-alkyl, -C(=0)-Ci- C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=S)-Ci-C6-haloalkyl, -C(=0)-0-Ci-C6-alkyl, -C(=0)-0-Ci- C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl (phenyl), heteroaryl, C3-Cio-carbocyclyl-Ci-C6-alkyl, C3-Cio-carbocyclyl-Ci-C6-haloalkyl, aryl-Ci-C6-alkyl, aryl-Ci- C6-haloalkyl, heteroaryl-Ci-C6-alkyl and heteroaryl-Ci-C6-haloalkyl, wherein said acyclic and cyclic R4 may be substituted with one or more substituents selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
R5 is hydrogen or fluorine;
R1a, R2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, Ci-Ce-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Ce-haloalkylsulfonyl, Ci-Cs-alkylsulfonylamino, Ci-Cs-haloalkylsulfonylamino, sulfamoyl, Ci-C8-alkylsulfamoyl and di-Ci-Cs-alkylsulfamoyl;
R1b, R2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, Ci-C6-alkyl-C(=0)-NH-, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, hydroxy- Ci-C6-alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, C1-C6- alkoxycarbonyl, Ci-C6-haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci-Cs-haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, C1-C6- haloalkylsulfonylamino, sulfamoyl, Ci-Cs-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy.
In embodiment (l-c), Cy (C3-Ci0-carbocyclyl) is as described herein.
In some embodiments (referred herein as embodiment Id), the compounds used according to the present invention are compounds of formula (I)
Figure imgf000022_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C7-carbocyclyl, or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl (e.g.
cyclopropyl) or a 3- to 10-membered heterocyclyl,
wherein R1 and R2 may be substituted as described herein;
Cy is a 3- to 10-membered-heterocyclyl;
n is 0, 1 , 2, 3 or 4;
R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci-C6-hydroxyalkyl, C1-C6- alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, C1-C6- haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs- alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-C6-haloalkylsulfonylamino, sulfamoyl, Ci-Ce-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl-Ci-C6-alkyl and heteroaryl,
wherein said acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy; R4 is selected from the group consisting of hydrogen, formyl, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -C(=0)-Ci-C6-alkyl, -C(=0)-Ci- C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=S)-Ci-C6-haloalkyl, -C(=0)-0-Ci-C6-alkyl, -C(=0)-0-Ci- C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl (phenyl), heteroaryl, C3-Cio-carbocyclyl-Ci-C6-alkyl, C3-Cio-carbocyclyl-Ci-C6-haloalkyl, aryl-Ci-C6-alkyl, aryl-Ci- C6-haloalkyl, heteroaryl-Ci-C6-alkyl and heteroaryl-Ci-C6-haloalkyl, wherein said acyclic and cyclic R4 may be substituted with one or more substituents selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
R5 is hydrogen or fluorine;
R1a, R2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- Cyhalocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, Ci-Ce-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Ce-haloalkylsulfonyl, Ci-Cs-alkylsulfonylamino, Ci-Cs-haloalkylsulfonylamino, sulfamoyl, Ci-Ce-alkylsulfamoyl and di-Ci-Cs-alkylsulfamoyl;
R1b, R2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, Ci-C6-alkyl-C(=0)-NH-, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, hydroxy- Ci-C6-alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, C1-C6- alkoxycarbonyl, Ci-C6-haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci-Cs-haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, C1-C6- haloalkylsulfonylamino, sulfamoyl, Ci-Cs-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy.
In embodiment (l-d), Cy (3- to 10-membered-heterocyclyl) is as described herein.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R1 and R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl. In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R1 and R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl (preferably phenyl), or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl ring. R1 and R2 may be substituted as described herein. In particular, R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl, and halogen.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R1 and R2 are independently selected from the group consisting of hydrogen, methyl and phenyl, or R1 and R2 form, together with the carbon atom to which they are linked, a cyclopropyl or cyclobutyl ring, wherein the cyclopropyl and cyclobutyl ring may be substituted with one or more substituents selected from hydroxy, methyl and fluorine.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), n is 0, 1 or 2.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), n is 1 , 2, 3 or 4.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), n is 1 or 2.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, carboxyl, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy- Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci- C6-hydroxy alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, Ci-C8-alkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-Cs-alkylsulfamoylaryl and heteroaryl, wherein acyclic and cyclic R3 may be substituted as described herein.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy. In some of these embodiments, R3 is independently selected from the group consisting of fluorine, chlorine, bromine, methyl, tert-butyl, trifluoromethyl, 2,2,2-trifluoroethoxy and methoxy.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl and Ci-C6-haloalkyl.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R3 is independently selected from the group consisting of halogen, in particular fluorine.
In some embodiments in accordance with embodiment (la), R4 is selected from the group consisting of hydrogen, hydroxy, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, -C(=0)-Ci-C6-alkyl, - C(=0)-Ci-C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=0)-0-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C1-C6- alkylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, C3-Cio-carbocyclyl-Ci-C6-alkyl, aryl- Ci-C6-alkyl and heteroaryl-Ci-C6-alkyl, wherein acyclic and cyclic R4 may be substituted as described herein. In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R4 is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, -C(=0)-Ci-C6- alkyl, -C(=0)-Ci-C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=0)-0-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, C3-Cio-carbocyclyl-Ci-C6-alkyl, aryl-Ci-C6-alkyl and heteroaryl-Ci-C6-alkyl, wherein acyclic and cyclic R4 may be substituted as described herein.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R4 is selected from the group consisting of hydrogen, hydroxy, Ci-C6-alkyl, Ci-C6-haloalkyl, -C(=0)-Ci-C6-alkyl, -C(=0)-Ci-C6- haloalkyl, -C(=S)-Ci-C6-alkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R4 is selected from the group consisting of hydrogen, hydroxy, C(=0)-Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R4 is selected from the group consisting of hydrogen, C(=0)-Ci-C6-alkyl and -C(=0)-Ci-C6-haloalkyl.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R4 is hydrogen.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), R5 is hydrogen.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), X is fluorine.
In some embodiments in accordance with embodiments (la), (lb), (lc) and (Id), X is chlorine.
In some embodiments (referred herein as embodiment le), the compounds used according to the present invention are compounds of formula (I)
Figure imgf000025_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl
(preferably phenyl), or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen; Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
n is 0, 1 or 2;
R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, C(=0)-Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy;
R5 is hydrogen or fluorine, preferably hydrogen; provided that the compound of formula (I) is not:
(a) N-[1 -(pyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(b) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-[1 -(pyridin-2-yl)cyclobutyl]pyrimidin-2-amine;
(c) N-(1 -phenylcyclopropyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(d) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-(1 -phenylcyclopropyl)pyrimidin-2-amine.
In some embodiments (referred herein as embodiment If), the compounds used according to the present invention are compounds of formula (I)
Figure imgf000026_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl
(preferably phenyl), or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen;
Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
n is 1 or 2;
R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, C(=0)-Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy;
R5 is hydrogen or fluorine, preferably hydrogen. In some preferred embodiments in accordance with embodiments (le) and (If), Cy is phenyl or 5- or 6- membered heteroaryl, preferably selected from the group consisting of phenyl, furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl. In some of these embodiments, Cy is selected from the group consisting of phenyl, thienyl, isothiazolyl, pyrazolyl, thiazolyl, imidazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl and pyrazinyl.
In some particularly preferred embodiments in accordance with embodiments (le) and (If), Cy is phenyl or pyridinyl.
In some preferred embodiments in accordance with embodiments (le) and (If), R5 is hydrogen.
In some preferred embodiments in accordance with embodiments (le) and (If), R4 is selected from the group consisting of hydrogen, C(=0)-Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy. Even more preferred, R4 is hydrogen.
In some embodiments in accordance with embodiments (le) and (If),
R1 , R2 are independently selected from the group consisting of hydrogen, methyl and phenyl, or R1 and R2 form, together with the carbon atom to which they are linked, a cyclopropyl or cyclobutyl ring, wherein the cyclopropyl and cyclobutyl ring may be substituted with one or more substituents selected from hydroxy, methyl and fluorine;
R3 is independently selected from the group consisting of fluorine, chlorine, bromine, methyl, tert-butyl, trifluoromethyl, 2,2,2-trifluoroethoxy and methoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, methoxy and 2-chloro-2,2-difluoroacetyl, preferably R4 is hydrogen; and
R5 is hydrogen.
In some embodiments in accordance with embodiment (le), n is 1 or 2.
In some embodiments in accordance with embodiments (le) and (If), X is fluorine.
In some embodiments in accordance with embodiments (le) and (If), X is chlorine.
In some embodiments in accordance with embodiments (le) and (If), R3 is halogen, in particular fluorine.
In some embodiments in accordance with embodiments (le) and (If),
R1 , R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl (e.g. cyclopropyl),
R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl and Ci-C6-haloalkyl, preferably halogen;
Cy is phenyl or 5- or 6-membered heteroaryl, preferably phenyl or pyridinyl; and R4 is selected from the group consisting of hydrogen, C(=0)-Ci-C6-alkyl and -C(=0)-Ci-C6- haloalkyl, preferably R4 is hydrogen.
The present invention also relates to the use of any compounds of formula (I) disclosed in Table 1 for controlling phytopathogenic fungi on plants (in particular fungi causing rust diseases in crop protection). Accordingly, the present invention also relates to the use of compounds of the formula (I) selected from the group consisting of
N-[(2-chloro-6-fluorophenyl)methyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(3-fluoropyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(6-fluoropyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-(3,3-difluoro-1 -phenylcyclobutyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[(2-chloro-6-fluorophenyl)methyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(3-fluoropyridin-2-yl)cyclobutyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(6-fluoropyridin-2-yl)cyclobutyl]pyrimidin-2-amine, N-[1 -(2-chlorophenyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(3-bromophenyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2-chlorophenyl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(3-bromophenyl)ethyl]pyrimidin-2-amine, N-[1 -(2-fluoro-3-methoxyphenyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(2,3-dichlorophenyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2-fluoro-3-methoxyphenyl)ethyl]pyrimidin-2- amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2,3-dichlorophenyl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2-fluorophenyl)ethyl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2-chloropyridin-3-yl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(5-chloropyridin-2-yl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(6-chloropyridin-2-yl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(3-methylpyridin-2-yl)ethyl]pyrimidin-2-amine,
N-[(1 S)-1 -pyridin-2-ylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[(1 R)-1 -pyridin-2-ylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[phenyl(pyridin-2-yl)methyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(3-fluoropyridin-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[3,3-difluoro-1 -(2-fluorophenyl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[3-fluoro-1 -(2-fluorophenyl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(2-fluorophenyl)-3-methylcyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(2,6-difluorophenyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -cyclopropylethyl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-(pyridin-2-ylmethyl)pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -pyridin-4-ylethyl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -pyrimidin-4-ylethyl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -pyrazin-2-ylethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[(2-fluorophenyl)methyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(1 -methylpyrazol-3-yl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -thiophen-2-ylethyl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(1 ,3-thiazol-4-yl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(1 -methylcyclopropyl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[(2,6-difluorophenyl)methyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(4-methoxyphenyl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2-methoxyphenyl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[(6-fluoropyridin-2-yl)methyl]pyrimidin-2-amine, N-[1 -quinolin-2-ylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -pyridin-3-ylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -pyridin-4-ylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -pyrazin-2-ylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[(2-fluorophenyl)methyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(1 -methylpyrazol-3-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[(6-fluoropyridin-2-yl)methyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(4-methyl-1 ,2,4-triazol-3-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -thiophen-2-ylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(1 ,3-thiazol-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(1 ,3-thiazol-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(1 -methylcyclopropyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(2-methyl-1 ,3-thiazol-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[(2,6-difluorophenyl)methyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(4-methoxyphenyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(2-methoxyphenyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(6-chloropyridin-3-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(1 ,2-thiazol-3-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(1 -methylimidazol-2-yl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(1 ,2-thiazol-3-yl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -quinolin-2-ylethyl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2,6-difluorophenyl)ethyl]pyrimidin-2-amine, N-(pyridin-2-ylmethyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -cyclopropylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine, N-[1 -phenylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -pyridin-2-ylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(4-chlorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -pyridin-2-ylethyl]pyrimidin-2-amine,
N-[1 -(3-chlorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(3-methylphenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(5-chloropyridin-3-yl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-(2-phenylpropan-2-yl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, 5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-N-[1 -[3-(trifluoromethyl)phenyl]cyclopropyl]pyrimidin-2-amine, 2-chloro-N-[5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-yl]-2,2-difluoro-N-(1 - phenylcyclopropyl)acetamide,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2,6-difluorophenyl)cyclopropyl]pyrimidin-2- amine,
N-[1 -(2-chlorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
2-chloro-N-[5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-yl]-N-[1 -(2- chlorophenyl)cyclopropyl]-2,2-difluoroacetamide,
N-(2-pyridin-2-ylpropan-2-yl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(3-bromophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(5-fluoropyridin-3-yl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(3,5-dichlorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(4-chloropyridin-2-yl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(3-chloropyridin-2-yl)ethyl]pyrimidin-2-amine, N-[1 -(1 ,2,5-thiadiazol-3-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(4-chloropyridin-3-yl)ethyl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(5-chloropyridin-2-yl)cyclopropyl]pyrimidin-2- amine,
N-[1 -(5-fluoropyridin-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(4-chloropyridin-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(5-fluoropyridin-2-yl)ethyl]pyrimidin-2-amine, N-[1 -(3-chloropyridin-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -(2-chloropyridin-3-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1 -[5-(trifluoromethyl)pyridin-2-yl]ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1 -(2-fluorophenyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[2-(2-fluorophenyl)propan-2-yl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-(2-pyridin-2-ylpropan-2-yl)pyrimidin-2-amine, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-(1 -pyridin-2-ylcyclopropyl)pyrimidin-2-amine, N-[1 -(4-chloropyridin-3-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[2-(2-fluorophenyl)propan-2-yl]pyrimidin-2-amine,
3-(2-fluorophenyl)-3-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-yl]amino]cyclobutan-1 -ol, 5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1 -(2-fluorophenyl)-3-methylcyclobutyl]pyrimidin-2- amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[3-fluoro-1 -(2-fluorophenyl)cyclobutyl]pyrimidin-2- amine,
3-[[5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-yl]amino]-3-(2-fluorophenyl)cyclobutan- 1 -ol,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[3,3-difluoro-1 -(2-fluorophenyl)cyclobutyl]pyrimidin- 2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[(2,6-dichlorophenyl)methyl]pyrimidin-2-amine, N-[(2,6-dichlorophenyl)methyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1-(2,6-dichlorophenyl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
5-[5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl]-N-[1-(2,6-dichlorophenyl)ethyl]pyrimidin-2-amine, N-[1-(2-chlorophenyl)ethyl]-N-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-yl]hydroxylamine, N-methoxy-N-[1-phenylethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[2-(4-methylpyridin-2-yl)propan-2-yl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2- amine,
N-[1-(3-methylpyridin-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[2-(3-bromophenyl)propan-2-yl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1-[5-(2,2,2-trifluoroethoxy)pyridin-2-yl]ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2- amine,
N-[1-(6-chloropyridin-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1-(5-chloropyridin-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1-(3,4-difluorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1-(2,4-dichlorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1-(4-chloropyridin-2-yl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1-(3,5-dichloropyridin-2-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1-(4-tert-butylphenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1-(3,4-dimethoxyphenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-(1-pyridin-2-ylcyclopropyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
N-[1-(4-methylpyridin-2-yl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine, N-[1-(2,6-difluorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine and N-[1-(2-fluorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine for controlling phytopathogenic fungi on plants (in particular fungi causing rust diseases in crop protection).
The present invention also relates to compounds of formula (G):
Figure imgf000031_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, cyano, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-Cs-haloalkynyl, C3-C7- carbocyclyl, aryl, 3- to 10-membered-heterocyclyl, heteroaryl, aryl-Ci-Cs-alkyl, 3- to 10- membered-heterocyclyl-Ci-C8-alkyl, heteroaryl-Ci-Cs-alkyl and C3-C7-carbocyclyl-Ci-C8-alkyl, wherein said acyclic R1 and R2 may be substituted with, respectively one or more R1a and R2a substituents and said cyclic R1 and R2 may be substituted with, respectively one or more R1b and R2b substituents, or
R1 , R2 may form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl or a 3- to 10-membered heterocyclyl, wherein said C3-C7-carbocyclyl or 3- to 10-membered heterocyclyl may be substituted with one or more R1 b substituents;
Cy is C3-Cio-carbocyclyl, 3- to 10-membered heterocyclyl, aryl or heteroaryl;
n is 0, 1 , 2, 3 or 4;
R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci-C6-hydroxyalkyl, C1-C6- alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, C1-C6- haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs- alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-C6-haloalkylsulfonylamino, sulfamoyl, Ci-Ce-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl-Ci-C6-alkyl and heteroaryl,
wherein said acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, formyl, Ci-C6-alkyl, C1-C6- haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -C(=0)-Ci-C6- alkyl, -C(=0)-Ci-C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=S)-Ci-C6-haloalkyl, -C(=0)-0-Ci-C6- alkyl, -C(=0)-0-Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, C1-C6- haloalkylsulfonyl, phenylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl (phenyl), heteroaryl, C3-Cio-carbocyclyl-Ci-C6-alkyl, C3-Cio-carbocyclyl-Ci-C6-haloalkyl, aryl- Ci-C6-alkyl, aryl-Ci-C6-haloalkyl, heteroaryl-Ci-C6-alkyl and heteroaryl-Ci-C6-haloalkyl, wherein said acyclic and cyclic R4 may be substituted with one or more substituents selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R5 is hydrogen or fluorine;
R1a, R2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- C8-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, Ci-C8-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Ce-haloalkylsulfonyl, Ci-Cs-alkylsulfonylamino, Ci-Cs-haloalkylsulfonylamino, sulfamoyl, Ci-Ce-alkylsulfamoyl and di-Ci-Cs-alkylsulfamoyl;
Ri b p2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, Ci-C6-alkyl-C(=0)-NH-, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, hydroxy- Ci-C6-alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, C1-C6- alkoxycarbonyl, Ci-C6-haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci-Cs-haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, C1-C6- haloalkylsulfonylamino, sulfamoyl, Ci-Cs-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
wherein when X is fluorine and R4 is hydrogen or Ci-C6-alkyl, R1 and R2 are not both hydrogen;
wherein compounds are excluded in which X is fluorine, Cy is phenyl or 6-membered heteroaryl, n is 0 and R1 , R2 and R4 are each independently selected from hydrogen and Ci-C3-alkyl; and
provided that the compound of formula (G) is not:
(a) N-[1 -(pyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(b) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-[1 -(pyridin-2-yl)cyclobutyl]pyrimidin-2-amine;
(c) N-(1 -phenylcyclopropyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(d) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-(1 -phenylcyclopropyl)pyrimidin-2-amine;
(e) N-[1 -(2-methylpyridin-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine.
Compounds (a), (b), (c) and (d) are disclosed in WO2019/122323. Compound (e) is disclosed in WO2013/080120.
The above specified embodiments for the use of the compounds of formula (I) according to the invention, e.g. embodiments (la), (lb), (lc), (Id), (le) and (If), also apply to the compounds of formula (G) according to the invention, with the following restrictions:
(i) compounds are excluded in which in formula (G), X is fluorine, R4 is hydrogen or Ci-C6-alkyl, and R1 and R2 are both hydrogen;
(ii) compounds are excluded in which X is fluorine, Cy is phenyl or 6-membered heteroaryl, n is 0 and R1 , R2 and R4 are each independently selected from hydrogen and Ci-C3-alkyl; and (iii) the compound of formula (G) is not N-[1 -(2-methylpyridin-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]pyrimidin-2-amine.
(iv)
Those embodiments of the compound of formula (G) that correspond to the embodiments (la), (lb), (lc), (Id), (le) and (If) of the compound of formula (I) with the above specified restrictions (i)-(iii) are hereinafter also referred to as embodiments (I’a), (I’b), (I’c), (I’d), (I’e) and (I’f).
In some embodiments of the compounds of formula (I’) according to the invention, compounds are excluded in which X is fluorine, Cy is phenyl or 6-membered heteroaryl and R1 , R2 and R4 are each independently selected from hydrogen and Ci-C3-alkyl.
In some embodiments of the compounds of formula (I’) according to the invention,
n is 1 or 2,
R1 and R2 are not both hydrogen,
and the compound of formula (I’) is not:
(e) N-[1 -(2-methylpyridin-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine,
In some embodiments of the compounds of formula (I’) according to the invention, R1 , R2, R3, R4, Cy and n are defined according to embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f), and X is chlorine.
In some embodiments of the compounds of formula (I’) according to the invention, R1 , R2, R3, R4, X and n are as defined in embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f), and Cy is an unsubstituted or substituted 5-membered heteroaryl.
In some embodiments of the compounds of formula (I’) according to the invention, R3, R4, Cy, X and n are as defined in embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f), and R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl, wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen.
In some embodiments of the compounds of formula (I’) according to the invention, R1 , R2, R3, R4, Cy and X are as defined in embodiment (I’a), (I’b), (I’c), (I’d) or (I’e) and n is 1 or 2.
In some embodiments of the compounds of formula (I’) according to the invention, R1 , R2, R3, R4, Cy and X are defined according to embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f),
n is 1 or 2,
R1 and R2 are not both hydrogen,
and the compound of formula (I’) is not:
(e) N-[1 -(2-methylpyridin-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine In some embodiments of the compounds of formula (G) according to the invention, R1 , R2, R3, n, Cy and X are as defined in embodiment (I’a), (I’b), (I’c), (I’d), (I’e) or (I’f), and R4 is hydrogen.
In particular, in some embodiments (referred herein as embodiment I’g), the present invention also relates to the compounds of formula (I’)
Figure imgf000035_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl
(preferably phenyl), or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen;
Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
n is 0, 1 or 2;
R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, C(=0)-Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy;
R5 is hydrogen or fluorine, preferably hydrogen; wherein when X is fluorine and R4 is hydrogen or Ci-C6-alkyl, R1 and R2 are not both hydrogen; wherein compounds are excluded in which X is fluorine, Cy is phenyl or 6-membered heteroaryl, n is 0 and R1 , R2 and R4 are each independently selected from hydrogen and Ci-C3-alkyl; and
provided that the compound of formula (I’) is not:
(a) N-[1-( yridine-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(b) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-[1-( yridine-2-yl)cyclobutyl]pyrimidin-2-amine;
I N-(1 -phenylcyclopropyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(d) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-(1-phenylcyclopropyl)pyrimidin-2-amine;
I N-[1-(2-methylpyridin-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine.
In some embodiments in accordance with embodiment (I’g) (referred herein as embodiment I’h), R1 , R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl (e.g. cyclopropyl),
R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl and Ci-C6-haloalkyl; Cy is phenyl or 5- or 6-membered heteroaryl;
R4 is selected from the group consisting of hydrogen, C(=0)-Ci-C6-alkyl and -C(=0)-Ci-C6- haloalkyl, preferably R4 is hydrogen; and
R5 is hydrogen.
In some embodiments (referred herein as embodiment I’i), the present invention also relates to the compounds of formula (G)
Figure imgf000036_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl
(preferably phenyl), or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen;
Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
n is 1 or 2;
R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, C(=0)-Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy;
R5 is hydrogen or fluorine, preferably hydrogen;
wherein when X is fluorine and R4 is hydrogen or Ci-C6-alkyl, R1 and R2 are not both hydrogen;
provided that the compound of formula (G) is not:
I N-[1-(2-methylpyridin-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine.
In some embodiments in accordance with embodiment (I’i) (referred herein as embodiment I’j),
R1 , R2 are independently selected from the group consisting of hydrogen and Ci-Cs-alkyl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl (e.g. cyclopropyl), R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl and Ci-C6-haloalkyl; Cy is phenyl or 5- or 6-membered heteroaryl;
R4 is selected from the group consisting of hydrogen, C(=0)-Ci-C6-alkyl and -C(=0)-Ci-C6- haloalkyl, preferably R4 is hydrogen; and
R5 is hydrogen.
In some embodiments in accordance with embodiment (I’g), (I’h), (I’i) or (I’j), X is chlorine.
In some embodiments in accordance with embodiment (I’g), (I’h), (I’i) or (I’j), Cy is an unsubstituted or substituted 5-membered heteroaryl.
In some embodiments in accordance with embodiment (I’g), (I’h), (I’i) or (I’j), Cy is an unsubstituted or substituted 6-membered heteroaryl.
In some embodiments in accordance with embodiment (I’g), (I’h), (I’i) or (I’j), Cy is unsubstituted or substituted phenyl.
In some embodiments in accordance with embodiment (I’g), (I’h), (I’i) or (I’j), R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl, wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen.
In some embodiments in accordance with embodiment (I’g), (I’h), (I’i) or (I’j), R3 is selected from halogen and Ci-C6-haloalkyl, preferably halogen, more preferably fluorine.
In some embodiments in accordance with embodiment (I’g), (I’h), (I’i) or (I’j), compounds are excluded in which X is fluorine, Cy is phenyl or 6-membered heteroaryl and R1 , R2 and R4 are each independently selected from hydrogen and Ci-C3-alkyl.
In some embodiments in accordance with embodiment (l‘i) or (I’j),
n is 1 or 2,
R1 and R2 are not both hydrogen,
and the compound of formula (I’) is not:
(e) N-[1 -(2-methylpyridin-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine. The present invention also relates to any compounds of formula (G) disclosed in Table 1.
PROCESSES FOR PREPARING COMPOUNDS OF FORMULAE (\) AND (P The following table lists the abbreviations used in this paragraph and in the Examples section as far as they are not explained within the text body.
Figure imgf000038_0001
General synthetic routes to the compounds of general formulae (1 ) and (P
The present invention also relates to processes for the preparation of compounds of formula (I) respectively (I’). Unless indicated otherwise, the radicals R1 , R2, R3, R4, R5 and X have the meanings given above for the compounds of formula (I) respectively (I’). These definitions apply not only to the end products of the formula (I) respectively (I’) but likewise to all intermediates.
Compounds of formula (I) and (I’) can be prepared, according to process P1 , by reacting amidoximes of formula (II) respectively (II’) with haloalkylacetic anhydride or haloalkylacetyl chloride in a suitable solvent such as tetrahydrofurane or dichloromethane optionally in presence of a base such as triethylamine or pyridine, preferably at room temperature, as previously described in WO2013080120.
Figure imgf000039_0001
Process P1
Amidoximes of formulae (II) and (II’) can be prepared according to known procedures (see for examples WO2013080120), as shown in process P2 by treating nitriles of formula (III) respectively (III’) with hydroxylamine (or its hydrochloride salt) in the presence of a base such as triethylamine in a solvent such as ethanol.
Figure imgf000039_0002
(HD / ("I')
(II) / (ID
Process P2
Compounds of formulae (III) and (IN’) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
Alternatively compounds of formula (III) and (IN’) can be prepared, according to process P3, from compounds of formula (IV) respectively (IV’), wherein LG1 is a leaving group as for example bromide with a suitable cyanide reagent such as for example zinc cyanide in presence of palladium (0) in a solvent such as N,N-dimethylformamide as described for example in ACS Medicinal Chemistry Letters, 8(9), 919-924, 2017. Process P3
Compounds of formulae (IV) and (IV’) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
Alternatively compounds of formulae (I) and (G) can be prepared, according to process P4, from a compound of formula (V) respectively (V’), wherein LG2 is a leaving group by nucleophilic substitution with a compound of formula (VI) respectively (VI’) (as described for example in European Journal of Medicinal Chemistry, 135, 531 -543; 2017 or Bioorganic & Medicinal Chemistry, 25(17), 4553-4559; 2017) optionally in presence of a base (like for example triethylamine) or an acid (like for example p- toluenesulfonic acid or (1 S)-(+)-10-camphorsulfonic acid) in a solvent such as for example dichloromethane or dioxane. It may be necessary to activate the leaving group for example by oxidation with 3-chloroperbenzoic acid when LG2 is SMe.
Figure imgf000040_0001
Process P4
Compounds of formulae (V) and (V’) can be commercially available or may be prepared starting from readily available compounds analogously to process P1 and P2.
Compounds of formulae (VI) and (VI’) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
Alternatively compounds of formulae (I) and (G) can be prepared, according to process P5, from a compound of formula (VII’) with a compound of formula (VIM’) wherein LG3 is a leaving group such as chlorine by nucleophilic substitution (as described for example in European Journal of Medicinal Chemistry, 135, 531 -543; 2017 or Bioorganic & Medicinal Chemistry, 25(17), 4553-4559; 2017) optionally in presence of a base (like for example triethylamine) or an acid (like for example p- toluenesulfonic acid or (1 S)-(+)-10-Camphorsulfonic acid) in a solvent such as for example dichloromethane or dioxane. (VII) / (VII') © / (!')
Process R5
Compounds of formulae (VII) and (Vll·) can be commercially available or may be prepared starting from readily available compounds analogously to process P1 and P2.
Compounds of formulae (VIII) and (VIII’) can be commercially available or may be prepared starting from readily available compounds according to known procedures. Alternatively compounds of formulae (I) and (G) can be prepared, according to process P6, from a compound of formula (IX) respectively (IX’) with a compound of formula (X) respectively (X’), wherein LG4 is a leaving group, by nucleophilic substitution (as described for example in Medicinal Chemistry Research, 22(1 1), 5267-5273; 2013 or W02013080120) optionally in presence of a base (like for example triethylamine), optionally in presence of a solvent such as for example dichloromethane.
Figure imgf000041_0001
/ ) (0 / (0
Process P6
Compounds of formulae (IX) and (IX’) can be commercially available or may be prepared starting from readily available compounds analogously to process P1 and P2.
Compounds of formulae (X) and (X’) can be commercially available or may be prepared starting from readily available compounds according to known procedures. Alternatively compounds of formulae (III) and (IN’) can be prepared, according to process P7, from a compound of formula (XI) respectively (XI’), wherein LG5 is a leaving group as for example chlorine by nucleophilic substitution with a compound of formula (VI) respectively (VI’) (as described for example in European Journal of Medicinal Chemistry, 135, 531 -543; 2017 or Bioorganic & Medicinal Chemistry, 25(17), 4553-4559; 2017) optionally in presence of a base (like for example triethylamine) or an acid (like for example p-toluenesulfonic acid or (1 S)-(+)-10-camphorsulfonic acid) in a solvent such as for example dichloromethane or dioxane. It may be necessary to activate the leaving group for example by oxidation with 3-chloroperbenzoic acid when LG5 is SMe.
Figure imgf000042_0001
Process P7
Compounds of formulae (XI) and (XI’) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
According to the invention, processes P1 to P7 can be performed if appropriate in the presence of a solvent and if appropriate in the presence of a base.
Suitable solvents for carrying out processes P1 to P7 according to the invention are customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2- diethoxyethane or anisole ; nitriles, such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile ; amides, such as A/,A/-dimethylformamide, A/,A/-dimethylacetamide, /V-methylformanilide, /V-methyl- pyrrolidone or hexamethylphosphoric triamide ; esters, such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide or sulfones, such as sulfolane.
Suitable bases for carrying out processes P1 to P7 according to the invention are inorganic and organic bases which are customary for such reactions. Preference is given to using alkaline earth metal, alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, A/,A/-dimethylaniline, pyridine, /V-methylpiperidine, A/,A/-dimethylaminopyridine, 1 ,4-diazabicyclo[2.2.2]octane (DABCO), 1 ,5- diazabicyclo[4.3.0]non-5-ene (DBN) or 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
When carrying out processes P1 to P7, according to the invention, the reaction temperature can independently be varied within a relatively wide range. Generally, processes according to the invention are carried out at temperatures between -20°C and 160°C. Processes P1 to P7 according to the invention are generally independently carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.
Work-up is carried out by customary methods. Generally, the reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can be freed by customary methods, such as chromatography or recrystallization, from any impurities that can still be present.
Compounds according to the invention can be prepared according to the above described processes. 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.
Aspects of the present teaching may be further understood in light of the following examples, which should not be construed as limiting the scope of the present teaching in any way.
Compositions and formulations
The present invention further relates to a composition, in particular a composition for controlling unwanted microorganisms, comprising one or more compounds of formula (I) or (I’). The composition is preferably is a fungicidal composition.
The composition typically comprises one or more compounds of formula (I) or (I’) and one or more acceptable carriers, in particular one or more agriculturally acceptable carriers.
A carrier is a solid or liquid, natural or synthetic, organic or inorganic substance that is generally inert. The carrier generally improves the application of the compounds, for instance, to plants, plants parts or seeds. Examples of suitable solid carriers include, but are not limited to, ammonium salts, natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates. Examples of typically useful solid carriers for preparing granules include, but are not limited to crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks. Examples of suitable liquid carriers include, but are not limited to, water, organic solvents and combinations thereof. Examples of suitable solvents include polar and nonpolar organic chemical liquids, for example from the classes of aromatic and nonaromatic hydrocarbons (such as cyclohexane, paraffins, alkylbenzenes, xylene, toluene alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride), alcohols and polyols (which may optionally also be substituted, etherified and/or esterified, such as butanol or glycol), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides (such as dimethylformamide), lactams (such as N- alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide). The carrier may also be a liquefied gaseous extender, i.e. liquid which is gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, butane, propane, nitrogen and carbon dioxide. The amount of carrier typically ranges from 1 to 99.99%, preferably from 5 to 99.9%, more preferably from 10 to 99.5%, and most preferably from 20 to 99 % by weight of the composition.
The composition may further comprise one or more acceptable auxiliaries which are customary for formulating compositions (e.g. agrochemical compositions), such as one or more surfactants.
The surfactant can be an ionic (cationic or anionic) or non-ionic surfactant, such as ionic or non-ionic emulsifier(s), foam former(s), dispersant(s), wetting agent(s) and any mixtures thereof. Examples of suitable surfactants include, but are not limited to, salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene and/or propylene oxide with fatty alcohols, fatty acids or fatty amines (polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols and derivatives of compounds containing sulfates, sulfonates, phosphates (for example, alkylsulfonates, alkyl sulfates, arylsulfonates) and protein hydrolysates, lignosulfite waste liquors and methylcellulose. A surfactant is typically used when the compound of the formula (I) respectively (G) and/or the carrier is insoluble in water and the application is made with water. Then, the amount of surfactants typically ranges from 5 to 40 % by weight of the composition.
Further examples of auxiliaries which are customary for formulating agrochemical compositions include water repellents, siccatives, binders (adhesive, tackifier, fixing agent, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids such as cephalins and lecithins and synthetic phospholipids, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose), thickeners, stabilizers (e.g. cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents which improve chemical and/or physical stability), dyes or pigments (such as inorganic pigments, e.g. iron oxide, titanium oxide and Prussian Blue ; organic dyes, e.g. alizarin, azo and metal phthalocyanine dyes), antifoams (e.g. silicone antifoams and magnesium stearate), preservatives (e.g. dichlorophene and benzyl alcohol hemiformal), secondary thickeners (cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica), stickers, gibberellins and processing auxiliaries, mineral and vegetable oils, perfumes, waxes, nutrients (including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc), protective colloids, thixotropic substances, penetrants, sequestering agents and complex formers.
The choice of the auxiliaries is related to the intended mode of application of the compound of the formula (I) respectively (G) and/or on the physical properties. Furthermore, the auxiliaries may be chosen to impart particular properties (technical, physical and/or biological properties) to the compositions or use forms prepared therefrom. The choice of auxiliaries may allow customizing the compositions to specific needs. The composition may be in any customary form, such as solutions (e.g. aqueous solutions), emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural or synthetic products impregnated with the compound of the invention, fertilizers and also microencapsulations in polymeric substances. The compound of formula (I) respectively (G) may be present in a suspended, emulsified or dissolved form.
The composition may be provided to the end user as ready-for-use formulation, i.e. the compositions may be directly applied to the plants or seeds by a suitable device, such as a spraying or dusting device. Alternatively, the composition may be provided to the end user in the form of concentrates which have to be diluted, preferably with water, prior to use.
The composition can be prepared in conventional manners, for example by mixing the compound formula (I) respectively (I’) with one or more suitable auxiliaries, such as disclosed herein above.
The composition contains generally from 0.01 to 99% by weight, from 0.05 to 98% by weight, preferably from 0.1 to 95% by weight, more preferably from 0.5 to 90% by weight, most preferably from 1 to 80 % by weight of the compound of formula (I) respectively (I’).
The compound(s) and composition(s) comprising thereof can be mixed with other active ingredients like fungicides, bactericides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners or semiochemicals. This may allow to broaden the activity spectrum or to prevent development of resistance. Examples of known fungicides, insecticides, acaricides, nematicides and bactericides are disclosed in the Pesticide Manual, 17th Edition.
Examples of fungicides which could be mixed with the compound(s) of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and the composition of the invention are:
1) Inhibitors of the ergosterol biosynthesis, for example (1 .001) cyproconazole, (1 .002) difenoconazole, (1 .003) epoxiconazole, (1 .004) fenhexamid, (1 .005) fenpropidin, (1 .006) fenpropimorph, (1 .007) fenpyrazamine, (1 .008) fluquinconazole, (1 .009) flutriafol, (1 .010) imazalil, (1 .01 1) imazalil sulfate, (1 .012) ipconazole, (1 .013) metconazole, (1 .014) myclobutanil, (1 .015) paclobutrazol, (1 .016) prochloraz, (1 .017) propiconazole, (1 .018) prothioconazole, (1 .019) pyrisoxazole, (1 .020) spiroxamine, (1 .021) tebuconazole, (1 .022) tetraconazole, (1 .023) triadimenol, (1 .024) tridemorph, (1 .025) triticonazole, (1 .026) (1 R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1 -(1 H-1 ,2,4-triazol-1 - ylmethyl)cyclopentanol, (1 .027) (1 S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1 -(1 H-1 ,2,4- triazol-1 -ylmethyl)cyclopentanol, (1 .028) (2R)-2-(1 -chlorocyclopropyl)-4-[(1 R)-2,2-dichlorocyclopropyl]-1 - (1 H-1 ,2,4-triazol-1 -yl)butan-2-ol, (1 .029) (2R)-2-(1 -chlorocyclopropyl)-4-[(1 S)-2,2-dichlorocyclopropyl]-1 - (1 H-1 ,2,4-triazol-1 -yl)butan-2-ol, (1 .030) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 H- 1 ,2,4-triazol-1 -yl)propan-2-ol, (1 .031) (2S)-2-(1 -chlorocyclopropyl)-4-[(1 R)-2,2-dichlorocyclopropyl]-1 - (1 H-1 ,2,4-triazol-1 -yl)butan-2-ol, (1 .032) (2S)-2-(1 -chlorocyclopropyl)-4-[(1 S)-2,2-dichlorocyclopropyl]-1 - (1 H-1 ,2,4-triazol-1 -yl)butan-2-ol, (1 .033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 H- 1 ,2,4-triazol-1 -yl)propan-2-ol, (1 .034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1 ,2-oxazol- 4-yl](pyridin-3-yl)methanol, (1 .035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1 ,2-oxazol-4- yl](pyridin-3-yl)methanol, (1 .036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1 ,2-oxazol-4- yl](pyridin-3-yl)methanol, (1 .037) 1 -({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1 ,3- dioxolan-2-yl}methyl)-1 H-1 ,2,4-triazole, (1 .038) 1 -({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4- methyl-1 ,3-dioxolan-2-yl}methyl)-1 H-1 ,2,4-triazole, (1 .039) 1 -{[3-(2-chlorophenyl)-2-(2,4- difluorophenyl)oxiran-2-yl]methyl}-1 H-1 ,2,4-triazol-5-yl thiocyanate, (1 .040) 1 -{[rel(2R,3R)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1 H-1 ,2,4-triazol-5-yl thiocyanate, (1 .041) 1 -
{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1 H-1 ,2,4-triazol-5-yl thiocyanate, (1 .042) 2-[(2R,4R,5R)-1 -(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4- dihydro-3H-1 ,2,4-triazole-3-thione, (1 .043) 2-[(2R,4R,5S)-1 -(2,4-dichlorophenyl)-5-hydroxy-2,6,6- trimethylheptan-4-yl]-2,4-dihydro-3H-1 ,2,4-triazole-3-thione, (1 .044) 2-[(2R,4S,5R)-1 -(2,4- dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1 ,2,4-triazole-3-thione, (1 .045) 2- [(2R,4S,5S)-1 -(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1 ,2,4-triazole- 3-thione, (1 .046) 2-[(2S,4R,5R)-1 -(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro- 3H-1 ,2,4-triazole-3-thione, (1 .047) 2-[(2S,4R,5S)-1 -(2,4-dichlorophenyl)-5-hydroxy-2,6,6- trimethylheptan-4-yl]-2,4-dihydro-3H-1 ,2,4-triazole-3-thione, (1 .048) 2-[(2S,4S,5R)-1 -(2,4- dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1 ,2,4-triazole-3-thione, (1 .049) 2- [(2S,4S,5S)-1 -(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1 ,2,4-triazole-3- thione, (1 .050) 2-[1 -(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1 ,2,4- triazole-3-thione, (1 .051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1 -(1 H-1 ,2,4-triazol-1 -yl)propan-2-ol, (1 .052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 H-1 ,2,4-triazol-1 -yl)butan-2-ol, (1 .053) 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 H-1 ,2,4-triazol-1 -yl)butan-2-ol, (1 .054) 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 H-1 ,2,4-triazol-1 -yl)pentan-2-ol, (1 .055) mefentrifluconazole, (1 .056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro- 3H-1 ,2,4-triazole-3-thione, (1 .057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2- yl]methyl}-2,4-dihydro-3H-1 ,2,4-triazole-3-thione, (1 .058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4- difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1 ,2,4-triazole-3-thione, (1 .059) 5-(4-chlorobenzyl)-2- (chloromethyl)-2-methyl-1 -(1 H-1 ,2,4-triazol-1 -ylmethyl)cyclopentanol, (1 .060) 5-(allylsulfanyl)-1 -{[3-(2- chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1 H-1 ,2,4-triazole, (1 .061 ) 5-(allylsulfanyl)-1 - {[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1 H-1 ,2,4-triazole, (1 .062) 5-
(allylsulfanyl)-1 -{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1 H-1 ,2,4- triazole, (1 .063) N'-(2,5-dimethyl-4-{[3-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N- methylimidoformamide, (1 .064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N- ethyl-N-methylimidoformamide, (1 .065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]- sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1 .066) N'-(2,5-dimethyl-4-{[3-(pentafluoro- ethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1 .067) N'-(2,5-dimethyl-4-{3-[(1 ,1 ,2,2- tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1 .068) N'-(2,5-dimethyl-4- {3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1 .069) N'-(2,5- dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1 .070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N- methylimidoformamide, (1 .071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide, (1 .072) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimido- formamide, (1 .073) N'-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N- methylimidoformamide, (1 .074) N'-[5-bromo-6-(2,3-dihydro-1 H-inden-2-yloxy)-2-methylpyridin-3-yl]-N- ethyl-N-methylimidoformamide, (1 .075) N'-{4-[(4,5-dichloro-1 ,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N- ethyl-N-methylimidoformamide, (1 .076) N'-{5-bromo-6-[(1 R)-1 -(3,5-difluorophenyl)ethoxy]-2- methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1 .077) N'-{5-bromo-6-[(1 S)-1 -(3,5-difluoro- phenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1 .078) N'-{5-bromo-6-[(cis-4- isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1 .079) N'-{5-bromo-6- [(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1 .080) N'-{5- bromo-6-[1 -(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1 .081) ipfentrifluconazole, (1 .082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 H-1 ,2,4-triazol-1 - yl)propan-2-ol, (1 .083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1 -(1 ,2,4-triazol-1 -yl)propan- 2-ol, (1 .084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol,
(1 .085) 3-[2-(1 -chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, (1 .086) 4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1 ,1 -difluoro-2-hydroxy-3-(5-thioxo-4H-1 ,2,4-triazol-1 - yl)propyl]-3-pyridyl]oxy]benzonitrile, (1 .087) N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1 - hydroxy-1 -phenylethyl)phenyl]-N-methylimidoformamide, (1 .088) N'-{5-bromo-2-methyl-6-[(1 - propoxypropan-2-yl)oxy]pyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1 .089) hexaconazole, (1 .090) penconazole, (1 .091) fenbuconazole and (1 .092) methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2- hydroxy-3-(1 ,2,4-triazol-1 -yl)propanoate.
2) Inhibitors of the respiratory chain at complex I or II, for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) Isofetamid, (2.010) isopyrazam (anti-epimeric enantiomer 1 R,4S,9S), (2.01 1) isopyrazam (anti-epimeric enantiomer 1 S,4R,9R), (2.012) isopyrazam (anti-epimeric racemate 1 RS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate 1 RS,4SR,9RS and anti-epimeric racemate 1 RS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enantiomer 1 R,4S,9R), (2.015) isopyrazam (syn-epimeric enantiomer 1 S,4R,9S), (2.016) isopyrazam (syn-epimeric racemate 1 RS,4SR,9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pydiflumetofen, (2.020) Pyraziflumid, (2.021) sedaxane, (2.022) 1 ,3-dimethyl-N-(1 ,1 ,3-trimethyl-2, 3-dihydro- 1 H-inden-4-yl)-1 H-pyrazole-4-carboxamide, (2.023) 1 ,3-dimethyl-N-[(3R)-1 ,1 ,3-trimethyl-2,3-dihydro-1 H-inden-4-yl]-1 H-pyrazole-4-carboxamide, (2.024) 1 ,3- dimethyl-N-[(3S)-1 ,1 ,3-trimethyl-2,3-dihydro-1 H-inden-4-yl]-1 H-pyrazole-4-carboxamide, (2.025) 1 - methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1 H-pyrazole-4-carboxamide, (2.026) 2- fluoro-6-(trifluoromethyl)-N-(1 ,1 ,3-trimethyl-2,3-dihydro-1 H-inden-4-yl)benzamide, (2.027) 3-
(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethyl-2,3-dihydro-1 H-inden-4-yl)-1 H-pyrazole-4-carboxamide, (2.028) inpyrfluxam, (2.029) 3-(difluoromethyl)-1 -methyl-N-[(3S)-1 ,1 ,3-trimethyl-2,3-dihydro-1 H-inden-4- yl]-1 H-pyrazole-4-carboxamide, (2.030) fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1 ,1 ,3- trimethyl-2,3-dihydro-1 H-inden-4-yl]-1 -methyl- 1 H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N- [(3S)-7-fluoro-1 ,1 ,3-trimethyl-2,3-dihydro-1 H-inden-4-yl]-1 -methyl-1 H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl- 1 H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 - methyl-1 H-pyrazole-4-carboxamide, (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)- 5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide, (2.038) isoflucypram, (2.039) N-[(1 R,4S)-9-
(dichloromethylene)-l ,2,3,4-tetrahydro-1 ,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1 -methyl-1 H- pyrazole-4-carboxamide, (2.040) N-[(1 S,4R)-9-(dichloromethylene)-1 ,2,3,4-tetrahydro-1 ,4- methanonaphthalen-5-yl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide, (2.041) N-[1 -(2,4- dichlorophenyl)-1 -methoxypropan-2-yl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5- fluoro-1 -methyl- 1 H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N- cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3- (difluoromethyl)-5-fluoro-1 -methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1 H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1 -methyl-1 H-pyrazole-4- carboxamide, (2.047) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1 -methyl- 1 H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1 - methyl-1 H-pyrazole-4-carbothioamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2- isopropylbenzyl)-1 -methyl-1 H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5- fluoro-N-(5-fluoro-2-isopropylbenzyl)-1 -methyl-1 H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3- (difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide, (2.053) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1 -methyl-1 H- pyrazole-4-carboxamide, (2.054) N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5- fluoro-1 -methyl- 1 H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3- (difluoromethyl)-5-fluoro-1 -methyl- 1 H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2- cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide, (2.057) pyrapropoyne, (2.058) N-[rac-(1 S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide, (2.059) N-[(1 S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide.
3) Inhibitors of the respiratory chain at complex III, for example (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.01 1) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2-{2-[({[(1 E)-1 -(3-{[(E)-1 -fluoro-2- phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1 -(4-chlorophenyl)-1 H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3- enamide, (3.023) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) fenpicoxamid, (3.026) mandestrobin, (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2- hydroxybenzamide, (3.028) (2E,3Z)-5-{[1 -(4-chloro-2-fluorophenyl)-1 H-pyrazol-3-yl]oxy}-2-
(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) methyl {5-[3-(2,4-dimethylphenyl)-1 H-pyrazol-1-yl]- 2-methylbenzyl}carbamate, (3.030) metyltetraprole, (3.031) florylpicoxamid.
4) Inhibitors of the mitosis and cell division, for example (4.001) carbendazim, (4.002) diethofencarb,
(4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) pyridachlometyl, (4.010) 3-chloro-5-(4-chlorophenyl)-4- (2,6-difluorophenyl)-6-methylpyridazine, (4.01 1) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6- trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1 ,3-dimethyl-1 H- pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1 ,3-dimethyl-1 H- pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1 ,3-dimethyl-1 H-pyrazol-5- amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5-amine, (4.017) 4-(2- bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5-amine, (4.018) 4-(2-chloro-4- fluorophenyl)-N-(2,6-difluorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5-amine, (4.019) 4-(2-chloro-4- fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5-amine, (4.020) 4-(2-chloro-4- fluorophenyl)-N-(2-chlorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)- N-(2-fluorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)- 3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1 ,3-dimethyl-1 H- pyrazol-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5- amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5- amine, (4.026) fluopimomide.
5) Compounds capable to have a multisite action, for example (5.001) bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper(2+) sulfate, (5.010) dithianon, (5.01 1) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) metiram zinc, (5.017) oxine-copper, (5.018) propineb, (5.019) sulfur and sulfur preparations including calcium polysulfide, (5.020) thiram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H- pyrrolo[3',4':5,6][1 ,4]dithiino[2,3-c][1 ,2]thiazole-3-carbonitrile.
6) Compounds capable to induce a host defence, for example (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) tiadinil.
7) Inhibitors of the amino acid and/or protein biosynthesis, for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1 -yl)quinoline.
8) Inhibitors of the ATP production, for example (8.001) silthiofam.
9) Inhibitors of the cell wall synthesis, for example (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1 -(morpholin-4-yl)prop-2-en-1 -one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1 -(morpholin-4-yl)prop-2-en-1 -one.
10) Inhibitors of the lipid and membrane synthesis, for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
1 1) Inhibitors of the melanin biosynthesis, for example (1 1 .001) tricyclazole, (1 1 .002) tolprocarb.
12) Inhibitors of the nucleic acid synthesis, for example (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).
13) Inhibitors of the signal transduction, for example (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.
14) Compounds capable to act as an uncoupler, for example (14.001) fluazinam, (14.002) meptyldinocap.
15) Further fungicides selected from the group consisting of (15.001 ) abscisic acid, (15.002) benthiazole, (15.003) bethoxazin, (15.004) capsimycin, (15.005) carvone, (15.006) chinomethionat, (15.007) cufraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.01 1) flutianil, (15.012) fosetyl-aluminium, (15.013) fosetyl-calcium, (15.014) fosetyl-sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyldithiocarbamate, (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiprolin, (15.023) oxyfenthiin, (15.024) pentachlorophenol and salts, (15.025) phosphorous acid and its salts, (15.026) propamocarb-fosetylate, (15.027) pyriofenone (chlazafenone), (15.028) tebufloquin, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) 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 -yljethanone, (15.032) 1 -(4- {4-[(5S)-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)-l H-pyrazol-1 -yljethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipymetitrone, (15.035) 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-(prop-2-yn-1 - yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, (15.036) 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -yloxy)phenyl]-4, 5-dihydro- 1 ,2- oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, (15.037) 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]- 1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 - yljethanone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2- {(5R)-3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-
1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.040) 2-{(5S)-3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihyd ro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.041) ipflufenoquin, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3- yl)oxy]phenyl}propan-2-ol, (15.043) fluoxapiprolin, (15.044) 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihyd ro-1 ,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-phenylphenol and salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 - yl)quinoline, (15.047) quinofumelin, (15.048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5- fluoropyrimidin-2(1 H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid, (15.050) 5-amino-
1 .3.4-thiadiazole-2-thiol, (15.051 ) 5-chloro-N'-phenyl-N'-(prop-2-yn-1 -yl)thiophene-2-sulfonohydrazide,
(15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.053) 5-fluoro-2-[(4- methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1 ,4- benzoxazepine, (15.055) but-3-yn-1 -yl {6-[({[(Z)-(1 -methyl-1 H-tetrazol-5- yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) ethyl (2Z)-3-amino-2-cyano-3- phenylacrylate, (15.057) phenazine-1 -carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) tert-butyl {6-[({[(1 -methyl-1 H-tetrazol- 5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1 - [(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1 H)-one, (15.063) aminopyrifen, (15.064) (N'-[2- chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide), (15.065) (N'-(2-chloro-5- methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide), (15.066) (2-{2-[(7,8-difluoro-2- methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), (15.067) (5-bromo-1 -(5,6-dimethylpyridin-3-yl)-3,3- dimethyl-3,4-dihydroisoquinoline), (15.068) (3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin- 7-yl)quinoline), (15.069) (1 -(4,5-dimethyl-1 H-benzimidazol-1 -yl)-4,4-difluoro-3,3-dimethyl-3,4- dihydroisoquinoline), (15.070) 8-fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinolone, (15.071) 8-fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1 -yl)quinolone, (15.072) 3-(4,4- difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)-8-fluoroquinoline, (15.073) (N-methyl-N-phenyl-4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]benzamide), (15.074) methyl {4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl}carbamate, (15.075) (N-{4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzyl}cyclopropane- carboxamide), (15.076) N-methyl-4-(5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide, (15.077) N-[(E)- methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide, (15.078) N-[(Z)- methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide, (15.079) N-[4-[5-
(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]cyclopropanecarboxamide, (15.080) N-(2-fluorophenyl)-4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-
1 .2.4-oxadiazol-3-yl]phenyl]acetamide, (15.082) N-allyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl)phenyl]methyl]acetamide, (15.083) N-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-(5-(trifluoromethyl)-
1 .2.4-oxadiazol-3-yl]benzamide, (15.084) N-[(Z)-N-methoxy-C-methyl-carbonimidoyl]-4-[5-
(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]benzamide, (15.085) N-allyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]propanamide, (15.086) 4,4-dimethyl-1 -[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.087) N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]benzenecarbothioamide, (15.088) 5-methyl-1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]pyrrolidin-2-one, (15.089) N-((2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]-3,3,3-trifluoro-propanamide, (15.090) 1 -methoxy-1 -methyl-3-[[4-[5-(trifluoromethyl}-
1 .2.4-oxadiazol-3-yl]phenyl]methyl]urea, (15.091) 1 ,1 -diethyl-3-[[4-[5-(trifluoromethyl}-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea, (15.092) N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phen- yl]methyl]propanamide, (15.093) N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]- methyl]cyclopropanecarboxamide, (15.094) 1 -methoxy-3-methyl-1 -[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl)cyclopropanecarboxamide, (15.096) N,2-dimethoxy-N-[[4-[5-(trifluoromethyl}-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]propanamide, (15.097) N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl)phenyl]methyl]propanamide, (15.098) 1 -methoxy-3-methyl-1 -[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1 ,3-dimethoxy-1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea, (15.100) 3-ethyl-1 -methoxy-1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea, (15.101 ) 1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2- one, (15.102) 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isooxazolidin-3- one, (15.103) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3- one, (15.104) 3,3-dimethyl-1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.105) 1 -[[3-fluoro-4-(5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one, (15.106)
4.4-dimethyl-2-[[4-(5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.107)
5.5-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.108) ethyl 1 -{4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzyl}-1 H-pyrazole-4-carboxylate, (15.109) N,N- dimethyl-1 -{4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzyl}-1 H-1 ,2,4-triazol-3-amine, (15.1 10) N-{2,3- difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzyl}butanamide, (15.1 1 1) N-(l -methylcyclopropyl)- 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide, (15.1 12) N-(2,4-difluorophenyl)-4-[5-
(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]benzamide, (15.1 13) 1 -(5,6-dimethylpyridin-3-yl)-4,4-difluoro-3,3- dimethyl-3,4-dihydroisoquinoline, (15.1 14) 1 -(6-(difluoromethyl)-5-methyl-pyridin-3-yl)-4,4-difluoro-3,3- dimethyl-3,4-dihydroisoquinoline, (15.1 15) 1 -(5-(fluoromethyl)-6-methyl-pyridin-3-yl)-4,4-difluoro-3,3- dimethyl-3,4-dihydroisoquinoline, (15.1 16) 1 -(6-(difluoromethyl)-5-methoxy-pyridin-3-yl)-4,4-difluoro-3,3- dimethyl-3,4-dihydroisoquinoline, (15.1 17) 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl dimethyl- carbamate, (15.1 18) N-{4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl}propanamide, (15.1 19) 3-[2-(1 - {[5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-1 ,5-di hydro-2, 4- benzodioxepin-6-yl methanesulfonate, (15.120) 9-fluoro-3-[2-(1 -{[5-methyl-3-(trifluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-1 ,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.121) 3-[2-(1 -{[3, 5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-1 ,5- dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.122) 3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-9-fluoro-1 ,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate,
(15.123) 1 -(6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline,
(15.124) 8-fluoro-N-(4,4,4-trifluoro-2-methyl-1 -phenylbutan-2-yl)quinoline-3-carboxamide, (15.125) 8- fluoro-N-[(2S)-4,4,4-trifluoro-2-methyl-1 -phenylbutan-2-yl]quinoline-3-carboxamide, (15.126) N-(2,4- dimethyl-1 -phenylpentan-2-yl)-8-fluoroquinoline-3-carboxamide and (15.127) N-[(2S)-2,4-dimethyl-1 - phenylpentan-2-yl]-8-fluoroquinoline-3-carboxamide.
All named mixing partners of the classes (1) to (15) as described here above can be present in the form of the free compound and/or, if their functional groups enable this, an agriculturally acceptable salt thereof.
The compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof may be combined with one or more biological control agents. Examples of biological control agents which may be combined with the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof are:
(A) Antibacterial agents selected from the group of:
(A1) bacteria, such as (A1 .1) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 and described in U.S. Patent No. 6,060,051); (A1.2) Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); (A1 .3) Bacillus pumilus, in particular strain BU F-33 (having NRRL Accession No. 50185); (A1.4) Bacillus subtilis var. amyloliquefaciens strain FZB24 (available as Taegro® from Novozymes, US); (A1.5) a Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129 and described in International Patent Publication No. WO 2016/154297; and
(A2) fungi, such as (A2.1) Aureobasidium pullulans, in particular blastospores of strain DSM14940; (A2.2) Aureobasidium pullulans blastospores of strain DSM 14941 ; (A2.3) Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM14941 ;
(B) Fungicides selected from the group of:
(B1) bacteria, for example (B1.1) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 and described in U.S. Patent No. 6,060,051); (B1 .2) Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B- 30087 and described in U.S. Patent No. 6,245,551); (B1.3) Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE); (B1 .4) Bacillus pumilus, in particular strain BU F-33 (having NRRL Accession No. 50185); (B1.5) Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); (B1.6) Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277); (B1 .7) Bacillus amyloliquefaciens strain MBI 600 (available as SUBTILEX from BASF SE); (B1 .8) Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE); (B1 .9) Bacillus subtilis var. amyloliquefaciens strain FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as the fungicide TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5); (B1.10) Bacillus mycoides, isolate J (available as BmJ TGAI or WG from Certis USA); (B1.11) Bacillus licheniformis, in particular strain SB3086 (available as EcoGuard TM Biofungicide and Green Releaf from Novozymes); (B1 .12) a Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129 and described in International Patent Publication No. WO 2016/154297.
In some embodiments, the biological control agent is a Bacillus subtilis or Bacillus amyloliquefaciens strain that produces a fengycin or plipastatin-type compound, an iturin-type compound, and/or a surfactin-type compound. For background, see the following review article: Ongena, M., et al.,“Bacillus Lipopeptides: Versatile Weapons for Plant Disease Biocontrol,” Trends in Microbiology, Vol 16, No. 3, March 2008, pp. 1 15-125. Bacillus strains capable of producing lipopeptides include Bacillus subtilis QST713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 and described in U.S. Patent No. 6,060,051), Bacillus amyloliquefaciens strain D747 (available as Double Nickel™ from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); Bacillus subtilis MBI600 (available as SUBTILEX® from Becker Underwood, US EPA Reg. No. 71840-8); Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277); Bacillus amyloliquefaciens, in particular strain FZB42 (available as RHIZOVITAL® from ABiTEP, DE); and Bacillus subtilis var. amyloliquefaciens FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as the fungicide TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5); and
(B2) fungi, for example: (B2.1) Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM-9660; e.g. Contans ® from Bayer); (B2.2) Metschnikowia fructicola, in particular strain NRRL Y- 30752 (e.g. Shemer®); (B2.3) Microsphaeropsis ochracea (e.g. Microx® from Prophyta); (B2.5) Trichoderma spp., including Trichoderma atroviride, strain SC1 described in International Application No. PCT/IT2008/000196); (B2.6) Trichoderma harzianum rifai strain KRL-AG2 (also known as strain T- 22, /ATCC 208479, e.g. PLANTSHIELD T-22G, Rootshield®, and TurfShield from BioWorks, US); (B2.14) Gliocladium roseum, strain 321 U from W.F. Stoneman Company LLC; (B2.35) Talaromyces flavus, strain V117b; (B2.36) Trichoderma asperellum, strain ICC 012 from Isagro; (B2.37) Trichoderma asperellum, strain SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry); (B2.38) Trichoderma atroviride, strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR); (B2.39) Trichoderma atroviride, strain no. V08/002387; (B2.40) Trichoderma atroviride, strain NMI no. V08/002388; (B2.41) Trichoderma atroviride, strain NMI no. V08/002389; (B2.42) Trichoderma atroviride, strain NMI no. V08/002390; (B2.43) Trichoderma atroviride, strain LC52 (e.g. Tenet by Agrimm Technologies Limited); (B2.44) Trichoderma atroviride, strain ATCC 20476 (IMI 206040); (B2.45) Trichoderma atroviride, strain T11 (IMI352941 / CECT20498); (B2.46) Trichoderma harmatum ; (B2.47) Trichoderma harzianum ; (B2.48) Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US); (B2.49) Trichoderma harzianum, in particular, strain KD (e.g. Trichoplus from Biological Control Products, SA (acquired by Becker Underwood)); (B2.50) Trichoderma harzianum, strain ITEM 908 (e.g. Trianum-P from Koppert); (B2.51) Trichoderma harzianum, strain TH35 (e.g. Root-Pro by Mycontrol); (B2.52) Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (e.g. SoilGard 12G by Certis, US); (B2.53) Trichoderma viride, strain TV1 (e.g. Trianum-P by Koppert); (B2.54) Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia); (B2.56) Aureobasidium pullulans, in particular blastospores of strain DSM14940; (B2.57) Aureobasidium pullulans, in particular blastospores of strain DSM 14941 ; (B2.58) Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. Botector® by bio-ferm, CH); (B2.64) Cladosporium cladosporioides, strain H39 (by Stichting Dienst Landbouwkundig Onderzoek); (B2.69) Gliocladium catenulatum (Synonym: Clonostachys rosea f catenuiate) strain J1446 (e.g. Prestop ® by AgBio Inc. and also e.g. Primastop® by Kemira Agro Oy); (B2.70) Lecanicillium lecanii (formerly known as Verticillium lecanii ) conidia of strain KV01 (e.g. Vertalec® by Koppert/Arysta); (B2.71) PeniciIHum vermiculatum·, (B2.72) Pichia anomala, strain WRL-076 (NRRL Y-30842); (B2.75) Trichoderma atroviride, strain SKT-1 (FERM P-16510); (B2.76) Trichoderma atroviride, strain SKT-2 (FERM P-16511); (B2.77) Trichoderma atroviride, strain SKT-3 (FERM P-17021); (B2.78) Trichoderma gamsii (formerly T. viride), strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.); (B2.79) Trichoderma harzianum, strain DB 103 (e.g., T-Gro 7456 by Dagutat Biolab); (B2.80) Trichoderma polysporum, strain IMI 206039 (e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden); (B2.81) Trichoderma stromaticum (e.g. Tricovab by Ceplac, Brazil); (B2.83) Ulocladium oudemansii, in particular strain HRU3 (e.g. Botry-Zen® by Botry-Zen Ltd, NZ); (B2.84) Verticillium albo-atrum (formerly V. dahliae), strain WCS850 (CBS 276.92; e.g. Dutch Trig by Tree Care Innovations); (B2.86) Verticillium chlamydosporium ; (B2.87) mixtures of Trichoderma asperellum strain ICC 012 and Trichoderma gamsii strain ICC 080 (product known as e.g. BIO-TAM™from Bayer CropScience LP, US).
Further examples of biological control agents which may be combined with the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof are:
bacteria selected from the group consisting of Bacillus cereus, in particular B. cereus strain CNCM I- 1562 and Bacillus ftrmus, strain 1-1582 (Accession number CNCM 1-1582), Bacillus subtilis strain OST 30002 (Accession No. NRRL B-50421), Bacillus thuringiensis, in particular B. thuringiensis subspecies israelensis (serotype H-14), strain AM65-52 (Accession No. ATCC 1276), B. thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372), B. thuringiensis subsp. kurstaki strain HD-1 , B. thuringiensis subsp. tenebrionis strain NB 176 (SD-5428), Pasteuria penetrans, Pasteuria spp. (Rotylenchulus reniformis nematode)-PR3 (Accession Number ATCC SD-5834), Streptomyces microflavus strain AQ6121 (= QRD 31.013, NRRL B-50550), and Streptomyces galbus strain AQ 6047 (Acession Number NRRL 30232); fungi and yeasts selected from the group consisting of Beauveria bassiana, in particular strain ATCC 74040, Lecanicillium spp., in particular strain HRO LEC 12, Metarhizium anisopliae, in particular strain F52 (DSM3884 or ATCC 90448), Paecilomyces fumosoroseus (now: Isaria fumosorosea), in particular strain IFPC 200613, or strain Apopka 97 (Accesion No. ATCC 20874), and Paecilomyces lilacinus, in particular P. lilacinus strain 251 (AGAL 89/030550); viruses selected from the group consisting of Adoxophyes orana (summer fruit tortrix) granulosis virus (GV), Cydia pomonella (codling moth) granulosis virus (GV), Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, and Spodoptera littoralis (African cotton leafworm) NPV. bacteria and fungi which can be added as 'inoculant' to plants or plant parts or plant organs and which, by virtue of their particular properties, promote plant growth and plant health. Examples are: Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp., or Gigaspora monosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp., and Streptomyces spp. plant extracts and products formed by microorganisms including proteins and secondary metabolites which can be used as biological control agents, such as Allium sativum, Artemisia absinthium, azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, chitin, Armour-Zen, Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Fungastop, Heads Up (' Chenopodium quinoa saponin extract), Pyrethrum/Pyrethrins, Quassia amara, Quercus, Quillaja, Regalia, "Requiem ™ Insecticide", rotenone, ryanial ryanodine, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae extract, in particular oilseed rape powder or mustard powder.
Examples of insecticides, acaricides and nematicides, respectively, which could be mixed with the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof are:
(1) Acetylcholinesterase (AChE) inhibitors, such as, for example, carbamates, for example alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or organophosphates, for example acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon and vamidothion.
(2) GABA-gated chloride channel blockers, such as, for example, cyclodiene-organochlorines, for example chlordane and endosulfan or phenylpyrazoles (fiproles), for example ethiprole and fipronil.
(3) Sodium channel modulators, such as, for example, pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(I R)-trans-isomer], deltamethrin, empenthrin [(EZ)-(1 R)-isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(I R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1 R)- isomer)], tralomethrin and transfluthrin or DDT or methoxychlor.
(4) Nicotinic acetylcholine receptor (nAChR) competitive modulators, such as, for example, neonicotinoids, e.g. acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone. (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators, such as, for example, spinosyns, e.g. spinetoram and spinosad.
(6) Glutamate-gated chloride channel (GluCI) allosteric modulators, such as, for example, avermectins/milbemycins, for example abamectin, emamectin benzoate, lepimectin and milbemectin.
(7) Juvenile hormone mimics, such as, for example, juvenile hormone analogues, e.g. hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen.
(8) Miscellaneous non-specific (multi-site) inhibitors, such as, for example, alkyl halides, e.g. methyl bromide and other alkyl halides; or chloropicrine or sulfuryl fluoride or borax or tartar emetic or methyl isocyanate generators, e.g. diazomet and metam.
(9) Modulators of Chordotonal Organs, such as, for example pymetrozine or flonicamid.
(10) Mite growth inhibitors, such as, for example clofentezine, hexythiazox and diflovidazin or etoxazole.
(11) Microbial disruptors of the insect gut membrane, such as, for example Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and B.t. plant proteins: CrylAb, CrylAc, Cryl Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1/35Ab1 .
(12) Inhibitors of mitochondrial ATP synthase, such as, ATP disruptors such as, for example, diafenthiuron or organotin compounds, for example azocyclotin, cyhexatin and fenbutatin oxide or propargite or tetradifon.
(13) Uncouplers of oxidative phosphorylation via disruption of the proton gradient, such as, for example, chlorfenapyr, DNOC and sulfluramid.
(14) Nicotinic acetylcholine receptor channel blockers, such as, for example, bensultap, cartap hydrochloride, thiocylam, and thiosultap-sodium.
(15) Inhibitors of chitin biosynthesis, type 0, such as, for example, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.
(16) Inhibitors of chitin biosynthesis, type 1 , for example buprofezin.
(17) Moulting disruptor (in particular for Diptera, i.e. dipterans), such as, for example, cyromazine.
(18) Ecdysone receptor agonists, such as, for example, chromafenozide, halofenozide, methoxyfenozide and tebufenozide.
(19) Octopamine receptor agonists, such as, for example, amitraz.
(20) Mitochondrial complex III electron transport inhibitors, such as, for example, hydramethylnone or acequinocyl or fluacrypyrim.
(21) Mitochondrial complex I electron transport inhibitors, such as, for example from the group of the METI acaricides, e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).
(22) Voltage-dependent sodium channel blockers, such as, for example indoxacarb or metaflumizone.
(23) Inhibitors of acetyl CoA carboxylase, such as, for example, tetronic and tetramic acid derivatives, e.g. spirodiclofen, spiromesifen and spirotetramat.
(24) Mitochondrial complex IV electron transport inhibitors, such as, for example, phosphines, e.g. aluminium phosphide, calcium phosphide, phosphine and zinc phosphide or cyanides, e.g. calcium cyanide, potassium cyanide and sodium cyanide. (25) Mitochondrial complex II electron transport inhibitors, such as, for example, befa-ketonitrile derivatives, e.g. cyenopyrafen and cyflumetofen and carboxanilides, such as, for example, pyflubumide. (28) Ryanodine receptor modulators, such as, for example, diamides, e.g. chlorantraniliprole, cyantraniliprole and flubendiamide, further active compounds such as, for example, Afidopyropen, Afoxolaner, Azadirachtin, Benclothiaz, Benzoximate, Bifenazate, Broflanilide, Bromopropylate, Chinomethionat, Chloroprallethrin, Cryolite, Cyclaniliprole, Cycloxaprid, Cyhalodiamide, Dicloromezotiaz, Dicofol, epsilon-Metofluthrin, epsilon- Momfluthrin, Flometoquin, Fluazaindolizine, Fluensulfone, Flufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon, Fluopyram, Fluralaner, Fluxametamide, Fufenozide, Guadipyr, Heptafluthrin, Imidaclothiz, Iprodione, kappa-Bifenthrin, kappa-Tefluthrin, Lotilaner, Meperfluthrin, Paichongding, Pyridalyl, Pyrifluquinazon, Pyriminostrobin, Spirobudiclofen, Tetramethylfluthrin, Tetraniliprole, Tetrachlorantraniliprole, Tigolaner, Tioxazafen, Thiofluoximate, Triflumezopyrim and iodomethane; furthermore preparations based on Bacillus firmus (1-1582, BioNeem, Votivo), and also the following compounds: 1 -{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1 H-1 ,2,4- triazole-5-amine (known from W02006/043635) (CAS 885026-50-6), {1 '-[(2E)-3-(4-chlorophenyl)prop-2- en-1 -yl]-5-fluorospiro[indol-3,4'-piperidin]-1 (2H)-yl}(2-chloropyridin-4-yl)methanone (known from W02003/106457) (CAS 637360-23-7), 2-chloro-N-[2-{1 -[(2E)-3-(4-chlorophenyl)prop-2-en-1 -yl]piperidin- 4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from W02006/003494) (CAS 872999-66-1), 3-(4- chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1 ,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1 ,8- diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP2647626) (CAS 1440516-42-6) , 4-(but-2- yn-1 -yloxy)-6-(3,5-dimethylpiperidin-1 -yl)-5-fluoropyrimidine (known from W02004/099160) (CAS 792914-58-0), PF1364 (known from JP2010/018586) (CAS 1204776-60-2), N-[(2E)-1 -[(6- chloropyridin-3-yl)methyl]pyridin-2(1 H)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012/029672) (CAS 1363400-41 -2), (3E)-3-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1 ,1 ,1 -trifluoro-propan-2-one (known from WO2013/144213) (CAS 1461743-15-6), , A/-[3-(benzylcarbamoyl)-4-chlorophenyl]-1 - methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1 /-/-pyrazole-5-carboxamide (known from
WO2010/051926) (CAS 1226889-14-0), 5-bromo-4-chloro-A/-[4-chloro-2-methyl-6-
(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-/V- (c/s-1 -oxido-3-thietanyl)-benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3- isoxazolyl]-2-methyl-A/-(frans-1 -oxido-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5- dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-A/-(c/s-1 -oxido-3-thietanyl)benzamide (known from WO 2013/050317 A1) (CAS 1332628-83-7), A/-[3-chloro-1 -(3-pyridinyl)-1 H-pyrazol-4-yl]-A/-ethyl-3-[(3,3, 3-trifluoropropyl)sulfinyl]-propanamide, (+)-A/-[3-chloro-1 -(3-pyridinyl)-1 /-/-pyrazol-4-yl]-A/-ethyl-3-[(3,3,3- trifluoropropyl)sulfinyl]-propanamide and (-)-A/-[3-chloro-1 -(3-pyridinyl)-1 /-/-pyrazol-4-yl]-A/-ethyl-3-[(3,3,3- trifluoropropyl)sulfinyl]-propanamide (known from WO 2013/162715 A2, WO 2013/162716 A2, US 2014/0213448 A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1 -yl]amino]-1 -[2,6-dichloro-4- (trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1 /-/-pyrazole-3-carbonitrile (known from
CN 101337937 A) (CAS 1 105672-77-2), 3-bromo-A/-[4-chloro-2-methyl-6-[(methylamino)thioxomethyl] phenyl]-1-(3-chloro-2-pyridinyl)-1 /-/-pyrazole-5-carboxamide, (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9); A/-[4-chloro-2-[[(1 ,1-dimethylethyl)amino]carbonyl]-6- methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1/-/-Pyrazole-5-carboxamide (known from WO 2012/034403 A1) (CAS 1268277-22-0), A/-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6- methylphenyl]-3-bromo-1 -(3-chloro-2-pyridinyl)-1 /-/-pyrazole-5-carboxamide (known from
WO 2011/085575 A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-dichloro-2-propen-1-yl)oxy] phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN 101337940 A) (CAS 1108184-52-6); (2 £)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-A/-[4-
(difluoromethoxy)phenyl]-hydrazinecarboxamide (known from CN 101715774 A) (CAS 1232543-85-9);
3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1 /-/-benzimidazol-2-yl)phenyl-cyclopropanecarboxylic acid ester (known from CN 103524422 A) (CAS 1542271-46-4); (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl) [4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]-indeno[1 ,2-e][1 ,3,4]oxadiazine-4a(3/-/)-carboxylic acid methyl ester (known from CN 102391261 A) (CAS 1370358-69-2); 6-deoxy-3-0-ethyl-2,4-di-0-methyl-, 1 -[A/-[4-[1 -[4-(1 , 1 ,2,2,2-pentafluoroethoxy)phenyl]-1 H- 1 ,2,4-triazol-3-yl]phenyl]carbamate]-a-L- mannopyranose (known from US 2014/0275503 A1) (CAS 1181213-14-8); 8-(2-cyclopropylmethoxy-4- trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1 Joctane (CAS 1253850- 56-4), (8-anf/)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3- aza-bicyclo[3.2.1 Joctane (CAS 933798-27-7), (8-syn)-8-(2-cyclopropylmethoxy-4-trifluoromethyl- phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1 Joctane (known from WO 2007040280 A1 , WO 2007040282 A1) (CAS 934001-66-8), N-[3-chloro-1 -(3-pyrid inyl)-1 H-pyrazol-
4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)thio]-propanamide (known from WO 2015/058021 A1 , WO
2015/058028 A1) (CAS 1477919-27-9) and N-[4-(aminothioxomethyl)-2-methyl-6-
[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1 /-/-pyrazole-5-carboxamide (known from CN 103265527 A) (CAS 1452877-50-7), 5-(1 ,3-dioxan-2-yl)-4-[[4-(trifluoromethyl)phenyl]methoxy]- pyrimidine (known from WO 2013/1 15391 A1) (CAS 1449021-97-9), 3-(4-chloro-2,6-dimethylphenyl)-4- hydroxy-8-methoxy-1 -methyl-1 ,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010/066780 A1 , WO 201 1/151146 A1) (CAS 1229023-34-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1 -methyl-1 ,8- diazaspiro[4.5]decane-2,4-dione (known from WO 2014/187846 A1) (CAS 1638765-58-8), 3-(4-chloro-2, 6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1 ,8-diazaspiro[4.5]dec-3-en-4-yl-carbonic acid ethyl ester (known from WO 2010/066780 A1 , WO 2011151 146 A1) (CAS 1229023-00-0), N-[1-[(6-chloro-3- pyridinyl)methyl]-2(1 /-/)-pyridinylidene]-2,2,2-trifluoro-acetamide (known from DE 3639877 A1 , WO 2012029672 A1) (CAS 1363400-41-2), [N(E)]-N-[1 -[(6-chloro-3-pyridinyl)methyl]-2(1 H)-pyridinylidene]-2, 2,2-trifluoro-acetamide, (known from WO 2016005276 A1) (CAS 1689566-03-7), [N(Z)]-N-[1-[(6-chloro- 3-pyridinyl)methyl]-2(1 H)-pyridinylidene]-2, 2,2-trifluoro-acetamide, (CAS 1702305-40-5), Z-endo-Z-[2- propoxy-4-(trifluoromethyl)phenoxy]-9-[[5-(trifluoromethyl)-2-pyridinyl]oxy]-9-azabicyclo[3.3.1]nonane (known from WO 201 1/105506 A1 , WO 2016/133011 A1) (CAS 1332838-17-1).
Examples of safeners which could be mixed with the compounds of formula (I) used according to the invention, the compound(s) of formula (I’) according to the invention and compositions comprising thereof are, for example, benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole (-ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}- sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526- 07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1 ,3-oxazolidine (CAS 52836-31-4).
Examples of herbicides which could be mixed with the compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof are:
Acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, amitrole, ammoniumsulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyron, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil-butyrate, -potassium, -heptanoate, and -octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlorthal-dimethyl, chlorsulfuron, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, -butyl, - dimethylammonium, -diolamin, -ethyl, -2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, - potassium, -triisopropanolammonium, and -trolamine, 2,4-DB, 2,4-DB-butyl, -dimethylammonium, - isooctyl, -potassium, and -sodium, daimuron (dymron), dalapon, dazomet, n-decanol, desmedipham, detosyl-pyrazolate (DTP), dicamba, dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1 ,2-oxazolidin-3- one, 2-(2,5-dichlorobenzyl)-4,4-dimethyl-1 ,2-oxazolidin-3-one, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr- sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat, diquat-dibromid, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-9600, F-5231 , i.e. N-{2- chloro-4-fluoro-5-[4-(3-fluoropropyl)-5-oxo-4,5-dihydro-1 H-tetrazol-1-yl]phenyl}ethanesulfonamide, F- 7967, i. e. 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1 H-benzimidazol-4-yl]-1 -methyl-6-
(trifluoromethyl)pyrimidine-2,4(1 H,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop- P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M- methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl, -dimethylammonium and -methyl, fluorogly cofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate- ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, -sodium, and -trimesium, H-9201 , i.e. 0-(2,4-dimethyl-6-nitrophenyl) O-ethyl isopropylphosphoramidothioate, halauxifen, halauxifen-methyl .halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e. l -(dimethoxyphosphoryl) ethyl-(2,4-dichlorophenoxy)acetate, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil- octanoate, -potassium and -sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043, i.e. 3-({[5-(difluoromethyl)-1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-4- yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1 ,2-oxazole, ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium, and -sodium, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium, and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl, and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozolin, methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinat, monolinuron, monosulfuron, monosulfuron-ester, MT-5950, i.e. N-(3-chloro-4-isopropylphenyl)-2-methylpentan amide, NGGC-01 1 , napropamide, NC-310, i.e. [5- (benzyloxy)-1 -methyl-1 H-pyrazol-4-yl](2,4-dichlorophenyl)methanone, neburon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorphenol, pentoxazone, pethoxamid, petroleum oils, phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron- methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac- methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P- tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261 , sulcotrion, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249, i.e. 1 -ethoxy-3- methyl-1 -oxobut-3-en-2-yl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. 1 -[7- fluoro-3-oxo-4-(prop-2-yn-1 -yl)-3,4-dihydro-2H-1 ,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidine-4,5- dione, 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazin, terbutryn, thenylchlor, thiazopyr, thien- carbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfu ron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862, i.e. 3,4- dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline, and the following compounds:
Figure imgf000062_0001
Examples for plant growth regulators are:
Acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine, Brassinolid, catechine, chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-1 -enyl) propionic acid, daminozide, dazomet, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dipotassium, -disodium, and - mono(N,N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indol-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, maleic hydrazide, mepiquat chloride, 1 -methylcyclopropene, methyl jasmonate, 2-(1 -naphthyl)acetamide, 1 -naphthylacetic acid, 2- naphthyloxyacetic acid, nitrophenolate-mixture, paclobutrazol, N-(2-phenylethyl)-beta-alanine, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone, salicylic acid, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P.
Methods and uses
The compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and the compositions comprising thereof have potent microbicidal activity. They can be used for controlling unwanted microorganisms, such as unwanted fungi and bacteria. They can be particularly useful in crop protection (they control microorganisms that cause plants diseases) or for protecting materials (e.g. industrial materials, timber, storage goods) as described in more details herein below. More specifically, the compounds of formula (I) used according to the invention, the compounds of formula (G) according to the invention and the compositions comprising thereof can be used to protect seeds, germinating seeds, emerged seedlings, plants, plant parts, fruits, harvest goods and/or the soil in which the plants grow from unwanted microorganisms.
Control or controlling as used herein encompasses protective, curative and eradicative treatment of unwanted microorganisms. Unwanted microorganisms may be pathogenic bacteria, pathogenic virus, pathogenic oomycetes or pathogenic fungi, more specifically phytopathogenic bacteria phytopathogenic virus, phytopathogenic oomycetes or phytopathogenic fungi. As detailed herein below, these phytopathogenic microorganims are the causal agents of a broad spectrum of plants diseases.
More specifically, the compounds of formula (I) used according to the invention, the compounds of formula (G) according to the invention and compositions comprising thereof can be used as fungicides. For the purpose of the specification, the term“fungicide” refers to a compound or composition that can be used in crop protection for the control of unwanted fungi, such as Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes and/or for the control of Oomycetes, more preferably for the control of Basidiomycetes (causing rust diseases).
The present invention also relates to a method for controlling unwanted microorganisms, such as phytopathogenic fungi, oomycetes and bacteria, comprising the step of applying at least one compound of formula (I) or at least one composition comprising thereof to the microorganisms and/or their habitat (to the plants, plant parts, seeds, fruits or to the soil in which the plants grow).
Typically, when the compound and the composition of the invention are used in curative or protective methods for controlling phytopathogenic fungi and/or phytopathogenic oomycetes, an effective and plant-compatible amount thereof is applied to the plants, plant parts, fruits, seeds or to the soil or substrates in which the plants grow. Suitable substrates that may be used for cultivating plants include inorganic based substrates, such as mineral wool, in particular stone wool, perlite, sand or gravel; organic substrates, such as peat, pine bark or sawdust; and petroleum based substrates such as polymeric foams or plastic beads. Effective and plant-compatible amount means an amount that is sufficient to control or destroy the fungi present or liable to appear on the cropland and that does not entail any appreciable symptom of phytotoxicity for said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the crop growth stage, the climatic conditions and the respective compound or composition of the invention used. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.
Plants and plant parts
The compounds of formula (I) used according to the invention, the compound(s) of formula (G) according to the invention and compositions comprising thereof may be applied to any plants or plant parts.
Plants mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the genetically modified plants (GMO or transgenic plants) and the plant cultivars which are protectable and non-protectable by plant breeders’ rights.
Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples of which include leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes. The plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
Plants which may be treated in accordance with the methods of the invention include the following: cotton, flax, grapevine, fruit, vegetables, such as Rosaceae sp. (for example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example banana trees and plantations), Rubiaceae sp. (for example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for example lemons, oranges and grapefruit); Solanaceae sp. (for example tomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (for example cucumber), Alliaceae sp. (for example leek, onion), Papilionaceae sp. (for example peas); major crop plants, such as Gramineae sp. (for example maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (for example sunflower), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, and oilseed rape, mustard, horseradish and cress), Fabacae sp. (for example bean, peanuts), Papilionaceae sp. (for example soya bean), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example sugar beet, fodder beet, swiss chard, beetroot); useful plants and ornamental plants for gardens and wooded areas; and genetically modified varieties of each of these plants.
In some preferred embodiments, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated in accordance with the methods of the invention.
In some other preferred embodiments, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated in accordance with the methods of the invention. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention. Plant cultivars are understood to mean plants which have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
The methods according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds. Genetically modified plants (or transgenic plants) are plants of which a heterologous gene has been stably integrated into genome. The 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 down regulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microRNA - miRNA - 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.
Plants and plant cultivars which can be treated by the above disclosed methods 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 can be treated by the above disclosed methods include plants and plant cultivars which 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 can be treated by the above disclosed methods include those plants which are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
Plants and plant cultivars which can be treated by the above disclosed methods include 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 and composition for example cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
Plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars which are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars which 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.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars which 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. Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars which 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.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars which show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars, 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.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars, such as Tobacco plants, with altered post-translational protein modification patterns.
Pathogens and diseases
The methods disclosed above can be used to control microorganisms, in particular phytopathogenic microorganisms such as phytopathogenic fungi, causing diseases, such as: diseases caused by powdery mildew pathogens, such as Blumeria species (e.g. Blumeria graminis), Podosphaera species (e.g. Podosphaera leucotricha), Sphaerotheca species (e.g. Sphaerotheca fuliginea), Uncinula species (e.g. Uncinula necator);
diseases caused by rust disease pathogens, such as Gymnosporangium species (e.g. Gymnosporangium sabinae), Hemileia species (e.g. Hemileia vastatrix), Phakopsora species (e.g. Phakopsora pachyrhizi or Phakopsora meibomiae), Puccinia species (e.g. Puccinia recondita, Puccinia graminis or Puccinia striiformis), Uromyces species (e.g. Uromyces appendiculatus) ;
diseases caused by pathogens from the group of the Oomycetes, such as Albugo species (e.g. Albugo Candida), Bremia species (e.g. Bremia lactucae), Peronospora species (e.g. Peronospora pisi or P. brassicae), Phytophthora species (e.g. Phytophthora infestans), Plasmopara species (e.g. Plasmopara viticola), Pseudoperonospora species (e.g. Pseudoperonospora humuli or Pseudoperonospora cubensis), Pythium species (e.g. Pythium ultimum) ;
leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species (e.g. Alternaria solani), Cercospora species (e.g. Cercospora beticola), Cladiosporium species (e.g. Cladiosporium cucumerinum), Cochliobolus species (e.g. Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium) or Cochliobolus miyabeanus), Colletotrichum species (e.g. Colletotrichum lindemuthanium), Cycloconium species (e.g. Cycloconium oleaginum), Diaporthe species (e.g. Diaporthe citri), Elsinoe species (e.g. Elsinoe fawcettii), Gloeosporium species (e.g. Gloeosporium laeticolor), Glomerella species (e.g. Glomerella cingulate), Guignardia species (e.g. Guignardia bidwelli), Leptosphaeria species (e.g. Leptosphaeria maculans), Magnaporthe species (e.g. Magnaporthe grisea), Microdochium species (e.g. Microdochium nivale), Mycosphaerella species (e.g. Mycosphaerella graminicola, Mycosphaerella arachidicola or Mycosphaerella fijiensis), Phaeosphaeria species (e.g. Phaeosphaeria nodorum), Pyrenophora species (e.g. Pyrenophora teres or Pyrenophora tritici repentis), Ramularia species (e.g. Ramularia collo-cygni or Ramularia areola), Rhynchosporium species (e.g. Rhynchosporium secalis), Septoria species (e.g. Septoria apii or Septoria lycopersici), Stagonospora species (e.g. Stagonospora nodorum), Typhula species (e.g. Typhula incarnate), Venturia species (e.g. Venturia inaequalis),
root and stem diseases caused, for example, by Corticium species (e.g. Corticium graminearum), Fusarium species (e.g. Fusarium oxysporum), Gaeumannomyces species, (e.g. Gaeumannomyces graminis), Plasmodiophora species, (e.g. Plasmodiophora brassicae), Rhizoctonia species, (e.g. Rhizoctonia solani), Sarocladium species, (e.g. Sarocladium oryzae), Sclerotium species, (e.g. Sclerotium oryzae), Tapesia species, (e.g. Tapesia acuformis), Thielaviopsis species, (e.g. Thielaviopsis basicola);
ear and panicle diseases (including corn cobs) caused, for example, by Alternaria species, (e.g. Alternaria spp.), Aspergillus species (e.g. Aspergillus flavus), Cladosporium species (e.g. Cladosporium cladosporioides, Claviceps species (e.g. Claviceps purpurea), Fusarium species, (e.g. Fusarium culmorum), Gibberella species (e.g. Gibberella zeae), Monographella species, (e.g. Monographella nivalis), Stagnospora species, (e.g. Stagnospora nodorum);
diseases caused by smut fungi, for example Sphacelotheca species (e.g. Sphacelotheca reiliana), Tilletia species (e.g. Tilletia caries or Tilletia controversa), Urocystis species (e.g. Urocystis occulta), Ustilago species (e.g. Ustilago nuda);
fruit rot caused, for example, by Aspergillus species (e.g. Aspergillus flavus), Botrytis species (e.g. Botrytis cinerea), Penicillium species (e.g. Penicillium expansum or Penicillium purpurogenum), Rhizopus species (e.g. Rhizopus stolonifer), Sclerotinia species (e.g. Sclerotinia sclerotiorum), Verticilium species (e.g. Verticilium alboatrum) ; seed- and soil-borne rot and wilt diseases, and also diseases of seedlings, caused, for example, by Alternaria species (e.g. Alternaria brassicicola), Aphanomyces species (e.g. Aphanomyces euteiches), Ascochyta species (e.g. Ascochyta lentis), Aspergillus species (e.g. Aspergillus flavus), Cladosporium species (e.g. Cladosporium herbarum), Cochliobolus species (e.g. Cochliobolus sativus (conidial form: Drechslera, Bipolaris Syn: Helminthosporium)), Colletotrichum species (e.g. Colletotrichum coccodes), Fusarium species (e.g. Fusarium culmorum), Gibberella species (e.g. Gibberella zeae), Macrophomina species (e.g. Macrophomina phaseolina), Microdochium species (e.g. Microdochium nivale), Monographella species (e.g. Monographella nivalis), Penicillium species(e.g. Penicillium expansum), Phoma species (e.g. Phoma lingam), Phomopsis species (e.g. Phomopsis sojae), Phytophthora species (e.g. Phytophthora cactorum), Pyrenophora species (e.g. Pyrenophora graminea), Pyricularia species (e.g. Pyricularia oryzae), Pythium species (e.g. Pythium ultimum), Rhizoctonia species (e.g. Rhizoctonia solani), Rhizopus species (e.g. Rhizopus oryzae), Sclerotium species (e.g. Sclerotium rolfsii), Septoria species (e.g. Septoria nodorum), Typhula species (e.g. Typhula incarnate), Verticillium species (e.g. Verticillium dahlia);
cancers, galls and witches’ broom caused, for example, by Nectria species (e.g. Nectria galligena); wilt diseases caused, for example, by Monilinia species (e.g. Monilinia laxa);
deformations of leaves, flowers and fruits caused, for example, by Exobasidium species (e.g. Exobasidium vexans), Taphrina species (e.g. Taphrina deformans);
degenerative diseases in woody plants, caused, for example, by Esca species (e.g. Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranea), Ganoderma species (e.g. Ganoderma boninense);
diseases of flowers and seeds caused, for example, by Botrytis species (e.g. Botrytis cinerea);
diseases of plant tubers caused, for example, by Rhizoctonia species (e.g. Rhizoctonia solani), Helminthosporium species (e.g. Helminthosporium solani);
diseases caused by bacterial pathogens, for example Xanthomonas species (e.g. Xanthomonas campestris pv. Oryzae), Pseudomonas species (e.g. Pseudomonas syringae pv. Lachrymans), Erwinia species (e.g. Erwinia amylovora).
In particular, the compounds of formula (I) used according to the invention, the compounds of formula (G) according to the invention and compositions comprising thereof are efficient in controlling pythopathogenic fungi causing rust diseases.
Seed Treatment
The method for controlling unwanted microorganisms may be used to protect seeds from phytopathogenic microorganisms, such as fungi.
The term“seed(s)” as used herein include dormant seed, primed seed, pregerminated seed and seed with emerged roots and leaves.
Thus, the present invention also relates to a method for protecting seeds and/or crops from unwanted microorganisms, such as bacteria or fungi, which comprises the step of treating the seeds with one or more compounds of formula (I) or a composition comprising thereof. The treatment of seeds with the compound(s) of formula (I) or or a composition comprising thereof not only protects the seeds from phytopathogenic microorganisms, but also the germinating plants, the emerged seedlings and the plants after emergence.
The seeds treatment may be performed prior to sowing, at the time of sowing or shortly thereafter.
When the seeds treatment is performed prior to sowing (e.g. so-called on-seed applications), the seeds treatment may be performed as follows: the seeds may be placed into a mixer with a desired amount of compound(s) of formula (I) or a composition comprising thereof (either as such or after dilution), the seeds and the compound(s) of formula (I) or the composition comprising thereof are mixed until a homogeneous distribution on seeds is achieved. If appropriate, the seeds may then be dried.
The invention also relates to seeds treated with one or more compounds of formula (I) or a composition comprising thereof. As said before, the use of treated seeds allows not only protecting the seeds before and after sowing from unwanted microorganisms, such as phytopathogenic fungi, but also allows protecting the germinating plants and young seedlings emerging from said treated seeds. A large part of the damage to crop plants caused by harmful organisms is triggered by the infection of the seeds before sowing or after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even small damage may result in the death of the plant.
Therefore, the present invention also relates to a method for protecting seeds, germinating plants and emerged seedlings, more generally to a method for protecting crop from phytopathogenic microorganisms, which comprises the step of using seeds treated by one or more compounds of formula (I) or a composition comprising thereof.
Preferably, the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment. In general, seeds can be treated at any time between harvest and shortly after sowing. It is customary to use seeds which have been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seeds which have been harvested, cleaned and dried down to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seeds which, after drying, for example, have been treated with water and then dried again, or seeds just after priming, or seeds stored in primed conditions or pre-germinated seeds, or seeds sown on nursery trays, tapes or paper.
The amount of compound(s) of formula (I) or composition comprising thereof applied to the seed is typically such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This must be ensured particularly in case the active ingredients would exhibit phytotoxic effects at certain application rates. The intrinsic phenotypes of transgenic plants should also be taken into consideration when determining the amount of compound(s) of formula (I) or composition comprising thereof to be applied to the seed in order to achieve optimum seed and germinating plant protection with a minimum amount of compound(s) of formula (I) or composition comprising thereof being employed. As indicated above, the compounds of the formula (I) can be applied, as such, directly to the seeds, i.e. without the use of any other components and without having been diluted, or a composition comprising the compounds of formula (I) can be applied. Preferably, the compositions are applied to the seed in any suitable form. Examples of suitable formulations include solutions, emulsions, suspensions, powders, foams, slurries or combined with other coating compositions for seed, such as film forming materials, pelleting materials, fine iron or other metal powders, granules, coating material for inactivated seeds, and also ULV formulations. The formulations may be ready-to-use formulations or may be concentrates that need to be diluted prior to use.
These formulations are prepared in a known manner, for instance by mixing the active ingredient or mixture thereof with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
These formulations are prepared in a known manner, by mixing the active ingredients or active ingredient combinations with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
Useful dyes which may be present in the seed dressing formulations are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.l. Pigment Red 112 and C.l. Solvent Red 1 . Useful wetting agents which may be present in the seed dressing formulations are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients. Usable with preference are alkylnaphthalenesulfonates, such as diisopropyl- or diisobutylnaphthalenesulfonates. Useful dispersants and/or emulsifiers which may be present in the seed dressing formulations are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Usable with preference are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Useful nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sulfated derivatives thereof. Suitable anionic dispersants are especially lignosulfonates, polyacrylic acid salts and arylsulfonate/formaldehyde condensates. Antifoams which may be present in the seed dressing formulations are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference. Preservatives which may be present in the seed dressing formulations are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal. Secondary thickeners which may be present in the seed dressing formulations are all substances usable for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica. Adhesives which may be present in the seed dressing formulations are all customary binders usable in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
The compounds of the formula (I) and the compositions comprising thereof are suitable for protecting seeds of any plant variety which is used in agriculture, in greenhouses, in forests or in horticulture. More particularly, the seed is that of cereals (such as wheat, barley, rye, millet, triticale, and oats), oilseed rape, maize, cotton, soybean, rice, potatoes, sunflower, beans, coffee, peas, beet (e.g. sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onions and lettuce), lawns and ornamental plants. Of particular significance is the treatment of the seed of wheat, soybean, oilseed rape, maize and rice.
The compounds of formula (I) or the compositions comprising thereof can be used for treating transgenic seeds, in particular seeds of plants capable of expressing a protein which acts against pests, herbicidal damage or abiotic stress, thereby increasing the protective effect. Synergistic effects may also occur in interaction with the substances formed by expression.
Application
The compound of formula (I) can be applied as such, or for example in the form of as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with the compound of formula (I), synthetic substances impregnated with the compound of formula (I), fertilizers or microencapsulations in polymeric substances.
Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading-on and the like. It is also possible to deploy the compound of formula (I) by the ultra-low volume method, via a drip irrigation system or drench application, to apply it infurrow or to inject it into the soil stem or trunk. It is further possible to apply the compound of formula (I) by means of a wound seal, paint or other wound dressing.
The effective and plant-compatible amount of the compound of formula (I) which is applied to the plants, plant parts, fruits, seeds or soil will depend on various factors, such as the compound/composition employed, the subject of the treatment (plant, plant part, fruit, seed or soil), the type of treatment (dusting, spraying, seed dressing), the purpose of the treatment (curative and protective), the type of microorganisms, the development stage of the microorganisms, the sensitivity of the microorganisms, the crop growth stage and the environmental conditions.
When the compound of formula (I) is used as a fungicide, the application rates can vary within a relatively wide range, depending on the kind of application. For the treatment of plant parts, such as leaves, the application rate may range from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more preferably from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used). For the treatment of seeds, the application rate may range from 0.1 to 200 g per 100 kg of seeds, preferably from 1 to 150 g per 100 kg of seeds, more preferably from 2.5 to 25 g per 100 kg of seeds, even more preferably from 2.5 to 12.5 g per 100 kg of seeds. For the treatment of soil, the application rate may range from 0.1 to 10 000 g/ha, preferably from 1 to 5000 g/ha.
These application rates are merely examples and are not intended to limit the scope of the present invention.
Material Protection
The compound and the composition of the invention may also be used in the protection of materials, especially for the protection of industrial materials against attack and destruction by unwanted microorganisms.
In addition, the compound and the composition of the invention may be used as antifouling compositions, alone or in combinations with other active ingredients.
Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry. For example, industrial materials which are to be protected from microbial alteration or destruction may be adhesives, glues, paper, wallpaper and board/cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms. Parts of production plants and buildings, for example cooling-water circuits, cooling and heating systems and ventilation and air-conditioning units, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood.
The compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
In the case of treatment of wood the compound and the composition of the invention may also be used against fungal diseases liable to grow on or inside timber.
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. In addition, the compound and the composition of the invention may be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signaling systems, from fouling.
The compound and the composition of the invention may also be employed for protecting storage goods. Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired. Storage goods of vegetable origin, for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, may be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting. Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture. Storage goods of animal origin are, for example, hides, leather, furs and hairs. The compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
Microorganisms capable of degrading or altering industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms. The compound and the composition of the invention preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi ( Ascomycetes , Basidiomycetes, Deuteromycetes and Zygomycetes), and against slime organisms and algae. Examples include microorganisms of the following genera: Alternaria, such as Altemaria tenuis Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana Lentinus, such as Lentinus tigrinus ; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans ; Sclerophoma, such as Sclerophoma pityophila ; Trichoderma, such as Trichoderma viride Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Cladosporium spp., Paecilomyces spp. Mucor spp., Escherichia, such as Escherichia coir, Pseudomonas, such as Pseudomonas aeruginosa ; Staphylococcus, such as Staphylococcus aureus, Candida spp. and Saccharomyces spp., such as Saccharomyces cerevisae.
Aspects of the present teaching may be further understood in light of the following examples, which should not be construed as limiting the scope of the present teaching in any way.
EXAMPLES
The following examples illustrate in a non-limiting manner the preparation and efficacy of the compounds of formulae (I) and (G) according to the invention.
Synthesis of intermediate of formula (III) / (III·)
2-f[1 -(2,6-Difluorophenyl')cvclopropyl1amino>pyrimidine-5-carbonitrile
Figure imgf000074_0001
To a solution of 2-chloropyrimidine-5-carbonitrile (1 .07 mmol, 1 .00 eq) in dioxane (1 .80 ml) at r.t was added 1 -(2,6-difluorophenyl)cyclopropanamine (1 .12 mmol, 1 .05 eq) and N,N-diisopropylethylamine (3.22 mmol, 3.00 eq). The reaction mixture was heated at 100°C in the microwave for 20 min. Water was then added and the aqueous phase was extracted three times with ethyl acetate. The organic layers were combined, dried over MgSC , filtered and evaporated. The residue was purified with flash chromatography (ethylacetate: Heptane) to afford the title compound (192 mg, 64% yield) as a white solid.
MS (ESI): 273 ([M+H]+)
Synthesis of intermediate of formula (II) / (ID
2-f[1 -(2.6-Difluorophenyl)cvclopropyl1amino)-N'-hvdroxypyrimidine-5-carboximidamide
Figure imgf000074_0002
To a suspension of 2-{[1 -(2,6-difluorophenyl)cyclopropyl]amino}pyrimidine-5-carbonitrile (170 mg, 0.62 mmol, 1 .00 eq) in ethanol (5 ml) was added hydroxylamine hydrochloride (88 mg, 1 .24 mmol, 2.00 eq) followed by triethylamine (0.39 ml, 2.81 mmol, 4.5 eq). The reaction was stirred overnight at r.t. The solvent was evaporated to afford the title compound (376 mg, 50% purity, 100% yield) as a white solid which was used for next step without further purification.
MS (ESI): 306 ([M+H]+) Synthesis of intermediate of formula (V) / (V’)
2-(MethylsulfonvD-5-[5-(trifluoromethvD-1 .2.4-oxadiazol-3-yllpyrimidine
Figure imgf000075_0001
Stepl :
To a mixture of 2-(methylsulfanyl)pyrimidine-5-carbonitrile (25.00 g, 165.35 mmol, 1 .00 eq) and hydroxylamine hydrochloride (22.98 g, 330.70 mmol, 2.00 eq) in ethanol (250.00 ml) and water (250.00 ml) was added sodium hydrogen carbonate (27.78 g, 330.70 mmol, 2.00 eq). The reaction was stirred at 70 °C for 16 h. This mixture was filtered and washed with water (50 ml*4). The residue was collected and evaporated. This residue N'-hydroxy-2-(methylsulfanyl)pyrimidine-5-carboximidamide (29.00 g, crude) was used for next step without further purification. Step2
A mixture of N'-hydroxy-2-(methylsulfanyl)pyrimidine-5-carboximidamide (16.28 mmol, 1 .00 eq) and trifluoroacetic anhydride (24.43 mmol, 1 .50 eq) was stirred at 45 °C for 16 h. The mixture was poured into ice and filtered. The residue was washed with water and collected. The product 2-(methylsulfanyl)- 5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidine was used for next step without further purification.
Step3
To a solution of 2-(methylsulfanyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidine (10.89 mmol, 1 .00 eq) in dichloromethane (30.00 ml) was added 3-chloroperbenzoic acid (23.96 mmol, 2.20 eq) with stirring. The mixture was stirred at 25 °C for 16 h. The mixture was diluted with water (100 ml) and quenched with sodium sulfite. The mixture was extracted with dichloromethane (100 ml*3). The organic layer was collected and evaporated. The residue was purified with flash chromatography (ethylacetate: Petroleum ether 3:5). 2-(methylsulfonyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidine (7.85 mmol) was obtained as a white solid.
Synthesis of compounds of formula (I) / (G)
N-(2-Phenylpropan-2-vD-5-[5-(trifluoromethvD-1 .2.4-oxadiazol-3-yllpyrimidin-2-amine (Compound I-004)
Figure imgf000076_0001
To a solution of 2-(methylsulfonyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidine (0.23 mmol, 1 .00 eq) in dioxane (1 .00 ml) at r.t was added 2-phenylpropan-2-amine (0.71 mmol, 3.0 eq), followed by paratoluenesulfonic acid (0.1 1 mmol, 0.5 eq). The reaction mixture was heated in the microwave for 10 min at 150°C and then left standing overnight at r.t. Water was then added and the aqueous phase was extracted three times with ethyl acetate. The organic layers were combined, dried over MgSC , filtered and evaporated. The residue was purified with flash chromatography (ethylacetate: Heptane) to afford the title compound (22 mg, 25% yield) as a white solid.
MS (ESI): 350 ([M+H]+)
N-[1 -(2.6-Difluorophenyl)cvclopropyl1-5-[5-(trifluoromethyl)-1 ,2.4-oxadiazol-3-yllPyrimidin-2-amine (Compound 1-002)
Figure imgf000076_0002
To a solution of 2-(methylsulfonyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidine (0.17 mmol, 1 .00 eq) in dioxane (1 .00 ml) at r.t was added 1 -(2,6-difluorophenyl)cyclopropanamine (0.51 mmol, 3.0 eq). The pale yellow solution was stirred at 100°C for 3 h. Water was then added and the aqueous phase was extracted three times with ethyl acetate. The organic layers were combined, dried over MgSC , filtered and evaporated. The residue was purified with flash chromatography (ethylacetate: Heptane) to afford the title compound (22 mg, 32% yield) as a white solid.
MS (ESI): 384 ([M+H]+) 5-{5-[Chloro(difluoro)methyl1-1 .2.4-oxadiazol-3-yl)-N-[1 -(2.6-difluorophenvDcvclopropyllpyrimidin-2- amine (Compound 1-009)
Figure imgf000077_0001
To a suspension of 2-{[1 -(2,6-difluorophenyl)cyclopropyl]amino}-N'-hydroxypyrimidine-5- carboxi mid amide (0.62 mmol, 1 .00 eq) in THF (5 ml) at r.t was added chlorodifluoroacetic anhydride (0.74 mmol, 1 .20 eq) followed by triethylamine (0.74 mmol, 1 .20 eq). The pale yellow suspension was stirred overnight at r.t. A saturated sodium hydrogen carbonate solution was then added and the aqueous phase was extracted three times with ethyl acetate. The organic layers were combined, dried over MgSC>4, filtered and evaporated. The residue was purified with flash chromatography (ethylacetate: Heptane) to afford the title compound (88 mg, 35% yield) as a white solid. MS (ESI): 400 ([M+H]+)
N-[1 -Pyridin-2-ylethyl1-5-[5-(trifluoromethyl)-1 .2,4-oxadiazol-3-yl1oyrimidin-2-amine _ (Compound
1.005)
Figure imgf000077_0002
To a solution of 2-(methylsulfonyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidine (100 mg, 0.34 mmol) in dichloromethane (1 .00 ml) at r.t were added 2-(2-pyridyl)ethylamine (83 mg, 0.68 mmol), and triethylamine (0.047 ml, 0.34 mmol). The reaction mixture was stirred at r.t for 1 h. Water was then added and the aqueous phase was extracted three times with ethyl acetate. The organic layers were combined, dried over MgSC , filtered and evaporated. The residue was purified with flash chromatography (ethylacetate: Heptane) to afford the title compound (82 mg, 70% yield).
MS (ESI): 337 ([M+H]+) N-[3.3-Difluoro-1 -(2-fluorophenvDcvclobutyl1-5-[5-(trifluoromethvD-1 .2.4-oxadiazol-3-yllpyrimidin-2-amine (Compound 1.039)
Figure imgf000078_0001
To a mixture of 2-chloro-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidine (100 mg, 0.39 mmol) and 3,3-difluoro-1 -(2-fluorophenyl)cyclobutanamine hydrochloride (100 mg, 0.41 mmol) in dioxane (1 .5 ml) at r.t was added N,N-diisopropylethylamine (0.28 ml, 1 .59 mmol). The reaction mixture was refluxed for 18h and then cooled down to r.t. Water was then added and the aqueous phase was extracted three times with ethyl acetate. The organic layers were combined, dried over MgSC , filtered and evaporated. The residue was purified by preparative HPLC-MS (eluent: acetonitrile/water (0.1 % formic acid)) to afford the title compound (40 mg, 24% yield) as a beige solid.
MS (ESI): 416 ([M+H]+)
The compounds in table 1 were prepared in analogy with the examples provided above.
Table 1 : Compounds according to formula (I) / (G)
Figure imgf000078_0002
Figure imgf000078_0003
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Notes :
(*) 1.060 is (R)-enantiomer; 1.061 is (S)-enantiomer
(**) 1.047 and 1.068 are a mixture of 2 isomers; 1.038, l;048, 1.056 and 1.069 are single isomers.
Measurement of LogP values was performed according to EEC directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversed phase columns with the following methods:
[al LogP value is determined by measurement of LC-UV, in an acidic range, with 0.1 % formic acid in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
[bl LogP value is determined by measurement of LC-UV, in a neutral range, with 0.001 molar ammonium acetate solution in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
[cl LogP value is determined by measurement of LC-UV, in an acidic range, with 0.1 % phosphoric acid and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
If more than one LogP value is available within the same method, all the values are given and separated by“+”.
Calibration was done with straight-chain alkan2-ones (with 3 to 16 carbon atoms) with known LogP values (measurement of LogP values using retention times with linear interpolation between successive alkanones). Lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.
NMR-Peak lists
1 H-NMR data of selected examples are written in form of 1 H-NMR-peak lists. To each signal peak are listed the d-value in ppm and the signal intensity in round brackets. Between the 5-value - signal intensity pairs are semicolons as delimiters.
The peak list of an example has therefore the form: di (intensityi); 82 (intensityz); . ; 5, (intensity,); ; 5n (intensityn)
Intensity of sharp signals correlates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectrum can be shown.
For calibrating chemical shift for 1 H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilane peak can occur but not necessarily.
The 1 H-NMR peak lists are similar to classical 1 H-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation.
Additionally they can show like classical 1 H-NMR prints signals of solvents, stereoisomers of the target compounds, which are also object of the invention, and/or peaks of impurities.
To show compound signals in the delta-range of solvents and/or water the usual peaks of solvents, for example peaks of DMSO in DMSO-D6 and the peak of water are shown in our 1 H-NMR peak lists and have usually on average a high intensity .
The peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).
Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore their peaks can help to recognize the reproduction of our preparation process via“side-products-fingerprints”.
An expert, who calculates the peaks of the target compounds with known methods (MestreC, ACD- simulation, but also with empirically evaluated expectation values) can isolate the peaks of the target compounds as needed optionally using additional intensity filters. This isolation would be similar to relevant peak picking at classical 1 H-NMR interpretation.
Further details of NMR-data description with peak lists you find in the publication“Citation of NMR Peaklist Data within Patent Applications” of the Research Disclosure Database Number 564025.
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
BIOLOGICAL DATA
Example: in vivo preventive test on Puccinia recondita (brown rust on wheat)
Solvent: 5% by volume of Dimethyl sulfoxide
10% by volume of Acetone
Emulsifier: 1 mI of Tween® 80 per mg of active ingredient
The active ingredients were made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween® 80 and then diluted in water to the desired concentration. The young plants of wheat were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores. The contaminated wheat plants were incubated for 24 hours at 20°C and at 100% relative humidity and then for 9 days at 20°C and at 70-80% relative humidity. The test was evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 250 ppm of active ingredient: 1.125; 1.126 In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 250 ppm of active ingredient: 1.001
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 250 ppm of active ingredient: 1.008; 1.01 1
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 100 ppm of active ingredient: 1.087; 1.100
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 100 ppm of active ingredient: 1.085; 1.086; 1.091 ; 1.095; 1.103; 1.105; 1.1 15; 1.124; 1.129
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 100 ppm of active ingredient: 1.005; 1.007; 1.010; 1.036; 1.072; 1.077; 1.080; 1.083; 1.106; 1.109; 1.1 16; 1.1 19
Example: in vivo preventive test on Phakosoora pachyrhizi (soybean rust)
Solvent: 5% by volume of Dimethyl sulfoxide
10% by volume of Acetone
Emulsifier: 1 pi of Tween® 80 per mg of active ingredient
The active ingredients were made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of soybean were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Phakospora pachyrhizi spores. The contaminated soybean plants were incubated for 24 hours at 24°C and at 100% relative humidity and then for 10 days at 24°C and at 70-80% relative humidity.
The test was evaluated 1 1 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 250 ppm of active ingredient: 1.027; 1.028
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 250 ppm of active ingredient: 1.01 1 ; 1.029 In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 250 ppm of active ingredient: 1.001 ; 1.008; 1.009; 1.013; 1.014; 1.022; 1.024; 1.025; 1.031 ; 1.032; 1.034; I.065; 1.071 ; 1.082; 1.092; 1.094; 1.1 17; 1.123; 1.125; 1.126
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 100 ppm of active ingredient: 1.080; 1.084; 1.088; 1.1 14
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 100 ppm of active ingredient: 1.003; 1.100; 1.104; 1.1 13
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 100 ppm of active ingredient: 1.002; 1.004; 1.005; 1.006; 1.007; 1.010; 1.020; 1.023;
1.036; 1.038; 1.039; 1.068; I.069; 1.072; I.075; 1.077; 1.081 ; I.083; 1.085; I.086; 1.087; 1.089; I.090; 1.091 ;
1.093; 1.095; 1.097; I.098; I.099; 1.101 ; 1.102; 1.103; 1.105; 1.106; 1.107; 1.108; 1.109; 1.1 10; 1.1 1 1 ; 1.1 15;
1.1 16; 1.1 18; 1.1 19; 1.120; 1.121 ; 1.122; 1.124; 1.129
Example: Rhizoctonia solani in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1 g Mycological Peptone (Oxoid), 1 .4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: mycelial suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was <D1 %.
Inoculum was prepared from a pre-culture of R. solani grown in liquid medium by homogenization using a blender. The concentration of ground mycelium in the inoculum was estimated and adjusted to the desired optical density (OD).
Fungicides were evaluated for their ability to inhibit mycelium growth in liquid culture assay. The compounds were added in the desired concentrations to culture medium containing the mycelial suspension. After 5 days of incubation, the fungicidal efficacy of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 20 ppm of active ingredient: 1.006; 1.008; 1.036; 1.072; 1.073; 1.088; 1.098; 1.101 ; 1.106; 1.120 In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 1.020; 1.075; 1.086; 1.089; 1.093; 1.094; 1.097; 1.102; 1.103; 1.1 10; 1.1 15; 1.1 19; 1.129
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 1.005; 1.081 ; 1.091 ; 1.096; 1.109; 1.1 16; 1.124; 1.127
Example: Colletotrichum lindemuthianum in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1 g Mycological Peptone (Oxoid), 1 .4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: spores suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was <D1 %.
A spore suspension of C. lindemuthianum was prepared and diluted to the desired spore density.
Fungicides were evaluated for their ability to inhibit spores germination and mycelium growth in liquid culture assay. The compounds were added in the desired concentration to the culture medium with spores. After 6 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 20 ppm of active ingredient: 1.002; 1.003; 1.014; 1.025; 1.031 ; 1.087
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 1.004; 1.006; 1.008; 1.013; 1.024; 1.028; 1.032; 1.037;
1.039; 1.059; 1.061 ; I.063; I.065; 1.066; I.069; 1.071 ; 1.088; I.094; 1.099; 1.100; 1.107; 1.1 1 1 ; 1.1 17; 1.121 ;
1.122; 1.123; 1.125; 1.126; 1.129; 1.130
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 1.001 ; 1.005; 1.010; 1.016; 1.020; 1.021 ; 1.023; 1.036;
1.038; 1.058; 1.060; I.067; I.072; 1.074; I.075; 1.076; 1.081 ; I.084; 1.085; I.086; 1.089; 1.090; 1.091 ; 1.093;
1.096; 1.097; 1.098; 1.101 ; 1.102; 1.103; 1.105; 1.106; 1.108; 1.109; 1.1 10; 1.1 15; 1.1 16; 1.1 18; 1.1 19; 1.120;
1.124; 1.127 Example: in vivo preventive test on Phakopsora test (soybeans)
Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of dimethyl sulfoxide
Emulsifier: 1 part by weight of polyoxyethylene sorbitan monooleate
To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.
To test for preventive activity, young plants were sprayed with the preparation of active compound at the stated rate of application. After the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of the causal agent of soybean rust ( Phakopsora pachyrhizi) and stay for 24h without light in an incubation cabinet at approximately 24°C and a relative atmospheric humidity of 95 %.
The plants remained in the incubation cabinet at approximately 24°C and a relative atmospheric humidity of approximately 80 % and a day / night interval of 12h.
The test was 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: in vivo curative test on Phakopsora test (soybeans)
Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of dimethyl sulfoxide
Emulsifier: 1 part by weight of polyoxyethylene sorbitan monooleate
To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.
To test for curative activity, young plants were inoculated with an aqueous spore suspension of the causal agent of soybean rust ( Phakopsora pachyrhizi) and stay for 24h without light in an incubation cabinet at approximately 24°C and a relative atmospheric humidity of 95 %
The plants remained in the incubation cabinet at approximately 24°C and a relative atmospheric humidity of approximately 80 % and a day / night interval of 12h.
2 days after inoculation the plants were sprayed with the preparation of active compound at the stated rate of application and remained furthermore in the incubation cabinet.
The test was 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: in vivo lonqlastinq activity test on Phakoosora test (soybeans)
Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of dimethyl sulfoxide
Emulsifier: 1 part by weight of polyoxyethylene sorbitan monooleate To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.
To test for longlasting activity, young plants were sprayed with the preparation of active compound at the stated rate of application. After the spray coating had dried on, the plants were placed in an incubation cabinet at approximately 24°C and a relative atmospheric humidity of approximately 80 % and a day / night interval of 12h.
8 days after the application the plant were inoculated with an aqueous spore suspension of the causal agent of soybean rust ( Phakopsora pachyrhizi) and stay for 24h without light in the incubation cabinet at approximately 24°C and a relative atmospheric humidity of 95 %. The plants remained in the incubation cabinet at approximately 24°C and a relative atmospheric humidity of approximately 80 % and a day / night interval of 12h.
The test was 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.

Claims

1 . Use of a compound of formula (I) for controlling phytopathogenic fungi on plants:
Figure imgf000097_0001
wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, cyano, Ci-Cs-alkyl, Ci-Cs- haloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-Cs-haloalkynyl, C3-C7- carbocyclyl, aryl, 3- to 10-membered-heterocyclyl, heteroaryl, aryl-Ci-Cs-alkyl, 3- to 10- membered-heterocyclyl-Ci-C8-alkyl, heteroaryl-Ci-Cs-alkyl and C3-C7-carbocyclyl-Ci-C8-alkyl, wherein said acyclic R1 and R2 may be substituted with, respectively one or more R1a and R2a substituents and said cyclic R1 and R2 may be substituted with, respectively one or more R1b and R2b substituents, or
R1 , R2 may form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl or a 3- to 10-membered heterocyclyl, wherein said C3-C7-carbocyclyl or 3- to 10-membered heterocyclyl may be substituted with one or more R1 b substituents;
Cy is aryl, heteroaryl, C3-Cio-carbocyclyl or 3- to 10-membered heterocyclyl;
n is 0, 1 , 2, 3 or 4;
R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci-C6-hydroxyalkyl, C1-C6- alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, C1-C6- haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs- alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-C6-haloalkylsulfonylamino, sulfamoyl, Ci-Ce-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl-Ci-C6-alkyl and heteroaryl,
wherein said acyclic and cyclic R3 may be substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, formyl, Ci-C6-alkyl, C1-C6- haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -C(=0)-Ci-C6- alkyl, -C(=0)-Ci-C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=S)-Ci-C6-haloalkyl, -C(=0)-0-Ci-C6- alkyl, -C(=0)-0-Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, C1-C6- haloalkylsulfonyl, phenylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl (phenyl), heteroaryl, C3-Cio-carbocyclyl-Ci-C6-alkyl, C3-Cio-carbocyclyl-Ci-C6-haloalkyl, aryl- Ci-C6-alkyl, aryl-Ci-C6-haloalkyl, heteroaryl-Ci-C6-alkyl and heteroaryl-Ci-C6-haloalkyl, wherein said acyclic and cyclic R4 may be substituted with one or more substituents selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R5 is hydrogen or fluorine;
R1a, R2a are independently selected from the group consisting of nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3- C7-halocycloalkyl, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- C8-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, Ci-C8-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-C8-haloalkylsulfonyl, Ci-Cs-alkylsulfonylamino, Ci-Cs-haloalkylsulfonylamino, sulfamoyl, Ci-Ce-alkylsulfamoyl and di-Ci-Cs-alkylsulfamoyl;
R1b, R2b are independently selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, carboxyl, sulfanyl, pentafluoro- 6-sulfanyl, formyl, carbamoyl, carbamate, Ci-C6-alkyl, Ci-C6-cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, Ci-C6-alkyl-C(=0)-NH-, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, hydroxy- Ci-C6-alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, C1-C6- alkoxycarbonyl, Ci-C6-haloalkoxycarbonyl Ci-C6-alkylcarbamoyl, di-Ci-C6-alkylcarbamoyl, aminocarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci-Cs-haloalkylcarbonylamino, Ci-C6-alkylsulfonylamino, C1-C6- haloalkylsulfonylamino, sulfamoyl, Ci-Cs-alkylsulfamoyl, di-Ci-Cs-alkylsulfamoyl, aryl (e.g. phenyl), aryl -Ci-C6-alkyl and heteroaryl, wherein said aryl (phenyl) or heteroaryl is optionally substituted by one or more substituents, which may be the same or different, selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
or a salt, N-oxide or solvate thereof;
provided that the compound of formula (I) is not:
(a) N-[1 -(pyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(b) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-[1 -(pyridin-2-yl)cyclobutyl]pyrimidin-2-amine;
(c) N-(1 -phenylcyclopropyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(d) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-(1 -phenylcyclopropyl)pyrimidin-2-amine.
2. Use of the compound of formula (I) according to claim 1 wherein R1 and R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl, or R1 and R2 form, together with the carbon atom to which they are linked, a C3-C7-cycloalkyl, wherein R1 and R2 may be substituted as recited in claim 1 , preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl, and halogen.
3. Use of the compound according to claim 1 or 2 wherein n is 0, 1 or 2.
4. Use of the compound according to any of the preceding claims wherein R3 is independently selected from the group consisting of halogen, cyano, hydroxy, amino, carboxyl, Ci-C6-alkyl, C1-C6- cyanoalkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkoxy- Ci-C6-alkyl, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, C3-C7-carbocyclyl, C3-C7-halocarbocyclyl, Ci- C6-hydroxy alkyl, Ci-C6-alkylamino, di-Ci-C6-alkylamino, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, Ci-Ce-alkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-C6-alkylsulfonylamino, Ci-Cs-alkylsulfamoylaryl and heteroaryl, wherein acyclic and cyclic R3 may be substituted as recited in claim 1.
5. Use of the compound according to any of the preceding claims wherein R4 is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, -C(=0)-Ci-C6- alkyl, -C(=0)-Ci-C6-haloalkyl, -C(=S)-Ci-C6-alkyl, -C(=0)-0-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfonyl, C3-Cio-carbocyclyl, 3- to 10-membered-heterocyclyl, C3-Cio-carbocyclyl-Ci-C6-alkyl, aryl-Ci-C6-alkyl and heteroaryl-Ci-C6-alkyl, wherein acyclic and cyclic R4 may be substituted as recited in claim 1.
6. Use of the compound according to any of the preceding claims wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl, or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen;
Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
n is 0, 1 or 2;
R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, C(=0)-Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy;
R5 is hydrogen or fluorine, preferably hydrogen;
provided that the compound of formula (I) is not:
(a) N-[1 -(pyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(b) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-[1 -(pyridin-2-yl)cyclobutyl]pyrimidin-2-amine;
(c) N-(1 -phenylcyclopropyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine; (d) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-(1 -phenylcyclopropyl)pyrimidin-2-amine.
7. Use of the compound according to any of the preceding claims wherein
X is fluorine or chlorine;
R1 , R2 are independently selected from the group consisting of hydrogen, Ci-Cs-alkyl and aryl, or
R1 , R2 form, together with the carbon atom to which they are linked, a C3-C7-carbocyclyl,
wherein R1 and R2 may be substituted as described herein, preferably R1 and R2 may be substituted with one or more substituents selected from hydroxy, Ci-Cs-alkyl and halogen;
Cy is C3-Cio-carbocyclyl, phenyl, a 5- or 6-membered heteroaryl or a benzofused 9- or 10- membered heteroaryl,
n is 1 or 2;
R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl and Ci-C6-haloalkoxy;
R4 is selected from the group consisting of hydrogen, hydroxy, C(=0)-Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy; and
R5 is hydrogen or fluorine, preferably hydrogen.
8. Use of the compound according to any of the preceding claims wherein R3 is independently selected from the group consisting of halogen, Ci-C6-alkyl and Ci-C6-haloalkyl.
9. Use of the compound according to any of the preceding claims wherein R4 is selected from the group consisting of hydrogen, C(=0)-Ci-C6-alkyl and -C(=0)-Ci-C6-haloalkyl, preferably R4 is hydrogen.
10. Use of the compound according to any of the preceding claims wherein Cy is phenyl or 5- or 6- membered heteroaryl, preferably Cy is phenyl, furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
1 1 . Use of the compound according to any of the preceding claims wherein Cy is phenyl.
12. Use of the compound according to any of claims 1 to 10 wherein Cy is 6-membered heteroaryl selected from the group consisting of pyridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
13. A method for controlling phytopathogenic fungi which comprises the step of applying at least one compound of formula (I) according any one of claims 1 to 12 to the plants, plant parts, seeds, fruits or to the soil in which the plants grow.
14. A compound of formula (G) or a salt, N-oxide or solvate thereof;
Figure imgf000101_0001
wherein X, R1 , R2, R3, R4, R5, Cy and n are as defined in any of claims 1 to 12,
wherein when X is fluorine and R4 is hydrogen or Ci-C6-alkyl, R1 and R2 are not both hydrogen;
wherein compounds are excluded in which X is fluorine, Cy is phenyl or 6-membered heteroaryl, n is 0 and R1 , R2 and R4 are each independently selected from hydrogen and Ci-C3-alkyl; and
provided that the compound of formula (G) is not:
(a) N-[1 -(pyridin-2-yl)cyclobutyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(b) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-[1 -(pyridin-2-yl)cyclobutyl]pyrimidin-2-amine;
(c) N-(1 -phenylcyclopropyl)-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine;
(d) 5-{5-[chloro(difluoro)methyl]-1 ,2,4-oxadiazol-3-yl}-N-(1 -phenylcyclopropyl)pyrimidin-2-amine;
(e) N-[1 -(2-methylpyridin-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine.
15. The compound of formula (G) according to claim 14, or a salt, N-oxide or solvate thereof; wherein
n is 1 or 2,
R1 and R2 are not both hydrogen,
and provided that the compound of formula (G) is not:
(e) N-[1 -(2-methylpyridin-4-yl)ethyl]-5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]pyrimidin-2-amine.
16. A composition comprising at least one compound of formula (G) according to claim 14 or 15 and at least one agriculturally acceptable carrier.
PCT/EP2020/066947 2019-06-21 2020-06-18 Fungicidal oxadiazoles WO2020254494A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR112021025300A BR112021025300A2 (en) 2019-06-21 2020-06-18 fungicidal oxadiazoles
EP20734340.1A EP3986889A1 (en) 2019-06-21 2020-06-18 Fungicidal oxadiazoles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19181819 2019-06-21
EP19181819.4 2019-06-21

Publications (1)

Publication Number Publication Date
WO2020254494A1 true WO2020254494A1 (en) 2020-12-24

Family

ID=67001713

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/066947 WO2020254494A1 (en) 2019-06-21 2020-06-18 Fungicidal oxadiazoles

Country Status (6)

Country Link
EP (1) EP3986889A1 (en)
AR (1) AR119218A1 (en)
BR (1) BR112021025300A2 (en)
TW (1) TW202115045A (en)
UY (1) UY38761A (en)
WO (1) WO2020254494A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021177160A1 (en) * 2020-03-04 2021-09-10 日本曹達株式会社 Azinyl azole compound and pest control agent
WO2021255093A1 (en) * 2020-06-19 2021-12-23 Bayer Aktiengesellschaft Active compound combination
WO2023286855A1 (en) 2021-07-15 2023-01-19 クミアイ化学工業株式会社 Formamide derivative and agricultural or horticultural plant disease control agent
US11938134B2 (en) 2017-03-10 2024-03-26 Eikonizo Therapeutics, Inc. Metalloenzyme inhibitor compounds

Citations (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3639877A1 (en) 1986-11-21 1988-05-26 Bayer Ag HETARYLALKYL SUBSTITUTED 5- AND 6-RINGHETEROCYCLES
US6060051A (en) 1997-05-09 2000-05-09 Agraquest, Inc. Strain of bacillus for controlling plant diseases and corn rootworm
US6245551B1 (en) 1999-03-30 2001-06-12 Agraquest, Inc. Strain of Bacillus pumilus for controlling plant diseases caused by fungi
WO2003106457A1 (en) 2002-06-14 2003-12-24 Syngenta Limited Spiroindolinepiperidine derivatives
WO2004099160A1 (en) 2003-05-12 2004-11-18 Sumitomo Chemical Company, Limited Pyrimidine compounds and pests controlling composition containing the same
WO2006003494A2 (en) 2004-06-28 2006-01-12 Syngenta Participations Ag Piperidine derivatives and their use as insecticides, acaricides, molluscicides or nematicides
WO2006043635A1 (en) 2004-10-20 2006-04-27 Kumiai Chemical Industry Co., Ltd. 3-triazolylphenyl sulfide derivative and insecticide/acaricide/nematicide containing the same as active ingredient
US7094592B2 (en) 2001-11-26 2006-08-22 Kumiai Chemical Industry Co., Ltd. Bacillus sp. D747 strain, plant disease controlling agents and insect pest controlling agents using the same and control method using the agents
WO2007040282A1 (en) 2005-10-06 2007-04-12 Nippon Soda Co., Ltd. Bridged cyclic amine compound and pest control agent
CN101337937A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 N-benz-3-substituted amino pyrazoles compounds with insecticidal activity
CN101337940A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity
JP2010018586A (en) 2008-07-14 2010-01-28 Meiji Seika Kaisha Ltd Substance pf1364, its manufacturing method, producing strain and agricultural/horticultural insecticide having the substance as active ingredient
WO2010052161A2 (en) 2008-11-06 2010-05-14 Syngenta Participations Ag Herbicidal compositions
WO2010051926A2 (en) 2008-11-05 2010-05-14 Bayer Cropscience Aktiengesellschaft New halogen-substituted bonds
CN101715774A (en) 2008-10-09 2010-06-02 浙江化工科技集团有限公司 Preparation and use of compound having insecticidal activity
WO2010066780A1 (en) 2008-12-12 2010-06-17 Syngenta Participations Ag Spiroheterocyclic n-oxypiperidines as pesticides
WO2011085575A1 (en) 2010-01-15 2011-07-21 江苏省农药研究所股份有限公司 Ortho-heterocyclyl formanilide compounds, their synthesis methods and use
WO2011105506A1 (en) 2010-02-25 2011-09-01 日本曹達株式会社 Cyclic amine compound and miticide
WO2011151146A1 (en) 2010-05-31 2011-12-08 Syngenta Participations Ag Method of crop enhancement
WO2012029672A1 (en) 2010-08-31 2012-03-08 Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 Noxious organism control agent
WO2012034403A1 (en) 2010-09-14 2012-03-22 中化蓝天集团有限公司 Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof
CN102391261A (en) 2011-10-14 2012-03-28 上海交通大学 N-substituted dioxazine compound as well as preparation method and application thereof
WO2013050317A1 (en) 2011-10-03 2013-04-11 Syngenta Limited Polymorphs of an isoxazoline derivative
WO2013066839A2 (en) * 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
CN103109816A (en) 2013-01-25 2013-05-22 青岛科技大学 Thiobenzamide compounds and application thereof
WO2013080120A1 (en) 2011-11-28 2013-06-06 Novartis Ag Novel trifluoromethyl-oxadiazole derivatives and their use in the treatment of disease
CN103232431A (en) 2013-01-25 2013-08-07 青岛科技大学 Dihalogenated pyrazole amide compound and its use
WO2013115391A1 (en) 2012-02-01 2013-08-08 日本農薬株式会社 Arylalkyloxy pyrimidine derivative, pesticide for agricultural and horticultural use containing arylalkyloxy pyrimidine derivative as active ingredient, and use of same
CN103265527A (en) 2013-06-07 2013-08-28 江苏省农用激素工程技术研究中心有限公司 Anthranilamide compound as well as preparation method and application thereof
WO2013144213A1 (en) 2012-03-30 2013-10-03 Basf Se N-substituted pyridinylidene compounds and derivatives for combating animal pests
EP2647626A1 (en) 2012-04-03 2013-10-09 Syngenta Participations AG. 1-Aza-spiro[4.5]dec-3-ene and 1,8-diaza-spiro[4.5]dec-3-ene derivatives as pesticides
WO2013162716A2 (en) 2012-04-27 2013-10-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
CN103524422A (en) 2013-10-11 2014-01-22 中国农业科学院植物保护研究所 Benzimidazole derivative, and preparation method and purpose thereof
US20140213448A1 (en) 2012-04-27 2014-07-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US20140275503A1 (en) 2013-03-13 2014-09-18 Dow Agrosciences Llc Process for the preparation of certain triaryl rhamnose carbamates
WO2014187846A1 (en) 2013-05-23 2014-11-27 Syngenta Participations Ag Tank-mix formulations
WO2015058021A1 (en) 2013-10-17 2015-04-23 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
WO2015058028A1 (en) 2013-10-17 2015-04-23 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
WO2016005276A1 (en) 2014-07-07 2016-01-14 Bayer Cropscience Aktiengesellschaft Process for preparing fluorinated iminopyridine compounds
WO2016133011A1 (en) 2015-02-17 2016-08-25 日本曹達株式会社 Agrochemical composition
WO2016154297A1 (en) 2015-03-26 2016-09-29 Bayer Cropscience Lp A novel paenibacillus strain, antifungal compounds, and methods for their use
WO2017085098A1 (en) * 2015-11-19 2017-05-26 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017110862A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Oxadiazole compound and use thereof
WO2018055135A1 (en) * 2016-09-23 2018-03-29 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018187553A1 (en) 2017-04-06 2018-10-11 Fmc Corporation Fungicidal oxadiazoles
WO2019122323A1 (en) 2017-12-22 2019-06-27 Bayer Aktiengesellschaft Fungicidal oxadiazoles
WO2020127974A1 (en) * 2018-12-21 2020-06-25 Bayer Aktiengesellschaft 1,3,4-oxadiazoles and their derivatives as new antifungal agents

Patent Citations (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3639877A1 (en) 1986-11-21 1988-05-26 Bayer Ag HETARYLALKYL SUBSTITUTED 5- AND 6-RINGHETEROCYCLES
US6060051A (en) 1997-05-09 2000-05-09 Agraquest, Inc. Strain of bacillus for controlling plant diseases and corn rootworm
US6245551B1 (en) 1999-03-30 2001-06-12 Agraquest, Inc. Strain of Bacillus pumilus for controlling plant diseases caused by fungi
US7094592B2 (en) 2001-11-26 2006-08-22 Kumiai Chemical Industry Co., Ltd. Bacillus sp. D747 strain, plant disease controlling agents and insect pest controlling agents using the same and control method using the agents
WO2003106457A1 (en) 2002-06-14 2003-12-24 Syngenta Limited Spiroindolinepiperidine derivatives
WO2004099160A1 (en) 2003-05-12 2004-11-18 Sumitomo Chemical Company, Limited Pyrimidine compounds and pests controlling composition containing the same
WO2006003494A2 (en) 2004-06-28 2006-01-12 Syngenta Participations Ag Piperidine derivatives and their use as insecticides, acaricides, molluscicides or nematicides
WO2006043635A1 (en) 2004-10-20 2006-04-27 Kumiai Chemical Industry Co., Ltd. 3-triazolylphenyl sulfide derivative and insecticide/acaricide/nematicide containing the same as active ingredient
WO2007040282A1 (en) 2005-10-06 2007-04-12 Nippon Soda Co., Ltd. Bridged cyclic amine compound and pest control agent
WO2007040280A1 (en) 2005-10-06 2007-04-12 Nippon Soda Co., Ltd. Cyclic amine compound and pest control agent
JP2010018586A (en) 2008-07-14 2010-01-28 Meiji Seika Kaisha Ltd Substance pf1364, its manufacturing method, producing strain and agricultural/horticultural insecticide having the substance as active ingredient
CN101337940A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity
CN101337937A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 N-benz-3-substituted amino pyrazoles compounds with insecticidal activity
CN101715774A (en) 2008-10-09 2010-06-02 浙江化工科技集团有限公司 Preparation and use of compound having insecticidal activity
WO2010051926A2 (en) 2008-11-05 2010-05-14 Bayer Cropscience Aktiengesellschaft New halogen-substituted bonds
WO2010052161A2 (en) 2008-11-06 2010-05-14 Syngenta Participations Ag Herbicidal compositions
WO2010066780A1 (en) 2008-12-12 2010-06-17 Syngenta Participations Ag Spiroheterocyclic n-oxypiperidines as pesticides
WO2011085575A1 (en) 2010-01-15 2011-07-21 江苏省农药研究所股份有限公司 Ortho-heterocyclyl formanilide compounds, their synthesis methods and use
WO2011105506A1 (en) 2010-02-25 2011-09-01 日本曹達株式会社 Cyclic amine compound and miticide
WO2011151146A1 (en) 2010-05-31 2011-12-08 Syngenta Participations Ag Method of crop enhancement
WO2012029672A1 (en) 2010-08-31 2012-03-08 Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 Noxious organism control agent
WO2012034403A1 (en) 2010-09-14 2012-03-22 中化蓝天集团有限公司 Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof
WO2013050317A1 (en) 2011-10-03 2013-04-11 Syngenta Limited Polymorphs of an isoxazoline derivative
CN102391261A (en) 2011-10-14 2012-03-28 上海交通大学 N-substituted dioxazine compound as well as preparation method and application thereof
WO2013066839A2 (en) * 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
WO2013080120A1 (en) 2011-11-28 2013-06-06 Novartis Ag Novel trifluoromethyl-oxadiazole derivatives and their use in the treatment of disease
WO2013115391A1 (en) 2012-02-01 2013-08-08 日本農薬株式会社 Arylalkyloxy pyrimidine derivative, pesticide for agricultural and horticultural use containing arylalkyloxy pyrimidine derivative as active ingredient, and use of same
WO2013144213A1 (en) 2012-03-30 2013-10-03 Basf Se N-substituted pyridinylidene compounds and derivatives for combating animal pests
EP2647626A1 (en) 2012-04-03 2013-10-09 Syngenta Participations AG. 1-Aza-spiro[4.5]dec-3-ene and 1,8-diaza-spiro[4.5]dec-3-ene derivatives as pesticides
US20140213448A1 (en) 2012-04-27 2014-07-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
WO2013162716A2 (en) 2012-04-27 2013-10-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
WO2013162715A2 (en) 2012-04-27 2013-10-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
CN103232431A (en) 2013-01-25 2013-08-07 青岛科技大学 Dihalogenated pyrazole amide compound and its use
CN103109816A (en) 2013-01-25 2013-05-22 青岛科技大学 Thiobenzamide compounds and application thereof
US20140275503A1 (en) 2013-03-13 2014-09-18 Dow Agrosciences Llc Process for the preparation of certain triaryl rhamnose carbamates
WO2014187846A1 (en) 2013-05-23 2014-11-27 Syngenta Participations Ag Tank-mix formulations
CN103265527A (en) 2013-06-07 2013-08-28 江苏省农用激素工程技术研究中心有限公司 Anthranilamide compound as well as preparation method and application thereof
CN103524422A (en) 2013-10-11 2014-01-22 中国农业科学院植物保护研究所 Benzimidazole derivative, and preparation method and purpose thereof
WO2015058021A1 (en) 2013-10-17 2015-04-23 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
WO2015058028A1 (en) 2013-10-17 2015-04-23 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
WO2016005276A1 (en) 2014-07-07 2016-01-14 Bayer Cropscience Aktiengesellschaft Process for preparing fluorinated iminopyridine compounds
WO2016133011A1 (en) 2015-02-17 2016-08-25 日本曹達株式会社 Agrochemical composition
WO2016154297A1 (en) 2015-03-26 2016-09-29 Bayer Cropscience Lp A novel paenibacillus strain, antifungal compounds, and methods for their use
WO2017085098A1 (en) * 2015-11-19 2017-05-26 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017110862A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Oxadiazole compound and use thereof
WO2018055135A1 (en) * 2016-09-23 2018-03-29 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018187553A1 (en) 2017-04-06 2018-10-11 Fmc Corporation Fungicidal oxadiazoles
WO2019122323A1 (en) 2017-12-22 2019-06-27 Bayer Aktiengesellschaft Fungicidal oxadiazoles
WO2020127974A1 (en) * 2018-12-21 2020-06-25 Bayer Aktiengesellschaft 1,3,4-oxadiazoles and their derivatives as new antifungal agents

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
"Database", Database accession no. 564025
ACS MEDICINAL CHEMISTRY LETTERS, vol. 8, no. 9, 2017, pages 919 - 924
BIOORGANIC & MEDICINAL CHEMISTRY, vol. 25, no. 17, 2017, pages 4553 - 4559
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 1332838-17-1
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY, vol. 135, 2017, pages 531 - 543
MEDICINAL CHEMISTRY RESEARCH, vol. 22, no. 11, 2013, pages 5267 - 5273
ONGENA, M. ET AL.: "Bacillus Lipopeptides: Versatile Weapons for Plant Disease Biocontrol", TRENDS IN MICROBIOLOGY, vol. 16, no. 3, March 2008 (2008-03-01), pages 115 - 125, XP022509718, DOI: 10.1016/j.tim.2007.12.009

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11938134B2 (en) 2017-03-10 2024-03-26 Eikonizo Therapeutics, Inc. Metalloenzyme inhibitor compounds
WO2021177160A1 (en) * 2020-03-04 2021-09-10 日本曹達株式会社 Azinyl azole compound and pest control agent
WO2021255093A1 (en) * 2020-06-19 2021-12-23 Bayer Aktiengesellschaft Active compound combination
WO2023286855A1 (en) 2021-07-15 2023-01-19 クミアイ化学工業株式会社 Formamide derivative and agricultural or horticultural plant disease control agent

Also Published As

Publication number Publication date
AR119218A1 (en) 2021-12-01
BR112021025300A2 (en) 2022-02-01
TW202115045A (en) 2021-04-16
EP3986889A1 (en) 2022-04-27
UY38761A (en) 2021-01-29

Similar Documents

Publication Publication Date Title
EP3752492B1 (en) Fungicidal oxadiazoles
AU2019297401B2 (en) Substituted thiophenecarboxamides and analogues as antibacterials agents
WO2020254494A1 (en) Fungicidal oxadiazoles
EP3774748A1 (en) Oxadiazoline derivatives
WO2020254493A1 (en) Thienylhydroxyisoxazolines and derivatives thereof
WO2019154665A1 (en) New pyridine carboxamides
WO2019122319A1 (en) Trisubstitutedsilylmethylheteroaryloxyquinolines and analogues
WO2021122976A1 (en) Substituted thiophene carboxamides and derivatives thereof
WO2021122986A1 (en) Thienyloxazolones and analogues
WO2021001331A1 (en) Substituted thiophene carboxamides and derivatives thereof as microbicides
WO2019162228A1 (en) 1-(5-substituted imidazol-1-yl)but-3-en derivatives and their use as fungicides
EP3986892A1 (en) Hydroxyisoxazolines and use thereof as fungicides
WO2020254492A1 (en) Hydroxyisoxazolines and derivatives thereof
WO2020254486A1 (en) Hydroxyisoxazolines and derivatives thereof
EP3986877A1 (en) Hydroxyisoxazolines and derivatives thereof
WO2018202715A1 (en) Trisubstitutedsilylbenzylbenzimidazoles and analogues
WO2018202712A1 (en) Trisubstitutedsilylmethylphenoxyquinolines and analogues
AU2020410375A1 (en) Substituted thiophene carboxamides and derivatives thereof as microbicides
WO2020020813A1 (en) Fungicidal active compound combinations

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20734340

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112021025300

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 2020734340

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 112021025300

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20211215