WO2021255091A1 - 1,3,4-oxadiazoles and their derivatives as fungicides - Google Patents

1,3,4-oxadiazoles and their derivatives as fungicides Download PDF

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WO2021255091A1
WO2021255091A1 PCT/EP2021/066237 EP2021066237W WO2021255091A1 WO 2021255091 A1 WO2021255091 A1 WO 2021255091A1 EP 2021066237 W EP2021066237 W EP 2021066237W WO 2021255091 A1 WO2021255091 A1 WO 2021255091A1
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alkyl
group
substituents
cycloalkyl
substituted
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PCT/EP2021/066237
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French (fr)
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Anne-Sophie Rebstock
Jeremy Dufour
Aurelie MALLINGER
Jacopo NEGRONI
Sophie DUCERF
Vincent Thomas
Christoph Andreas Braun
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Bayer Aktiengesellschaft
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Priority to BR112022025692A priority Critical patent/BR112022025692A2/en
Publication of WO2021255091A1 publication Critical patent/WO2021255091A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems

Definitions

  • the present invention relates to the use of 1,3,4-oxadiazole compounds for controlling harmful microorganisms, in particular phytopathogenic fungi, in crop protection.
  • 1.2.4-oxadiazoles derivatives are well known to be useful as crop protection agents to combat or prevent microorganisms’ infestations.
  • WO-2018/118781 and WO-2018/080859 disclose 1,2,4- oxadiazol-3-ylpyrimidines and l,2,4-oxadiazol-3-ylpyridines derivatives that may be used for the control of microbial pests, particularly fungal pests, on plants.
  • Fungicidally active 1,2,4-oxadiazoles are further known from US 2018/317490, WO-2017/076740 and WO 2019/155066.
  • 1.3.4-oxadiazoles derivatives are far less common and seldomly used for the control of microbial pests.
  • WO-2019/027054 and WO-2020/158762 disclose 1,3,4-oxadiazol compounds comprising a bicyclic partly aromatic heterocycle that have a HDAC inhibitory action and may be used for the treatment of central nervous diseases in humans.
  • Some fungicidally active 1,3,4-oxadiazoles are disclosed in WO2020127974 and EP 0 152 021.
  • fungicidal agents Numerous fungicidal agents have been developed until now. However, the need remains for the development of further fungicidal compounds, 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 identify further fungicidal compounds to prevent the emergence of fungicides resistances.
  • the present invention provides a new use of 1,3,4-oxadiazole compounds for controlling phytopathogenic fungi in crop protection, which has advantages over known uses of fungicidal compounds in at least some of these aspects.
  • the present invention relates to the use of compounds of formula (I) for controlling harmful microorganisms, in particular phytopathogenic fungi, in crop protection: (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 , X, W 1 , W 2 , W 3 , m and n are as recited herein, as well as their salts, N-oxides and solvates.
  • the present invention also relates to a composition
  • a composition comprising at least one compound of formula (I) as defined herein and at least one agriculturally suitable auxiliary.
  • the present invention relates to a method for controlling harmful microorganisms in crop protection which comprises the step of applying at least one compound of formula (I) as defined herein or a composition as defined herein to the harmful microorganisms and/or their habitat.
  • halogen refers to fluorine, chlorine, bromine or iodine atom.
  • oxo refers to an oxygen atom which is bound to a carbon atom or sulfur atom via a double bound.
  • C 1 -C 8 -alkyl refers to a saturated, branched or straight hydrocarbon chain having 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms.
  • Examples of Ci -Cx-alkyl include but are not limited to methyl, ethyl, propyl (n-propyl), 1-methylethyl (iso-propyl), butyl (n-butyl), 1-methylpropyl (sec-butyl), 2-methylpropyl (iso-butyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,
  • said hydrocarbon chain has 1, 2, 3, 4, 5 or 6 carbon atoms (“C 1 -C 6 -alkyl”).
  • said hydrocarbon chain has 1, 2, 3 or 4 carbon atoms (“C 1 -C 4 -alkyl”), e.g. methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl or tert-butyl.
  • C 2 -C 8 -alkenyl refers to an unsaturated, branched or straight hydrocarbon chain having 2, 3, 4, 5, 6, 7 or 8 carbon atoms and comprising at least one double bond.
  • Examples of CVCx- alkenyl include but are not limited to ethenyl (or "vinyl"), prop-2-en-l-yl (or “allyl”), prop-l-en-l-yl, but- 3-enyl, but-2-enyl, but-l-enyl, pent-4-enyl, pent-3-enyl, pent-2-enyl, pent-l-enyl, hex-5 -enyl, hex-4-enyl, hex-3-enyl, hex-2-enyl, hex- 1 -enyl, prop-l-en-2-yl (or “isopropenyl”), 2-methylprop-2-enyl, 1- methylprop-2-enyl
  • C 2 -C 8 -alkynyl refers to a branched or straight hydrocarbon chain having 2, 3, 4, 5, 6, 7 or 8 carbon atoms and comprising at least one triple bond.
  • Examples of C 2 -C 8 -alkynyl include but are not limited to ethynyl, prop-l-ynyl, prop-2-ynyl (or "propargyl"), but-l-ynyl, but-2-ynyl, but-3- ynyl, pent-l-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-l-ynyl, hex-2 -ynyl, hex-3 -ynyl, hex-4-ynyl, hex-5-ynyl, l-methylprop-2-ynyl, 2-methylbut-3-ynyl, l-methylbut-3-ynyn
  • C 1 -C 8 -haloalkyl refers to a C 1 -C 8 -alkyl group as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 1 - C 8 -haloalkyl comprises up to 9 halogen atoms that can be the same or different.
  • C 2 -C 8 -haloalkenyl refers to a C 2 -C 8 -alkenyl group as defined above in which one or more hydrogen atoms are replaced with one or more halogen atoms that may be the same or different.
  • C 2 -C 8 -haloalkenyl comprises up to 9 halogen atoms that can be the same or different.
  • C 2 -C 8 -haloalkynyl refers to a C 2 -C 8 -alkynyl group as defined above in which one or more hydrogen atoms are replaced with one or more halogen atoms that may be the same or different.
  • C 2 -C 8 -haloalkynyl comprises up to 9 halogen atoms that can be the same or different.
  • C 1 -C 6 -alkoxy refers to a group of formula (C 1 -C 6 -alkyl)-O-. in which the term "C 1 -C 6 -alkyl" is as defined herein.
  • C 1 -C 6 -alkoxy examples include but are not limited to methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, n-hexyloxy, 1-methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2- dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2- trimethylpropoxy, 1,2,2-trimethylpropoxy, 1 -ethyl- 1-methylpropoxy and l-e
  • C 1 -C 6 -haloalkoxy refers to a C 1 -C 6 -alkoxy group as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 1 -C 6 -haloalkoxy examples include but are not limited to chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2- fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2- difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1- trifluoroprop-2-oxy.
  • C 1 -C 6 -hydroxyalkyl refers to a C 1 -C 6 -alkyl group as defined above in which at least one hydrogen atom is replaced with a hydroxyl group.
  • Examples of C 1 -C 6 -hydroxyalkyl include but are not limited to hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl,l,2-dihydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 1-hydroxypropyl, l-hydroxypropan-2-yl, 2-hydroxypropan-2-yl, 2,3-dihydroxypropyl and l,3-dihydroxypropan-2-yl.
  • C 1 -C 6 -cyanoalkyl refers to a C 1 -C 6 -alkyl group as defined above in which at least one hydrogen atom is replaced with a cyano group.
  • C 1 -C 8 -alkylsulfanyl refers to a saturated, linear or branched group of formula (C 1 -C 8 -alkyl)-S-, in which the term “C 1 -C 8 -alkyl” is as defined herein.
  • Examples of C 1 -C 8 -alkylsulfanyl include but are not limited to methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, .sec-butylsulfanyl. isobutylsulfanyl, tert-butylsulfanyl, pentylsulfanyl, isopentylsulfanyl, hexylsulfanyl group.
  • C 1 -C 8 -haloalkylsulfanyl refers to a C 1 -C 8 -alkylsulfanyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • arylsulfanyl refers to a group of formula aryl-S-, in which the term “aryl” is as defined herein.
  • C 1 -C 8 - alkylsulfinyl examples include but are not limited to saturated, straight-chain or branched alkylsulfinyl radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) methylsulfmyl, ethylsulfmyl, propylsulfmyl, 1-methylethylsulfinyl, butylsulfmyl, 1-methylpropyl- sulfmyl, 2-methylpropylsulfmyl, 1,1-dimethylethylsulfmyl, pentylsulfmyl, 1-methylbutylsulfinyl, 2- methylbutylsulfmyl, 3-methylbutylsulfmyl, 2,2-dimethylpropylsulfmyl, 1-ethylpropylsulfinyl, 1,1- dimethylpropylsulfmyl, 1,2-d
  • C 1 -C 8 -haloalkylsulfmyl refers to a C 1 -C 8 -alkylsulfmyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 1 -C 8 - alkylsulfonyl examples include but are not limited to methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1 -methyl - ethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1- dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3- methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1, 1-dimethylpropylsulfonyl,
  • C 1 -C 8 -haloalkylsulfonyl refers to a C 1 -C 8 -alkylsulfonyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 1 -C 8 -haloalkylsulfonylamino refers to a C 1 -C 8 -alkylsulfonylamino as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 1 -C 8 -alkylsulfamoyl refers to a sulfamoyl radical having one C 1 -C 8 -alkyl group as defined herein.
  • di-(C 1 -C 8 -alkyl)sulfamoyl refers to a sulfamoyl radical having two independently selected C 1 -C 8 -alkyl groups as defined herein.
  • C 1 -C 6 -alkylcarbamoyl refers to a carbamoyl radical having one C 1 -C 6 -alkyl group as defined herein.
  • di-(C 1 -C 6 -alkyl)carbamoyl refers to a carbamoyl radical having two independently selected C 1 -C 6 -alkyl groups as defined herein.
  • C 1 -C 6 -haloalkylcarbonyl refers to a C 1 -C 6 -alkylcarbonyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 1 -C 6 -haloalkylcarbonyloxy refers to a C 1 -C 6 -alkylcarbonyloxy as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 1 -C 6 -haloalkylcarbonylamino refers to a C 1 -C 6 -alkylcarbonylamino as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 1 -C 6 -haloalkoxycarbonyl refers to a C 1 -C 6 -alkoxycarbonyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 1 -C 6 -alkylamino refers to an amino radical having one C 1 -C 6 -alkyl group as defined herein.
  • Examples of C 1 -C 6 -alkylamino include but are not limited to N-methylamino. N-cthyl- amino, N-isopropylamino. N-n-propylamino. N-isopropylamino and N-tert-butylamino.
  • di-(C 1 -C 6 -alkyl)amino refers to an amino radical having two independently selected C 1 -C 6 -alkyl groups as defined herein.
  • di-(C 1 -C 6 -dialkyl)amino include but are not limited to N, N-dimethylamino, N, N-diethylamino. N, N-d i i so p ro p y l am i n o .
  • N-ethyl-N-methylamino N-methyl-N-n-propylamino. N-isopropyl-N-n-propylamino and N-tert-butyl-N-methylamino.
  • C 3 -C 10 -carbocyclyl refers to a non-aromatic, saturated or partially unsaturated, hydrocarbon ring system in which all of the ring members, which vary from 3 to 10, are carbon atoms.
  • the ring system may be monocyclic orbicyclic (fused, spiro or bridged).
  • C 3 -C 10 -carbocycles include but are not limited to C 3 -C 10 -cycloalkyl (mono or bicyclic), C 3 -C 10 -cycloalkenyl (mono or bicyclic), bicylic system comprising an aryl (e.g.
  • phenyl fused to a monocyclic C 3 -C 6 -cycloalkyl (e.g. tetrahydronaphthalenyl, indanyl) and bicylic system comprising an aryl (e.g. phenyl) fused to a monocyclic C 3 -C 6 -cycloalkenyl (e.g. indenyl, dihydronaphthalenyl).
  • the C 3 -C 10 -carbocycle can be attached to the parent molecular moiety through any carbon atom.
  • C 3 -C 10 -cycloalkyl refers to a saturated, monovalent, mono- or bicylic hydrocarbon ring which contains 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.
  • C 3 -C 7 -cycloalkyl designates monocyclic C 3 -C 7 -cycloalkyls which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
  • C 3 -C 5 -cycloalkyl designates monocyclic C 3 -C 5 -cycloalkyls which include cyclopropyl, cyclobutyl and cyclopentyl.
  • bicyclic CVCm-cycloalkyls include but are not limited to bicyclo[3.1.1]heptane, bicyclo[2.2.1 ]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, bicyclo[4.2.0]octyl, octahydropentalenyl and bicyclo[4.2.1 ]nonane.
  • C 3 -C 7 -halocycloalkyl refers to a C 3 -C 7 -cycloalkyl group as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • C 3 -C 10 -halocarbocyclyl refers to a C 3 -C 10 -carbocyclyl group as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
  • aryl refers to an aromatic hydrocarbon ring system in which all of the ring members, which vary from 6 to 14, preferably from 6 to 10, are carbon atoms.
  • the ring system may be monocyclic or fused polycyclic (e.g. bicyclic or tricyclic). Examples of aryl include but are not limited to phenyl, azulenyl, naphthyl and fluorenyl.
  • the aryl can be attached to the parent molecular moiety through any carbon atom. 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.
  • 3- to 10-membered heterocyclyl refers to a non-aromatic, saturated or partially unsaturated non-aromatic ring system comprising 1 to 4, or 1 to 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur. If the ring system contains more than one oxygen atoms, they are not directly adjacent.
  • 3- to 10-membered heterocycles include but are not limited to 3- to 7-membered monocyclic non-aromatic heterocycles (“3- to 7- membered heterocyclyl”) and 6- to 10-membered polycyclic (e.g. bicyclic or tricyclic) non-aromatic heterocycles.
  • the 3- to 10-membered heterocyclyl can be connected to the parent molecular moiety through any carbon atom or nitrogen atom contained within the heterocycle.
  • heterocycle refers to a 3-, 4-, 5-, 6- or 7-membered monocyclic ring system containing 1, 2 or 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur where the ring system is saturated or unsaturated but not aromatic.
  • the heterocycle may comprise one to three nitrogen atoms, or one or two oxygen atoms, or one or two sulfur atoms, or one to three nitrogen atoms and one oxygen atom, or one to three nitrogen atoms and a sulfur atom or one sulfur atom and one oxygen atom.
  • saturated non-aromatic heterocycles include but are not limited to 3-membered ring such as oxiranyl, aziridinyl, 4-membered ring such as azetidinyl, oxetanyl, thietanyl, 5-membered ring such as tetrahydrof iranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, 6-membered ring such as piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydro
  • unsaturated non-aromatic hererocyles include but are not limited to 5-membered ring such as dihydrof iranyl, 1,3-dioxolyl, dihydrothienyl, pyrrolinyl, dihydroimidazolyl, dihydropyrazolyl, isoxazolinyl, dihydrooxazolyl, dihydrothiazolyl or 6-membered ring such as pyranyl, thiopyranyl, thiazinyl and thiadiazinyl.
  • 5-membered ring such as dihydrof iranyl, 1,3-dioxolyl, dihydrothienyl, pyrrolinyl, dihydroimidazolyl, dihydropyrazolyl, isoxazolinyl, dihydrooxazolyl, dihydrothiazolyl or 6-membered ring such as pyranyl, thiopyranyl, thiazinyl and
  • non-aromatic 6- to 10-membered polycyclic heterocycle refers to a 6-, 7-, 8-, 9-, 10-membered polycyclic (e.g. bicyclic or tricyclic) ring system containing 1, 2 or 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur where the ring system is saturated or unsaturated but not aromatic.
  • Non-aromatic bicyclic heterocycles may consist of a monocyclic heteroaryl as defined herein fused to a monocyclic C 3 -C 7 -cycloalkyl, a monocyclic C 3 -C 8 -cycloalkenyl or a monocyclic non-aromatic heterocycle or may consist of a monocyclic non-aromatic heterocycle fused either to an aryl (e.g. phenyl), a monocyclic C 3 -C 7 -cycloalkyl, a monocyclic C 3 -C 8 -cycloalkenyl or a monocyclic non-aromatic heterocycle.
  • aryl e.g. phenyl
  • nitrogen atom may be at the bridgehead (e.g. 4, 5,6,7- tetrahydropyrazolo[l,5-a]pyridinyl, 5,6,7,8-tetrahydro-[l,2,4]triazolo[l,5-a]pyridinyl, 5, 6, 7, 8- tetrahydroimidazo[l,2-a]pyridinyl).
  • Non-aromatic tricyclic heterocycles may consist of a monocyclic cycloalkyl connected through one common atom to a non-aromatic bicyclic heterocycle.
  • aromatic 5- to 14-membered heterocycle or “heteroaryl” as used herein refers to an aromatic ring system comprising 1 to 4 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur. If the ring system contains more than one oxygen atom, they are not directly adjacent.
  • Aromatic heterocycles include aromatic 5- or 6-membered monocyclic heterocycles and 6- to 14- membered polycyclic (e.g. bicyclic or tricyclic) aromatic heterocycles.
  • the 5- to 14-membered aromatic heterocycle can be connected to the parent molecular moiety through any carbon atom or nitrogen atom contained within the heterocycle.
  • aromatic 5- or 6-membered monocyclic heterocycle or “monocyclic heteroaryl” as used herein refers to a 5- or 6-membered monocyclic ring system containing 1, 2, 3 or 4 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur.
  • Examples of 5-membered monocyclic heteroaryl include but are not limited to furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, isoxazolyl, oxazolyl, oxadiazolyl, oxatriazolyl, isothiazolyl, thiazolyl, thiadiazolyl and thiatriazolyl.
  • Examples of 6-membered monocyclic heteroaryl include but are not limited to pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl.
  • 6- to 14-membered polycyclic aromatic heterocycle or “polycyclic heteroaryl” as used herein refers to a 6-, 7-, 8-, 9-, 10-, 11-,12-, 13- or 14-membered polycyclic (e.g. bicyclic or tricyclic) ring system containing 1, 2 or 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur.
  • Aromatic bicyclic heterocycles may consist of a monocyclic heteroaryl as defined herein fused to an aryl (e.g. phenyl) or to a monocyclic heteroaryl.
  • bicyclic aromatic heterocycle examples include but are not limited to 9-membered ring such as indolyl, indolizinyl, isoindolyl, benzimadozolyl, imidazopyridinyl, indazolyl, benzotriazolyl, purinyl, benzofuranyl, benzothiophenyl, benzothiazolyl, benzoxazolyl and benzisoxazolyl or 10-membered ring such as quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, pteridinal and benzodioxinyl.
  • 9-membered ring such as indolyl, indolizinyl, isoindolyl, benzimadozolyl, imidazopyridinyl, indazolyl, benzotriazolyl,
  • nitrogen atom may be at the bridgehead (e.g. imidazo[l,2-a]pyridinyl, [l,2,4]triazolo[4,3- a]pyridinyl, imidazo[l,2-a]pyridinyl, imidazo [2, 1-b] oxazolyl, furo[2,3-d]isoxazolyl).
  • Examples of tricyclic aromatic heterocyle include but are not limited to carbazolyl, acridinyl and phenazinyl.
  • aryl-C 1 -C 6 -alkyl designate a group of formula “-C 1 -C 6 -alkyl-R”, wherein R is respectively an aryl, 3- to 10-membered heterocyclyl, heteroaryl or C 3 -C 10 -carbocyclyl as defined herein, “C 1 -C 6 -alkyl” is a saturated, branched or straight hydrocarbon chain having 1, 2, 3, 4, 5 or 6 carbon atoms and wherein the group “-C 1 -C 6 -alkyl-R” is attached to the parent moiety via the “C 1 -C 6 - alkyl” group.
  • substituents refers to a number of substituents that ranges from one to the maximum number of substituents possible based on the number of available bonding sites, provided that the conditions of stability and chemical feasibility are met.
  • 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 trifluoromethanesulfonate (“triflate”) group, alkoxy, methanesulfonate, p-toluenesulfonate, etc.
  • variable xxxx incorporates by reference the broad definition of the variable as well as preferred, more preferred and even more preferred definitions, if any.
  • the present invention relates to the use of compounds of formula (I) for controlling harmful microorganisms, in particular phytopathogenic fungi, in crop protection: wherein
  • X is hydrogen or fluorine; W 1 , W 2 and W 3 are independently CH, CF or N, wherein W 1 and W 3 cannot both be N; n is 1 or 2, wherein if n is 2, the two [CR 2 R 3 ] groups may be the same or different; m is 0, 1 or 2, wherein if m is 2, the two [CR 4 R 5 ] groups may be the same or different;
  • R 1 is aryl, heteroaryl, C 3 -C 10 -carbocyclyl or 3- to 10-membered heterocyclyl, each of which may be substituted with one or more R 1c substituents;
  • R 2 and R 3 form, together with the carbon atom to which they are linked, a C 3 -C 6 -cycloalkyl wherein said C 3 -C 6 -cycloalkyl may be substituted with one or more R 2c substituents;
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 8 -haloalkyl and C 1 -C 8 -alkyl, wherein the C 1 -C 8 -alkyl may be substituted with one or more R 4a substituents,
  • R 1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfinyl, sulfonyl, amino, nitro, pentafluoro-l 6 - sulfanyl, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -hydroxyalkyl, C 1 -C 6 -cyanoalkyl, C 1 -C 6 -alkoxy, C 1 - C 6 -haloalkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -alkylsulfanyl, CVC g -haloalkylsulfanyl.
  • C 1 -C 6 - haloalkyl C 3 -C 10 -carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C 1 -C 6 -alkyl may be substituted with one or more R a substituents and wherein the C 3 -C 10 -carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more R c substituents;
  • R 2a , R 4a and R a are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- ⁇ 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 6 -alkylamino, di-(C 1 -C 6 - alkyl)amino, -Si(C 1 -C 6 -alkyl) 3 , -Si(aryl)(C 1 -C 6 -alkyl) 2 , C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 - alkylsulfanyl, C 1 -C 6 -alkylcarbony
  • R 2c and R c are independently selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -
  • C 1 -C 6 - haloalkylcarbonyl C 1 -C 6 -alkylcarbamoyl. di-(C 1 -C 6 -alkyl)carbamoyl, C 1 -C 6 -alkoxycarbonyl. C 1 - C 6 -haloalkoxycarbonyl, aryloxy, C 1 -C 6 -alkylcarbonyloxy. C 1 -C 6 -alkylcarbonylam ino. C 1 -C 6 - haloalkylcarbonylamino, C 1 -C 8 -alkylsulfanyl. C 1 -C 8 -alkylsiilfinyl.
  • C 1 -C 8 -alkylsiilfonyl C 1 -C 8 - alkylsulfonylamino, C 1 -C 8 -haloalkylsulfonylamino, C 1 -C 8 -alkylsulfamoyl and di-(C 1 -C 8 - alkyl)sulfamoyl; as well as their salts, N-oxides and solvates.
  • the compounds of formula (I) are used for controlling harmful microorganisms, in particular phytopathogenic fungi, in crop protection.
  • the phytopathogenic fungi are selected from the group consisting of the Puccinia species, for example Puccinia recondita, Puccinia graminis or Puccinia striiformis ; the Uromyces species, for example Uromyces appendiculatus and the rust disease pathogens, in particular selected from the group consisting of the Gymnosporangium species, for example Gymnosporangium sabinae Hemileia species, for example Hemileia vastatrix, and Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae .
  • the rust disease pathogens in particular Phakopsora pachyrhizi and Phakopsora meibomiae.
  • the compounds of formula (I) can suitably be in their free form, salt form, N-oxide form or solvate form (e.g. hydrate).
  • the compound of formula (I) 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) 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
  • the compounds of the invention may exist in multiple crystalline and/or amorphous forms.
  • Crystalline forms include unsolvated crystalline forms, solvates and hydrates.
  • Solvates of the compounds of the invention or their salts are stoichiometric compositions of the compounds with solvents.
  • X is hydrogen
  • At most one of W 1 , W 2 and W 3 is N.
  • W 1 is N, CH or CF, and W 2 and W 3 are independently selected from CH and CF.
  • W 1 is N
  • W 2 and W 3 are independently selected from CH and CF, preferably, W 2 and W 3 are CH.
  • W 1 , W 2 and W 3 are each independently selected from CH and CF, preferably W 1 , W 2 and W 3 are CH.
  • n 1
  • m is 0 or 1.
  • m is 1.
  • R 1 is an aryl selected from phenyl and naphthyl, a heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinolinyl, a C 3 -C 7 -cycloalkyl or a 3- to 7-membered heterocyclyl selected from the group consisting of selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl,
  • R 1 is phenyl or C 3 -C 7 -cycloalkyl, wherein the phenyl and C 3 - C 7 -cycloalkyl may be substituted with one to three R 1c substituents as defined herein.
  • R 1 is aryl, preferably phenyl or naphthyl, more preferably phenyl, wherein the aryl may be substituted with one to three R 1c substituents as defined herein.
  • R 1 is heteroaryl, preferably selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinolinyl, more preferably a 5 - or 6-membered heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyr
  • R 1 is C 3 -C 10 -carbocyclyl, preferably C 3 -C 7 -cycloalkyl, which may be substituted with one to three R 1c substituents as defined herein.
  • the C 3 -C 10 -carbocyclyl is substituted with one phenyl R 1c substituent and optionally one or two non-cyclic R 1c substituents selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy and C 1 -C 6 -haloalkoxy, wherein the phenyl may be substituted with one to three R c substituents selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 - alkoxy carbonyl. More
  • R 1 is 3- to 10-membered-heterocyclyl, preferably a 3 - to 7-membered heterocyclyl selected from the group consisting of selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, t
  • R 1 is phenyl, C 3 -C 7 -cycloalkyl, a 6-membered heteroaryl, preferably selected from the group consisting of pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, or a 5-membered heteroaryl, preferably selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl and thiazolyl, wherein the phenyl, C 3 -C 6 -cycloalkyl, 6-membered heteroaryl and 5-membered heteroaryl may be substituted with one to three R 1c substituents as defined herein.
  • R 1 is phenyl, a 6-membered heteroaryl, preferably selected from the group consisting of pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, or a 5- membered heteroaryl, preferably selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl and thiazolyl, wherein the phenyl, 6-membered heteroaryl and 5-membered heteroaryl may be substituted with one to three R 1c substituents as defined herein.
  • the R 1c substituents are selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy. C 1 -C 6 -haloalkoxy. C 3 -G-cycloalkyl.
  • 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three R c substituents as described herein; and wherein each R 21 is independently selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 - haloalkyl and C 3 -C 7 -cycloalkyl.
  • the R c substituents are selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 3 - G-cycloalkyl.
  • the R 1c substituents are selected from the group consisting of halogen, cyano, C1-C 6 - alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 3 -C 6 -cycloalkyl, phenyl, 5- to 6-membered heteroaryl selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, 3- to 7-membered heterocyclyl selected from the group consisting of tetrahydrofuranyl, 1,3- dioxolanyl
  • each R 21 is independently selected from the group consisting of hydrogen, C 1 -C 6 -alkyl.
  • the R c substituents are selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 3 - Cvcycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxycarbonyl.
  • R 1 is selected from aryl, heteroaryl, C 3 -C 7 - cycloalkyl and 3- to 7-membered heterocyclyl, which is substituted with one cyclic R 1c substituent selected from the group consisting of C 3 -C 7 -cycloalkyl, aryl, heteroaryl and 3- to 7-membered heterocyclyl and may additionally be substituted with one or two non-cyclic R 1c substituents selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl. C 1 -C 6 -haloalkyl.
  • the C 3 -C 7 -cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three R c substituents as described herein.
  • the R c substituents are selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 - haloalkoxy and C 1 -C 6 -alkoxycarbonyl.
  • R 2 and R 3 are independently selected from hydrogen and C 1 -C 8 - alkyl.
  • R 2 and R 3 are hydrogen.
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C t -haloalkyl and C1-C4- alkyl, wherein the C 1 - C 4 -alkyl may be substituted with one to three R 4a substituents as described herein.
  • the R 4a substituents are selected from the group consisting of halogen atom, cyano, carboxyl, formyl, carbamoyl, carbamate, C 3 -C 7 -cycloalkyl, C 1 -C 6 -alkylcarbonyl.
  • R 4 and R 5 are independently selected from hydrogen and C 1 - C 4 -alkyl.
  • W 1 with one or more preferred features of X, W 2 , W 3 , n, m, R 1 , R 2 , R 3 , R 4 and R 5 ;
  • W 2 with one or more preferred features of X, W 1 , W 3 , n, m, R 1 , R 2 , R 3 , R 4 and R 5 ;
  • W 3 with one or more preferred features of X, W 1 , W 2 , n, m, R 1 , R 2 , R 3 , R 4 and R 5 ;
  • n with one or more preferred features of X, W 1 , W 2 , W 3 , m, R 1 , R 2 , R 3 , R 4 and R 5 ;
  • R 1 with one or more preferred features of X, W 1 , W 2 , W 3 , n, m, R 2 , R 3 , R 4 and R 5 ;
  • R 2 with one or more preferred features of X, W 1 , W 2 , W 3 , n, m, R 1 , R 3 , R 4 and R 5 ;
  • R 3 with one or more preferred features of X, W 1 , W 2 , W 3 , n, m, R 1 , R 2 , R 4 and R 5 ;
  • R 4 with one or more preferred features of X, W 1 , W 2 , W 3 , n, m, R 1 , R 2 , R 3 and R 5 ;
  • R 5 with one or more preferred features of X, W 1 , W 2 , W 3 , n, m, R 1 , R 2 , R 3 and R 4 .
  • the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof: wherein
  • X is hydrogen or fluorine, preferably hydrogen; W 1 is CH, CF or N, preferably W 1 is N; W 2 and W 3 are each independently selected from CH and CF; n is 1 or 2, wherein if n is 2, the two [CR 2 R 3 ] groups may be the same or different; preferably n is 1 ; m is 0, 1 or 2, wherein if m is 2, the two [CR 4 R 5 ] groups may be the same or different;
  • R 1 is aryl, heteroaryl, C 3 -C 10 -carbocyclyl or 3- to 10-membered-heterocyclyl, each of which may be substituted with one or more R 1c substituents;
  • R 2 and R 3 are hydrogen
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 8 -haloalkyl and C 1 -C 8 -alkyl, wherein the C 1 -C 8 -alkyl may be substituted with one or more R 4a substituents, R 1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l 6 - sulfanyl, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -hydroxyalkyl, C 1 -C 6 -cyanoalkyl, C 1 -C 6 -alkoxy, C 1 - C 6 -haloalkoxy, C 2 -C 6 -alkenyl, C
  • R c substituents are each independently selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 - haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- ⁇ 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 - C 8 -halocycloalkyl, C 1 -C 6 -alkylamino, di-(C 1 -C 6 -alkyl)amino, -Si(C 1 -C 6 -alkyl)3, -Si(aryl)(C 1 -C 6 - alkyl) 2 , C 1 -C 6 -al
  • R 1 is an aryl selected from phenyl and naphthyl, a heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinobnyl, a C 3 -C 7 -cycloalkyl or a 3- to 7-membered heterocyclyl selected from the group consisting of selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidiny
  • R 1 is an aryl selected from phenyl and naphthyl or a heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinolinyl, wherein the aryl and heteroaryl may be substituted with one to three R 1c substituents as defined herein.
  • the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof: wherein
  • X is hydrogen or fluorine, preferably hydrogen; W 1 is CH, CF or N, preferably W 1 is N; W 2 and W 3 are each independently selected from CH and CF; n is 1 or 2, wherein if n is 2, the two [CR 2 R 3 ] groups may be the same or different, preferably n is 1 ; m is 0, 1 or 2, wherein if m is 2, the two [CR 4 R 5 ] groups may be the same or different;
  • R 1 is aryl, preferably phenyl, which may be substituted with one or more R 1c substituents;
  • R 2 and R 3 are hydrogen
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 8 -haloalkyl and C 1 -C 8 -alkyl, wherein the C 1 -C 8 -alkyl may be substituted with one or more R 4a substituents, R 1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfinyl, sulfonyl, amino, nitro, pentafluoro-l 6 - sulfanyl, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -hydroxyalkyl, C 1 -C 6 -cyanoalkyl, C 1 -C 6 -alkoxy, C 1 - C 6 -haloalkoxy, C 2 -C 6 -alkenyl,
  • R 4a and R a are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoroG 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 6 -alkylamino. di-(C 1 -CValkyl)amino.
  • R c substituents are each independently selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 - haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- ⁇ 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 - C 8 -halocycloalkyl, C 1 -C 6 -alkylamino, di-(C 1 -C 6 -alkyl)amino, -Si(C 1 -C 6 -alkyl)3, -Si(aryl)(C 1 -C 6 - alkyl) 2 , C 1 -C 6 -al
  • the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof: wherein
  • X is hydrogen or fluorine, preferably hydrogen; W 1 is CH, CF or N, preferably W 1 is N; W 2 and W 3 are each independently selected from CH and CF; n is 1 or 2, wherein if n is 2, the two [CR 2 R 3 ] groups may be the same or different, preferably n is 1 ; m is 0, 1 or 2, wherein if m is 2, the two [CR 4 R 5 ] groups may be the same or different;
  • R 1 is heteroaryl, preferably selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinolinyl, wherein the heteroaryl may be substituted with one or more R 1c substituents;
  • R 2 and R 3 are hydrogen
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 8 -haloalkyl and C 1 -C 8 -alkyl, wherein the C 1 -C 8 -alkyl may be substituted with one or more R 4a substituents, R 1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l 6 - sulfanyl, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -hydroxyalkyl, C 1 -C 6 -cyanoalkyl, C 1 -C 6 -alkoxy, C 1 - C 6 -haloalkoxy, C 2 -C 6 -alkenyl, C
  • C 2 -G,-alkcnyl and C 2 -G,-alkynyl may be substituted with one or more R a substituents; wherein the C 3 -C 10 -carbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, arylsulfanyl and arylsulfmyl may be substituted with one or more R c substituents; and wherein R 21 is independently selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 - haloalkyl, C 3 -C 10 -carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C 1 -C 6 -alkyl may be substituted with one or more R a substituents and wherein the C 3 -C 10 -carbocyclyl, 3-
  • R 4a and R a are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoroG 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 6 -alkylamino, di-(C 1 -C 6 -alkyl)amino, -Si(C 1 -C 6 -alkyl) 3 , -Si(aryl)(C 1 -C 6 -alkyl) 2 , C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylsulfanyl, C 1 -C 6 -alkylcarbonyl, C 1 -
  • C 1 -C 6 -haloalkylcarbonylamino C 1 -C 8 - alkylsulfanyl, C 1 -C 8 -alkylsulfmyl, C 1 -C 8 -alkylsulfonyl. C 1 -C 8 -alkylsulfonylamino. C 1 -C 8 - haloalkylsulfonylamino, C 1 -C 8 -alkylsiilfamoyl and di-(C 1 -C 8 -alkyl)sulfamoyl;
  • R c substituents are each independently selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 - haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- ⁇ 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 - C 8 -halocycloalkyl, C 1 -C 6 -alkylamino, di-(C 1 -C 6 -alkyl)amino, -Si(C 1 -C 6 -alkyl) 3 , -Si(aryl)(C 1 -C 6 - alkyl) 2 , C 1 -C 6
  • the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof: wherein
  • X is hydrogen or fluorine, preferably hydrogen; W 1 is CH, CF or N, preferably W 1 is N; W 2 and W 3 are each independently selected from CH and CF; n is 1 or 2, wherein if n is 2, the two [CR 2 R 3 ] groups may be the same or different, preferably n is 1 ; m is 0, 1 or 2, wherein if m is 2, the two [CR 4 R 5 ] groups may be the same or different;
  • R 1 is C 3 -C 10 -carbocyclyl, preferably C 3 -C 7 -cycloalkyl, which may be substituted with one or more R 1c substituents;
  • R 2 and R 3 are hydrogen
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 8 -haloalkyl and C 1 -C 8 -alkyl, wherein the C 1 -C 8 -alkyl may be substituted with one or more R 4a substituents, R 1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l 6 - sulfanyl, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -hydroxyalkyl, C 1 -C 6 -cyanoalkyl, C 1 -C 6 -alkoxy, C 1 - C 6 -haloalkoxy, C 2 -C 6 -alkenyl, C
  • arylsulfmyl C 3 -C 10 -carbocyclyl, C 3 - C 10 -halocarbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, aryl-C 1 -C 6 -alkyl. 3- to 10- membered-heterocyclyl-C 1 -C 6 -alkyl, heteroaryl -C 1 -C 6 -alkyl.
  • R 4a and R a are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoroG 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 6 -alkylamino. di-(C 1 -CValkyl)amino. -Si(C 1 -C 6 -alkyl)3, -Si (aryl )(C 1 - ,-alky l ) 2 .
  • R c substituents are each independently selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 - haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- ⁇ 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 - C 8 -halocycloalkyl, C 1 -C 6 -alkylamino, di-(C 1 -C 6 -alkyl)amino, -Si(C 1 -C 6 -alkyl)3, -Si(aryl)(C 1 -C 6 - alkyl)2, C 1 -C 6 -alkoxy
  • X is hydrogen
  • W 1 is N
  • W 2 and W 3 are each independently selected from CH and CF. More preferably, W 1 is N, and W 2 and W 3 are CH.
  • n is 1.
  • m is 0 or 1.
  • the R c substituents are selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 3 - C 7 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxycarbonyl.
  • the R 1c substituents are selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 - haloalkoxy, C 3 -C 6 -cycloalkyl, phenyl, 5- to 6-membered heteroaryl selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, 3- to 7-membered heterocyclyl selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C
  • the R c substituents are selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 3 - C 7 -cycloalkyl.
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -Crhaloalkyl and C1-C4- alkyl, wherein the C 1 -C 4 -alkyl may be substituted with one to three R 4a substituents as described herein.
  • the R 4a substituents are selected from the group consisting of halogen atom, cyano, carboxyl, formyl, carbamoyl, carbamate, C 3 -C 7 -cycloalkyl, C 1 -CValkylcarbonyl.
  • m is 0.
  • m is 1 or 2, preferably 1.
  • one to three R 1c substituent are present in residue R 1 : one cyclic R 1c substituent selected from the group consisting of C 3 -C 7 -cycloalkyl.
  • the R c substituents are selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 1 - C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxycarbonyl.
  • the cyclic R 1c substituent is C 3 -C 6 -cycloalkyl, phenyl, a 5- to 6- membered heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, or a 3- to 7-membered heterocyclyl selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolid
  • the R c substituents are selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxycarbonyl.
  • embodiments in accordance with embodiment (la), (lb), (Ic) or (Id) (referred herein as embodiments (la*), (lb*), (Ic*) and (Id*)),
  • X is hydrogen; W 1 is N or CH, W 2 and W 3 are CH; n is 1; m is 0 or 1;
  • R 1 contains one cyclic R 1c substituent selected from the group consisting of C 3 -C 7 -cycloalkyl, aryl, heteroaryl and 3- to 7-membered heterocyclyl and optionally one or two non-cyclic R 1c substituents selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl.
  • C 1 -C 6 -alkoxy and C 1 - C 6 -haloalkoxy wherein the C 3 -C 7 -cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three R c substituents; and R 2 and R 3 are hydrogen.
  • the cyclic R 1c substituent is C 3 - C 6 -cycloalkyl, phenyl, a 5- or 6-membered heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, or a 3- to 7-membered heterocyclyl selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl
  • the cyclic R 1c substituent is selected from phenyl and 5- to 6-membered heteroaryl, preferably selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, wherein the phenyl and 5- to 6-membered heteroaryl may be substituted with one to three R c substituents, preferably selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 6 -haloalkyl
  • the cyclic R 1c substituent is phenyl, which may be substituted with one to three R c substituents, preferably selected from the group consisting ofhalogen, cyano, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 - C 6 -haloalkoxy and C 1 -C 6 -alkoxycarbonyl.
  • X is hydrogen; W 1 is N or CH, preferably N; W 2 and W 3 are CH; n is 1; m is 0;
  • R 1 is C 3 -C 10 -carbocyclyl, preferably C 3 -C 7 -cycloalkyl, which is substituted with one phenyl (as cyclic R 1c substituent) and optionally one or two non-cyclic R 1c substituents selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl. C 1 -C 6 -haloalkyl. C 1 -C 6 -alkoxy and C 1 -C 6 - haloalkoxy, wherein the phenyl may be substituted with one to three R c substituents selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl.
  • C 1 -C 6 - alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxycarbonyl, and R 2 and R 3 are hydrogen.
  • R 1 is cyclopropyl, which is substituted with phenyl, wherein the phenyl is substituted with one or two halogen, preferably fluorine substituents.
  • W 1 is N
  • W 2 and W 3 are CH.
  • m is 0. In some other preferred embodiments in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), m is 1 or 2, preferably 1.
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -Crhaloalkyl and C 1 -C 4 -alkyl, wherein the C 1 -C 4 -alkyl may be substituted with one to three R 4a substituents as described herein.
  • the R 4a substituents are selected from the group consisting of halogen atom, cyano, carboxyl, formyl, carbamoyl, carbamate, C 3 -C 7 -cycloalkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylcarbamoyl, di-(C 1 -C 6 -alkyl)carbamoyl, C 1 -C 6 - alkoxycarbonyl and C 1 -C 6 -haloalkoxycarbonyl.
  • the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof: wherein
  • X is hydrogen or fluorine; W 1 , W 2 and W 3 are independently CH, CF or N, wherein W 1 and W 3 cannot both be N; n is 1 or 2, wherein if n is 2, the two [CR 2 R 3 ] groups may be the same or different; m is 0 or 1;
  • R 1 is phenyl or C 3 -C 7 -cycloalkyl, each of which may be substituted with one or more R 1c substituents;
  • R 2 and R 3 form, together with the carbon atom to which they are linked, a C 3 -C 6 -cycloalkyl wherein said C 3 -C 6 -cycloalkyl may be substituted with one or more R 2c substituents;
  • R 2a and R 4a are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- ⁇ 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 6 -alkylamino, di-(C 1 -C 6 -alkyl)amino, - Si(C 1 -C 6 -alkyl) 3 , -Si(aryl)(C 1 -C 6 -alkyl) 2 , C 1 -C 6 -alkoxy, C 1 -C 6 -haloalk
  • R 2c is selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, CVC 6 - alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- ⁇ 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 6 - alkylamino, di-(C 1 -C 6 -alkyl)amino, -Si(C 1 -C 6 -alkyl) 3 , -Si(aryl)(C 1 -C 6 -alkyl) 2 , C 1 -C 6 -alkoxy, C 1 -
  • R 2 , R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen and C 1 -C 8 -alkyl. in particular hydrogen, methyl and ethyl.
  • At most one of W 1 , W 2 and W 3 is N.
  • the present invention also relates to the use of any compounds of formula (I) disclosed in Table 1.
  • the present invention also relates to compounds of formula (G) wherein
  • X is fluorine; W 1 , W 2 and W 3 are independently CH, CF or N, wherein W 1 and W 3 cannot both be N; n is 1 or 2, wherein if n is 2, the two [CR 2 R 3 ] groups may be the same or different; m is 0, 1 or 2, wherein if m is 2, the two [CR 4 R 5 ] groups may be the same or different;
  • R 1 is aryl, heteroaryl, C 3 -C 10 -carbocyclyl or 3- to 10-membered-heterocyclyl, each of which may be substituted with one or more R 1c substituents;
  • R 2 and R 3 form, together with the carbon atom to which they are linked, a C 3 -C 6 -cycloalkyl wherein said C 3 -C 6 -cycloalkyl may be substituted with one or more R 2c substituents;
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 8 -haloalkyl and C 1 -C 8 -alkyl, wherein the C 1 -C 8 -alkyl may be substituted with one or more R 4a substituents, R 1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l 6 - sulfanyl, C 1 -C 6 -alkyl. C 1 -C 6 -haloalkyl.
  • R 2a , R 4a and R a are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- ⁇ 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 6 -alkylamino, di-(C 1 -C 6 - alkyl)amino, -Si(C 1 -C 6 -alkyl)3, -Si(aryl)(C 1 -C 6 -alkyl)2, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 - alkylsulfanyl, C 1 -C 6 -alkylcarbonyl, C 1
  • C 1 -C 6 -haloalkylcarbonylamino C 1 -C 8 - alkylsulfanyl, C 1 -C 8 -alkylsulfmyl, C 1 -C 8 -alkylsulfonyl. C 1 -C 8 -alkylsulfonylamino. C 1 -C 8 - haloalkylsulfonylamino, C 1 -C 8 -alkylsulfamoyl and di-(C 1 -C 8 -alkyl)sulfamoyl;
  • R 2c and R c are independently selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl.
  • C 1 -C 8 -alkylsulfonyl C 1 -C 8 -alkylsulfonyl. C 1 -C 8 - alkylsulfonylamino, C 1 -C 8 -haloalkylsulfonylamino, C 1 -C 8 -alkylsulfamoyl and di-(C 1 -C 8 - alkyl)sulfamoyl; as well as their salts, N-oxides and solvates.
  • the present invention also relates to compounds of formula (I”) wherein
  • X is hydrogen or fluorine;
  • W 1 , W 2 and W 3 are independently CH, CF or N, wherein W 1 and W 3 cannot both be N;
  • n is 2, wherein the two [CR 2 R 3 ] groups may be the same or different;
  • m is 0, 1 or 2, wherein if m is 2, the two [CR 4 R 5 ] groups may be the same or different;
  • R 1 is aryl, heteroaryl, C 3 -C 10 -carbocyclyl or 3- to 10-membered-heterocyclyl, each of which may be substituted with one or more R 1c substituents;
  • R 2 and R 3 form, together with the carbon atom to which they are linked, a C 3 -C 6 -cycloalkyl wherein said C 3 -C 6 -cycloalkyl may be substituted with one or more R 2c substituents;
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 8 -haloalkyl and C 1 -C 8 -alkyl, wherein the C 1 -C 8 -alkyl may be substituted with one or more R 4a substituents, R 1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l 6 - sulfanyl, C 1 -C 6 -alkyl. C 1 -C 6 -haloalkyl.
  • C 1 -C 6 -hydroxyalkyl C 1 -C 6 -cyanoalkyl.
  • C 1 -C 6 -alkoxy C 1 - C 6 -haloalkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl.
  • R 2a , R 4a and R a are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro- ⁇ 6 -sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C 3 -C 7 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 6 -alkylamino, di-(C 1 -C 6 - alkyl)amino, -Si(C 1 -C 6 -alkyl)3, -Si(aryl)(C 1 -C 6 -alkyl) 2 , C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 - alkylsulfanyl, C 1 -C 6 -alkylcarbonyl,
  • C 1 -C 6 -haloalkylcarbonylamino C 1 -C 8 - alkylsulfanyl, C 1 -C 8 -alkylsulfinyl, C 1 -C 8 -alkylsulfonyl. C 1 -C 8 -alkylsulfonylamino, C 1 -C 8 - haloalkylsulfonylamino, C 1 -C 8 -alkylsulfamoyl and di-(C 1 -C 8 -alkyl)sulfamoyl;
  • R 2c and R c are independently selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl.
  • C 1 -C 8 -alkylsulfonyl C 1 -C 8 -alkylsulfonyl. C 1 -C 8 - alkylsulfonylamino, C 1 -C 8 -haloalkylsulfonylamino, C 1 -C 8 -alkylsulfamoyl and di-(C 1 -C 8 - alkyl)sulfamoyl; as well as their salts, N-oxides and solvates.
  • the present invention relates to processes for the preparation of compounds of formula (I) and their intermediates.
  • the radicals and indices R 1 , R 2 , R 3 , R 4 , R 5 , X, W 1 , W 2 , W 3 , m and n have the meanings given above for the compounds of formula (I). These definitions apply not only to the end products of formula (I) but also to all intermediates.
  • Compounds of formula (I) can be prepared, according to process PI, by reacting intermediates of formula (II) with a dehydrating agent, such as methyl N-(triethylammoniumsulfonyl)carbamate (Burgess reagent) or 4-toluenesulfonyl chloride, in a suitable solvent such as tetrahydrofurane, as previously described in WO2017065473.
  • a dehydrating agent such as methyl N-(triethylammoniumsulfonyl)carbamate (Burgess reagent) or 4-toluenesulfonyl chloride
  • Carbohydrazides of formula (III) can be prepared, according to process P3, by reacting a compound of formula (IV), wherein LG1 is a leaving group as for example ethoxy with hydrazine hydrate in a suitable solvent such as ethanol, as previously described in WO2017065473.
  • Compounds of formula (IV) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
  • compounds of formula IV can be prepared by carbonylation as described for example in W02017040449, US20160122318 or WO2018218051.
  • carbohydrazides of formula (III) can be prepared, according to process P4, by reacting a compound of formula (V) with an acid such as trifluoroacetic acid in a suitable solvent such as dichloromethane, preferably at room temperature, as previously described in Bioorganic & Medicinal Chemistry, 20(1), 487-497; 2012.
  • Compounds of formula (V) may be prepared, according to process P5, by reacting a compound of formula (IV), wherein LG1 is a leaving group, as for example hydroxy with tert- butyl carbazate, optionally in presence of a coupling agent like for example ( 1 -[bis(dimethylamino)methylene]- 1 H- 1 2,3-triazolo
  • a coupling agent like for example ( 1 -[bis(dimethylamino)methylene]- 1 H-
  • intermediates of formula (II) can be prepared according to process P6, by reacting a compound of formula (IV), wherein LG1 is a leaving group as for example chlorine with 2,2- difluoroacetohydrazide or 2,2,2-trifluoroacetohydrazide in a suitable solvent such as tetrahydrofuran, acetonitrile or dichloromethane optionally in presence of a base such as triethylamine, as previously described in Russian Journal of Organic Chemistry, 43(11), 1686-1695; 2007 or Yingyong Huaxue, 13(5), 5-9; 1996.
  • a suitable solvent such as tetrahydrofuran, acetonitrile or dichloromethane
  • a base such as triethylamine
  • 2,2-Difluoroacetohydrazide and 2,2,2-trifluoroacetohydrazide can be commercially available or may be prepared, according to known processes, as previously described in Synlett, (12), 1939-1941; 2005, Journal of Organic Chemistry, 78(16), 8054-8064; 2013, Chemistry of Heterocyclic Compounds (New York, NY, United States), 52(2), 133-139; 2016 or WO 2018233633.
  • compounds of formula (VII) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
  • compounds of formula (VII) can be prepared, according to process P8, by reacting a compound of formula (VIII), wherein LG1 is a leaving group as for example ethoxy and wherein LG3 is a leaving group like for example ethoxy or methoxy with an halogenating agent like for example isocyanuric chloride, as described for example in W02019027054 or with N-bromosuccinimide, as described for examples in Journal of Medicinal Chemistry, 60(19), 8027-8054; 2017.
  • Process P8 Compounds of formula (VIII) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
  • compounds of formula (I) can be prepared, according to process P9, from a compound of formula (IX), by reaction with a compound of formula (X), wherein LG4 is a leaving group like for example bromine, as described for example in Journal of the American Chemical Society, 142(16), 7379- 7385; 2020, Organic Letters, 22(8), 2999-3003; 2020 or European Journal of Medicinal Chemistry, 138,
  • Compounds of formula (IX) may be prepared starting from readily available compounds analogously to process PI and P2 or P3 and P4 or P6.
  • compounds of formula (X) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
  • compounds of formula (IX) can be prepared, according to process P10, from a compound of formula (XI), wherein PG is a protecting group like for example 4-methoxybenzyl, by state of the art deprotection method such as for example trifluoroacetic acid in a solvent such as dichloromethane as described in Journal of Medicinal Chemistry, 63(2), 656-675; 2020.
  • Process P10 Compounds of formula (XI) may be prepared starting from readily available compounds analogously to process PI and P2 or P3 and P4 or P6.
  • Intermediates of formula (XIV) can be prepared, according to process P14, by reacting a compound of formula (XV), wherein LG1 is a leaving group as for example ethoxy and LG2 is a leaving group like for example bromine by nucleophilic substitution, optionally in presence of a base, like for example N,N- diisopropylethylamine or potassium carbonate, in a solvent such as for example acetonitrile or N,N- dimethylformamide as previously described in Tetrahedron 2006, 62, 8707-8714.
  • a base like for example N,N- diisopropylethylamine or potassium carbonate
  • Process P14 Intermediates of formula (XV), can be prepared, according to process P15, by reacting a compound of formula (XVI), wherein LG1 is a leaving group as for example ethoxy with an halogenating agent like for example isocyanuric chloride, as described for example in WO2015173035.
  • LG1 is a leaving group as for example ethoxy
  • an halogenating agent like for example isocyanuric chloride
  • Intermediates of formula (XVII) can be prepared, according to process PI 7, from a compound of formula (XVIII), by reaction with a compound of formula (X), wherein LG4 is a leaving group like for example bromine, in presence of a catalyst like for example copper iodide, optionally in presence of a base such as potassium phosphate, in a solvent such as for example dimethyl sulfoxide as described in WO2014210255.
  • Alternatively intermediates of formula (XVII) can be prepared by substitution nucleophile in presence of a base like sodium hydride in a solvent such as DMF as described in US201134450.
  • processes PI to P17 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 PI to P17 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, dichloroethane or trichloroethane ; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran
  • N,N-dimethylacetamide N-methylform anilide.
  • Suitable bases for carrying out processes PI to P17 according to the invention are inorganic and organic bases which are customary for such reactions.
  • pyridine N-methylpiperidine, N,N-dimethyl- aminopyridine, l,4-diazabicyclo[2.2.2]octane (DABCO), l,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1 , 8 -diazabicyclo [5.4.0]undec-7 -ene (DBU) .
  • DABCO diazabicyclo[2.2.2]octane
  • DBN l,5-diazabicyclo[4.3.0]non-5-ene
  • DBU 8 -diazabicyclo [5.4.0]undec-7 -ene
  • 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.
  • a way to control the temperature for the processes is to use microwave technology.
  • Processes PI to P17 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 compositions, in particular compositions for controlling unwanted microorganisms.
  • the composition may be applied to the microorganisms and/or in their habitat.
  • composition comprises at least one compound of the invention and at least one agriculturally suitable auxiliary, e.g. carrier(s) and/or surfactant(s).
  • 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, in particular ammonium sulfates, ammonium phosphates and ammonium nitrates, natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, silica gel and synthetic rock flours, such as finely divided silica, alumina and silicates.
  • ammonium salts in particular ammonium sulfates, ammonium phosphates and ammonium nitrates
  • natural rock flours such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth
  • silica gel 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, tetrahydronaphthalene, 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 ethanol, propanol, butanol, benzylalcohol, cyclohexanol 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, amide
  • 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.
  • a liquefied gaseous extender i.e. liquid which is gaseous at standard temperature and under standard pressure
  • aerosol propellants such as halohydrocarbons, butane, propane, nitrogen and carbon dioxide.
  • Preferred solid carriers are selected from clays, talc and silica.
  • Preferred liquid carriers are selected from water, fatty acid amides and esters thereof, aromatic and nonaromatic hydrocarbons, lactams and carbonic acid esters.
  • 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.
  • Liquid carriers are typically present in a range of from 20 to 90%, for example 30 to 80% by weight of the composition.
  • Solid carriers are typically present in a range of from 0 to 50%, preferably 5 to 45%, for example 10 to 30% by weight of the composition.
  • composition comprises two or more carriers, the outlined ranges refer to the total amount of carriers.
  • the surfactant can be an ionic (cationic or anionic), amphoteric or non-ionic surfactant, such as ionic or non-ionic emulsifier(s), foam former(s), dispersant(s), wetting agent(s), penetration enhancer(s) and any mixtures thereof.
  • Suitable surfactants include, but are not limited to, salts of polyacrylic acid, salts of bgnosulfonic acid (such as sodium lignosulfonate), salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids or fatty amines (for example, polyoxyethylene fatty acid esters such as castor oil ethoxylate, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols) and ethoxylates thereof (such as tristyrylphenol ethoxylate), salts of sulfosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols (such a fatty acid esters of
  • Preferred surfactants are selected from polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty acid esters, alkylbenzene sulfonates, such as calcium dodecylbenzenesulfonate, castor oil ethoxylate, sodium lignosulfonate and arylphenol ethoxylates, such as tristyrylphenol ethoxylate.
  • the amount of surfactants typically ranges from 5 to 40%, for example 10 to 20%, by weight of the composition.
  • auxiliaries 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 and tylose), thickeners and secondary thickeners (such as cellulose ethers, acrylic acid derivatives, xanthan gum, modified clays, e.g. the products available under the name Bentone, and finely divided silica), stabilizers (e.g.
  • cold stabilizers preservatives (e.g. dichlorophene and benzyl alcohol hemiformal), antioxidants, light stabilizers, in particular UV 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 silicone antifoams and magnesium stearate
  • antifreezes 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.
  • auxiliaries depends on the intended mode of application of the compound of the invention and/or on the physical properties of the compound(s). 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.
  • composition of the invention 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 compositions may be provided to the end user in the form of concentrates which have to be diluted, preferably with water, prior to use.
  • composition of the invention can be prepared in conventional manners, for example by mixing the compound of the invention with one or more suitable auxiliaries, such as disclosed herein above.
  • the composition comprises a f mgicidally effective amount of the compound(s) of the invention.
  • effective amount denotes an amount, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the f ingal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound of the invention used.
  • the composition according to the invention contains from 0.01 to 99% by weight, preferably from 0.05 to 98% by weight, more preferred from 0.1 to 95% by weight, even more preferably from 0.5 to 90% by weight, most preferably from 1 to 80% by weight of the compound of the invention. It is possible that a composition comprises two or more compounds of the invention. In such case the outlined ranges refer to the total amount of compounds of the present invention.
  • composition of the invention may be in any customary composition type such as solutions (e.g. aqueous solutions), emulsions, water- and oil-based suspensions, powders (e.g. wettable powders, soluble powders), dusts, pastes, granules (e.g. 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 the invention may be present in a suspended, emulsified or dissolved form. Examples of particular suitable composition types are solutions, water-soluble concentrates (e.g.
  • SL LS
  • dispersible concentrates DC
  • suspensions and suspension concentrates e.g. SC, OD, OF, FS
  • emulsifiable concentrates e.g. EC
  • emulsions e.g. EW, EO, ES, ME, SE
  • capsules e.g. CS, ZC
  • pastes pastilles
  • wettable powders or dusts e.g. WP, SP, WS, DP, DS
  • pressings e.g. BR, TB, DT
  • granules e.g. WG, SG, GR, FG, GG, MG
  • insecticidal articles e.g.
  • compositions types are defined by the Food and Agriculture Organization of the United Nations (FAO). An overview is given in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
  • the composition of the invention is in form of one of the following types: EC, SC, FS, SE, OD and WG, more preferred EC, SC, OD and WG. Further details about examples of composition types and their preparation are given below. If two or more compounds of the invention are present, the outlined amount of compound of the invention refers to the total amount of compounds of the present invention. This applies mutatis mutandis for any further component of the composition, if two or more representatives of such component, e.g. wetting agent, binder, are present. i) Water-soluble concentrates (SL, LS)
  • ком ⁇ онент 5-40 % by weight of at least one compound of the invention and 1-10 % by weight surfactant (e.g. amixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 % by weight water- insoluble organic solvent (e.g. aromatic hydrocarbon).
  • surfactant e.g. amixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water- insoluble organic solvent e.g. aromatic hydrocarbon
  • This mixture is added to such amount of water by means of an emulsifying machine to result in a total amount of 100 % by weight.
  • the resulting composition is a homogeneous emulsion. Before application the emulsion may be further diluted with water.
  • a suitable grinding equipment e.g. an agitated ball mill
  • 20-60 % by weight of at least one compound of the invention are comminuted with addition of 2-10 % by weight surfactant (e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1 -2 % by weight thickener (e.g. xanthan gum) and water to give a fine active substance suspension.
  • surfactant e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether
  • thickener e.g. xanthan gum
  • water e.g. xanthan gum
  • the water is added in such amount to result in a total amount of 100 % by weight. Dilution with water gives a stable suspension of the active substance.
  • binder e.g. polyvinylalcohol
  • a suitable grinding equipment e.g. an agitated ball mill
  • 20-60 % by weight of at least one compound of the invention are comminuted with addition of 2-10 % by weight surfactant (e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1-2 % by weight thickener (e.g. modified clay, in particular Bentone, or silica) and an organic carrier to give a fine active substance oil suspension.
  • the organic carrier is added in such amount to result in a total amount of 100 % by weight. Dilution with water gives a stable dispersion of the active substance.
  • 50-80 % by weight of at least one compound of the invention are ground finely with addition of surfactant (e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether) and converted to water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed).
  • surfactant e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether
  • the surfactant is used in such amount to result in a total amount of 100 % by weight. Dilution with water gives a stable dispersion or solution of the active substance.
  • WP, SP, WS Water-dispersible powders and water-soluble powders
  • % by weight of at least one compound of the invention are ground in a rotor-stator mill with addition of 1-8 % by weight surfactant (e.g. sodium lignosulfonate, polyoxyethylene fatty alcohol ether) and such amount of solid carrier, e.g. silica gel, to result in a total amount of 100 % by weight. Dilution with water gives a stable dispersion or solution of the active substance.
  • surfactant e.g. sodium lignosulfonate, polyoxyethylene fatty alcohol ether
  • solid carrier e.g. silica gel
  • agitated ball mill 5-25 % by weight of at least one compound of the invention are comminuted with addition of 3-10 % by weight surfactant (e.g. sodium lignosulfonate), 1-5 % by weight binder (e.g. carboxymethylcellulose) and such amount of water to result in a total amount of 100 % by weight.
  • surfactant e.g. sodium lignosulfonate
  • binder e.g. carboxymethylcellulose
  • 5-20 % by weight of at least one compound of the invention are added to 5-30 % by weight organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 % by weight surfactant blend (e.g. polyoxyethylene fatty alcohol ether and arylphenol ethoxylate), and such amount of water to result in a total amount of 100 % by weight.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. polyoxyethylene fatty alcohol ether and arylphenol ethoxylate
  • An oil phase comprising 5-50 % by weight of at least one compound of the invention, 0-40 % by weight water-insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 % by weight acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 % by weight of at least one compound of the invention, 0-40 % by weight water-insoluble organic solvent (e.g.
  • At least one compound of the invention are ground finely and associated with such amount of solid carrier (e.g. silicate) to result in atotal amount of 100 % by weight.
  • Granulation is achieved by extrusion, spray-drying or the fluidized bed.
  • compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 % by weight preservatives, 0.1-1 % by weight antifoams, 0.1-1 % by weight dyes and/or pigments, and 5-10% by weight antifreezes.
  • the compound and the composition of the invention can be mixed with other active ingredients like fungicides, bactericides, acaricides, nematicides, insecticides, biological control agents or herbicides. Mixtures with fertilizers, growth regulators, safeners, nitrification inhibitors, semiochemicals and/or other agriculturally beneficial agents are also possible. 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 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, (1.011) 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) t
  • 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 1R,4S,9S), (2.011) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.012) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enantiomer 1R,4S
  • 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, (3.011) 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-[( ⁇ [(lE)-l-(3- ⁇ [((l
  • 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-l-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 -(morphobn-4-yl)prop-2-en- 1 -one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-l-(morpholin-4-yl)prop-2-en-l-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 (11.001) tricyclazole, (11.002) 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, (15.011) 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)
  • the compound and the composition of the invention may also be combined with one or more biological control agents.
  • biological control is defined as control of harmful organisms such as a phytopathogenic fungi and/or insects and/or acarids and/or nematodes by the use or employment of a biological control agent.
  • biological control agent is defined as an organism other than the harmful organisms and / or proteins or secondary metabolites produced by such an organism for the purpose of biological control. Mutants of the second organism shall be included within the definition of the biological control agent.
  • mutant refers to a variant of the parental strain as well as methods for obtaining a mutant or variant in which the pesticidal activity is greater than that expressed by the parental strain.
  • the ’’parent strain“ is defined herein as the original strain before mutagenesis.
  • the parental strain may be treated with a chemical such as N-methyl-N'-nitro-N-nitrosoguanidine, ethylmethanesulfone, or by irradiation using gamma, x-ray, or UV-irradiation, or by other means well known to those skilled in the art.
  • a chemical such as N-methyl-N'-nitro-N-nitrosoguanidine, ethylmethanesulfone, or by irradiation using gamma, x-ray, or UV-irradiation, or by other means well known to those skilled in the art.
  • Known mechanisms of biological control agents comprise enteric bacteria that control root rot by out-competing fungi for space on the surface of the root.
  • Bacterial toxins, such as antibiotics have been used to control pathogens.
  • the toxin can be isolated and applied directly to the plant or the bacterial species may be administered so it produces the toxin in situ.
  • a ’’variant is a strain having all the identifying characteristics of the NRRL or ATCC Accession Numbers as indicated in this text and can be identified as having a genome that hybridizes under conditions of high stringency to the genome of the NRRL or ATCC Accession Numbers.
  • Hybridization refers to a reaction in which one or more polynucleotides react to form a complex that is stabilized via hydrogen bonding between the bases of the nucleotide residues.
  • the hydrogen bonding may occur by Watson-Crick base pairing, Hoogstein binding, or in any other sequence-specific manner.
  • the complex may comprise two strands forming a duplex structure, three or more strands forming a multi- stranded complex, a single self-hybridizing strand, or any combination of these.
  • Hybridization reactions can be performed under conditions of different “stringency”. In general, a low stringency hybridization reaction is carried out at about 40 °C in 10 X SSC or a solution of equivalent ionic strength/temperature. A moderate stringency hybridization is typically performed at about 50 °C in 6 X SSC, and a high stringency hybridization reaction is generally performed at about 60 °C in 1 X SSC.
  • a variant of the indicated NRRL or ATCC Accession Number may also be defined as a strain having a genomic sequence that is greater than 85%, more preferably greater than 90% or more preferably greater than 95% sequence identity to the genome of the indicated NRRL or ATCC Accession Number.
  • a polynucleotide or polynucleotide region (or a polypeptide or polypeptide region) has a certain percentage (for example, 80%, 85%, 90%, or 95%) of “sequence identity” to another sequence means that, when aligned, that percentage of bases (or amino acids) are the same in comparing the two sequences. This alignment and the percent homology or sequence identity can be determined using software programs known in the art, for example, those described in Current Protocols in Molecular Biology (F. M. Ausubel et al., eds., 1987).
  • NRRL is the abbreviation for the Agricultural Research Service Culture Collection, an international depositary authority for the purposes of deposing microorganism strains under the Budapest treaty on the international recognition of the deposit of microorganisms for the purposes of patent procedure, having the address National Center for Agricultural Utilization Research, Agricultural Research service, U.S. Department of Agriculture, 1815 North university Street, Peroira, Illinois 61604 USA.
  • ATCC is the abbreviation for the American Type Culture Collection, an international depositary authority for the purposes of deposing microorganism strains under the Budapest treaty on the international recognition of the deposit of microorganisms for the purposes of patent procedure, having the address ATCC Patent Depository, 10801 University Boulevard., Manassas, VA 10110 USA.
  • biological control agents which may be combined with the compound and the composition of the invention are:
  • Antibacterial agents selected from the group of:
  • (Al) bacteria such as (ATI) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661, U.S. Patent No. 6,060,051);
  • Bacillus subtilis strain BU1814 (available as VELONDIS ® PLUS, VELONDIS ® FLEX and VELONDIS ® EXTRA from BASF SE);
  • Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC, a subsidiary of Mitsui & Co.;
  • Paenibacillus polymyxa in particular strain AC-1 (e.g.
  • Pseudomonas proradix e.g. PRORADIX ® from Sourcon Padena
  • Al.l l Pantoea agglomerans, in particular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICALTM FD BIOPESTICIDE from Northwest Agri Products); and
  • (A2) fungi such as (A2.1) Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 ormixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR ® and BLOSSOM PROTECT ® from bio-ferm, CH); (A2.2) Pseudozyma aphidis (as disclosed in WO2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem); (A2.3) Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR;
  • (Bl) bacteria for example (Bl.l) 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);
  • Bacillus amyloliquefaciens in particular strain D747 (available as Double NickelTM from Kumiai Chemical Industry Co., Ltd., having accession number FERM BP-8234, US Patent 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); (B 1.7) Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF SE), having Accession Number NRRL B-50595, U.S. Patent No. 5,061,495; (B1.8) Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE); (B 1.9) Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No.
  • DSM 10271 (available from Novozymes as TAEGRO ® or TAEGRO ® ECO (EPA Registration No. 70127- 5)); (B1.10) Bacillus mycoides, isolate J , having Accession No. B-30890 (available as BMJ TGAI ® or WG and LifeGardTM from Certis USA LLC, a subsidiary of Mitsui & Co.); (Bl.l 1) Bacillus licheniformis, in particular strain SB3086 , having Accession No. ATCC 55406, WO 2003/000051 (available as ECOGUARD ® Biofungicide and GREEN RELEAFTM from Novozymes); (B1.12) a Paenibacillus sp. strain having Accession No.
  • Bacillus amyloliquefaciens strain FZB42 Bacillus amyloliquefaciens strain FZB42, Accession No. DSM 23117 (available as RHIZOVITAL ® from ABiTEP, DE); (B1.17) Bacillus licheniformis FMCHOOl and Bacillus subtilis FMCH002 (QUARTZO ® (WG) and PRESENCE ® (WP) from FMC Corporation); (Bl.l 8) Bacillus mojavensis strain R3B (Accession No.
  • NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC, a subsidiary of Mitsui & Co.; (B1.19) Paenibacillus polymyxa ssp. plantarum (WO 2016/020371) from BASF SE; (B1.20) Paenibacillus epiphyticus (WO 2016/020371) from BASF SE; (B.1.21) Pseudomonas chlororaphis strain AFS009, having Accession No.
  • NRRL B-50897, WO 2017/019448 e.g., HOWLERTM and ZIO ® from AgBiome Innovations, US
  • B1.22 Pseudomonas chlororaphis, in particular strain MA342 (e.g. CEDOMON ® , CERALL ® , and CEDRESS ® by Bioagri and Koppert);
  • B1.23 Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO-IRON ® and ACTINOVATE ® from Novozymes);
  • B1.24 Agrobacterium radiobacter strain K84 (e.g.
  • (B2) fungi for example: (B2.1) Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM-9660; e.g. Contans ® from Bayer CropScience Biologies GmbH); (B2.2) Metschnikowia fructicola, in particular strain NRRL Y-30752; (B2.3) Microsphaeropsis ochracea; (B2.5) Trichoderma atroviride, in particular strain SCI (having Accession No. CBS 122089, WO 2009/116106 and U.S. Patent No. 8,431,120 (from Bi-PA)), strain 77B (T77 from Andermatt Biocontrol) or strain LU132 (e.g.
  • Trichoderma harzianum strain T-22 e.g. Trianum-P from Andermatt Biocontrol or Koppert
  • strain Cepa Simb-T5 from Simbiose Agro
  • Gliocladium roseum also known as Clonostachys rosea f. rosea
  • strain 321U from Adjuvants Plus
  • strain ACM941 as disclosed in Xue (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 83(3): 519-524), or strain IK726 (Jensen DF, et al.
  • Trichoderma atroviride strain ATCC 20476 (IMI 206040); (B2.45) Trichoderma atroviride, strain Til (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 asperellum, in particular, strain kd (e.g. T-Gro from Andermatt Biocontrol); (B2.50) Trichoderma harzianum, strain ITEM 908 (e.g.
  • Trianum-P Trianum-P from Koppert
  • B2.51 Trichoderma harzianum, strain TH35 (e.g. Root-Pro by Mycontrol);
  • Trichoderma virens also known as Gliocladium virens), in particular strain GL-21 (e.g. SoilGard by Certis, US);
  • B2.53 Trichoderma viride, strain TVl(e.g. Trianum-P by Koppert);
  • Ampelomyces quisqualis in particular strain AQ 10 (e.g.
  • NM 99/06216 e.g., BOTRY- ZEN ® by Botry-Zen Ltd, New Zealand and BOTRYSTOP ® from BioWorks, Inc.
  • Verticillium albo-atrum (formerly V dahliae), strain WCS850 having Accession No. WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG ® by Tree Care Innovations);
  • Verticillium chlamydosporium B2.87) mixtures of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012), having Accession No.
  • CABI CC IMI 392716 and Trichoderma gamsii (formerly T. viride) strain ICC 080 having Accession No. IMI 392151 (e.g., BIO-TAMTM from Isagro USA, Inc. and BIODERMA ® by Agrobiosol de Mexico, S.A. de C.V.); (B2.88) Trichoderma asperelloides IM41R (Accession No. NRRL B-50759) (TRICHO PUUS ® from BASF SE); (B2.89) Aspergillus flavus strain NRRL 21882 (products known as AFLA-GUARD ® from Syngenta/ChemChina); (B2.90) Chaetomium cupreum (Accession No.
  • CABI 353812 (e.g. BIOKUPRUMTM by AgriLife); (B2.91) Saccharomyces cerevisiae, in particular strain LAS02 (from Agro-Levures et Derives), strain LAS 117 cell walls (CEREVISANE ® from Lesaffre; ROMEO ® from BASF SE), strains CNCM No. I- 3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR; (B2.92) Trichoderma virens strain G-41, formerly known as Gliocladium virens (Accession No.
  • ATCC 20906 (e.g., ROOTSHIELD ® PLUS WP and TURFSHIELD ® PLUS WP from BioWorks, US); (B2.93) Trichoderma hamatum, having Accession No. ATCC 28012; (B2.94) Ampelomyces quisqualis strain AQ 10, having Accession No.
  • CNCMI-807 e.g., AQ 10 ® by IntrachemBio Italia
  • B2.95 Phlebiopsis gigantea strain VRA 1992 (ROTSTOP ® C from Danstar Ferment);
  • B2.96 Penicillium steckii (DSM 27859; WO 2015/067800) from BASF SE;
  • B2.97 Chaetomium glohosum (available as RIVADIOM ® by Rivale);
  • B2.99) Dactylaria Candida (B2.100) Dilophosphora alopecuri (available as TWIST FUNGUS ® );
  • B2.101 Fusarium oxysporum, strain Fo47 (available as FUSACLEAN ® by Natural Plant Protection);
  • B2.102 Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX ® L by Plant
  • strain ICC 080 IMI CC 392151 CABI
  • BIODERMA ® AGROBIOSOL DE MEXICO, S .A. DE C.V.
  • B2.104 Trichoderma fertile (e.g. product TrichoPlus from BASF);
  • B2.105 Muscodor roseus, in particular strain A3-5 (Accession No. NRRL 30548);
  • B2.106 Simplicillium lanosoniveum; biological control agents having an effect for improving plant growth and/or plant health which may be combined in the compound combinations according to the invention including
  • (Cl) bacteria selected from the group consisting of Bacillus pumilus, in particular strain QST2808 (having Accession No. NRRL No. B-30087); Bacillus suhtilis, in particular strain QST713/AQ713 (having NRRL Accession No. B-21661and described in U.S. Patent No. 6,060,051; available as SERENADE ® OPTI or SERENADE ® ASO from Bayer CropScience LP, US); Bacillus suhtilis, in particular strain AQ30002 (having Accession Nos. NRRL B-50421 and described in U.S. Patent Application No.
  • Bacillus mycoides EE118 (NRRL No. B-50918), Bacillus mycoides EE141 (NRRL No. B-50916), Bacillus mycoides BT46-3 (NRRL No. B-50922), Bacillus cereus family member EE128 (NRRL No. B-50917), Bacillus thuringiensis BT013A (NRRL No. B-50924) also known as Bacillus thuringiensis 4Q7, Bacillus cereus family member EE349 (NRRL No.
  • Bacillus amyloliquefaciens SB3281 ATCC # PTA- 7542; WO 2017/205258
  • Bacillus amyloliquefaciens TJ1000 available as QUIKROOTS ® from Novozymes
  • Bacillus firmus in particular strain CNMC 1-1582 (e.g. VOTIVO ® from BASL SE)
  • Bacillus pumilus in particular strain GB34 (e.g. YIELD SHIELD ® from Bayer Crop Science, DE); Bacillus amyloliquefaciens, in particular strain IN937a; Bacillus amyloliquefaciens, in particular strain FZB42 (e.g.
  • RHIZOVITAL ® from ABiTEP, DE
  • Bacillus amyloliquefaciens BS27 (Accession No. NRRL B-5015); a mixture of Bacillus licheniformis FMCHOOl and Bacillus subtilis FMCH002 (available as QUARTZO ® (WG), PRESENCE ® (WP) from FMC Corporation); Bacillus cereus, in particular strain BP01 (ATCC 55675; e.g. MEPICHLOR ® from Arysta Lifescience, US); Bacillus subtilis, in particular strain MBI 600 (e.g. SUBTILEX ® from BASF SE); Bradyrhizobium japonicum (e.g.
  • OPTIMIZE ® from Novozymes Mesorhizobium cicer (e.g., NODULATOR from BASF SE); Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE); Delftia acidovorans, in particular strain RAY209 (e.g. BIOBOOST ® from Brett Young Seeds); Lactobacillus sp. (e.g. LACTOPLANT ® from LactoPAFI); Paenibacillus polymyxa, in particular strain AC-1 (e.g. TOPSEED ® from Green Biotech Company Ltd.); Pseudomonas proradix (e.g.
  • PRORADIX ® from Sourcon Padena
  • Azospirillum brasilense e.g., VIGOR ® from KALO, Inc.
  • Azospirillum lipoferum e.g., VERTEX-IFTM from TerraMax, Inc.
  • a mixture of Azotobacter vinelandii and Clostridium pasteurianum available as INVIGORATE ® from Agrinos
  • Pseudomonas aeruginosa in particular strain PN 1 ; Rhizobium leguminosarum, in particular bv. viceae strain Z25 (Accession No.
  • C2 fungi selected from the group consisting of Purpureoci Ilium lilacinum (previously known as Paecilomyces lilacinus) strain 251 (AGAL 89/030550; e.g. BioAct from Bayer CropScience Biologies GmbH)Penicillium bilaii, strain ATCC 22348 (e.g. JumpStart ® from Acceleron BioAg), Talaromyces flavus, strain VI 17b; Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR), Trichoderma viride, e.g.
  • Trichoderma atroviride strain LC52 also known as Trichoderma atroviride strain LU132; e.g. Sentinel from Agrimm Technologies Limited
  • Trichoderma asperellum strain kd e.g. T-Gro from Andermatt Biocontrol
  • Trichoderma asperellum strain Eco-T Plantt Health Products, ZA
  • Trichoderma harzianum strain T-22 e.g.
  • Trianum-P from Andermatt Biocontrol or Koppert Myrothecium verrucaria strain AARC-0255 (e.g. DiTeraTM from Valent Biosciences); Penicillium bilaii strain ATCC ATCC20851; Pythium oligandrum strain Ml (ATCC 38472; e.g. Polyversum from Bioprepraty, CZ); Trichoderma virens strain GL-21 (e.g. SoilGard® from Certis, USA); Verticillium albo-atrum (formerly V dahliae) strain WCS850 (CBS 276.92; e.g. Dutch Trig from Tree Care Innovations); Trichoderma atroviride, in particular strain no.
  • AARC-0255 e.g. DiTeraTM from Valent Biosciences
  • Penicillium bilaii strain ATCC ATCC20851 e.g. Polyversum from Bioprepraty, CZ
  • (Dl) bacteria selected from the group consisting of Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372; e.g. XENTARI ® from Valent BioSciences); Bacillus mycoides, isolate J. (e.g. BmJ from Certis USA LLC, a subsidiary of Mitsui & Co.); Bacillus sphaericus, in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. VECTOLEX ® from Valent BioSciences, US); Bacillus thuringiensis subsp.
  • israelensis strain BMP 144 (e.g.
  • Burkholderia spp. in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319; WO 2011/106491 and WO 2013/032693; e.g. MBI-206 TGAI and ZELTO ® from Marrone Bio Innovations); Chromobacterium subtsugae, in particular strain PRAA4-1T (MBI-203; e.g.
  • GRANDEVO GRANDEVO ® from Marrone Bio Innovations
  • Paenibacillus popilliae (formerly Bacillus popilliae, ⁇ e.g. MILKY SPORE POWDERTM and MILKY SPORE GRANULARTM from St. Gabriel Laboratories);
  • Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC ® by Valent BioSciences, US); Bacillus thuringiensis var. kurstaki strain EVB-113-19 (e.g., BIOPROTEC ® from AEF Global); Bacillus thuringiensis subsp.
  • tenebrionis strain NB 176 SD-5428; e.g. NOVODOR ® FC from BioFa DE
  • Bacillus thuringiensis var. japonensis strain Buibui Bacillus thuringiensis subsp. kurstaki strain ABTS 351; Bacillus thuringiensis subsp. kurstaki strain PB 54; Bacillus thuringiensis subsp. kurstaki strain SA 11; Bacillus thuringiensis subsp. kurstaki strain SA 12; Bacillus thuringiensis subsp. kurstaki strain EG 2348; Bacillus thuringiensis var. Colmeri (e.g.
  • 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;
  • (L) bacteria and fungi which can be added as 'inoculanf 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.
  • G 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, mr/mr/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, as well as bioinsecticidal / acaricidal active substances obtained from olive oil, in particular unsaturated fatty/carboxylic acids having carbon chain lengths C16-C20 as active ingredients, such as, for example, contained in the product with the trade name FLiPPER®.
  • insects may be combined with one or more active ingredients selected from insecticides, acaricides and nematicides.
  • active ingredients selected from insecticides, acaricides and nematicides.
  • Insecticides as well as the term “insecticidal” refers to the ability of a substance to increase mortality or inhibit growth rate of insects.
  • insects comprises all organisms in the class “Insecta”.
  • nematode and “nematicidal” refers to the ability of a substance to increase mortality or inhibit the growth rate of nematodes.
  • nematode comprises eggs, larvae, juvenile and mature forms of said organism.
  • Acaricide and “acaricidal” refers to the ability of a substance to increase mortality or inhibit growth rate of ectoparasites belonging to the class Arachnida, sub-class Acari.
  • insecticides examples include insecticides, acaricides and nematicides, respectively, which could be mixed with the compound and the composition of the invention 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 [(lR)-trans-isomer], deltamethrin, empenthrin [(EZ)-(lR)-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.
  • 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 (GluCl) 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 sulphuryl 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 tenehrionis, and B.t. plant proteins: CrylAb, CrylAc, CrylFa, CrylA.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Abl/35Abl.
  • 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 ortetradifon.
  • ATP disruptors such as, for example, diafenthiuron or organotin compounds, for example azocyclotin, cyhexatin and fenbutatin oxide or propargite ortetradifon.
  • 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, fteto-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, Fluxamet
  • - propanamide known from WO 2013/162715 A2, WO 2013/162716 A2, US 2014/0213448 Al
  • herbicides which could be mixed with the compound and the composition of the invention are:
  • plant growth regulators are:
  • safeners which could be mixed with the compound and the composition of the invention 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 ⁇ - sulphonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-l-oxa-4-azaspiro[4.5]decane (CAS 71526- 07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-l,3-oxazolidine (
  • nitrification inhibitors which can be mixed with the compound and the composition of the invention are selected from the group consisting of 2-(3, 4-dimethyl- 1 H-pyrazol-1 -yl)succinic acid, 2- (4,5-dimethyl-l H-pyrazol-1 -yl)succinic acid, 3,4-dimethyl pyrazolium glycolate, 3,4-dimethyl pyrazolium citrate, 3,4-dimethyl pyrazolium lactate, 3,4-dimethyl pyrazolium mandelate, 1 ,2,4-triazole, 4-Chloro-3-methylpyrazole, N-((3(5)-methyl-lH-pyrazole-l-yl)methyl)acetamide, N-((3(5)-methyl-l H- pyrazole-l-yl)methyl)formamide, N-((3(5),4-dimethylpyrazole-l-yl)methyl)formamide, N-((4-chloro- 3(5)-methyl-methyl
  • the compound and the composition of the invention may be combined with one or more agriculturally beneficial agents.
  • agriculturally beneficial agents include biostimulants, plant growth regulators, plant signal molecules, growth enhancers, microbial stimulating molecules, biomolecules, soil amendments, nutrients, plant nutrient enhancers, etc., such as lipo-chitooligosaccharides (LCO), chitooligosaccharides (CO), chitinous compounds, flavonoids, jasmonic acid or derivatives thereof (e.g., jasmonates), cytokinins, auxins, gibberellins, absiscic acid, ethylene, brassinosteroids, salicylates, macro- and micro-nutrients, linoleic acid or derivatives thereof, linolenic acid or derivatives thereof, karrikins, and beneficial microorganisms (e.g., Rhizobium spp., Bradyrhizobium spp., Sinorhizobium spp., Azorhizobium spp., Glomus spp., Gigaspora
  • Arlhrobacler spp. Arthrobotrys spp., Aspergillus spp., Azospirillum spp., Bacillus spp., Burkholderia spp., Candida spp., Chryseomonas spp., Enterobacter spp., Eupenicillium spp., Exiguobacterium spp., Klebsiella spp., Kluyvera spp., Microbacterium spp., Mucor spp., Paecilomyces spp., Paenibacillus spp., Penicillium spp., Pseudomonas spp., Serratia spp., Stenotrophomonas spp., Streptomyces spp., Streptosporangium spp., Swaminathania spp., Thiobacillus spp., Torulospora
  • the compound and the composition of the invention have potent microbicidal activity and/or plant defense modulating potential. They can be used for controlling unwanted microorganisms, such as unwanted fungi and bacteria, on plants. 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 compound and the composition of the invention 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 compound and the composition of the invention can be used as fungicides.
  • 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.
  • the compound and the composition of the invention may also be used as antibacterial agent.
  • they may be used in crop protection, for example for the control of unwanted bacteria, such as Pseudomonadaceae, Rhizobiaceae, Xanthomonadaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae .
  • the compound and the composition of the invention may also be used as antiviral agent in crop protection.
  • the compound and the composition of the invention may have effects on diseases from plant viruses, such as the tobacco mosaic virus (TMV), tobacco rattle virus, tobacco stunt virus (TStuV), tobacco leaf curl virus (VLCV), tobacco nervilia mosaic virus (TVBMV), tobacco necrotic dwarf virus (TNDV), tobacco streak virus (TSV), potato virus X (PVX), potato viruses Y, S, M, and A, potato acuba mosaic virus (PAMV), potato mop-top virus (PMTV), potato leaf-roll virus (PLRV), alfalfa mosaic virus (AMV), cucumber mosaic virus (CMV), cucumber green mottlemosaic virus (CGMMV), cucumber yellows virus (CuYV), watermelon mosaic virus (WMV), tomato spotted wilt virus (TSWV), tomato ringspot virus (TomRSV), sugarcane mosaic virus (SCMV), rice drawf virus, rice stripe virus, rice black- streaked drawf virus, strawberry mo
  • the present invention also relates to a method for controlling unwanted microorganisms, such as unwanted fungi, oomycetes and bacteria, on plants comprising the step of applying at least one compound of the invention or at least one composition of the invention 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 unwanted 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 compound and the composition of the invention 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 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.
  • Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoots, leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, 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
  • 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.
  • Plants and plant cultivars which may 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 may 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 may be treated by the above disclosed methods include those plants characterized by enhanced yield characteristics. Increased yield in said plants may 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 may 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, intemode 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 may 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.
  • the compound according to the invention can be advantageously used to treat transgenic plants, plant cultivars or plant parts that received genetic material which imparts advantageous and/or useful properties (traits) to these plants, plant cultivars or plant parts. Therefore, it is contemplated that the present invention may be combined with one or more recombinant traits or transgenic event(s) or a combination thereof.
  • a transgenic event is created by the insertion of a specific recombinant DNA molecule into a specific position (locus) within the chromosome of the plant genome.
  • the insertion creates a novel DNA sequence referred to as an “event” and is characterized by the inserted recombinant DNA molecule and some amount of genomic DNA immediately adjacent to/flanking both ends of the inserted DNA.
  • trait(s) or transgenic event(s) include, but are not limited to, pest resistance, water use efficiency, yield performance, drought tolerance, seed quality, improved nutritional quality, hybrid seed production, and herbicide tolerance, in which the trait is measured with respect to a plant lacking such trait or transgenic event.
  • Such advantageous and/or useful properties are better plant growth, vigor, stress tolerance, standability, lodging resistance, nutrient uptake, plant nutrition, and/or yield, in particular improved growth, increased tolerance to high or low temperatures, increased tolerance to drought or to levels of water or soil salinity, enhanced flowering performance, easier harvesting, accelerated ripening, higher yields, higher quality and/or a higher nutritional value of the harvested products, better storage life and/or processability of the harvested products, and increased resistance against animal and microbial pests, such as against insects, arachnids, nematodes, mites, slugs and snails.
  • Bt Cry or VIP proteins which include the CrylA, CrylAb, CrylAc, CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF proteins or toxic fragments thereof and also hybrids or combinations thereof, especially the CrylF protein or hybrids derived from a CrylF protein (e.g. hybrid CrylA-CrylF proteins or toxic fragments thereof), the CrylA-type proteins or toxic fragments thereof, preferably the CrylAc protein or hybrids derived from the CrylAc protein (e.g.
  • hybrid CrylAb-CrylAc proteins or the CrylAb or Bt2 protein or toxic fragments thereof, the Cry2Ae, Cry2Af or Cry2Ag proteins or toxic fragments thereof, the CrylA.105 protein or a toxic fragment thereof, the VIP3Aal9 protein, the VIP3Aa20 protein, the VIP3A proteins produced in the COT202 or COT203 cotton events, the VIP3Aa protein ora toxic fragment thereof as described in Estruch et al. (1996), Proc Natl Acad Sci US A.
  • Another and particularly emphasized example of such properties is conferred tolerance to one or more herbicides, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin.
  • herbicides for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin.
  • DNA sequences encoding proteins which confer properties of tolerance to certain herbicides on the transformed plant cells and plants mention will be particularly be made to the bar or PAT gene or the Streptomyces coelicolor gene described in WO2009/152359 which confers tolerance to glufosinate herbicides, a gene encoding a suitable EPSPS (5-Enolp ⁇ Tuv ⁇ lshikimat-3-phosphat- nthasc) which confers tolerance to herbicides having EPSPS as a target, especially herbicides such as glyphosate and its salts, a gene encoding glyphosate-
  • herbicide tolerance traits include at least one ALS (acetolactate synthase) inhibitor (e.g. W02007/024782), a mutated Arabidopsis ALS/AHAS gene (e.g. U.S. Patent 6,855,533), genes encoding 2,4-D- monooxygenases conferring tolerance to 2,4-D (2,4- dichlorophenoxyacetic acid) and genes encoding Dicamba monooxygenases conferring tolerance to dicamba (3,6-dichloro-2- methoxybenzoic acid).
  • ALS acetolactate synthase
  • W02007/024782 e.g. W02007/024782
  • a mutated Arabidopsis ALS/AHAS gene e.g. U.S. Patent 6,855,533
  • Yet another example of such properties is resistance to one or more phytopathogenic fungi, for example Asian Soybean Rust.
  • DNA sequences encoding proteins which confer properties of resistance to such diseases mention will particularly be made of the genetic material from glycine tomentella, for example from any one of publically available accession lines PI441001 , PI483224, PI583970, PI446958, PI499939, PI505220, PI499933, PI441008, PI505256 or PI446961 as described in W02019/103918.
  • SAR systemic acquired resistance
  • phytoalexins phytoalexins
  • elicitors resistance genes and correspondingly expressed proteins and toxins.
  • Particularly useful transgenic events in transgenic plants or plant cultivars which can be treated with preference in accordance with the invention include Event 531/ PV-GHBK04 (cotton, insect control, described in W02002/040677), Event 1143-14A (cotton, insect control, not deposited, described in WO2006/128569); Event 1143-5 IB (cotton, insect control, not deposited, described in W02006/128570); Event 1445 (cotton, herbicide tolerance, not deposited, described in US-A 2002- 120964 or W02002/034946); Event 17053 (rice, herbicide tolerance, deposited as PTA-9843, described in WO2010/117737); Event 17314 (rice, herbicide tolerance, deposited as PTA-9844, described in WO2010/117735); Event 281-24-236 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in W02005/103266 or US-A 2005-216969); Event 3006-210-23 (cotton, insect control - herb
  • Event BLR1 (oilseed rape, restoration of male sterility, deposited as NCIMB 41193, described in W02005/074671), Event CE43-67B (cotton, insect control, deposited as DSM ACC2724, described in US-A 2009-217423 or WO2006/128573); Event CE44-69D (cotton, insect control, not deposited, described in US-A 2010- 0024077); Event CE44-69D (cotton, insect control, not deposited, described in WO2006/128571); Event CE46-02A (cotton, insect control, not deposited, described in WO2006/128572); Event COT102 (cotton, insect control, not deposited, described in US-A 2006-130175 or W02004/039986); Event COT202 (cotton, insect control, not deposited, described in US-A 2007-067868 or W02005/054479); Event COT203 (cotton, insect control, not deposited, described, described in US-A 2007-067868 or
  • event DP-040416-8 (com, insect control, ATCC Accession N° PTA-11508, WO2011/075593A1), event DP-043A47-3 (com, insect control, ATCC Accession N° PTA-11509, WO2011/075595A1), event DP- 004114-3 (com, insect control, ATCC Accession N° PTA-11506, WO2011/084621A1), event DP-032316-8 (com, insect control, ATCC Accession N° PTA-11507, WO2011/084632A1), event MON-88302-9 (oilseed rape, herbicide tolerance, ATCC Accession N° PTA-10955, WO2011/153186A1), event DAS-21606-3 (soybean, herbicide tolerance, ATCC Accession No.
  • transgenic event(s) is provided by the United States Department of Agriculture’s (USDA) Animal and Plant Health Inspection Service (APHIS) and can be found on their website on the world wide web at anhis.usda.gov. For this application, the status of such list as it is/was on the fding date of this application, is relevant.
  • USDA United States Department of Agriculture
  • APIHIS Animal and Plant Health Inspection Service
  • transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice, triticale, barley, rye, oats), maize, soya beans, potatoes, sugar beet, sugar cane, tomatoes, peas and other types of vegetable, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), with particular emphasis being given to maize, soya beans, wheat, rice, potatoes, cotton, sugar cane, tobacco and oilseed rape.
  • Traits which are particularly emphasized are the increased resistance of the plants to insects, arachnids, nematodes and slugs and snails, as well as the increased resistance of the plants to one or more herbicides.
  • Non-limiting examples of pathogens of fungal diseases which may be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis, Podosphaera species, for example Podosphaera leucotricha Sphaerotheca species, for example Sphaerotheca fuliginea ; Uncinula species, for example Uncinula necator ; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae Hemileia species, for example Hemileia vastatrix Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striiformis ; Uromyces species, for example Uromyces appendiculatus
  • Pseudomonas species for example Pseudomonas syringae pv. lachrymans
  • Erwinia species for example Erwinia amylovora
  • Liberibacter species for example Liberibacter asiaticus
  • Xyella species for example Xylella fastidiosa
  • Ralstonia species for example Ralstonia solanacearum
  • Dickeya species for example Dickeya solani, Clavibacter species, for example Clavibacter michiganensis
  • Streptomyces species for example Streptomyces scabies. diseases of soya beans:
  • Rhizoctonia solani sclerotinia stem decay ( Sclerotinia sclerotiorum), sclerotinia southern blight ( Sclerotinia rolfsii), thielaviopsis root rot ( Thielaviopsis basicola).
  • the compound and the composition of the invention may reduce the mycotoxin content in the harvested material and the foods and feeds prepared therefrom.
  • Mycotoxins include particularly, but not exclusively, the following: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2- toxin, fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol (DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins which can be produced, for example, by the following fungi: Fusarium spec., such as F.
  • verticillioides and also by Aspergillus spec., such a A.flavus, A. parasiticus, A. nomius,A. ochraceus, A. clavatus,A. terreus,A. versicolor, Penicillium spec., such asP. verrucosum,P. viridicatum,P. citrinum, P. expansum, P. claviforme, P. roqueforti, Claviceps spec., such as C. purpurea, C. fusiformis, C. paspali, C. africana, Stachybotrys spec and others.
  • Penicillium spec. such asP. verrucosum,P. viridicatum,P. citrinum, P. expansum, P. claviforme, P. roqueforti
  • Claviceps spec. such as C. purpurea, C. fusiformis, C
  • 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 phytopathogenic fungi.
  • 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 signalling 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 Alternaria 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
  • the compound and the composition of the invention may also be used to protect seeds from unwanted microorganisms, such as phytopathogenic microorganisms, for instance phytopathogenic fungi or phytopathogenic oomycetes.
  • seedfsf as used herein include dormant seeds, primed seeds, pregerminated seeds and seeds with emerged roots and leaves.
  • the present invention also relates to a method for protecting seeds from unwanted microorganisms which comprises the step of treating the seeds with the compound or the composition of the invention.
  • the treatment of seeds with the compound or the composition of the invention protects the seeds from phytopathogenic microorganisms, but also protects the germinating seeds, the emerging seedlings and the plants after emergence from the treated seeds. Therefore, the present invention also relates to a method for protecting seeds, germinating seeds and emerging seedlings.
  • 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 the compound or the composition of the invention, the seeds and the compound or the composition of the invention are mixed until an homogeneous distribution on seeds is achieved. If appropriate, the seeds may then be dried.
  • the invention also relates to seeds coated with the compound or the composition of the invention.
  • the seeds are 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 the compound or the composition of the invention applied to the seeds 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 compound of the invention 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 the compound of the invention to be applied to the seed in order to achieve optimum seed and germinating plant protection with a minimum amount of compound being employed.
  • the compound of the invention can be applied as such, directly to the seeds, i.e. without the use of any other components and without having been diluted. Also the composition of the invention can be applied to the seeds.
  • the compound and the composition of the invention are suitable for protecting seeds of any plant variety.
  • Preferred seeds are 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. More preferred are seeds of wheat, soybean, oilseed rape, maize and rice.
  • the compound and the composition of the invention may be used for treating transgenic seeds, in particular seeds of plants capable of expressing a polypeptide or protein which acts against pests, herbicidal damage or abiotic stress, thereby increasing the protective effect.
  • Seeds of plants capable of expressing a polypeptide or protein which acts against pests, herbicidal damage or abiotic stress may contain at least one heterologous gene which allows the expression of said polypeptide or protein.
  • These heterologous genes in transgenic seeds may originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • These heterologous genes preferably originate from Bacillus sp., in which case the gene product is effective against the European com borer and/or the Western com rootworm.
  • the heterologous genes originate from Bacillus thuringiensis.
  • the compound of the invention 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 the invention, synthetic substances impregnated with the compound of the invention, fertilizers or microencapsulations in polymeric substances.
  • Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming or spreading -on. It is also possible to deploy the compound of the invention by the ultra-low volume method, via a drip irrigation system or drench application, to apply it in-furrow or to inject it into the soil stem or trunk. It is further possible to apply the compound of the invention by means of a wound seal, paint or other wound dressing.
  • the effective and plant-compatible amount of the compound of the invention 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 can be used in combination with models e.g. embedded in computer programs for site specific crop management, satellite farming, precision farming or precision agriculture.
  • models support the site specific management of agricultural sites with data from various sources such as soils, weather, crops (e.g. type, growth stage, plant health), weeds (e.g. type, growth stage), diseases, pests, nutrients, water, moisture, biomass, satellite data, yield etc. with the purpose to optimize profitability, sustainability and protection of the environment.
  • crops e.g. type, growth stage, plant health
  • weeds e.g. type, growth stage
  • diseases, pests, nutrients, water, moisture, biomass, satellite data, yield etc. with the purpose to optimize profitability, sustainability and protection of the environment.
  • such models can help to optimize agronomical decisions, control the precision of pesticide applications and record the work performed.
  • the compound of the invention can be applied to a crop plant according to appropriate dose regime if a model models the development of a fungal disease and calculates that a threshold has been reached for which it is recommendable to apply the compound of the invention to the crop plant.
  • the compound of the invention can also be used in combination with smart spraying equipment such as e.g. spot spraying or precision spraying equipment attached to or housed within a farm vehicle such as a tractor, robot, helicopter, airplane, unmanned aerial vehicle (UAV) such as a drone, etc.
  • a farm vehicle such as a tractor, robot, helicopter, airplane, unmanned aerial vehicle (UAV) such as a drone, etc.
  • UAV unmanned aerial vehicle
  • Such an equipment usually includes input sensors (such as e.g. a camera) and a processing unit configured to analyze the input data and configured to provide a decision based on the analysis of the input data to apply the compound of the invention to the crop plants (respectively the weeds) in a specific and precise manner.
  • the use of such smart spraying equipment usually also requires positions systems (e.g. GPS receivers) to localize recorded data and to guide or to control farm vehicles; geographic information systems (GIS) to represent the information on intelligible maps, and appropriate farm vehicles to perform the required farm action such
  • fungal diseases can be detected from imagery acquired by a camera.
  • fungal diseases can be identified and/or classified based on that imagery.
  • identification and/ classification can make use of image processing algorithms.
  • image processing algorithms can utilize machine learning algorithms, such as trained neutral networks, decision trees and utilize artificial intelligence algorithms. In this manner, the compounds described herein can be applied only where needed.
  • [aI 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).
  • [cI 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).
  • 'H-NMR data of selected examples as provided herein are written in form of 'H-N R-pcak lists. To each signal peak are listed the d-value in ppm and the signal intensity in round brackets. Between the d-value - signal intensity pairs are semicolons as delimiters.
  • the peak list of an example has therefore the form: di (intensityi); d 2 (intensity2); . ; d ⁇ (intensity ; . ; d h (intensity n )
  • 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 and/or the chemical shift of the solvent used especially in the case of spectra measured in dimethyl sulfoxide (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-fmgerprints”.
  • 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 'H-NMR interpretation.
  • Table 1 illustrates in a non-limiting manner examples of compounds of formula (I) according to the invention:
  • the compounds of formula (I) which are mentioned in table 1 herein below were prepared in accordance with the procedures detailed herein below in connection with specific examples and with the general description of the processes herein disclosed.
  • Table 2 provides the NMR data ( 1 H) of a selected number of compounds from table 1 .
  • the crude product was purified by reverse phase chromatography with the following conditions (column, C18 silica gel; mobile phase, CH3CN in water, 3% to 100% gradient in 30 minutes; detector, UV 254 nm) to afford 6-[(2- fluorophenyl)methyl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carbohydrazide (400 mg, 84%) as a yellow solid.
  • Step 3
  • Step 3
  • Step 3
  • Step 3
  • Step 5
  • Step 2 In a 25 mL 2-neck round bottom flask, ethyl 5-cyano-2-[[2-(2,6-difluorophenyl)anilino]methyl]pyridine- 3-carboxylate (200 mg, 0.5 mmol) was suspended in 6N aqueous solution of hydrochloric acid (12 mL), heated to 80°C and maintained for 23 hrs.
  • Step 3
  • reaction mixture was allowed to cool, added to ice/water with stirring, pH adjusted to 2 with 1M aqueous solution of hydrochloric acid.
  • the solids were filtered, washed with water and dried, to afford 6- [2-(2,6-difluorophenyl)phenyl]-3-(lH-tetrazol-5-yl)-7H-pyrrolo[3,4-b]pyridin-5-one (55mg, 68%) as a yellow solid.
  • Step 3
  • Step 5
  • N'-(2,2-difluoroacetyl)- l-oxo-2 -phenyl-3, 4-dihydroisoquinoline-7- carbohydrazide (268.2 mg, 0.74 mmol) was suspended in tetrahydrofuran (5 mL) under Argon. The suspension was cooled to 0°C, N, N-d i i s o p ro p y l c th y l am i n c (289.45 mg, 2.24 mmol) was added followed by addition of p-tosylchloride (355.8 mg, 1.86 mmol).
  • Emulsifier 1 m ⁇ of polyoxyethylene sorbitan monooleate (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.
  • Emulsifier Im ⁇ of polyoxyethylene sorbitan monooleate (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 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.
  • 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 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.

Abstract

The present invention relates to the use of 1,3,4-oxadiazole compounds for controlling harmful microorganisms, in particular phytopathogenic fungi, in crop protection.

Description

1.3.4-OXADIAZOLES AND THEIR DERIVATIVES AS FUNGICIDES
TECHNICAL FIELD
The present invention relates to the use of 1,3,4-oxadiazole compounds for controlling harmful microorganisms, in particular phytopathogenic fungi, in crop protection.
BACKGROUND
1.2.4-oxadiazoles derivatives are well known to be useful as crop protection agents to combat or prevent microorganisms’ infestations. For instance, WO-2018/118781 and WO-2018/080859 disclose 1,2,4- oxadiazol-3-ylpyrimidines and l,2,4-oxadiazol-3-ylpyridines derivatives that may be used for the control of microbial pests, particularly fungal pests, on plants. Fungicidally active 1,2,4-oxadiazoles are further known from US 2018/317490, WO-2017/076740 and WO 2019/155066.
1.3.4-oxadiazoles derivatives are far less common and seldomly used for the control of microbial pests. WO-2019/027054 and WO-2020/158762 disclose 1,3,4-oxadiazol compounds comprising a bicyclic partly aromatic heterocycle that have a HDAC inhibitory action and may be used for the treatment of central nervous diseases in humans. Some fungicidally active 1,3,4-oxadiazoles are disclosed in WO2020127974 and EP 0 152 021.
Numerous fungicidal agents have been developed until now. However, the need remains for the development of further fungicidal compounds, 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 identify further fungicidal compounds to prevent the emergence of fungicides resistances.
The present invention provides a new use of 1,3,4-oxadiazole compounds for controlling phytopathogenic fungi in crop protection, which has advantages over known uses of fungicidal compounds in at least some of these aspects.
SUMMARY
The present invention relates to the use of compounds of formula (I) for controlling harmful microorganisms, in particular phytopathogenic fungi, in crop protection:
Figure imgf000002_0001
(I) wherein R1, R2, R3, R4, R5, X, W1, W2, W3, m and n are as recited herein, as well as their salts, N-oxides and solvates.
The present invention also relates to a composition comprising at least one compound of formula (I) as defined herein and at least one agriculturally suitable auxiliary.
The present invention relates to a method for controlling harmful microorganisms in crop protection which comprises the step of applying at least one compound of formula (I) as defined herein or a composition as defined herein to the harmful microorganisms and/or their habitat.
DEFINITIONS
Unless otherwise stated, the following definitions apply for the substituents and residues used throughout this specification and claims:
The term “halogen” as used herein refers to fluorine, chlorine, bromine or iodine atom.
The term “oxo” as used herein refers to an oxygen atom which is bound to a carbon atom or sulfur atom via a double bound.
The term C1 -C8-alkyl as used herein refers to a saturated, branched or straight hydrocarbon chain having 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms. Examples of Ci -Cx-alkyl include but are not limited to methyl, ethyl, propyl (n-propyl), 1-methylethyl (iso-propyl), butyl (n-butyl), 1-methylpropyl (sec-butyl), 2-methylpropyl (iso-butyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2- trim ethy lp ropy 1 , 1,2,2-trimethylpropyl, 1 -ethyl- 1-methylpropyl and l-ethyl-2-methylpropyl. Preferably, said hydrocarbon chain has 1, 2, 3, 4, 5 or 6 carbon atoms (“C1 -C6-alkyl”). Particularly, said hydrocarbon chain has 1, 2, 3 or 4 carbon atoms (“C1-C4-alkyl”), e.g. methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl or tert-butyl.
The term “C2 -C8-alkenyl” as used herein refers to an unsaturated, branched or straight hydrocarbon chain having 2, 3, 4, 5, 6, 7 or 8 carbon atoms and comprising at least one double bond. Examples of CVCx- alkenyl include but are not limited to ethenyl (or "vinyl"), prop-2-en-l-yl (or "allyl"), prop-l-en-l-yl, but- 3-enyl, but-2-enyl, but-l-enyl, pent-4-enyl, pent-3-enyl, pent-2-enyl, pent-l-enyl, hex-5 -enyl, hex-4-enyl, hex-3-enyl, hex-2-enyl, hex- 1 -enyl, prop-l-en-2-yl (or "isopropenyl"), 2-methylprop-2-enyl, 1- methylprop-2-enyl, 2-methylprop-l-enyl, 1 -methylprop-l-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, 2-methylbut-2-enyl, l-methylbut-2-enyl, 3-methylbut-l-enyl, 2- methylbut-l-enyl, 1-methylbut-l-enyl, l,l-dimethylprop-2-enyl, 1-ethylprop-l-enyl, 1-propylvinyl, 1- isopropylvinyl, 4-methylpent-4-enyl, 3-methylpent-4-enyl, 2-methylpent-4-enyl, l-methylpent-4-enyl, 4- methylpent-3-enyl, 3-methylpent-3-enyl, 2-methylpent-3-enyl, l-methylpent-3-enyl, 4-methylpent-2- enyl, 3-methylpent-2-enyl, 2-methylpent-2-enyl, l-methylpent-2-enyl, 4-methylpent-l-enyl, 3- methylpent-l-enyl, 2-methylpent-l-enyl, 1-methylpent-l-enyl, 3-ethylbut-3-enyl, 2-ethylbut-3-enyl, 1- ethylbut-3-enyl, 3-ethylbut-2-enyl, 2-ethylbut-2-enyl, l-ethylbut-2-enyl, 3-ethylbut-l-enyl, 2-ethylbut-l- enyl, 1-ethylbut-l-enyl, 2-propylprop-2-enyl, l-propylprop-2-enyl, 2-isopropylprop-2-enyl, 1- isopropylprop-2-enyl, 2-propylprop-l-enyl, 1-propylprop-l-enyl, 2-isopropylprop-l-enyl, 1- isopropylprop-l-enyl, 3,3-dimethylprop-l-enyl, l-(l,l-dimethylethyl)ethenyl, buta-l,3-dienyl, penta-1,4- dienyl, hexa-l,5-dienyl or methylhexadienyl group.
The term C2 -C8-alkynyl as used herein refers to a branched or straight hydrocarbon chain having 2, 3, 4, 5, 6, 7 or 8 carbon atoms and comprising at least one triple bond. Examples of C2-C8-alkynyl include but are not limited to ethynyl, prop-l-ynyl, prop-2-ynyl (or "propargyl"), but-l-ynyl, but-2-ynyl, but-3- ynyl, pent-l-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-l-ynyl, hex-2 -ynyl, hex-3 -ynyl, hex-4-ynyl, hex-5-ynyl, l-methylprop-2-ynyl, 2-methylbut-3-ynyl, l-methylbut-3-ynyl, l-methylbut-2-ynyl, 3- methylbut-l-ynyl, l-ethylprop-2-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1 -methyl- pent-4-ynyl,
2-methylpent-3-ynyl, l-methylpent-3-ynyl, 4-methylpent-2-ynyl, 1 -methyl- pent-2 -ynyl, 4-methylpent-l- ynyl, 3-methylpent-l-ynyl, 2-ethylbut-3-ynyl, l-ethylbut-3-ynyl, l-ethylbut-2-ynyl, l-propylprop-2-ynyl, l-isopropylprop-2-ynyl, 2,2-dimethylbut-3-ynyl, l,l-dimethylbut-3-ynyl, l,l-dimethylbut-2-ynyl or 3,3- dimethylbut-l-ynyl group.
The term C1 -C8-haloalkyl as used herein refers to a C1 -C8-alkyl group as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different. Typically, C1 - C8-haloalkyl comprises up to 9 halogen atoms that can be the same or different.
The term “C2-C8-haloalkenyl” as used herein refers to a C2-C8-alkenyl group as defined above in which one or more hydrogen atoms are replaced with one or more halogen atoms that may be the same or different. Typically, C2-C8-haloalkenyl comprises up to 9 halogen atoms that can be the same or different.
The term “C2-C8-haloalkynyl” as used herein refers to a C2-C8-alkynyl group as defined above in which one or more hydrogen atoms are replaced with one or more halogen atoms that may be the same or different. Typically, C2-C8-haloalkynyl comprises up to 9 halogen atoms that can be the same or different.
The term C1 -C6-alkoxy as used herein refers to a group of formula (C1 -C6-alkyl)-O-. in which the term "C1 -C6-alkyl" is as defined herein. Examples of C1 -C6-alkoxy include but are not limited to methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, n-hexyloxy, 1-methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2- dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2- trimethylpropoxy, 1,2,2-trimethylpropoxy, 1 -ethyl- 1-methylpropoxy and l-ethyl-2-methylpropoxy.
The term “C1 -C6-haloalkoxy” as used herein refers to a C1 -C6-alkoxy group as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different. Examples of C1 -C6-haloalkoxy include but are not limited to chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2- fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2- difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1- trifluoroprop-2-oxy.
The term C1 -C6-hydroxyalkyl as used herein refers to a C1 -C6-alkyl group as defined above in which at least one hydrogen atom is replaced with a hydroxyl group. Examples of C1 -C6-hydroxyalkyl include but are not limited to hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl,l,2-dihydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 1-hydroxypropyl, l-hydroxypropan-2-yl, 2-hydroxypropan-2-yl, 2,3-dihydroxypropyl and l,3-dihydroxypropan-2-yl.
The term “C1 -C6-cyanoalkyl” as used herein refers to a C1 -C6-alkyl group as defined above in which at least one hydrogen atom is replaced with a cyano group.
The term “C1 -C8-alkylsulfanyl” as used herein refers to a saturated, linear or branched group of formula (C1 -C8-alkyl)-S-, in which the term "C1 -C8-alkyl" is as defined herein. Examples of C1 -C8-alkylsulfanyl include but are not limited to methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, .sec-butylsulfanyl. isobutylsulfanyl, tert-butylsulfanyl, pentylsulfanyl, isopentylsulfanyl, hexylsulfanyl group.
The term “C1 -C8-haloalkylsulfanyl” as used herein refers to a C1 -C8-alkylsulfanyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term “arylsulfanyl” as used herein refers to a group of formula aryl-S-, in which the term "aryl" is as defined herein.
The term “C1 -C8-alkylsulfinyl” as used herein refers to a saturated, linear or branched group of formula (C1 -C8-alkyl)-S(=0)-, in which the term "C1 -C8-alkyl" is as defined herein. Examples of C1 -C8- alkylsulfinyl include but are not limited to saturated, straight-chain or branched alkylsulfinyl radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) methylsulfmyl, ethylsulfmyl, propylsulfmyl, 1-methylethylsulfinyl, butylsulfmyl, 1-methylpropyl- sulfmyl, 2-methylpropylsulfmyl, 1,1-dimethylethylsulfmyl, pentylsulfmyl, 1-methylbutylsulfinyl, 2- methylbutylsulfmyl, 3-methylbutylsulfmyl, 2,2-dimethylpropylsulfmyl, 1-ethylpropylsulfinyl, 1,1- dimethylpropylsulfmyl, 1,2-dimethylpropylsulfmyl, hexylsulfmyl, 1-methylpentylsulfinyl, 2 -methyl - pentylsulfmyl, 3-methylpentylsulfmyl, 4-methylpentylsulfmyl, 1,1-dimethylbutylsulfmyl, 1, 2-dimethyl - butylsulfmyl, 1,3-dimethylbutylsulfmyl, 2,2-dimethylbutylsulfmyl, 2,3-dimethylbutylsulfmyl, 3,3- dimethylbutylsulfmyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfmyl, 1,1,2-trimethylpropylsulfmyl, 1,2,2- trimethylpropylsulfmyl, 1 -ethyl- 1-methylpropylsulfinyl and l-ethyl-2-methylpropylsulfmyl.
The term “C1 -C8-haloalkylsulfmyl” as used herein refers to a C1 -C8-alkylsulfmyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term “arylsulfmyl” as used herein refers to a group of formula aryl-S(=0)-, in which the term "aryl" is as defined herein.
The term C1 -C8-alkylsulfonyl as used herein refers to a saturated, linear or branched group of formula (C1 -C8-alkyl)-S(=0)2-, in which the term "C1 -C8-alkyl" is as defined herein. Examples of C1 -C8- alkylsulfonyl include but are not limited to methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1 -methyl - ethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1- dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3- methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1, 1-dimethylpropylsulfonyl,
1.2-dimethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3- methylpentylsulfonyl, 4-methylpentylsulfonyl, 1 , 1 -dimethylbutylsulfonyl, 1 ,2-dimethylbutylsulfonyl,
1.3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3 -dimethylbutylsulfonyl, 3,3- dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2- trimethylpropylsulfonyl, 1 -ethyl- 1-methylpropylsulfonyl and l-ethyl-2-methylpropylsulfonyl.
The term “C1 -C8-haloalkylsulfonyl” as used herein refers to a C1 -C8-alkylsulfonyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term “C1 -C8-alkylsulfonylamino” as used herein refers to a saturated, linear or branched group of formula (C1 -C8-alkyl)-S(=0)2-NH-, in which the term "C1 -C8-alkyl" is as defined herein.
The term “C1 -C8-haloalkylsulfonylamino” as used herein refers to a C1 -C8-alkylsulfonylamino as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term C1 -C8-alkylsulfamoyl as used herein refers to a sulfamoyl radical having one C1 -C8-alkyl group as defined herein. The term “di-(C1 -C8-alkyl)sulfamoyl” as used herein refers to a sulfamoyl radical having two independently selected C1 -C8-alkyl groups as defined herein.
The term “C1 -C6-alkylcarbamoyl” as used herein refers to a carbamoyl radical having one C1 -C6-alkyl group as defined herein.
The term “di-(C1 -C6-alkyl)carbamoyl” as used herein refers to a carbamoyl radical having two independently selected C1 -C6-alkyl groups as defined herein.
The term “C1 -C6-alkylcarbonyl” as used herein refers to a saturated, linear or branched group of formula (C1 -C6-alkyl)-C(=0)-, in which the term "C1 -C6-alkyl" is as defined herein.
The term “C1 -C6-haloalkylcarbonyl” as used herein refers to a C1 -C6-alkylcarbonyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term “C1 -C6-alkylcarbonyloxy” as used herein refers to a saturated, linear or branched group of formula (C1 -C6-alkyl)-C(=0)-0-, in which the term "C1 -C6-alkyl" is as defined herein.
The term C1 -C6-haloalkylcarbonyloxy” as used herein refers to a C1 -C6-alkylcarbonyloxy as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term “C1 -C6-alkylcarbonylamino” as used herein refers to a saturated, linear or branched group of formula (C1 -C6-alkyl)-C(=0)-NH-, in which the term "C1 -C6-alkyl" is as defined herein.
The term “C1 -C6-haloalkylcarbonylamino” as used herein refers to a C1 -C6-alkylcarbonylamino as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term “C1 -C6-alkoxycarbonyl” as used herein refers to a saturated, linear or branched group of formula (C1 -C6-alkoxy)-C(=0)-, in which the term "C1 -C6-alkoxy" is as defined herein.
The term “C1 -C6-haloalkoxycarbonyl” as used herein refers to a C1 -C6-alkoxycarbonyl as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term “C1 -C6-alkylamino” as used herein refers to an amino radical having one C1 -C6-alkyl group as defined herein. Examples of C1 -C6-alkylamino include but are not limited to N-methylamino. N-cthyl- amino, N-isopropylamino. N-n-propylamino. N-isopropylamino and N-tert-butylamino.
The term “di-(C1 -C6-alkyl)amino” as used herein refers to an amino radical having two independently selected C1 -C6-alkyl groups as defined herein. Examples of di-(C1 -C6-dialkyl)amino include but are not limited to N, N-dimethylamino, N, N-diethylamino. N, N-d i i so p ro p y l am i n o . N-ethyl-N-methylamino. N-methyl-N-n-propylamino. N-isopropyl-N-n-propylamino and N-tert-butyl-N-methylamino.
The term “C3-C10-carbocyclyl” as used herein refers to a non-aromatic, saturated or partially unsaturated, hydrocarbon ring system in which all of the ring members, which vary from 3 to 10, are carbon atoms. The ring system may be monocyclic orbicyclic (fused, spiro or bridged). C3-C10-carbocycles include but are not limited to C3-C10-cycloalkyl (mono or bicyclic), C3-C10-cycloalkenyl (mono or bicyclic), bicylic system comprising an aryl (e.g. phenyl) fused to a monocyclic C3-C6-cycloalkyl (e.g. tetrahydronaphthalenyl, indanyl) and bicylic system comprising an aryl (e.g. phenyl) fused to a monocyclic C3-C6-cycloalkenyl (e.g. indenyl, dihydronaphthalenyl). The C3-C10-carbocycle can be attached to the parent molecular moiety through any carbon atom.
The term “ C3-C10-cycloalkyl” as used herein refers to a saturated, monovalent, mono- or bicylic hydrocarbon ring which contains 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. “C3-C7-cycloalkyl” as used herein designates monocyclic C3-C7-cycloalkyls which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. “ C3-C5-cycloalkyl” as used herein designates monocyclic C3-C5-cycloalkyls which include cyclopropyl, cyclobutyl and cyclopentyl. Examples of bicyclic CVCm-cycloalkyls include but are not limited to bicyclo[3.1.1]heptane, bicyclo[2.2.1 ]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, bicyclo[4.2.0]octyl, octahydropentalenyl and bicyclo[4.2.1 ]nonane.
The term “C3-C7-halocycloalkyl” as used herein refers to a C3-C7-cycloalkyl group as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term “C3-C10-halocarbocyclyl” as used herein refers to a C3-C10-carbocyclyl group as defined above in which one or more hydrogen atoms are replaced with halogen atoms that may be the same or different.
The term “aryl” as used herein refers to an aromatic hydrocarbon ring system in which all of the ring members, which vary from 6 to 14, preferably from 6 to 10, are carbon atoms. The ring system may be monocyclic or fused polycyclic (e.g. bicyclic or tricyclic). Examples of aryl include but are not limited to phenyl, azulenyl, naphthyl and fluorenyl. The aryl can be attached to the parent molecular moiety through any carbon atom. 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.
The term “3- to 10-membered heterocyclyl” or “heterocyclyl” as used herein refers to a non-aromatic, saturated or partially unsaturated non-aromatic ring system comprising 1 to 4, or 1 to 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur. If the ring system contains more than one oxygen atoms, they are not directly adjacent. 3- to 10-membered heterocycles include but are not limited to 3- to 7-membered monocyclic non-aromatic heterocycles (“3- to 7- membered heterocyclyl”) and 6- to 10-membered polycyclic (e.g. bicyclic or tricyclic) non-aromatic heterocycles. The 3- to 10-membered heterocyclyl can be connected to the parent molecular moiety through any carbon atom or nitrogen atom contained within the heterocycle.
The term “3- to 7-membered heterocyclyl” as used herein refers to a 3-, 4-, 5-, 6- or 7-membered monocyclic ring system containing 1, 2 or 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur where the ring system is saturated or unsaturated but not aromatic. For instance, the heterocycle may comprise one to three nitrogen atoms, or one or two oxygen atoms, or one or two sulfur atoms, or one to three nitrogen atoms and one oxygen atom, or one to three nitrogen atoms and a sulfur atom or one sulfur atom and one oxygen atom. Examples of saturated non-aromatic heterocycles include but are not limited to 3-membered ring such as oxiranyl, aziridinyl, 4-membered ring such as azetidinyl, oxetanyl, thietanyl, 5-membered ring such as tetrahydrof iranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, 6-membered ring such as piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2-oxazinanyl, oxathianyl, thiomorpholinyl or 7-membered ring such as oxepanyl, azepanyl, 1,4-diazepanyl and 1,4-oxazepanyl. Examples of unsaturated non-aromatic hererocyles include but are not limited to 5-membered ring such as dihydrof iranyl, 1,3-dioxolyl, dihydrothienyl, pyrrolinyl, dihydroimidazolyl, dihydropyrazolyl, isoxazolinyl, dihydrooxazolyl, dihydrothiazolyl or 6-membered ring such as pyranyl, thiopyranyl, thiazinyl and thiadiazinyl.
The term “non-aromatic 6- to 10-membered polycyclic heterocycle” as used herein refers to a 6-, 7-, 8-, 9-, 10-membered polycyclic (e.g. bicyclic or tricyclic) ring system containing 1, 2 or 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur where the ring system is saturated or unsaturated but not aromatic. Non-aromatic bicyclic heterocycles may consist of a monocyclic heteroaryl as defined herein fused to a monocyclic C3-C7-cycloalkyl, a monocyclic C3-C8-cycloalkenyl or a monocyclic non-aromatic heterocycle or may consist of a monocyclic non-aromatic heterocycle fused either to an aryl (e.g. phenyl), a monocyclic C3-C7-cycloalkyl, a monocyclic C3-C8-cycloalkenyl or a monocyclic non-aromatic heterocycle. When two monocyclic heterocycles (aromatic or non-aromatic) comprising nitrogen atoms are fused, nitrogen atom may be at the bridgehead (e.g. 4, 5,6,7- tetrahydropyrazolo[l,5-a]pyridinyl, 5,6,7,8-tetrahydro-[l,2,4]triazolo[l,5-a]pyridinyl, 5, 6, 7, 8- tetrahydroimidazo[l,2-a]pyridinyl). Non-aromatic tricyclic heterocycles may consist of a monocyclic cycloalkyl connected through one common atom to a non-aromatic bicyclic heterocycle.
The term “aromatic 5- to 14-membered heterocycle” or “heteroaryl” as used herein refers to an aromatic ring system comprising 1 to 4 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur. If the ring system contains more than one oxygen atom, they are not directly adjacent. Aromatic heterocycles include aromatic 5- or 6-membered monocyclic heterocycles and 6- to 14- membered polycyclic (e.g. bicyclic or tricyclic) aromatic heterocycles. The 5- to 14-membered aromatic heterocycle can be connected to the parent molecular moiety through any carbon atom or nitrogen atom contained within the heterocycle.
The term “aromatic 5- or 6-membered monocyclic heterocycle” or “monocyclic heteroaryl” as used herein refers to a 5- or 6-membered monocyclic ring system containing 1, 2, 3 or 4 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur. Examples of 5-membered monocyclic heteroaryl include but are not limited to furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, isoxazolyl, oxazolyl, oxadiazolyl, oxatriazolyl, isothiazolyl, thiazolyl, thiadiazolyl and thiatriazolyl. Examples of 6-membered monocyclic heteroaryl include but are not limited to pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl.
The term “6- to 14-membered polycyclic aromatic heterocycle” or “polycyclic heteroaryl” as used herein refers to a 6-, 7-, 8-, 9-, 10-, 11-,12-, 13- or 14-membered polycyclic (e.g. bicyclic or tricyclic) ring system containing 1, 2 or 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur. Aromatic bicyclic heterocycles may consist of a monocyclic heteroaryl as defined herein fused to an aryl (e.g. phenyl) or to a monocyclic heteroaryl. Examples of bicyclic aromatic heterocycle include but are not limited to 9-membered ring such as indolyl, indolizinyl, isoindolyl, benzimadozolyl, imidazopyridinyl, indazolyl, benzotriazolyl, purinyl, benzofuranyl, benzothiophenyl, benzothiazolyl, benzoxazolyl and benzisoxazolyl or 10-membered ring such as quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, pteridinal and benzodioxinyl. In 9- or 10- membered aromatic bicyclic heterocycles comprising two fused 5- or 6-membered monocyclic aromatic heterocycles, nitrogen atom may be at the bridgehead (e.g. imidazo[l,2-a]pyridinyl, [l,2,4]triazolo[4,3- a]pyridinyl, imidazo[l,2-a]pyridinyl, imidazo [2, 1-b] oxazolyl, furo[2,3-d]isoxazolyl). Examples of tricyclic aromatic heterocyle include but are not limited to carbazolyl, acridinyl and phenazinyl.
The terms “aryl-C1 -C6-alkyl”, “3- to 10-membered heterocyclyl-C1 -C6-alkyl”, “heteroaryl-C1 -C6-alkyl” and “C3-C10-carbocyclyl-C1 -C6-alkyl” as used herein designate a group of formula “-C1 -C6-alkyl-R”, wherein R is respectively an aryl, 3- to 10-membered heterocyclyl, heteroaryl or C3-C10-carbocyclyl as defined herein, “C1 -C6-alkyl” is a saturated, branched or straight hydrocarbon chain having 1, 2, 3, 4, 5 or 6 carbon atoms and wherein the group “-C1 -C6-alkyl-R” is attached to the parent moiety via the “C1 -C6- alkyl” group.
As used herein, when a group is said to be “substituted”, the group may be substituted with one or more substituents. The expression “one or more substituents” refers to a number of substituents that ranges from one to the maximum number of substituents possible based on the number of available bonding sites, provided that the conditions of stability and chemical feasibility are met. 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 trifluoromethanesulfonate (“triflate”) group, alkoxy, methanesulfonate, p-toluenesulfonate, etc.
The terms "as described herein" when referring to a variable xxxx incorporates by reference the broad definition of the variable as well as preferred, more preferred and even more preferred definitions, if any.
DETAILED DESCRIPTION
The present invention relates to the use of compounds of formula (I) for controlling harmful microorganisms, in particular phytopathogenic fungi, in crop protection:
Figure imgf000011_0001
wherein
X is hydrogen or fluorine; W1, W2 and W3 are independently CH, CF or N, wherein W1 and W3 cannot both be N; n is 1 or 2, wherein if n is 2, the two [CR2R3] groups may be the same or different; m is 0, 1 or 2, wherein if m is 2, the two [CR4R5] groups may be the same or different;
R1 is aryl, heteroaryl, C3-C10-carbocyclyl or 3- to 10-membered heterocyclyl, each of which may be substituted with one or more R1c substituents;
R2 and R3 are independently selected from the group consisting of hydrogen, halogen atom and C1 - C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R2a substituents, or R2 and R3 form, together with the carbon atom to which they are linked, a C=0 group, or
R2 and R3 form, together with the carbon atom to which they are linked, a C3-C6 -cycloalkyl wherein said C3-C6-cycloalkyl may be substituted with one or more R2c substituents;
R4and R5 are independently selected from the group consisting of hydrogen, C1 -C8-haloalkyl and C1 -C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R4a substituents,
R1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfinyl, sulfonyl, amino, nitro, pentafluoro-l6- sulfanyl, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-hydroxyalkyl, C1 -C6-cyanoalkyl, C1 -C6-alkoxy, C1 - C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1 -C6-alkylsulfanyl, CVCg-haloalkylsulfanyl. arylsulfanyl, C1 -C6-alkylsulfinyl, C1 -C6-haloalkylsulfinyl, arylsulfinyl, C3-C10-carbocyclyl, C3- C10-halocarbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, aryl-C1 -C6-alkyl, 3- to 10- membered-heterocyclyl-C1 -C6 -alkyl, heteroaryl-C1 -C6-alkyl, C3-C10-carbocyclyl-C1 -C6-alkyl, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, -C(=0)R21, -C(=0)0R21, -C(=0)N(R21)2,
-C(=0)N(0R21)R21, -C(=0)NR21N(R21)2, -C(=S)N(R21)2, -C(=NR21)R21, -C(=NR21)N(R21)2, -C(=NOR21)R21, -N(R21)2, -NR21C(=0)0R21, -N(0R21)C(=0)0R21, -NR21C(=0)N(R21)2,
-NR21C(=0)R21, -N(0R21)C(=0)R21, -NR21C(=S)R21, -NR21C(=S)N(R21)2, -NR21C(=NR21)R21, -OR21, -0C(=0)R21, -0C(=0)N(R21)2, -NR21S(=0)2R21, -N=CR21-N(R21)2, -S(=0)2R21,
-S(=0)2N(R21)2 and -P(=0)(0R21)2, wherein the C1 -C6 -alkyl, C1 -C6-alkoxy, C2-C6 -alkenyl and C2-C6-alkynyl may be substituted with one or more Ra substituents; wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, arylsulfanyl and arylsulfmyl may be substituted with one or more Rc substituents; and wherein R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl. C1 -C6- haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents and wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents;
R2a , R4a and Ra are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6- alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6- alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6-haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 -C6-haloalkoxycarbonyl, aryloxy, C1 -C6- alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1 -C6-haloalkylcarbonylamino, C1 -C6- alkylsulfanyl, C1 -C8-alkylsulfmvl. C1 -C8-alkylsulfonyl, C1 -C8-alkylsulfonylamino, C1 -C8- haloalkylsulfonylamino, C1 -C8-alkylsiilfamoyl and di-(C1 -C8-alkyl)sulfamoyl;
R2c and Rc are independently selected from the group consisting of C1 -C6-alkyl, C1 -C6-haloalkyl, C2-
C6-alkenyl, C2-C6-alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8- halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6- alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl. C1 -C6- haloalkylcarbonyl, C1 -C6-alkylcarbamoyl. di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxycarbonyl. C1 - C6-haloalkoxycarbonyl, aryloxy, C1 -C6-alkylcarbonyloxy. C1 -C6-alkylcarbonylam ino. C1 -C6- haloalkylcarbonylamino, C1 -C8-alkylsulfanyl. C1 -C8-alkylsiilfinyl. C1 -C8-alkylsiilfonyl. C1 -C8- alkylsulfonylamino, C1 -C8-haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8- alkyl)sulfamoyl; as well as their salts, N-oxides and solvates. 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.
According to the invention, the compounds of formula (I) are used for controlling harmful microorganisms, in particular phytopathogenic fungi, in crop protection. Preferably, the phytopathogenic fungi are selected from the group consisting of the Puccinia species, for example Puccinia recondita, Puccinia graminis or Puccinia striiformis ; the Uromyces species, for example Uromyces appendiculatus and the rust disease pathogens, in particular selected from the group consisting of the Gymnosporangium species, for example Gymnosporangium sabinae Hemileia species, for example Hemileia vastatrix, and Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae . Especially preferred are the rust disease pathogens, in particular Phakopsora pachyrhizi and Phakopsora meibomiae.
The compounds of formula (I) can suitably be in their 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) 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.
Depending on the nature of the substituents, the compound of formula (I) 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.
The compounds of the invention may exist in multiple crystalline and/or amorphous forms. Crystalline forms include unsolvated crystalline forms, solvates and hydrates.
Solvates of the compounds of the invention or their salts are stoichiometric compositions of the compounds with solvents.
Compounds of formula (I) are herein referred to as “active ingredient(s)”.
Preferably, in the above formula (I), X is hydrogen.
Preferably, in the above formula (I), at most one of W1, W2 and W3 is N.
More preferably, in the above formula (I), W1 is N, CH or CF, and W2 and W3 are independently selected from CH and CF.
In some preferred embodiments, in the above formula (I), W1 is N, and W2 and W3 are independently selected from CH and CF, preferably, W2 and W3 are CH.
In some other preferred embodiments, in the above formula (I), W1, W2 and W3 are each independently selected from CH and CF, preferably W1, W2 and W3 are CH.
Preferably, in the above formula (I), n is 1.
Preferably, in the above formula (I), m is 0 or 1.
In some preferred embodiments, in the above formula (I), m is 0.
In some other preferred embodiments, in the above formula (I), m is 1.
Preferably, in the above formula (I), R1 is an aryl selected from phenyl and naphthyl, a heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinolinyl, a C3-C7-cycloalkyl or a 3- to 7-membered heterocyclyl selected from the group consisting of selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2-oxazinanyl, oxathianyl and thiomorpholinyl, wherein the aryl, heteroaryl, C3-C7-cycloalkyl and 3- to 7-membered heterocyclyl may be substituted with one to three R1c substituents as defined herein.
More preferably, in the above formula (I), R1 is phenyl or C3-C7-cycloalkyl, wherein the phenyl and C3- C7-cycloalkyl may be substituted with one to three R1c substituents as defined herein.
In some preferred embodiments, in the above formula (I), R1 is aryl, preferably phenyl or naphthyl, more preferably phenyl, wherein the aryl may be substituted with one to three R1c substituents as defined herein.
In some other preferred embodiments, in the above formula (I), R1 is heteroaryl, preferably selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinolinyl, more preferably a 5 - or 6-membered heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl. The heteroaryl may be substituted with one to three R1c substituents as defined herein.
In still some other preferred embodiments, in the above formula (I), R1 is C3-C10-carbocyclyl, preferably C3-C7-cycloalkyl, which may be substituted with one to three R1c substituents as defined herein. In some of these embodiments, the C3-C10-carbocyclyl, preferably C3-C7-cycloalkyl, is substituted with one phenyl R1c substituent and optionally one or two non-cyclic R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy and C1 -C6-haloalkoxy, wherein the phenyl may be substituted with one to three Rc substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6- alkoxy carbonyl. More preferably, in these embodiments, R1 is cyclopropyl, which is substituted with phenyl, wherein the phenyl is substituted with one or two halogen, preferably fluorine substituents.
In yet some other preferred embodiments, in the above formula (I), R1 is 3- to 10-membered-heterocyclyl, preferably a 3 - to 7-membered heterocyclyl selected from the group consisting of selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2- oxazinanyl, oxathianyl and thiomorpholinyl. The 3- to 10-membered heterocyclyl, preferably 3- to 7- membered heterocyclyl may be substituted with one to three R1c substituents as defined herein.
In some preferred embodiments, in the above formula (I), R1 is phenyl, C3-C7-cycloalkyl, a 6-membered heteroaryl, preferably selected from the group consisting of pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, or a 5-membered heteroaryl, preferably selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl and thiazolyl, wherein the phenyl, C3-C6-cycloalkyl, 6-membered heteroaryl and 5-membered heteroaryl may be substituted with one to three R1c substituents as defined herein.
In some preferred embodiments, in the above formula (I), R1 is phenyl, a 6-membered heteroaryl, preferably selected from the group consisting of pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, or a 5- membered heteroaryl, preferably selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl and thiazolyl, wherein the phenyl, 6-membered heteroaryl and 5-membered heteroaryl may be substituted with one to three R1c substituents as defined herein.
Preferably, the R1c substituents are selected from the group consisting of halogen, cyano, C1 -C6 -alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy. C1 -C6-haloalkoxy. C3-G-cycloalkyl. aryl, heteroaryl, 3- to 7-membered heterocyclyl, -NR21C(=0)0R21, -NR21C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2 and -0C(=0)N(R21)2, wherein the C3-G-cycloalkyl. 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three Rc substituents as described herein; and wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6- haloalkyl and C3-C7-cycloalkyl.
Preferably, the Rc substituents are selected from the group consisting of halogen, cyano, C1 -C6 -alkyl, C3- G-cycloalkyl. C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl.
More preferably, the R1c substituents are selected from the group consisting of halogen, cyano, C1-C6- alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C3-C6-cycloalkyl, phenyl, 5- to 6-membered heteroaryl selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, 3- to 7-membered heterocyclyl selected from the group consisting of tetrahydrofuranyl, 1,3- dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2-oxazinanyl, oxathianyl and thiomorpholinyl, -NR21C(=0)0R21, -NR21C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2 and
-0C(=0)N(R21)2, wherein the C3-C7-cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three Rc substituents as described herein; and wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl. C1 -C6- haloalkyl and C3-C6-cycloalkyl. Preferably, the Rc substituents are selected from the group consisting of halogen, cyano, C1 -C6 -alkyl, C3- Cvcycloalkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl.
Most preferably, the R1c substituents are selected from the group consisting of halogen, cyano, C1 -C6- alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C3-C6 -cycloalkyl, phenyl, -NR21C(=0)0R21 and -NR21C(=0)R21, wherein the C3-C6-cycloalkyl and phenyl may be substituted with one to three Rc substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C1 -C6- haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxy carbonyl and wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl and C3-C6- cycloalkyl.
In some preferred embodiments, in the above formula (I), R1 is selected from aryl, heteroaryl, C3-C7- cycloalkyl and 3- to 7-membered heterocyclyl, which is substituted with one cyclic R1c substituent selected from the group consisting of C3-C7-cycloalkyl, aryl, heteroaryl and 3- to 7-membered heterocyclyl and may additionally be substituted with one or two non-cyclic R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl. C1 -C6-haloalkyl. C1 -C6-alkoxy and C|-G,-haloalkoxy. wherein the C3-C7-cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three Rc substituents as described herein. Preferably, the Rc substituents are selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6- haloalkoxy and C1 -C6-alkoxycarbonyl.
In some other preferred embodiments, in the above formula (I), R1 is selected from aryl, heteroaryl, C3- C7-cycloalkyl and 3- to 7-membered heterocyclyl, which is substituted with one R1c substituent selected from -NR21C(=0)0R21, -NR21C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2 and -0C(=0)N(R21)2 and may additionally be substituted with one or two R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy and C1 -C6-haloalkoxy, wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6- haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -G -alkyl may be substituted with one or more Ra substituents as defined herein and wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents as defined herein. Preferably, in these embodiments, each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl and C3-C6-cycloalkyl.
In some other preferred embodiments, in the above formula (I), R1 is selected from aryl, heteroaryl, C3- C7-cycloalkyl and 3- to 7-membered heterocyclyl, which is substituted with one R1c substituent selected from -NR21C(=0)0R21 and -NR21C(=0)R21 and may additionally be substituted with one or two R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6- alkoxy and C1 -C6-haloalkoxy, wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents as defined herein and wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents as defined herein. Preferably, R21 is independently selected from the group consisting of hydrogen, C1 -C6- alkyl, C1 -C6-haloalkyl and C3-C6 -cycloalkyl.
Preferably, in the above formula (I), R2 and R3 are independently selected from hydrogen and C1 -C8- alkyl.
More preferably, in the above formula (I), R2 and R3 are hydrogen.
Preferably, in the above formula (I),
R4and R5 are independently selected from the group consisting of hydrogen, C1 -Ct-haloalkyl and C1-C4- alkyl, wherein the C1 - C4-alkyl may be substituted with one to three R4a substituents as described herein. Preferably, the R4a substituents are selected from the group consisting of halogen atom, cyano, carboxyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C1 -C6-alkylcarbonyl. C1 -C6-alkylcarbamoyl. di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl and C1 -C6-haloalkoxycarbonyl .
More preferably, in the above formula (I), R4 and R5 are independently selected from hydrogen and C1 - C4-alkyl.
The above-mentioned preferences with regard to the substituents of the compounds according to the invention can be combined in various manners. These combinations of preferred features thus provide sub-classes of compounds according to the invention. Examples of such sub-classes of preferred compounds according to the invention are:
- preferred features of X with one or more preferred features of W1, W2, W3, n, m, R1, R2, R3, R4 and R5;
- preferred features of W1 with one or more preferred features of X, W2, W3, n, m, R1, R2, R3, R4 and R5;
- preferred features of W2 with one or more preferred features of X, W1, W3, n, m, R1, R2, R3, R4 and R5;
- preferred features of W3 with one or more preferred features of X, W1, W2, n, m, R1, R2, R3, R4 and R5;
- preferred features of n with one or more preferred features of X, W1, W2, W3, m, R1, R2, R3, R4 and R5;
- preferred features of m with one or more preferred features of X, W1, W2, W3, n, R1, R2, R3, R4 and R5;
- preferred features of R1 with one or more preferred features of X, W1, W2, W3, n, m, R2, R3, R4 and R5;
- preferred features of R2 with one or more preferred features of X, W1, W2, W3, n, m, R1, R3, R4 and R5;
- preferred features of R3 with one or more preferred features of X, W1, W2, W3, n, m, R1, R2, R4 and R5;
- preferred features of R4 with one or more preferred features of X, W1, W2, W3, n, m, R1, R2, R3 and R5;
- preferred features of R5 with one or more preferred features of X, W1, W2, W3, n, m, R1, R2, R3 and R4.
This also applies to the preferences with regard to the substituents of the compounds according to the embodiments (la), (lb), (Ic), (Id), (la*), (lb*), (Ic*) and (Id*) provided below. In these combinations of preferred features of the substituents of the compounds according to the invention, the said preferred features can also be selected among the more preferred features of each of X, W1, W2, W3, n, m, R1, R2, R3 and R4 and R5 so as to form more preferred subclasses of compounds according to the invention. This also applies to the preferences with regard to the substituents of the compounds according to the embodiments (la), (lb), (Ic), (Id), (la*), (lb*), (Ic*) and (Id*) provided below.
In some embodiments (referred herein as embodiment la), the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof:
Figure imgf000019_0001
wherein
X is hydrogen or fluorine, preferably hydrogen; W1 is CH, CF or N, preferably W1 is N; W2 and W3 are each independently selected from CH and CF; n is 1 or 2, wherein if n is 2, the two [CR2R3] groups may be the same or different; preferably n is 1 ; m is 0, 1 or 2, wherein if m is 2, the two [CR4R5] groups may be the same or different;
R1 is aryl, heteroaryl, C3-C10-carbocyclyl or 3- to 10-membered-heterocyclyl, each of which may be substituted with one or more R1c substituents;
R2 and R3 are hydrogen;
R4and R5 are independently selected from the group consisting of hydrogen, C1 -C8-haloalkyl and C1 -C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R4a substituents, R1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l6- sulfanyl, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-hydroxyalkyl, C1 -C6-cyanoalkyl, C1 -C6-alkoxy, C1 - C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1 -C6-alkylsulfanyl, C1 -C6-haloalkylsulfanyl, arylsulfanyl, C1 -C6-alkylsulfinyl, C1 -C6-haloalkylsulfinyl, arylsulfmyl, C3-C10-carbocyclyl, C3- C10-halocarbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, aryl-C1 -C6-alkyl, 3- to 10- membered-heterocyclyl-C1 -C6 -alkyl, heteroaryl-C1 -C6-alkyl, C3-C10-carbocyclyl-C1 -C6-alkyl, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, -C(=0)R21, -C(=0)0R21, -C(=0)N(R21)2,
-C(=0)N(0R21)R21, -C(=0)NR21N(R21)2, -C(=S)N(R21)2, -C(=NR21)R21, -C(=NR21)N(R21)2, -C(=NOR21)R21, -N(R21)2, -NR21C(=0)0R21, -N(0R21)C(=0)0R21, -NR21C(=0)N(R21)2,
-NR21C(=0)R21, -N(0R21)C(=0)R21, -NR21C(=S)R21, -NR21C(=S)N(R21)2, -NR21C(=NR21)R21, -OR21, -0C(=0)R21, -0C(=0)N(R21)2, -NR21S(=0)2R21, -N=CR21-N(R21)2, -S(=0)2R21, -S(=0)2N(R21)2 and -P(=0)(0R21)2, wherein the C1 -C6 -alkyl, C1 -C6-alkoxy, C2-C6 -alkenyl and C2-C6-alkynyl may be substituted with one or more Ra substituents; wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, arylsulfanyl and arylsulfmyl may be substituted with one or more Rc substituents; and wherein R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents and wherein the C3-C10-carbocyclyl, 3- to 10- membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents; R4a and Ra are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoroG6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6-alkylamino. di-(C1 -C6-alkyl)amino. -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, C1 -C6-alkoxy. C1 -C6-haloalkoxy. C1 -C6-alkylsulfanyl. C1 -C6-alkylcarbonyl, C1 -C6-haloalkylcarbonyl. C1 -Gralkylcarbamoyl. di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 -C6-haloalkoxycarbonyl, aryloxy, C1-C6- alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1 -C6-haloalkylcarbonylamino, C1 -C8- alkylsulfanyl, C1 -C8-alkylsulfmyl. C1 -C8-alkylsulfonyl. C1 -C8-alkylsulfonylamino, C1 -C8- haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8-alkyl)sulfamoyl;
Rc substituents are each independently selected from the group consisting of C1 -C6-alkyl, C1 -C6- haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3- C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6- alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6- haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 - C6-haloalkoxycarbonyl, aryloxy, C1 -C6-alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1-C6- haloalkylcarbonylamino, C1 -C8-alkylsulfanyl, C1 -C8-alkylsulfmyl, C1 -C8-alkylsulfonyl, C1 -C8- alkylsulfonylamino, C1 -C8-haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8- alkyl) sulfamoyl.
Preferably, in accordance with embodiment (la), R1 is an aryl selected from phenyl and naphthyl, a heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinobnyl, a C3-C7-cycloalkyl or a 3- to 7-membered heterocyclyl selected from the group consisting of selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazobdinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2-oxazinanyl, oxathianyl and thiomorpholinyl, wherein the aryl, heteroaryl, C3-C7-cycloalkyl and 3- to 7-membered heterocyclyl may be substituted with one to three R1c substituents as defined herein.
In some embodiments in accordance with embodiment (la), R1 is an aryl selected from phenyl and naphthyl or a heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinolinyl, wherein the aryl and heteroaryl may be substituted with one to three R1c substituents as defined herein.
In some embodiments (referred herein as embodiment lb), the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof: wherein
Figure imgf000021_0001
X is hydrogen or fluorine, preferably hydrogen; W1 is CH, CF or N, preferably W1 is N; W2 and W3 are each independently selected from CH and CF; n is 1 or 2, wherein if n is 2, the two [CR2R3] groups may be the same or different, preferably n is 1 ; m is 0, 1 or 2, wherein if m is 2, the two [CR4R5] groups may be the same or different;
R1 is aryl, preferably phenyl, which may be substituted with one or more R1c substituents;
R2 and R3 are hydrogen;
R4and R5 are independently selected from the group consisting of hydrogen, C1 -C8-haloalkyl and C1 -C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R4a substituents, R1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfinyl, sulfonyl, amino, nitro, pentafluoro-l6- sulfanyl, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-hydroxyalkyl, C1 -C6-cyanoalkyl, C1 -C6-alkoxy, C1 - C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1 -C6-alkylsulfanyl, C1 -C6-haloalkylsulfanyl, arylsulfanyl, C1 -C6-alkylsulfinyl, C1 -C6-haloalkylsulfinyl, arylsulfinyl, C3-C10-carbocyclyl, C3- C10-halocarbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, aryl-C1 -C6-alkyl. 3- to 10- membered-heterocyclyl-C1 -C6-alkyl, heteroaryl -C1 -C6-alkyl. C3-C10-carbocyclyl-C1 -C6-alkyl,
-Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, -C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2,
-C(=0)N(0R21)R21, -C(=0)NR21N(R21)2, -C(=S)N(R21)2, -C(=NR21)R21, -C(=NR21)N(R21)2, -C(=NOR21)R21, -N(R21)2, -NR21C(=0)0R21, -N(0R21)C(=0)0R21, -NR21C(=0)N(R21)2, -NR21C(=0)R21, -N(0R21)C(=0)R21, -NR21C(=S)R21, -NR21C(=S)N(R21)2, -NR21C(=NR21)R21, -OR21, -0C(=0)R21, -0C(=0)N(R21)2, -NR21S(=0)2R21, -N=CR21-N(R21)2, -S(=0)2R21,
-S(=0)2N(R21)2 and -P(=0)(0R21)2, wherein the C1 -C6 -alkyl, C1 -C6-alkoxy, C2-C6 -alkenyl and C2-C6-alkynyl may be substituted with one or more Ra substituents; wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, arylsulfanyl and arylsulfmyl may be substituted with one or more Rc substituents; and wherein R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6- haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents and wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents;
R4a and Ra are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoroG6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6-alkylamino. di-(C1 -CValkyl)amino. -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6-haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 -C6-haloalkoxycarbonyl, aryloxy, C1-C6- alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1 -C6-haloalkylcarbonylamino, C1 -C8- alkylsulfanyl, C1 -C8-alkylsulfmyl. C1 -C8-alkylsulfonyl, C1 -C8-alkylsulfonylamino, C1 -C8- haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8-alkyl)sulfamoyl;
Rc substituents are each independently selected from the group consisting of C1 -C6-alkyl, C1 -C6- haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3- C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6- alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1-C6- haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 - C6-haloalkoxycarbonyl, aryloxy, C1 -C6-alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1-C6- haloalkylcarbonylamino, C1 -C8-alkylsulfanyl, C1 -C8-alkylsulfmyl, C1 -C8-alkylsulfonyl, C1 -C8- alkylsulfonylamino, C1 -C8-haloalkylsulfonylamino. C1 -C8-alkylsiilfamoyl and di-(C1 -C8- alkyl) sulfamoyl.
In some embodiments (referred herein as embodiment Ic), the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof:
Figure imgf000023_0001
wherein
X is hydrogen or fluorine, preferably hydrogen; W1 is CH, CF or N, preferably W1 is N; W2 and W3 are each independently selected from CH and CF; n is 1 or 2, wherein if n is 2, the two [CR2R3] groups may be the same or different, preferably n is 1 ; m is 0, 1 or 2, wherein if m is 2, the two [CR4R5] groups may be the same or different;
R1 is heteroaryl, preferably selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinolinyl, wherein the heteroaryl may be substituted with one or more R1c substituents;
R2 and R3 are hydrogen;
R4and R5 are independently selected from the group consisting of hydrogen, C1 -C8-haloalkyl and C1 -C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R4a substituents, R1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l6- sulfanyl, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-hydroxyalkyl, C1 -C6-cyanoalkyl, C1 -C6-alkoxy, C1 - C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1 -C6-alkylsulfanyl, C1 -C6-haloalkylsulfanyl, arylsulfanyl, C1 -C6-alkylsulfinyl, C1 -C6-haloalkylsulfinyl, arylsulfmyl, C3-C10-carbocyclyl, C3- C10-halocarbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, aryl-C1 -C6-alkyl, 3- to 10- membered-heterocyclyl-C1 -C6 -alkyl, heteroaryl-C1 -C6-alkyl, C3-C10-carbocyclyl-C1 -C6-alkyl, -Si(C1 -C6-alkyl)3, -Si(aiyl)(C1 -C6-alkyl)2, -C(=0)R21, -C(=0)0R21, -C(=0)N(R21)2,
-C(=0)N(0R21)R21, -C(=0)NR21N(R21)2, -C(=S)N(R21)2, -C(=NR21)R21, -C(=NR21)N(R21)2, -C(=NOR21)R21, -N(R21)2, -NR21C(=0)0R21, -N(0R21)C(=0)0R21, -NR21C(=0)N(R21)2,
-NR21C(=0)R21, -N(0R21)C(=0)R21, -NR21C(=S)R21, -NR21C(=S)N(R21)2, -NR21C(=NR21)R21, -OR21, -0C(=0)R21, -0C(=0)N(R21)2, -NR21S(=0)2R21, -N=CR21-N(R21)2, -S(=0)2R21, -S(=0)2N(R21)2 and -P(=0)(0R21)2, wherein the C1 -C6-alkyl. C1 -C6-alkoxy. C2-G,-alkcnyl and C2-G,-alkynyl may be substituted with one or more Ra substituents; wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, arylsulfanyl and arylsulfmyl may be substituted with one or more Rc substituents; and wherein R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6- haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents and wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents;
R4a and Ra are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoroG6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6-haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 -C6-haloalkoxycarbonyl, aryloxy, C1 -C6- alkylcarbonyloxy, C1 -C6-alkylcarbonylamino. C1 -C6-haloalkylcarbonylamino. C1 -C8- alkylsulfanyl, C1 -C8-alkylsulfmyl, C1 -C8-alkylsulfonyl. C1 -C8-alkylsulfonylamino. C1 -C8- haloalkylsulfonylamino, C1 -C8-alkylsiilfamoyl and di-(C1 -C8-alkyl)sulfamoyl;
Rc substituents are each independently selected from the group consisting of C1 -C6-alkyl, C1 -C6- haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3- C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6- alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6- haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 - C6-haloalkoxycarbonyl, aryloxy, C1 -C6-alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1-C6- haloalkylcarbonylamino, C1 -C8-alkylsulfanyl. C1 -C8-alkylsulfmyl, C1 -C8-alkylsulfonyl, C1 -C8- alkylsulfonylamino, C1 -C8-haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8- alkyl) sulfamoyl.
In some embodiments (referred herein as embodiment Id), the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof:
Figure imgf000024_0001
wherein
X is hydrogen or fluorine, preferably hydrogen; W1 is CH, CF or N, preferably W1 is N; W2 and W3 are each independently selected from CH and CF; n is 1 or 2, wherein if n is 2, the two [CR2R3] groups may be the same or different, preferably n is 1 ; m is 0, 1 or 2, wherein if m is 2, the two [CR4R5] groups may be the same or different;
R1 is C3-C10-carbocyclyl, preferably C3-C7-cycloalkyl, which may be substituted with one or more R1c substituents;
R2 and R3 are hydrogen;
R4and R5 are independently selected from the group consisting of hydrogen, C1 -C8-haloalkyl and C1 -C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R4a substituents, R1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l6- sulfanyl, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-hydroxyalkyl, C1 -C6-cyanoalkyl, C1 -C6-alkoxy, C1 - C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1 -C6-alkylsulfanyl, C1 -C6-haloalkylsulfanyl, arylsulfanyl, C1 -C6-alkylsulfmyl, C1 -C6-haloalkylsulfmyl. arylsulfmyl, C3-C10-carbocyclyl, C3- C10-halocarbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, aryl-C1 -C6-alkyl. 3- to 10- membered-heterocyclyl-C1 -C6-alkyl, heteroaryl -C1 -C6-alkyl. C3-C10-carbocyclyl-C1 -C6-alkyl, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, -C(=0)R21, -C(=0)0R21, -C(=0)N(R21)2,
-C(=0)N(0R21)R21, -C(=0)NR21N(R21)2, -C(=S)N(R21)2, -C(=NR21)R21, -C(=NR21)N(R21)2, -C(=NOR21)R21, -N(R21)2, -NR21C(=0)0R21, -N(0R21)C(=0)0R21, -NR21C(=0)N(R21)2,
-NR21C(=0)R21, -N(0R21)C(=0)R21, -NR21C(=S)R21, -NR21C(=S)N(R21)2, -NR21C(=NR21)R21, -OR21, -0C(=0)R21, -0C(=0)N(R21)2, -NR21S(=0)2R21, -N=CR21-N(R21)2, -S(=0)2R21, -S(=0)2N(R21)2 and -P(=0)(0R21)2, wherein the C1 -C6-alkyl, C1 -C6-alkoxy, C2-C6 -alkenyl and C2-C6-alkynyl may be substituted with one or more Ra substituents; wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, arylsulfanyl and arylsulfmyl may be substituted with one or more Rc substituents; and wherein R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1-C6- haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents and wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents;
R4a and Ra are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoroG6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6-alkylamino. di-(C1 -CValkyl)amino. -Si(C1 -C6-alkyl)3, -Si (aryl )(C1 - ,-alky l )2. C1 -C6-alkoxy. C1 -CVhaloalkoxy. C1 -CValkylsulfanyl. C1 -C6-alkylcarbonyl, C1 -C6-haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 -C6-haloalkoxycarbonyl, aryloxy, C1-C6- alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1 -C6-haloalkylcarbonylamino, C1 -C8- alkylsulfanyl, C1 -C8-alkylsulfmyl. C1 -C8-alkylsulfonyl, C1 -C8-alkylsulfonylamino, C1 -C8- haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8-alkyl)sulfamoyl;
Rc substituents are each independently selected from the group consisting of C1 -C6-alkyl, C1 -C6- haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3- C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6- alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1-C6- haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 - C6-haloalkoxycarbonyl, aryloxy, C1 -C6-alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1-C6- haloalkylcarbonylamino, C1 -C8-alkylsulfanyl, C1 -C8-alkylsulfmyl, C1 -C8-alkylsulfonyl, C1 -C8- alkylsulfonylamino, C1 -C8-haloalkylsulfonylamino, Ci -C8-alkylsulfamoyl and di-(C1 -C8- alkyl) sulfamoyl.
Preferably, in accordance with embodiments (la), (lb), (Ic) and (Id), X is hydrogen;
Preferably, in accordance with embodiments (la), (lb), (Ic) and (Id), W1 is N, and W2 and W3 are each independently selected from CH and CF. More preferably, W1 is N, and W2 and W3 are CH.
Preferably, in accordance with embodiments (la), (lb), (Ic) and (Id), n is 1.
Preferably, in accordance with embodiments (la), (lb), (Ic) and (Id), m is 0 or 1.
Preferably, in accordance with embodiments (la), (lb), (Ic) and (Id), the R1c substituents are selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C3-C7-cycloalkyl, aryl, heteroaryl, 3- to 7-membered heterocyclyl, -NR21C(=0)0R21, -NR21C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2 and -0C(=0)N(R21)2, wherein the C3-C7-cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three Rc substituents as described herein; and wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6- haloalkyl and C3-C7-cycloalkyl.
Preferably, the Rc substituents are selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3- C7-cycloalkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl.
More preferably, in accordance with embodiments (la), (lb), (Ic) and (Id), the R1c substituents are selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6- haloalkoxy, C3-C6-cycloalkyl, phenyl, 5- to 6-membered heteroaryl selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, 3- to 7-membered heterocyclyl selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2-oxazinanyl, oxathianyl and thiomorpholinyl, -NR21C(=0)0R21, -NR21C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2 and -0C(=0)N(R21)2, wherein the C3-C6-cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three Rc substituents as described herein; and wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6- haloalkyl and C3-C6-cycloalkyl.
Preferably, the Rc substituents are selected from the group consisting of halogen, cyano, C1 -C6 -alkyl, C3- C7-cycloalkyl. C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl.
Preferably, in accordance with embodiment (la), (lb), (Ic) and (Id),
R4and R5 are independently selected from the group consisting of hydrogen, C1 -Crhaloalkyl and C1-C4- alkyl, wherein the C1 -C4-alkyl may be substituted with one to three R4a substituents as described herein. Preferably, the R4a substituents are selected from the group consisting of halogen atom, cyano, carboxyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C1 -CValkylcarbonyl. C1 -CValkylcarbamoyl. di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl and C1 -C6-haloalkoxycarbonyl.
In some preferred embodiments, in accordance with embodiment (la), (lb), (Ic) or (Id), m is 0.
In some other preferred embodiments, in accordance with embodiment (la), (lb), (Ic) or (Id), m is 1 or 2, preferably 1.
In some preferred embodiments, in accordance with embodiment (la), (lb), (Ic) or (Id), one to three R1c substituent are present in residue R1: one cyclic R1c substituent selected from the group consisting of C3-C7-cycloalkyl. aryl, heteroaryl and 3- to 7-membered heterocyclyl and optionally one or two non-cyclic R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy and C1 -C6-haloalkoxy, wherein the C3-C7-cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three Rc substituents as described herein. Preferably, the Rc substituents are selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C1 - C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl.
Preferably, in these embodiments the cyclic R1c substituent is C3-C6-cycloalkyl, phenyl, a 5- to 6- membered heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, or a 3- to 7-membered heterocyclyl selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2- oxazinanyl, oxathianyl and thiomorpholinyl. Preferably, in these embodiments the Rc substituents are selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl.
In some preferred embodiments, in accordance with embodiment (la), (lb), (Ic) or (Id) (referred herein as embodiments (la*), (lb*), (Ic*) and (Id*)),
X is hydrogen; W1 is N or CH, W2 and W3 are CH; n is 1; m is 0 or 1;
R1 contains one cyclic R1c substituent selected from the group consisting of C3-C7-cycloalkyl, aryl, heteroaryl and 3- to 7-membered heterocyclyl and optionally one or two non-cyclic R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl. C1 -C6-alkoxy and C1 - C6-haloalkoxy, wherein the C3-C7-cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three Rc substituents; and R2 and R3 are hydrogen.
Preferably, in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), the cyclic R1c substituent is C3- C6-cycloalkyl, phenyl, a 5- or 6-membered heteroaryl selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, or a 3- to 7-membered heterocyclyl selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2- oxazinanyl, oxathianyl and thiomorpholinyl, wherein the C3-C6-cycloalkyl, phenyl, 5- or 6-membered heteroaryl and 3- to 7-membered-heterocyclyl may be substituted with one to three Rc substituents, preferably selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C1 -C6- haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl.
In some embodiments in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), the cyclic R1c substituent is selected from phenyl and 5- to 6-membered heteroaryl, preferably selected from the group consisting of furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, wherein the phenyl and 5- to 6-membered heteroaryl may be substituted with one to three Rc substituents, preferably selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C1 -C6-haloalkyl, C1 -C6- alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl. In some embodiments in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), the cyclic R1c substituent is phenyl, which may be substituted with one to three Rc substituents, preferably selected from the group consisting ofhalogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 - C6-haloalkoxy and C1 -C6-alkoxycarbonyl.
In some preferred embodiments in accordance with embodiments (Id*),
X is hydrogen; W1 is N or CH, preferably N; W2 and W3 are CH; n is 1; m is 0;
R1 is C3-C10-carbocyclyl, preferably C3-C7-cycloalkyl, which is substituted with one phenyl (as cyclic R1c substituent) and optionally one or two non-cyclic R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl. C1 -C6-haloalkyl. C1 -C6-alkoxy and C1 -C6- haloalkoxy, wherein the phenyl may be substituted with one to three Rc substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl. C3-C7-cycloalkyl, C|-G,-haloalkyl. C1 -C6- alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl, and R2 and R3 are hydrogen.
More preferably, in these preferred embodiments in accordance with embodiments (Id*), R1 is cyclopropyl, which is substituted with phenyl, wherein the phenyl is substituted with one or two halogen, preferably fluorine substituents.
In some embodiments in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), one to three R1c substituent are present in residue R1: one R1c substituent selected from -NR21C(=0)0R21, -NR21C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2 and -0C(=0)N(R21)2 and optionally additionally one or two R1c substituents selected from the group consisting ofhalogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy and C1 - C6-haloalkoxy, wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6- haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 - -alkyl may be substituted with one or more Ra substituents as defined herein and wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents as defined herein. Preferably, in these embodiments, each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl. C1 -C6-haloalkyl and C3-C6-cycloalkyl.
In some embodiments in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), one to three R1c substituent are present in residue R1: one R1c substituent selected from -NR21C(=0)0R21 and -NR21C(=0)R21 and optionally additionally one or two R1c substituents selected from the group consisting ofhalogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy and C1 -C6-haloalkoxy, wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents as defined herein and wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents as defined herein. Preferably, in these embodiments R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl and C3-C6-cycloalkyl.
In some embodiments in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), W1is N, and W2 and W3 are CH.
In some preferred embodiments in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), m is 0. In some other preferred embodiments in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), m is 1 or 2, preferably 1.
Preferably, in accordance with embodiments (la*), (lb*), (Ic*) and (Id*), R4 and R5 are independently selected from the group consisting of hydrogen, C1 -Crhaloalkyl and C1 -C4-alkyl, wherein the C1 -C4-alkyl may be substituted with one to three R4a substituents as described herein. Preferably, the R4a substituents are selected from the group consisting of halogen atom, cyano, carboxyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C1 -C6-alkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6- alkoxycarbonyl and C1 -C6-haloalkoxycarbonyl.
In some embodiments (referred herein as embodiment Ie), the compounds used according to the present invention are compounds of the formula (I) or salts, N-oxides or solvates thereof:
Figure imgf000030_0001
wherein
X is hydrogen or fluorine; W1, W2 and W3 are independently CH, CF or N, wherein W1 and W3 cannot both be N; n is 1 or 2, wherein if n is 2, the two [CR2R3] groups may be the same or different; m is 0 or 1;
R1 is phenyl or C3-C7-cycloalkyl, each of which may be substituted with one or more R1c substituents; R2 and R3 are independently selected from the group consisting of hydrogen, halogen atom and C1 - C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R2a substituents, or R2 and R3 form, together with the carbon atom to which they are linked, a C=0 group, or
R2 and R3 form, together with the carbon atom to which they are linked, a C3-C6 -cycloalkyl wherein said C3-C6-cycloalkyl may be substituted with one or more R2c substituents;
R4and R5 are independently selected from the group consisting of hydrogen, C1 -C8-haloalkyl and C1 -C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R4a substituents, R1c substituents are independently selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C3-C6-cycloalkyl, phenyl, -NR21C(=0)0R21 and -NR21C(=0)R21, wherein the C3-C6-cycloalkyl and phenyl may be substituted with one to three Rc substituents and each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl and C3-C6-cycloalkyl; R1c substituents are independently selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C Cg-haloalkyl. C1 -C6-alkoxy, CVCg-haloalkoxy and C1 -C6-alkoxy carbonyl, R2a and R4a are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, - Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6-haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 -C6-haloalkoxycarbonyl, aryloxy, C1 -C6- alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1 -C6-haloalkylcarbonylamino, C1 -C8- alkylsulfanyl, C1 -C8-alkylsulfmyl, C1 -C8-alkylsulfonyl, C1 -C8-alkylsulfonylamino, C1 -C8- haloalkylsulfonylamino, C 1 -C8-alkylsulfamoyl and di-(C1 -C8-alkyl)sulfamoyl;
R2c is selected from the group consisting of C1 -C6-alkyl, C1 -C6-haloalkyl, C2-C6-alkenyl, CVC6- alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6- alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, C1 -C6-alkoxy, C1 - C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6-haloalkylcarbonyl, C1 -C6- alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 -C6-haloalkoxy carbonyl, aryloxy, C1 -C6-alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1 -C6-haloalkylcarbonylamino, C1 - C8-alkylsulfanyl, C1 -C8-alkylsulfmyl, C1 -C8-alkylsulfonyl, C 1 - C 8 -al k y l s ul fo n y l am i n o . C1 -C8- haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8-alkyl)sulfamoyl.
Preferably, in accordance with embodiment (Ie), R2, R3, R4 and R5 are independently selected from the group consisting of hydrogen and C1 -C8-alkyl. in particular hydrogen, methyl and ethyl.
Preferably, in accordance with embodiment (Ie), at most one of W1, W2 and W3 is N.
The present invention also relates to the use of any compounds of formula (I) disclosed in Table 1.
The present invention also relates to compounds of formula (G) wherein
Figure imgf000032_0001
X is fluorine; W1, W2 and W3 are independently CH, CF or N, wherein W1 and W3 cannot both be N; n is 1 or 2, wherein if n is 2, the two [CR2R3] groups may be the same or different; m is 0, 1 or 2, wherein if m is 2, the two [CR4R5] groups may be the same or different;
R1 is aryl, heteroaryl, C3-C10-carbocyclyl or 3- to 10-membered-heterocyclyl, each of which may be substituted with one or more R1c substituents;
R2 and R3 are independently selected from the group consisting of hydrogen, halogen atom and C1 - C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R2a substituents, or R2 and R3 form, together with the carbon atom to which they are linked, a C=0 group, or
R2 and R3 form, together with the carbon atom to which they are linked, a C3-C6 -cycloalkyl wherein said C3-C6-cycloalkyl may be substituted with one or more R2c substituents;
R4and R5 are independently selected from the group consisting of hydrogen, C1 -C8-haloalkyl and C1 -C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R4a substituents, R1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l6- sulfanyl, C1 -C6-alkyl. C1 -C6-haloalkyl. C1 -C6-hydroxyalkyl. C1 -C6-cyanoalkyl. C1 -C6-alkoxy. C1 - C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkynyl. C|-Gralkylsulfanyl. C1 -C6-haloalkylsulfanyl. arylsulfanyl, C1 -C6-alkylsulfmyl, C1 -C6-haloalkylsulfinyl, arylsulfmyl, C3-C10-carbocyclyl, C3- C10-halocarbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, aryl-C1 -C6-alkyl, 3- to 10- membered-heterocyclyl-C1 -C6-alkyl, heteroaryl-C1 -C6-alkyl, C3-C10-carbocyclyl-C1 -C6-alkyl, -Si(C1 -C6-alkyl)3, -Si(aiyl)(C1 -C6-alkyl)2, -C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2,
-C(=0)N(0R21)R21, -C(=0)NR21N(R21)2, -C(=S)N(R21)2, -C(=NR21)R21, -C(=NR21)N(R21)2, -C(=NOR21)R21, -N(R21)2, -NR21C(=0)0R21, -N(0R21)C(=0)0R21, -NR21C(=0)N(R21)2,
-NR21C(=0)R21, -N(0R21)C(=0)R21, -NR21C(=S)R21, -NR21C(=S)N(R21)2, -NR21C(=NR21)R21, -OR21, -OC(=0)R21, -0C(=0)N(R21)2, -NR21S(=0)2R21, -N=CR21-N(R21)2, -S(=0)2R21, -S(=0)2N(R21)2 and -P(=0)(0R21)2, wherein the C1 - -alkyl, C1 -C6-alkoxy, C2-C6 -alkenyl and C2-C6-alkynyl may be substituted with one or more Ra substituents; wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, arylsulfanyl and arylsulfmyl may be substituted with one or more Rc substituents; and wherein R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6- haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents and wherein the C3-C10- carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents;
R2a , R4a and Ra are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6- alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6- alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6-haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 -C6-haloalkoxycarbonyl, aryloxy, C1-C6- alkylcarbonyloxy, C1 -C6-alkylcarbonylamino. C1 -C6-haloalkylcarbonylamino. C1 -C8- alkylsulfanyl, C1 -C8-alkylsulfmyl, C1 -C8-alkylsulfonyl. C1 -C8-alkylsulfonylamino. C1 -C8- haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8-alkyl)sulfamoyl;
R2c and Rc are independently selected from the group consisting of C1 -C6-alkyl, C1 -C6-haloalkyl. C2- C6-alkenyl, C2-C6-alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8- halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6- alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1-C6- haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 - C6-haloalkoxycarbonyl, aryloxy, C1 -C6-alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1 -C6- haloalkylcarbonylamino, C1 -C8-alkylsulfanyl, C1 -C8-alky l sulfiny l . C1 -C8-alkylsulfonyl. C1 -C8- alkylsulfonylamino, C1 -C8-haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8- alkyl)sulfamoyl; as well as their salts, N-oxides and solvates.
The above specified preferred definitions of X, W1, W2, W3, m, R1, R2, R3, R4 and R5 for the use of the compounds of formula (I) according to the invention also apply to the compounds of formula (T) according to the invention. The above specified embodiments (la), (la*), (lb), (lb*), (Ic), (Ic*), (Id) and (Id*) for the use of the compounds of formula (I) according to the invention also apply to the compounds of formula (G) according to the invention, with the additional restriction that X is fluorine.
The present invention also relates to compounds of formula (I”) wherein
X is hydrogen or fluorine; W1, W2 and W3 are independently CH, CF or N, wherein W1 and W3 cannot both be N; n is 2, wherein the two [CR2R3] groups may be the same or different; m is 0, 1 or 2, wherein if m is 2, the two [CR4R5] groups may be the same or different;
R1 is aryl, heteroaryl, C3-C10-carbocyclyl or 3- to 10-membered-heterocyclyl, each of which may be substituted with one or more R1c substituents;
R2 and R3 are independently selected from the group consisting of hydrogen, halogen atom and C1 - C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R2a substituents, or R2 and R3 form, together with the carbon atom to which they are linked, a C=0 group, or
R2 and R3 form, together with the carbon atom to which they are linked, a C3-C6 -cycloalkyl wherein said C3-C6-cycloalkyl may be substituted with one or more R2c substituents;
R4and R5 are independently selected from the group consisting of hydrogen, C1 -C8-haloalkyl and C1 -C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R4a substituents, R1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l6- sulfanyl, C1 -C6-alkyl. C1 -C6-haloalkyl. C1 -C6-hydroxyalkyl. C1 -C6-cyanoalkyl. C1 -C6-alkoxy. C1 - C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkynyl. C|-Gralkylsulfanyl. C1 -C6-haloalkylsulfanyh arylsulfanyl, C1 -C6-alkylsulfinyl, C1 -C6-haloalkylsulfinyl, arylsulfmyl, C3-C10-carbocyclyl, C3- C10-halocarbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, aryl-C1 -C6-alkyl, 3- to 10- membered-heterocyclyl-C1 -C6-alkyl, heteroaryl-C1 -C6-alkyl, C3-C10-carbocyclyl-C1 -C6-alkyl, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, -C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2,
-C(=0)N(0R21)R21, -C(=0)NR21N(R21)2, -C(=S)N(R21)2, -C(=NR21)R21, -C(=NR21)N(R21)2, -C(=NOR21)R21, -N(R21)2, -NR21C(=0)0R21, -N(0R21)C(=0)0R21, -NR21C(=0)N(R21)2,
-NR21C(=0)R21, -N(0R21)C(=0)R21, -NR21C(=S)R21, -NR21C(=S)N(R21)2, -NR21C(=NR21)R21, -OR21, -OC(=0)R21, -0C(=0)N(R21)2, -NR21S(=0)2R21, -N=CR21-N(R21)2, -S(=0)2R21, -S(=0)2N(R21)2 and -P(=0)(0R21)2, wherein the C1 -C6-alkyl, C1 -C6-alkoxy, C2-C6 -alkenyl and C2-C6-alkynyl may be substituted with one or more Ra substituents; wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, arylsulfanyl and arylsulfmyl may be substituted with one or more Rc substituents; and wherein R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6- haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents and wherein the C3-C10- carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents;
R2a , R4a and Ra are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6- alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6- alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6-haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6- alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 -C6-haloalkoxycarbonyl, aryloxy, C1-C6- alkylcarbonyloxy, C1 -C6-alkylcarbonylamino. C1 -C6-haloalkylcarbonylamino. C 1 -C8- alkylsulfanyl, C1 -C8-alkylsulfinyl, C1 -C8-alkylsulfonyl. C1 -C8-alkylsulfonylamino, C 1 -C8- haloalkylsulfonylamino, C 1 -C8-alkylsulfamoyl and di-(C1 -C8-alkyl)sulfamoyl;
R2c and Rc are independently selected from the group consisting of C1 -C6-alkyl, C1 -C6-haloalkyl. C2- C6-alkenyl, C2-C6-alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8- halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6- alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1-C6- haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 - C6-haloalkoxycarbonyl, aryloxy, C1 -C6-alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1 -C6- haloalkylcarbonylamino, C1 -C8-alkylsulfanyl, C 1 -C8-alky l sulfiny l . C1 -C8-alkylsulfonyl. C1 -C8- alkylsulfonylamino, C1 -C8-haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8- alkyl)sulfamoyl; as well as their salts, N-oxides and solvates.
The above specified preferred definitions of X, W1, W2, W3, m, R1, R2, R3, R4 and R5 for the use of the compounds of formula (I) according to the invention also apply to the compounds of formula (I”) according to the invention. The above specified embodiments (la), (la*), (lb), (lb*), (Ic), (Ic*), (Id) and (Id*) for the use of the compounds of formula (I) according to the invention also apply to the compounds of formula (G) according to the invention, with the additional restriction that n is 2.
Processes for the preparation of compounds of formula (I) and intermediates
The present invention relates to processes for the preparation of compounds of formula (I) and their intermediates. Unless indicated otherwise, the radicals and indices R1, R2, R3, R4, R5, X, W1, W2, W3, m and n have the meanings given above for the compounds of formula (I). These definitions apply not only to the end products of formula (I) but also to all intermediates. Compounds of formula (I) can be prepared, according to process PI, by reacting intermediates of formula (II) with a dehydrating agent, such as methyl N-(triethylammoniumsulfonyl)carbamate (Burgess reagent) or 4-toluenesulfonyl chloride, in a suitable solvent such as tetrahydrofurane, as previously described in WO2017065473.
Figure imgf000036_0001
Intermediates of formula (II) can be prepared according to process P2, by reacting carbohydrazides of formula (III) with haloalkylacetic anhydride or haloalkylacetyl chloride in a suitable solvent such as tetrahydrofurane optionally in presence of a base such as triethylamine, as previously described in WO2017065473.
Figure imgf000036_0002
Process P2
Carbohydrazides of formula (III) can be prepared, according to process P3, by reacting a compound of formula (IV), wherein LG1 is a leaving group as for example ethoxy with hydrazine hydrate in a suitable solvent such as ethanol, as previously described in WO2017065473.
Figure imgf000036_0003
Process P3
Compounds of formula (IV) can be commercially available or may be prepared starting from readily available compounds according to known procedures. For example; compounds of formula IV can be prepared by carbonylation as described for example in W02017040449, US20160122318 or WO2018218051.
Alternatively, carbohydrazides of formula (III) can be prepared, according to process P4, by reacting a compound of formula (V) with an acid such as trifluoroacetic acid in a suitable solvent such as dichloromethane, preferably at room temperature, as previously described in Bioorganic & Medicinal Chemistry, 20(1), 487-497; 2012.
Figure imgf000037_0001
Process P4
Compounds of formula (V) may be prepared, according to process P5, by reacting a compound of formula (IV), wherein LG1 is a leaving group, as for example hydroxy with tert- butyl carbazate, optionally in presence of a coupling agent like for example ( 1 -[bis(dimethylamino)methylene]- 1 H- 1 2,3-triazolo|4.5- b]pyridinium 3-oxid hexafluorophosphate (HATU) or l-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC HCl), in a suitable solvent such as dichloromethane, optionally in presence of a base such as N,N-diisopropylethylamine, as previously described in Tetrahedron, 58(27), 5513-5523; 2002.
Figure imgf000037_0002
Process P5
Alternatively, intermediates of formula (II) can be prepared according to process P6, by reacting a compound of formula (IV), wherein LG1 is a leaving group as for example chlorine with 2,2- difluoroacetohydrazide or 2,2,2-trifluoroacetohydrazide in a suitable solvent such as tetrahydrofuran, acetonitrile or dichloromethane optionally in presence of a base such as triethylamine, as previously described in Russian Journal of Organic Chemistry, 43(11), 1686-1695; 2007 or Yingyong Huaxue, 13(5), 5-9; 1996.
Figure imgf000038_0001
Process P6
2,2-Difluoroacetohydrazide and 2,2,2-trifluoroacetohydrazide can be commercially available or may be prepared, according to known processes, as previously described in Synlett, (12), 1939-1941; 2005, Journal of Organic Chemistry, 78(16), 8054-8064; 2013, Chemistry of Heterocyclic Compounds (New York, NY, United States), 52(2), 133-139; 2016 or WO 2018233633.
Compounds of formula (IV’), wherein n = 1, can alternatively be prepared, according to process P7, by reacting a compound of formula (VII), wherein LG1 is a leaving group as for example ethoxy, wherein LG2 is a leaving group like for example bromine and wherein LG3 is a leaving group as for example methoxy or ethoxy by nucleophilic substitution and subsequent cyclisation with a compound of formula (VI) (as described for example in W02019027054 or European Journal of Organic Chemistry, 2020(17), 2565-2575) optionally in presence of a base, like for example N,N-diisopropylethylamine or potassium carbonate, in a solvent such as for example acetonitrile or N,N-dimethylformamide.
Figure imgf000038_0002
Process P7
Compounds of formula (VI) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
Compounds of formula (VII) can be commercially available or may be prepared starting from readily available compounds according to known procedures. Alternatively, compounds of formula (VII), can be prepared, according to process P8, by reacting a compound of formula (VIII), wherein LG1 is a leaving group as for example ethoxy and wherein LG3 is a leaving group like for example ethoxy or methoxy with an halogenating agent like for example isocyanuric chloride, as described for example in W02019027054 or with N-bromosuccinimide, as described for examples in Journal of Medicinal Chemistry, 60(19), 8027-8054; 2017.
Figure imgf000039_0001
Process P8 Compounds of formula (VIII) can be commercially available or may be prepared starting from readily available compounds according to known procedures.
Alternatively, compounds of formula (I), can be prepared, according to process P9, from a compound of formula (IX), by reaction with a compound of formula (X), wherein LG4 is a leaving group like for example bromine, as described for example in Journal of the American Chemical Society, 142(16), 7379- 7385; 2020, Organic Letters, 22(8), 2999-3003; 2020 or European Journal of Medicinal Chemistry, 138,
407-421; 2017, optionally in presence of a catalyst like for example copper iodide, optionally in presence of a base, like for example cesium carbonate or sodium hydride, in a solvent such as for example N,N- dimethylformamide, acetonitrile or tetrahydrofurane.
Figure imgf000039_0002
Compounds of formula (IX) may be prepared starting from readily available compounds analogously to process PI and P2 or P3 and P4 or P6.
Compounds of formula (X) can be commercially available or may be prepared starting from readily available compounds according to known procedures. Alternatively, compounds of formula (IX), can be prepared, according to process P10, from a compound of formula (XI), wherein PG is a protecting group like for example 4-methoxybenzyl, by state of the art deprotection method such as for example trifluoroacetic acid in a solvent such as dichloromethane as described in Journal of Medicinal Chemistry, 63(2), 656-675; 2020.
Figure imgf000040_0001
Process P10 Compounds of formula (XI) may be prepared starting from readily available compounds analogously to process PI and P2 or P3 and P4 or P6.
Compounds of formula (I) can be prepared, according to process PI 1, by reacting intermediates of formula (XII) with an acylating agent such as difluoroacetic anhydride, either neat or in a suitable solvent such as dichloromethane, as previously described in WO2018165520.
Figure imgf000040_0002
Process Pl l
Intermediates of formula (XII) can be prepared according to process P12, by reacting nitriles of formula (XIII) with a suitable reagent such as sodium azide in a suitable solvent such as N,N-dimethylformamide in presence of a base such as ammonium chloride or triethylamine, as previously described in WO200771455.
Figure imgf000040_0003
Process P12
Intermediates of formula (XIII) can be prepared, according to process PI 3, by treating a compound of formula (XIV), wherein LG1 is a leaving group as for example ethoxy with a suitable acid, such as hydrochloric acid or acetic acid, as previously described in WO201927054.
Figure imgf000041_0001
Process P13
Intermediates of formula (XIV) can be prepared, according to process P14, by reacting a compound of formula (XV), wherein LG1 is a leaving group as for example ethoxy and LG2 is a leaving group like for example bromine by nucleophilic substitution, optionally in presence of a base, like for example N,N- diisopropylethylamine or potassium carbonate, in a solvent such as for example acetonitrile or N,N- dimethylformamide as previously described in Tetrahedron 2006, 62, 8707-8714.
Figure imgf000041_0002
Process P14 Intermediates of formula (XV), can be prepared, according to process P15, by reacting a compound of formula (XVI), wherein LG1 is a leaving group as for example ethoxy with an halogenating agent like for example isocyanuric chloride, as described for example in WO2015173035.
Figure imgf000041_0003
Process P15 Compounds of formula (XVI) can be commercially available or may be prepared starting from readily available compounds according to known procedures
Intermediates of formula (IV), can alternatively be prepared, according to process PI 6, from a compound of formula (XVII), by esterification; a method known to the person skilled in the art. Process P16
Intermediates of formula (XVII), can be prepared, according to process PI 7, from a compound of formula (XVIII), by reaction with a compound of formula (X), wherein LG4 is a leaving group like for example bromine, in presence of a catalyst like for example copper iodide, optionally in presence of a base such as potassium phosphate, in a solvent such as for example dimethyl sulfoxide as described in WO2014210255. Alternatively intermediates of formula (XVII) can be prepared by substitution nucleophile in presence of a base like sodium hydride in a solvent such as DMF as described in US201134450.
Figure imgf000042_0001
Compounds of formula (XVIII) can be commercially available or may be prepared starting from readily available compounds according to known procedures
According to the invention, processes PI to P17 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 PI to P17 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, dichloroethane or trichloroethane ; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2- diethoxyethane or anisole ; nitriles, such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile ; amides, such as N,N-dimethylformamide. N,N-dimethylacetamide. N-methylform anilide. N- methylpyrrolidone 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 PI to P17 according to the invention are inorganic and organic bases which are customary for such reactions. Preference is given to using alkaline earth metal, alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-d i m e th y l an i l i n e . pyridine, N-methylpiperidine, N,N-dimethyl- aminopyridine, l,4-diazabicyclo[2.2.2]octane (DABCO), l,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1 , 8 -diazabicyclo [5.4.0]undec-7 -ene (DBU) .
When carrying out processes PI to PI 7, 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. A way to control the temperature for the processes is to use microwave technology.
Processes PI to P17 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.
Compositions and formulations
The present invention further relates to compositions, in particular compositions for controlling unwanted microorganisms. The composition may be applied to the microorganisms and/or in their habitat.
The composition comprises at least one compound of the invention and at least one agriculturally suitable auxiliary, e.g. carrier(s) and/or surfactant(s). 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, in particular ammonium sulfates, ammonium phosphates and ammonium nitrates, natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, silica gel 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, tetrahydronaphthalene, 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 ethanol, propanol, butanol, benzylalcohol, cyclohexanol 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 or fatty acid amides) and esters thereof, lactams (such as N-alkylpyrrolidones, in particular N-methylpyrrolidone) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide), oils of vegetable or animal origin. 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.
Preferred solid carriers are selected from clays, talc and silica.
Preferred liquid carriers are selected from water, fatty acid amides and esters thereof, aromatic and nonaromatic hydrocarbons, lactams and carbonic acid esters.
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.
Liquid carriers are typically present in a range of from 20 to 90%, for example 30 to 80% by weight of the composition.
Solid carriers are typically present in a range of from 0 to 50%, preferably 5 to 45%, for example 10 to 30% by weight of the composition.
If the composition comprises two or more carriers, the outlined ranges refer to the total amount of carriers.
The surfactant can be an ionic (cationic or anionic), amphoteric or non-ionic surfactant, such as ionic or non-ionic emulsifier(s), foam former(s), dispersant(s), wetting agent(s), penetration enhancer(s) and any mixtures thereof. Examples of suitable surfactants include, but are not limited to, salts of polyacrylic acid, salts of bgnosulfonic acid (such as sodium lignosulfonate), salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids or fatty amines (for example, polyoxyethylene fatty acid esters such as castor oil ethoxylate, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols) and ethoxylates thereof (such as tristyrylphenol ethoxylate), salts of sulfosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols (such a fatty acid esters of glycerol, sorbitol or sucrose), sulfates (such as alkyl sulfates and alkyl ether sulfates), sulfonates (for example, alkylsulfonates, arylsulfonates and alkylbenzene sulfonates), phosphate esters, protein hydrolysates, lignosulfite waste liquors and methylcellulose. Any reference to salts in this paragraph refers preferably to the respective alkali, alkaline earth and ammonium salts.
Preferred surfactants are selected from polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty acid esters, alkylbenzene sulfonates, such as calcium dodecylbenzenesulfonate, castor oil ethoxylate, sodium lignosulfonate and arylphenol ethoxylates, such as tristyrylphenol ethoxylate.
The amount of surfactants typically ranges from 5 to 40%, for example 10 to 20%, by weight of the composition.
Further examples of suitable auxiliaries 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 and tylose), thickeners and secondary thickeners (such as cellulose ethers, acrylic acid derivatives, xanthan gum, modified clays, e.g. the products available under the name Bentone, and finely divided silica), stabilizers (e.g. cold stabilizers, preservatives (e.g. dichlorophene and benzyl alcohol hemiformal), antioxidants, light stabilizers, in particular UV 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), antifreezes, 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 depends on the intended mode of application of the compound of the invention and/or on the physical properties of the compound(s). 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 of the invention 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 compositions 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 of the invention can be prepared in conventional manners, for example by mixing the compound of the invention with one or more suitable auxiliaries, such as disclosed herein above.
The composition comprises a f mgicidally effective amount of the compound(s) of the invention. The term "effective amount" denotes an amount, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the f ingal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound of the invention used. Usually, the composition according to the invention contains from 0.01 to 99% by weight, preferably from 0.05 to 98% by weight, more preferred from 0.1 to 95% by weight, even more preferably from 0.5 to 90% by weight, most preferably from 1 to 80% by weight of the compound of the invention. It is possible that a composition comprises two or more compounds of the invention. In such case the outlined ranges refer to the total amount of compounds of the present invention.
The composition of the invention may be in any customary composition type such as solutions (e.g. aqueous solutions), emulsions, water- and oil-based suspensions, powders (e.g. wettable powders, soluble powders), dusts, pastes, granules (e.g. 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 the invention may be present in a suspended, emulsified or dissolved form. Examples of particular suitable composition types are solutions, water-soluble concentrates (e.g. SL, LS), dispersible concentrates (DC), suspensions and suspension concentrates (e.g. SC, OD, OF, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME, SE), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GW, GF). These and further compositions types are defined by the Food and Agriculture Organization of the United Nations (FAO). An overview is given in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
Preferably, the composition of the invention is in form of one of the following types: EC, SC, FS, SE, OD and WG, more preferred EC, SC, OD and WG. Further details about examples of composition types and their preparation are given below. If two or more compounds of the invention are present, the outlined amount of compound of the invention refers to the total amount of compounds of the present invention. This applies mutatis mutandis for any further component of the composition, if two or more representatives of such component, e.g. wetting agent, binder, are present. i) Water-soluble concentrates (SL, LS)
10-60 % by weight of at least one compound of the invention and 5-15 % by weight surfactant (e.g. polyoxyethylene fatty alcohol ether) are dissolved in such amount of water and/or water-soluble solvent (e.g. alcohols such as propylene glycol or carbonates such as propylene carbonate) to result in a total amount of 100 % by weight. Before application the concentrate is diluted with water. ii) Dispersible concentrates (DC)
5-25 % by weight of at least one compound of the invention and 1-10 % by weight surfactant and/or binder (e.g. polyvinylpyrrolidone) are dissolved in such amount of organic solvent (e.g. cyclohexanone) to result in a total amount of 100 % by weight. Dilution with water gives a dispersion. iii) Emulsifiable concentrates (EC)
15-70 % by weight of at least one compound of the invention and 5-10 % by weight surfactant (e.g. a mixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in such amount of water-insoluble organic solvent (e.g. aromatic hydrocarbon or fatty acid amide) and if needed additional water-soluble solvent to result in a total amount of 100 % by weight. Dilution with water gives an emulsion. iv) Emulsions (EW, EO, ES)
5-40 % by weight of at least one compound of the invention and 1-10 % by weight surfactant (e.g. amixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 % by weight water- insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is added to such amount of water by means of an emulsifying machine to result in a total amount of 100 % by weight. The resulting composition is a homogeneous emulsion. Before application the emulsion may be further diluted with water. v) Suspensions and suspension concentrates v-1) Water-based (SC, FS)
In a suitable grinding equipment, e.g. an agitated ball mill, 20-60 % by weight of at least one compound of the invention are comminuted with addition of 2-10 % by weight surfactant (e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1 -2 % by weight thickener (e.g. xanthan gum) and water to give a fine active substance suspension. The water is added in such amount to result in a total amount of 100 % by weight. Dilution with water gives a stable suspension of the active substance. For FS type compositions up to 40 % by weight binder (e.g. polyvinylalcohol) is added. v-2) Oil-based (OD, OF)
In a suitable grinding equipment, e.g. an agitated ball mill, 20-60 % by weight of at least one compound of the invention are comminuted with addition of 2-10 % by weight surfactant (e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1-2 % by weight thickener (e.g. modified clay, in particular Bentone, or silica) and an organic carrier to give a fine active substance oil suspension. The organic carrier is added in such amount to result in a total amount of 100 % by weight. Dilution with water gives a stable dispersion of the active substance. vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 % by weight of at least one compound of the invention are ground finely with addition of surfactant (e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether) and converted to water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). The surfactant is used in such amount to result in a total amount of 100 % by weight. Dilution with water gives a stable dispersion or solution of the active substance. vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 % by weight of at least one compound of the invention are ground in a rotor-stator mill with addition of 1-8 % by weight surfactant (e.g. sodium lignosulfonate, polyoxyethylene fatty alcohol ether) and such amount of solid carrier, e.g. silica gel, to result in a total amount of 100 % by weight. Dilution with water gives a stable dispersion or solution of the active substance. viii) Gel (GW, GF)
In an agitated ball mill, 5-25 % by weight of at least one compound of the invention are comminuted with addition of 3-10 % by weight surfactant (e.g. sodium lignosulfonate), 1-5 % by weight binder (e.g. carboxymethylcellulose) and such amount of water to result in a total amount of 100 % by weight. This results in a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance. ix) Microemulsion (ME)
5-20 % by weight of at least one compound of the invention are added to 5-30 % by weight organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 % by weight surfactant blend (e.g. polyoxyethylene fatty alcohol ether and arylphenol ethoxylate), and such amount of water to result in a total amount of 100 % by weight. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion. x) Microcapsules (CS)
An oil phase comprising 5-50 % by weight of at least one compound of the invention, 0-40 % by weight water-insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 % by weight acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 % by weight of at least one compound of the invention, 0-40 % by weight water-insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 % by weight of the total CS composition. xi) Dustable powders (DP, DS)
1-10 % by weight of at least one compound of the invention are ground finely and mixed intimately with such amount of solid carrier, e.g. finely divided kaolin, to result in a total amount of 100 % by weight. xii) Granules (GR, FG)
0.5-30 % by weight of at least one compound of the invention are ground finely and associated with such amount of solid carrier (e.g. silicate) to result in atotal amount of 100 % by weight. Granulation is achieved by extrusion, spray-drying or the fluidized bed. xiii) Ultra-low volume liquids (UL)
1-50 % by weight of at least one compound of the invention are dissolved in such amount of organic solvent, e.g. aromatic hydrocarbon, to result in atotal amount of 100 % by weight.
The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 % by weight preservatives, 0.1-1 % by weight antifoams, 0.1-1 % by weight dyes and/or pigments, and 5-10% by weight antifreezes.
Mixtures/Combinations
The compound and the composition of the invention can be mixed with other active ingredients like fungicides, bactericides, acaricides, nematicides, insecticides, biological control agents or herbicides. Mixtures with fertilizers, growth regulators, safeners, nitrification inhibitors, semiochemicals and/or other agriculturally beneficial agents are also possible. 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 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, (1.011) 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,5 S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2 -methyl- 1 -( 1H- 1 ,2,4-triazol- 1 - ylmethyl)cyclopentanol, ( 1.027) ( 1 S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2 -methyl- 1 -( 1H- 1 ,2,4- triazol- l-ylmethyl)cyclopentanol, (1.028) (2R)-2-(l-chlorocyclopropyl)-4-[(lR)-2,2- dichlorocyclopropyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan-2-ol, ( 1.029) (2R)-2-( 1 -chlorocyclopropyl)-4- [( 1 S)- 2,2-dichlorocyclopropyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan-2-ol, ( 1.030) (2R)-2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl] - 1 -( 1H- 1,2,4-triazol- 1 -yl)propan-2-ol, (1.031) (2S)-2-( 1 -chlorocyclopropyl)-4- [( 1 R)-2,2-dichlorocyclopropyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan-2-ol, (1.032) (2S)-2-( 1 -chloro- cyclopropyl)-4-[(lS)-2,2-dichlorocyclopropyl]-l-(lH-l,2,4-triazol-l-yl)butan-2-ol, (1.033) (2S)-2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl] - 1 -( 1H- 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)-l,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-
({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-l,3-dioxolan-2-yl}methyl)-lH-l, 2,4- triazole, (1.038) l-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-l,3-dioxolan-2- yl (methyl)- 1H- 1 ,2,4-triazole, (1.039) 1 - { [3 -(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2- yl]methyl}-lH-l,2,4-triazol-5-yl thiocyanate, (1.040) l-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4- difluorophenyl)oxiran-2-yl]methyl}-lH-l,2,4-triazol-5-yl thiocyanate, (1.041) l-{[rel(2R,3S)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-lH-l,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)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]- 2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6- trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-l-(2,4-dichloro- phenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.046) 2-
[(2S, 4R,5R)-l-(2, 4-dichlorophenyl)-5-hydroxy-2, 6, 6-trimethylheptan-4-yl]-2,4-dihydro-3H-l, 2,4- triazole -3 -thione, (1.047) 2-[(2S,4R,5S)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]- 2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.048) 2-[(2S,4S,5R)-l-(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,5 S)- 1 -(2,4- dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.050) 2-[l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3- thione, ( 1.051 ) 2- [2-chloro-4-(2,4-dichlorophenoxy)phenyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)propan-2-ol,
(1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-l-(lH-l,2,4-triazol-l-yl)butan-2-ol, (1.053) 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan-2-ol, (1.054) 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl] - 1 -( 1H- 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-l,2,4-triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluoro- phenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-l,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-l,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-l-(lH-l,2,4-triazol-l-ylmethyl)cyclopentanol, (1.060) 5 -(allylsulfanyl)- 1 - { [3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl } - 1H- 1 ,2,4- triazole, (1.061) 5-(allylsulfanyl)-l-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2- yl]methyl } - 1H- 1 ,2,4-triazole, ( 1.062) 5 -(allylsulfanyl)- 1 - { [rel(2R,3 S)-3 -(2-chlorophenyl)-2-(2,4- difluorophenyl)oxiran-2-yl]methyl} - 1H- 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-methybmido- formamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)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-trifluoro- ethyl)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-methybmidoformamide, (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-methylimidoformamide, (1.073) N'- (4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N'-[5-bromo-6-(2, 3-dihydro- lH-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimido- formamide, (1.075) N'-{4-[(4,5-dichloro-l,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N- methybmidoformamide, (1.076) N'-{5-bromo-6-[(lR)-l-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3- yl}-N-ethyl-N-methylimidoformamide, (1.077) N'-{5-bromo-6-[(lS)-l-(3,5-difluorophenyl)ethoxy]-2- methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.078) N'-{5-bromo-6-[(cis-4-isopropyl- cyclohexyl)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 -methybmidoformamide, (1.080) N'- { 5 -bromo-6-[ 1 -(3 ,5 -difluorophenyl)ethoxy] -2-methylpyridin-3 -yl } -N-ethyl-N-methylimido- formamide, (1.081) ipfentrifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-l- (lH-l,2,4-triazol-l-yl)propan-2-ol, (1.083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-l- ( 1 ,2,4-triazol- 1 -yl)propan-2-ol, (1.084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3 -pyridyl] - 1 -( 1 ,2,4- triazol-l-yl)propan-2-ol, (1.085) 3-[2-(l-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy- propyl]imidazole-4-carbonitrile, (1.086) fluoxytioconazole (4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-l,l- difluoro-2-hydroxy-3-(5-thioxo-4H-l,2,4-triazol-l-yl)propyl]-3-pyridyl]oxy]benzonitrile), (1.087) N- isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-l-hydroxy-l-phenylethyl)phenyl]-N- methylimidoformamide, (1.088) N'-{5-bromo-2-methyl-6-[(l-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-(l,2,4-triazol-l-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 1R,4S,9S), (2.011) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.012) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (2.015) isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.016) isopyrazam (syn-epimeric racemate 1RS,4SR,9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pydiflumetofen, (2.020) Pyraziflumid, (2.021) sedaxane, (2.022) l,3-dimethyl-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)-lH-pyrazole-4-carboxamide, (2.023) 1,3- dimethyl-N-[(3R)-l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl]-lH-pyrazole-4-carboxamide, (2.024) 1,3- dimethyl-N-[(3S)-l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl]-lH-pyrazole-4-carboxamide, (2.025) 1- methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-lH-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(l, l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)benzamide, (2.027) 3-
(difluoromethyl)- 1 -methyl-N-( 1 , 1 ,3 -trimethyl-2,3 -dihydro- lH-inden-4-yl)- lH-pyrazole-4-carboxamide, (2.028) inpyrfluxam, (2.029) 3-(difluoromethyl)-l-methyl-N-[(3S)-l,l,3-trimethyl-2,3-dihydro-lH- inden-4-yl]-lH-pyrazole-4-carboxamide, (2.030) fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7- fluoro-1, l,3-trimethyl-2,3-dihydro-lH-inden-4-yl]-l-methyl-lH-pyrazole-4-carboxamide, (2.032) 3-
(difluoromethyl)-N-[(3S)-7-fluoro-l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl]-l-methyl-lH-pyrazole-4- carboxamide, (2.033) 5,8-difhroro-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-l-methyl-lH-pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5- methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4- carboxamide, (2.037) N-(5 -chloro-2-ethylbenzyl)-N-cyclopropyl-3 -(difluoromethyl)-5 -fluoro- 1 -methyl - lH-pyrazole-4-carboxamide, (2.038) isoflucypram, (2.039) N-[(lR,4S)-9-(dichloromethylene)-l, 2,3,4- tetrahydro- 1 ,4-methanonaphthalen-5 -yl] -3 -(difluoromethyl)- 1 -methyl- lH-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- lH-pyrazole-4-carboxamide, (2.041 ) N- [ 1 -(2,4-dichlorophenyl)- 1 - methoxypropan-2-yl]-3-(difluoromethyl)-l-methyl-lH-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6- (trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4- carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-
(difluoromethyl)-5-fluoro-l -methyl- lH-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-
(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4- carboxamide, (2.045) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-N-[5-methyl-2-
(trifluoromethyl)benzyl]-lH-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5- fluoro-N-(2-fluoro-6-isopropylbenzyl)-l -methyl- lH-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3- (difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-l-methyl-lH-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-l-methyl-lH-pyrazole-4- carbothioamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-l-methyl- lH-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3 -(difluoromethyl)-5 -fluoro-N-(5 -fluoro-2- isopropylbenzyl)-l -methyl- lH-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N- (2-ethyl-4,5-dimethylbenzyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3- (difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (2.053) N- cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-l-methyl-lH-pyrazole-4- carboxamide, (2.054) N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-l- methyl- lH-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3- (difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2- cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (2.057) pyrapropoyne, (2.058) N-[rac-(lS,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)- nicotinamide, (2.059) N-[(lS,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide, (2.060) flubeneteram and (2.061) thifluxamide.
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, (3.011) 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-[({[(lE)-l-(3-{[(E)-l-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 -dimethyl pent-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-{[l-(4-chloro-2-fluorophenyl)-lH-pyrazol-3-yl]oxy}-2- (methoxyimino)-N,3 -dimethylpent-3 -enamide, (3.029) methyl { 5 -[3 -(2,4-dimethylphenyl)- lH-pyrazol- l-yl]-2-methylbenzyl} carbamate, (3.030) metyltetraprole, (3.031) florylpicoxamid and (3.032) metarylpicoxamid .
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, (4.011) 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)-l, 3-dimethyl- lH-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-l,3-dimethyl- lH-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-l,3-dimethyl-lH-pyrazol- 5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-l,3-dimethyl-lH-pyrazol-5- amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-l,3-dimethyl-lH-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-l,3-dimethyl-lH-pyrazol-5-amine, (4.018) 4-(2- chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)- 1,3-dimethyl- lH-pyrazol-5 -amine, (4.019) 4-(2-chloro- 4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-l,3-dimethyl-lH-pyrazol-5-amine, (4.020) 4-(2-chloro-4- fluorophenyl)-N-(2-chlorophenyl)- 1 ,3 -dimethyl- lH-pyrazol-5 -amine, (4.021 ) 4-(2-chloro-4- fluorophenyl)-N-(2-fluorophenyl)-l, 3-dimethyl- lH-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)-l, 3-dimethyl- lH-pyrazol-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4- fluorophenyl)-l, 3-dimethyl- lH-pyrazol-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro- 4-fluorophenyl)-l,3-dimethyl-lH-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, (5.011) 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-l-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 -(morphobn-4-yl)prop-2-en- 1 -one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-l-(morpholin-4-yl)prop-2-en-l-one.
10) Inhibitors of the lipid and membrane synthesis, for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
11) Inhibitors of the melanin biosynthesis, for example (11.001) tricyclazole, (11.002) 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, (15.011) 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) l-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2- yl}piperidin-l-yl)-2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone, (15.032) l-(4-{4-[(5S)-5- (2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l-yl)-2-[5-methyl-3- (trifluoromethyl)-lH-pyrazol-l-yl]ethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipymetitrone, (15.035) 2-[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{5-[2-(prop-2-yn-l- 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)- lH-pyrazol- 1 -yl] - 1 -[4-(4- { 5 -[2-chloro-6-(prop-2-yn- 1 -yloxy)phenyl] -4,5 -dihydro-
1.2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (15.037) 2-[3,5-bis(difluoromethyl)-lH- 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 -yl]ethanone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2- yl]quinazoline, (15.039) 2-{(5R)-3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4- yl)- 1 ,3 -thiazol-4-yl] -4,5 -dihydro- 1 ,2-oxazol-5 -yl } -3 -chlorophenyl methanesulfonate, ( 15.040) 2- { (5 S)-3 - [2-(l-{ [3, 5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4, 5-dihydro-
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-(l- { [3,5-bis(difluoromethyl)- lH-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl] -4,5-dihydro- 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-l-yl)quinoline, (15.047) quinofumelin, (15.048) 4-amino-5- fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2(lH)-one), (15.049) 4-oxo-4-[(2- phenylethyl)amino] butanoic acid, (15.050) 5-amino-l,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'- phenyl-N'-(prop-2-yn-l-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 - lH-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) quinobn-8-ol, (15.060) quinolin-8-ol sulfate (2: 1), (15.061) tert-butyl {6- [( { [( 1 -methyl- lH-tetrazol-5 -yl)(phenyl)methylene]amino } oxy)methyl]pyridin-2-yl} carbamate, (15.062) 5-fluoro-4-imino-3-methyl-l-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(lH)-one, (15.063) aminopyrifen, (15.064) (N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimido- formamide), (15.065) (N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methybmidoformamide), (15.066) (2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), (15.067) (5- bromo-l-(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) (l-(4,5-dimethyl-lH- benzimidazol- 1 -yl)-4,4-difluoro-3 ,3 -dimethyl-3 ,4-dihydroisoquinobne), (15.070) 8-fluoro-3 -(5 -fluoro-
3.3-dimethyl-3,4-dihydroisoquinolin-l-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-dihydroisoquinobn- 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)-l,2,4-oxadiazol-3-yl]phenyl}carbamate, (15.075) (N-{4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzyl}cyclopropanecarboxamide), (15.076) N-methyl-4-(5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzamide, (15.077) N-[(E)-methoxyimino- methyl]-4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzamide, (15.078) N-[(Z)-methoxyiminomethyl]- 4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzamide, (15.079) N-[4-[5-(trifluoromethyl)-l,2,4- oxadiazol-3-yl]phenyl]cyclopropanecarboxamide, (15.080) flufenoxadiazam (N-(2-fluorophenyl)-4-[5- (trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzamide), (15.081) 2,2-difluoro-N-methyl-2-[4-[5- (trifluoromethyl)-l,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)-l,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)-l,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.086) 4,4-dimethyl-l-[[4-[5-
(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.087) N-methyl-4-[5- (trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzenecarbothioamide, (15.088) 5-methyl- 1-[[4-[5- (trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.089) N-((2,3-difluoro-4-[5- (trifluoromethyl)-l,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}-l,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092) N-[[4-[5-
(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]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-l-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-methoxy-N-[[4- [5-(trifluoromethyl)- l,2,4-oxadiazol-3-yl]phenyl]methyl)cyclopropanecarboxamide, ( 15.096) N,2- dimethoxy-N-[[4-[5-(trifluoromethyl}-l,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-l-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.101) l-[[4-[5-
(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.102) 4,4-dimethyl-2-[[4-[5- (trifluoromethyl)-l,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)-l,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.105) l-[[3-fluoro-4-(5- (trifluoromethyl)-l,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 l-{4-[5- (trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]benzyl} - lH-pyrazole-4-carboxylate, (15.109) N,N-dimethyl- 1 -
{4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzyl}-lH-l,2,4-triazol-3-amine, (15.110) N-{2,3- difluoro-4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzyl}butanamide, (15.111) N-(l- methylcyclopropyl)-4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzamide, (15.112) N-(2,4- difluorophenyl)-4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzamide, (15.113) l-(5,6- dimethylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.114) l-(6-
(difluoromethyl)-5-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.115) 1- (5-(fluoromethyl)-6-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.116) 1- (6-(difluoromethyl)-5-methoxy-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.117) 4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.118) N-{4-[5- (trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl}propanamide, (15.119) 3-[2-(l-{[5-methyl-3-
(trifluoromethyl)- lH-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl] - 1 ,5 -dihydro-2, 4- benzodioxepin-6-yl methanesulfonate, (15.120) 9-fluoro-3-[2-(l-{[5-methyl-3-(trifluoromethyl)-lH- 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-(l-{ [3 ,5 -bis(difluoromethyl)- lH-pyrazol- 1 -yl] acetyl }piperidin-4-yl)- l,3-thiazol-4-yl]-l,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.122) 3-[2-(l-{[3,5- bis(difluoromethyl)- lH-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) l-(6,7-dimethylpyrazolo[l,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-l- phenylbutan-2-yl]quinoline-3-carboxamide, (15.126) N-(2, 4-dimethyl- l-phenylpentan-2-yl)-8- fluoroquinoline-3-carboxamide, (15.127) N-[(2S)-2,4-dimethyl-l-phenylpentan-2-yl]-8-fluoroquinoline- 3 -carboxamide, (15.128) picarbutrazox, (15.129) metyltretrapole, (15.130) cyclobutrifluram and (15.131) chloroinconazide .
All named mixing partners of the classes (1) to (15) as described here above can be present in the form of the free compound or, if their functional groups enable this, an agrochemically active salt thereof.
The compound and the composition of the invention may also be combined with one or more biological control agents.
As used herein, the term ’’biological control” is defined as control of harmful organisms such as a phytopathogenic fungi and/or insects and/or acarids and/or nematodes by the use or employment of a biological control agent.
As used herein, the term “biological control agent” is defined as an organism other than the harmful organisms and / or proteins or secondary metabolites produced by such an organism for the purpose of biological control. Mutants of the second organism shall be included within the definition of the biological control agent. The term “mutant” refers to a variant of the parental strain as well as methods for obtaining a mutant or variant in which the pesticidal activity is greater than that expressed by the parental strain. The ’’parent strain“ is defined herein as the original strain before mutagenesis. To obtain such mutants the parental strain may be treated with a chemical such as N-methyl-N'-nitro-N-nitrosoguanidine, ethylmethanesulfone, or by irradiation using gamma, x-ray, or UV-irradiation, or by other means well known to those skilled in the art. Known mechanisms of biological control agents comprise enteric bacteria that control root rot by out-competing fungi for space on the surface of the root. Bacterial toxins, such as antibiotics, have been used to control pathogens. The toxin can be isolated and applied directly to the plant or the bacterial species may be administered so it produces the toxin in situ.
A ’’variant” is a strain having all the identifying characteristics of the NRRL or ATCC Accession Numbers as indicated in this text and can be identified as having a genome that hybridizes under conditions of high stringency to the genome of the NRRL or ATCC Accession Numbers.
“Hybridization” refers to a reaction in which one or more polynucleotides react to form a complex that is stabilized via hydrogen bonding between the bases of the nucleotide residues. The hydrogen bonding may occur by Watson-Crick base pairing, Hoogstein binding, or in any other sequence-specific manner. The complex may comprise two strands forming a duplex structure, three or more strands forming a multi- stranded complex, a single self-hybridizing strand, or any combination of these. Hybridization reactions can be performed under conditions of different “stringency”. In general, a low stringency hybridization reaction is carried out at about 40 °C in 10 X SSC or a solution of equivalent ionic strength/temperature. A moderate stringency hybridization is typically performed at about 50 °C in 6 X SSC, and a high stringency hybridization reaction is generally performed at about 60 °C in 1 X SSC.
A variant of the indicated NRRL or ATCC Accession Number may also be defined as a strain having a genomic sequence that is greater than 85%, more preferably greater than 90% or more preferably greater than 95% sequence identity to the genome of the indicated NRRL or ATCC Accession Number. A polynucleotide or polynucleotide region (or a polypeptide or polypeptide region) has a certain percentage (for example, 80%, 85%, 90%, or 95%) of “sequence identity” to another sequence means that, when aligned, that percentage of bases (or amino acids) are the same in comparing the two sequences. This alignment and the percent homology or sequence identity can be determined using software programs known in the art, for example, those described in Current Protocols in Molecular Biology (F. M. Ausubel et al., eds., 1987).
NRRL is the abbreviation for the Agricultural Research Service Culture Collection, an international depositary authority for the purposes of deposing microorganism strains under the Budapest treaty on the international recognition of the deposit of microorganisms for the purposes of patent procedure, having the address National Center for Agricultural Utilization Research, Agricultural Research service, U.S. Department of Agriculture, 1815 North university Street, Peroira, Illinois 61604 USA.
ATCC is the abbreviation for the American Type Culture Collection, an international depositary authority for the purposes of deposing microorganism strains under the Budapest treaty on the international recognition of the deposit of microorganisms for the purposes of patent procedure, having the address ATCC Patent Depository, 10801 University Blvd., Manassas, VA 10110 USA.
Examples of biological control agents which may be combined with the compound and the composition of the invention are:
(A) Antibacterial agents selected from the group of:
(Al) bacteria, such as (ATI) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661, U.S. Patent No. 6,060,051); (A1.2) Bacillus sp., in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No. FERM BP-8234, U.S. Patent No. 7,094,592; (Al .3) Bacillus pumilus, in particular strain BU F-33, having NRRL Accession No. 50185 (available as part of the CARTISSA® product from BASF, EPA Reg. No. 71840-19); (A1.4) Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5)); (A 1.5) a Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297; (A1.6) Bacillus subtilis strain BU1814, (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE); (A1.7) Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC, a subsidiary of Mitsui & Co.; (A1.8) Bacillus subtilis CX-9060 from Certis USA LLC, a subsidiary of Mitsui & Co.; (A1.9) Paenibacillus polymyxa, in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.); (A1.10) Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena); (Al.l l) Pantoea agglomerans, in particular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICAL™ FD BIOPESTICIDE from Northwest Agri Products); and
(A2) fungi, such as (A2.1) Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 ormixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT®from bio-ferm, CH); (A2.2) Pseudozyma aphidis (as disclosed in WO2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem); (A2.3) Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR;
(B) biological fungicides selected from the group of:
(Bl) bacteria, for example (Bl.l) 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 (available as part of the CARTISSA product from BASF, EPA Reg. No. 71840-19); (B 1 .5) Bacillus amyloliquefaciens , in particular strain D747 (available as Double Nickel™ from Kumiai Chemical Industry Co., Ltd., having accession number FERM BP-8234, 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); (B 1.7) Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF SE), having Accession Number NRRL B-50595, U.S. Patent No. 5,061,495; (B1.8) Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE); (B 1.9) Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127- 5)); (B1.10) Bacillus mycoides, isolate J , having Accession No. B-30890 (available as BMJ TGAI® or WG and LifeGard™ from Certis USA LLC, a subsidiary of Mitsui & Co.); (Bl.l 1) Bacillus licheniformis, in particular strain SB3086 , having Accession No. ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAF™ from Novozymes); (B1.12) a Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297; (B1.13) Bacillus subtilis strain BU1814, (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE); (Bl.14) Bacillus subtilis CX-9060 from Certis USA LLC, a subsidiary of Mitsui & Co.; (B1.15) Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No. B-50768; WO 2014/028521) (STARGUS® from Marrone Bio Innovations); (B1.16) Bacillus amyloliquefaciens strain FZB42, Accession No. DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE); (B1.17) Bacillus licheniformis FMCHOOl and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation); (Bl.l 8) Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC, a subsidiary of Mitsui & Co.; (B1.19) Paenibacillus polymyxa ssp. plantarum (WO 2016/020371) from BASF SE; (B1.20) Paenibacillus epiphyticus (WO 2016/020371) from BASF SE; (B.1.21) Pseudomonas chlororaphis strain AFS009, having Accession No. NRRL B-50897, WO 2017/019448 (e.g., HOWLER™ and ZIO® from AgBiome Innovations, US); (B1.22) Pseudomonas chlororaphis, in particular strain MA342 (e.g. CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert); (B1.23) Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO-IRON® and ACTINOVATE® from Novozymes); (B1.24) Agrobacterium radiobacter strain K84 (e.g. GALLTROL-A® from AgBioChem, CA); (B1.25) Agrobacterium radiobacter strain K1026 (e.g. NOGALL™ from BASF SE); (B1.26) Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys); (B1.27) Bacillus subtilis IAB/BS03 (AVIV™ from STK Bio-Ag Technologies); (B1.28) Bacillus subtilis strain Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277); (B1.29) Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREEN™ from University of Pretoria); (B1.30) Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology); (B1.31) Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena); (B1.32) Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession No. DSM 7206) (MYCOSTOP® from Verdera; PREFENCE® from BioWorks; cf. Crop Protection 2006, 25, 468-475); (B1.33) Pseudomonas fluorescens strain A506 (e.g. BLIGHTBAN® A506 by NuFarm); 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 CropScience Biologies GmbH); (B2.2) Metschnikowia fructicola, in particular strain NRRL Y-30752; (B2.3) Microsphaeropsis ochracea; (B2.5) Trichoderma atroviride, in particular strain SCI (having Accession No. CBS 122089, WO 2009/116106 and U.S. Patent No. 8,431,120 (from Bi-PA)), strain 77B (T77 from Andermatt Biocontrol) or strain LU132 (e.g. Sentinel from Agrimm Technologies Limited); (B2.6) Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) or strain Cepa Simb-T5 (from Simbiose Agro); (B2.14) Gliocladium roseum (also known as Clonostachys rosea f. rosea), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 83(3): 519-524), or strain IK726 (Jensen DF, et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial f mgal antagonist Clonostachys rosea strain ‘IK726’; Australas Plant Pathol. 2007;36:95-101); (B2.35) Talaromyces flavus, strain VI 17b; (B2.36) Trichoderma viride, in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137); (B2.37) Trichoderma asperellum, in particular strain SKT-1, having Accession No. FERM P-16510 (e.g. ECO-HOPE® from Kumiai Chemical Industry), strain T34 (e.g. T34 Biocontrol by Biocontrol Technologies S.L., ES) or strain ICC 012 from Isagro; (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 Til (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 asperellum, in particular, strain kd (e.g. T-Gro from Andermatt Biocontrol); (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 by Certis, US); (B2.53) Trichoderma viride, strain TVl(e.g. Trianum-P by Koppert); (B2.54) Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia); (B2.56) Aureohasidium pullulans, in particular blastospores of strain DSM14940; (B2.57) Aureohasidium pullulans, in particular blastospores of strain DSM 14941; (B2.58) Aureohasidium 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, having Accession No. CBS122244, US 2010/0291039 (by Stichting Dienst Landbouwkundig Onderzoek); (B2.69) Gliocladium catenulatum (Synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g. Prestop ® by Lallemand); (B2.70) Lecanicillium lecanii (formerly known as Verticillium lecanii) conidia of strain KV01 (e.g. Vertalec® by Koppert/Arysta); (B2.71) Penicillium vermiculatum, (B2.72) Pichia anomala, strain WRL-076 (NRRL Y-30842), U.S. Patent No. 7,579,183; (B2.75) Trichoderma atroviride, strain SKT-1 (FERM P-16510), JP Patent Publication (Kokai) 11-253151 A; (B2.76) Trichoderma atroviride, strain SKT-2 (FERM P- 16511), JP Patent Publication (Kokai) 11-253151 A; (B2.77) Trichoderma atroviride, strain SKT-3 (FERM P-17021), JP Patent Publication (Kokai) 11-253151 A; (B2.78) Trichoderma gamsii (formerly T. viride), strain ICC080 (IMI CC 392151 CABI, e.g. BioDermaby AGROBIOSOL DE MEXICO, S.A. DE C.V.); (B2.79) Trichoderma harzianum, strain DB 103 (available as 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, having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil); (B2.83) Ulocladium oudemansii strain U3, having Accession No. NM 99/06216 (e.g., BOTRY- ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.), (B2.84) Verticillium albo-atrum (formerly V dahliae), strain WCS850 having Accession No. WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations); (B2.86) Verticillium chlamydosporium; (B2.87) mixtures of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012), having Accession No. CABI CC IMI 392716 and Trichoderma gamsii (formerly T. viride) strain ICC 080, having Accession No. IMI 392151 (e.g., BIO-TAM™ from Isagro USA, Inc. and BIODERMA® by Agrobiosol de Mexico, S.A. de C.V.); (B2.88) Trichoderma asperelloides IM41R (Accession No. NRRL B-50759) (TRICHO PUUS® from BASF SE); (B2.89) Aspergillus flavus strain NRRL 21882 (products known as AFLA-GUARD®from Syngenta/ChemChina); (B2.90) Chaetomium cupreum (Accession No. CABI 353812) (e.g. BIOKUPRUM™ by AgriLife); (B2.91) Saccharomyces cerevisiae, in particular strain LAS02 (from Agro-Levures et Derives), strain LAS 117 cell walls (CEREVISANE® from Lesaffre; ROMEO® from BASF SE), strains CNCM No. I- 3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR; (B2.92) Trichoderma virens strain G-41, formerly known as Gliocladium virens (Accession No. ATCC 20906) (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks, US); (B2.93) Trichoderma hamatum, having Accession No. ATCC 28012; (B2.94) Ampelomyces quisqualis strain AQ 10, having Accession No. CNCMI-807 (e.g., AQ 10® by IntrachemBio Italia); (B2.95) Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from Danstar Ferment); (B2.96) Penicillium steckii (DSM 27859; WO 2015/067800) from BASF SE; (B2.97) Chaetomium glohosum (available as RIVADIOM® by Rivale); (B2.98) Cryptococcus flavescens, strain 3C (NRRL Y-50378); (B2.99) Dactylaria Candida, (B2.100) Dilophosphora alopecuri (available as TWIST FUNGUS®); (B2.101) Fusarium oxysporum, strain Fo47 (available as FUSACLEAN® by Natural Plant Protection); (B2.102) Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L by Plant Products Co., CA); (B2.103) Trichoderma gamsii (formerly T. viride ), strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S .A. DE C.V.); (B2.104) Trichoderma fertile (e.g. product TrichoPlus from BASF); (B2.105) Muscodor roseus, in particular strain A3-5 (Accession No. NRRL 30548); (B2.106) Simplicillium lanosoniveum; biological control agents having an effect for improving plant growth and/or plant health which may be combined in the compound combinations according to the invention including
(Cl) bacteria selected from the group consisting of Bacillus pumilus, in particular strain QST2808 (having Accession No. NRRL No. B-30087); Bacillus suhtilis, in particular strain QST713/AQ713 (having NRRL Accession No. B-21661and described in U.S. Patent No. 6,060,051; available as SERENADE® OPTI or SERENADE® ASO from Bayer CropScience LP, US); Bacillus suhtilis, in particular strain AQ30002 (having Accession Nos. NRRL B-50421 and described in U.S. Patent Application No. 13/330,576); Bacillus suhtilis, in particular strain AQ30004 (and NRRL B-50455 and described in U.S. Patent Application No. 13/330,576); Sinorhizobium meliloti strain NRG- 185-1 (NITRAGIN® GOLD from Bayer CropScience); Bacillus suhtilis strain BUI 814, (available as TEQUALIS® from BASF SE); Bacillus suhtilis rm303 (RHIZOMAX® from Biofdm Crop Protection); Bacillus amyloliquefaciens pm414 (LOLI- PEPTA® from Biofilm Crop Protection); Bacillus mycoides BT155 (NRRL No. B-50921), Bacillus mycoides EE118 (NRRL No. B-50918), Bacillus mycoides EE141 (NRRL No. B-50916), Bacillus mycoides BT46-3 (NRRL No. B-50922), Bacillus cereus family member EE128 (NRRL No. B-50917), Bacillus thuringiensis BT013A (NRRL No. B-50924) also known as Bacillus thuringiensis 4Q7, Bacillus cereus family member EE349 (NRRL No. B-50928), Bacillus amyloliquefaciens SB3281 (ATCC # PTA- 7542; WO 2017/205258), Bacillus amyloliquefaciens TJ1000 (available as QUIKROOTS® from Novozymes); Bacillus firmus, in particular strain CNMC 1-1582 (e.g. VOTIVO® from BASL SE); Bacillus pumilus, in particular strain GB34 (e.g. YIELD SHIELD® from Bayer Crop Science, DE); Bacillus amyloliquefaciens, in particular strain IN937a; Bacillus amyloliquefaciens, in particular strain FZB42 (e.g. RHIZOVITAL® from ABiTEP, DE); Bacillus amyloliquefaciens BS27 (Accession No. NRRL B-5015); a mixture of Bacillus licheniformis FMCHOOl and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation); Bacillus cereus, in particular strain BP01 (ATCC 55675; e.g. MEPICHLOR® from Arysta Lifescience, US); Bacillus subtilis, in particular strain MBI 600 (e.g. SUBTILEX® from BASF SE); Bradyrhizobium japonicum (e.g. OPTIMIZE® from Novozymes); Mesorhizobium cicer (e.g., NODULATOR from BASF SE); Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE); Delftia acidovorans, in particular strain RAY209 (e.g. BIOBOOST® from Brett Young Seeds); Lactobacillus sp. (e.g. LACTOPLANT® from LactoPAFI); Paenibacillus polymyxa, in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.); Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena); Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.); Azospirillum lipoferum (e.g., VERTEX-IF™ from TerraMax, Inc.); a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos); Pseudomonas aeruginosa, in particular strain PN 1 ; Rhizobium leguminosarum, in particular bv. viceae strain Z25 (Accession No. CECT 4585); Azorhizobium caulinodans, in particular strain ZB-SK-5; Azotobacter chroococcum, in particular strain H23; Azotobacter vinelandii, in particular strain ATCC 12837 ; Bacillus siamensis, in particular strain KCTC 13613T: Bacillus tequilensis, in particular strain Nil - 0943; Serratia marcescens, in particular strain SRM (Accession No. MTCC 8708); Thiobacillus sp. (e.g. CROPAID® from Cropaid Ltd UK); and
(C2) fungi selected from the group consisting of Purpureoci Ilium lilacinum (previously known as Paecilomyces lilacinus) strain 251 (AGAL 89/030550; e.g. BioAct from Bayer CropScience Biologies GmbH)Penicillium bilaii, strain ATCC 22348 (e.g. JumpStart® from Acceleron BioAg), Talaromyces flavus, strain VI 17b; Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR), Trichoderma viride, e.g. strain B35 (Pietr et ah, 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137); Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132; e.g. Sentinel from Agrimm Technologies Limited); Trichoderma atroviride strain SCI described in International Application No. PCT/IT2008/000196); Trichoderma asperellum strain kd (e.g. T-Gro from Andermatt Biocontrol); Trichoderma asperellum strain Eco-T (Plant Health Products, ZA); Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert); Myrothecium verrucaria strain AARC-0255 (e.g. DiTera™ from Valent Biosciences); Penicillium bilaii strain ATCC ATCC20851; Pythium oligandrum strain Ml (ATCC 38472; e.g. Polyversum from Bioprepraty, CZ); Trichoderma virens strain GL-21 (e.g. SoilGard® from Certis, USA); Verticillium albo-atrum (formerly V dahliae) strain WCS850 (CBS 276.92; e.g. Dutch Trig from Tree Care Innovations); Trichoderma atroviride, in particular strain no. V08/002387, strain no. NMI No. V08/002388, strain no. NMI No. V08/002389, strain no. NMI No. V08/002390; Trichoderma harzianum strain ITEM 908; Trichoderma harzianum, strain TSTh20; Trichoderma harzianum strain 1295-22; Pythium oligandrum strain DV74; Rhizopogon amylopogon (e.g. comprised in Myco-Sol from Helena Chemical Company); Rhizopogon fulvigleba (e.g. comprised in Myco-Sol from Helena Chemical Company); and Trichoderma virens strain GI-3; insecticidally active biological control agents selected from
(Dl) bacteria selected from the group consisting of Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372; e.g. XENTARI® from Valent BioSciences); Bacillus mycoides, isolate J. (e.g. BmJ from Certis USA LLC, a subsidiary of Mitsui & Co.); Bacillus sphaericus, in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. VECTOLEX® from Valent BioSciences, US); Bacillus thuringiensis subsp. kurstaki strain BMP 123 from Becker Microbial Products, IL; Bacillus thuringiensis subsp. aizawai, in particular serotype H-7 (e.g. FLORBAC® WG from Valent BioSciences, US); Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g. DIPEL® ES from Valent BioSciences, US); Bacillus thuringiensis subsp. kurstaki strain BMP 123 by Becker Microbial Products, IL; Bacillus thuringiensis israelensis strain BMP 144 (e.g. AQUABAC® by Becker Microbial Products IL); Burkholderia spp., in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319; WO 2011/106491 and WO 2013/032693; e.g. MBI-206 TGAI and ZELTO® from Marrone Bio Innovations); Chromobacterium subtsugae, in particular strain PRAA4-1T (MBI-203; e.g. GRANDEVO® from Marrone Bio Innovations); Paenibacillus popilliae (formerly Bacillus popilliae,· e.g. MILKY SPORE POWDER™ and MILKY SPORE GRANULAR™ from St. Gabriel Laboratories); Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC® by Valent BioSciences, US); Bacillus thuringiensis var. kurstaki strain EVB-113-19 (e.g., BIOPROTEC® from AEF Global); Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428; e.g. NOVODOR® FC from BioFa DE); Bacillus thuringiensis var. japonensis strain Buibui; Bacillus thuringiensis subsp. kurstaki strain ABTS 351; Bacillus thuringiensis subsp. kurstaki strain PB 54; Bacillus thuringiensis subsp. kurstaki strain SA 11; Bacillus thuringiensis subsp. kurstaki strain SA 12; Bacillus thuringiensis subsp. kurstaki strain EG 2348; Bacillus thuringiensis var. Colmeri (e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory); Bacillus thuringiensis subsp. aizawai strain GC-91; Serratia entomophila (e.g. INVADE® by Wrightson Seeds); Serratia marcescens, in particular strain SRM (Accession No. MTCC 8708); and Wolbachia pipientis ZAP strain (e.g., ZAP MALES® from MosquitoMate); and (D2) fungi selected from the group consisting of Isaria fumosorosea (previously known as Paecilomyces fumosoroseus) strain apopka 97; Beauveria bassiana strain ATCC 74040 (e.g. NATURALIS® from Intrachem Bio Italia); Beauveria bassiana strain GHA (Accession No. ATCC74250; e.g. BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation); Zoophtora radicans; Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073), Me tar hi zium robertsii 23013-3 (deposited under NRRL accession number 67075), and Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074) (WO 2017/066094; Pioneer Hi-Bred International); Beauveria bassiana strain ATP02 (Accession No. DSM 24665). Among these, Isaria fumosorosea (previously known as Paecilomyces fumosoroseus) strain apopka 97 is particularly preferred;
(E) 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;
(L) bacteria and fungi which can be added as 'inoculanf 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.; and
(G) 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, mr/mr/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, as well as bioinsecticidal / acaricidal active substances obtained from olive oil, in particular unsaturated fatty/carboxylic acids having carbon chain lengths C16-C20 as active ingredients, such as, for example, contained in the product with the trade name FLiPPER®.
The compound and the composition of the invention may be combined with one or more active ingredients selected from insecticides, acaricides and nematicides. “Insecticides” as well as the term “insecticidal” refers to the ability of a substance to increase mortality or inhibit growth rate of insects. As used herein, the term “insects” comprises all organisms in the class “Insecta”.
“Nematicide” and “nematicidal” refers to the ability of a substance to increase mortality or inhibit the growth rate of nematodes. In general, the term “nematode” comprises eggs, larvae, juvenile and mature forms of said organism.
“Acaricide” and “acaricidal” refers to the ability of a substance to increase mortality or inhibit growth rate of ectoparasites belonging to the class Arachnida, sub-class Acari.
Examples of insecticides, acaricides and nematicides, respectively, which could be mixed with the compound and the composition of the invention 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, triclorfbn 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 [(lR)-trans-isomer], deltamethrin, empenthrin [(EZ)-(lR)-isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(lR)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)- 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 (GluCl) 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 sulphuryl 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 tenehrionis, and B.t. plant proteins: CrylAb, CrylAc, CrylFa, CrylA.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Abl/35Abl.
(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 ortetradifon.
(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, fteto-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, Fotilaner, 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: l-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-3-(trifluoromethyl)-lH- l,2,4-triazole-5-amine (known from W02006/043635) (CAS 885026-50-6), {l'-[(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-{l-[(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-l,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-l,8-diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP2647626) (CAS 1440516-42-6) , 4-(but-2-yn-l-yloxy)-6-(3,5-dimethylpiperidin-l-yl)-5- fluoropyrimidine (known from W02004/099160) (CAS 792914-58-0), PF1364 (known from JP2010/018586) (CAS 1204776-60-2), N-[(2E)-l-[(6-chloropyridin-3-yl)methyl]pyridin-2(lH)- ylidene]-2,2,2-trifluoroacetamide (known from WO2012/029672) (CAS 1363400-41-2), (3E)-3-[l-[(6- chloro-3-pyridyl)methyl]-2-pyridylidene]-l,l,l-trifluoro-propan-2-one (known from WO2013/144213) (CAS 1461743-15-6), , N-|3-(bcnzylcarbamoyl)-4-chlorophcnyl |-l-methyl-3-(pcntafluorocthyl)-4-
(trifluoromethyl)-1H-pyrazole -5 -carboxamide (known from W02010/051926) (CAS 1226889-14-0), 5- bromo-4-chloro-/V-[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-N-(cis- 1 -oxido-3 -thietanyl)-benzamide, 4-[5 -(3 ,5 - dichlorophenyl)-4, 5 -dihydro-5 -(trifluoromethyl)-3 -isoxazolyl] - 2 -m c th y l - N- ( trans - 1 -oxido-3 -thietanyl)- benzamide and 4-|(5,S)-5-(3.5-dichlorophcnyl)-4.5-dihydro-5-(trifluoromethyl)-3-isoxazolyl |-2-methyl- N-(cis-l -oxido-3 -thietanyl)benzamide (known from WO 2013/050317 Al) (CAS 1332628-83-7), N-| 3- chloro- 1 -(3-pyridinyl)-1H-pyrazol-4-yl |-N-cthyl-3-|(3.3.3-trifluoropropyl)sulfmyl |-propan amide. (+)-N- [3 -chloro- 1 -(3 -pyridinyl)- 1H-pyrazol-4-yl | -N-cthyl-3 - [(3 ,3,3 -trifluoropropyl)sulfinyl] -propanamide and (-)-N-|3-chloro- 1 -(3-pyridinyl)- 1H-pyrazol-4-yl |-N-cthyl-3-| (3.3.3-trifluoropropyl)sulfmyl |- propanamide (known from WO 2013/162715 A2, WO 2013/162716 A2, US 2014/0213448 Al) (CAS 1477923-37-7), 5-[[(2£)-3-chloro-2-propen-l-yl]amino]-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4- I (trifluoromcthy l )sulfin1 ] |-1H-pyrazolc-3-carbonitrilc (known from CN 101337937 A) (CAS 1105672- 77-2), 3-bromo-N-|4-chloro-2-methyl-6-|(methylamino)thioxomethyl | phenyl |- 1 -(3-chloro-2-pyridinyl)-1H-pyrazole-5 -carboxamide, (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9);N-|4-chloro-2-||( 1 , 1 -dimethylethyl)amino] carbonyl] -6-methylphenyl] - 1 -(3-chloro-2-pyridinyl)-3- (fluoromethoxy)-1H-Pyrazole-5 -carboxamide (known from WO 2012/034403 Al) (CAS 1268277-22-0),N-|2-(5-amino- 1.3.4-th iadiazol-2-yl)-4-chloro-6-methylphenyl |-3-bromo- 1 -(3-chloro-2-pyridinyl)-1H- pyrazole-5 -carboxamide (known from WO 2011/085575 Al) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4- [(3,3-dichloro-2-propen-l-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN 101337940 A) (CAS 1108184-52-6); (2 E)- and 2(Z)-2-[2-(4-cyanophenyl)-l-[3- (trifluoromethyl)phcnyl |cthylidcnc |-N-|4-(difluoromcthoxy)phcnyl |-hydrazinccarboxamidc (known from CN 101715774 A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H- 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 lcarbonyl ]-indeno] 1.2-e]|| 1.3.4|oxadiazinc-4a(3H)-carboxylic acid methyl ester (known from CN 102391261 A) (CAS 1370358-69-2); 6-deoxy-3-0-ethyl-2,4-di-0-methyl-, l-[N-[4-[l-[4-(l,l,2,2,2- pentafluoroethoxy)phenyl] -1H-1 ,2,4-triazol-3 -yl]phenyl] carbamate] -a-L-mannopyranose (known from US 2014/0275503 Al) (CAS 1181213-14-8); 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3- (6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1 ]ocotane (CAS 1253850-56-4), (8-anti)-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-cyclopropylmcthoxy-4-trifluoromethyl-phcnoxy) -3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (known from WO 2007040280 Al, WO 2007040282 Al) (CAS 934001-66-8), N-[3-chloro-l-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3- [(3, 3, 3 -trifluoropropyl)thio] -propanamide (known from WO 2015/058021 Al, WO 2015/058028 Al) (CAS 1477919-27-9) and N-[4-(aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3- bromo- 1 -(3-chloro-2-pyridinyl)- 1H-pyrazolc-5-carboxamidc (known from CN 103265527 A) (CAS 1452877-50-7), 5-(l,3-dioxan-2-yl)-4-[[4-(trifluoromethyl)phenyl]methoxy]-pyrimidine (known from WO 2013/115391 Al) (CAS 1449021-97-9), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-l- methyl-l,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010/066780 Al, WO 2011/151146 Al) (CAS 1229023-34-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-l-methyl-l,8-diazaspiro[4.5]decane- 2,4-dione (known from WO 2014/187846 Al) (CAS 1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8- methoxy-l-methyl-2-oxo-l,8-diazaspiro[4.5]dec-3-en-4-yl-carbonic acid ethyl ester (known from WO 2010/066780 Al, WO 2011151146 Al) (CAS 1229023-00-0), N-[l-[(6-chloro-3-pyridinyl)methyl]- 2(1H)-pyridinylidene]-2,2,2-trifluoro-acetamide (known from DE 3639877 Al, WO 2012029672 Al) (CAS 1363400-41-2), | N(E) |-N-| 1 -| (6-chloro-3-pyridinyl)methyl |-2( 1 H)-pyridinylidcnc|-2.2.2-trifluoro- acetamide, (known from WO 2016005276 Al) (CAS 1689566-03-7), [N(Z)]-N-[l-[(6-chloro-3- pyridinyl)methyl]-2(lH)-pyridinylidene]-2,2,2-trifluoro-acetamide, (CAS 1702305-40-5), 3-endo-3-[ 2- propoxy-4-(trifluoromethyl)phenoxy]-9-[[5-(trifluoromethyl)-2-pyridinyl]oxy]-9- azabicyclo [3.3.1 Jnonane (known from WO 2011/105506 Al, WO 2016/133011 Al) (CAS 1332838-17- 1).
Examples of herbicides which could be mixed with the compound and the composition of the invention are:
Acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim- sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-lEl- indol-6-yl)pyridine-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, bixlozone, 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, l-{2-chloro-3-[(3-cyclopropyl-5- hydroxy-1 -methyl- lH-pyrazol-4-yl)carbonyl]-6-(trifluormethyl)phenyl}piperidin-2-on, 4-{2-chloro-3- [(3,5-dimethyl-lH-pyrazol-l-yl)methyl]-4-(methylsulfonyl)benzoyl}-l,3-dimethyl-lH-pyrazol-5-yl-l,3- dimethyl- lH-pyrazol-4-carboxylat, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, 2-[2-chloro-4-(methylsulfonyl)-3- (morpholin-4-ylmethyl)benzoyl] -3 -hydroxy cyclohex-2-en- 1 -on, 4- {2-chloro-4-(methylsulfonyl)-3 -
[(2,2,2-trifluorethoxy)methyl]benzoyl } - 1 -ethyl- lH-pyrazol-5 -yl- 1 ,3 -dimethyl- lH-pyrazol-4-carboxylat, chlorophthalim, chlorotoluron, chlorthal-dimethyl, 3-[5-chloro-4-(trifluormethyl)pyridine-2-yl]-4- hydroxy-l-methylimidazolidine-2-on, chlorsulfuron, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyranil, 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, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, 3-(2,6- dimethylphenyl)-6-[(2-hydroxy-6-oxocyclohex-l-en-l-yl)carbonyl]-l-methylchinazolin-2,4(lH,3H)- dion, 1 ,3 -dimethyl -4- [2-(methylsulfonyl)-4-(trifluormethyl)benzoyl] - lH-pyrazol-5 -yl- 1 ,3 -dimethyl- 1H- pyrazol-4-carboxylat, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat, diquat-dibromid, dithiopyr, diuron, DMPA, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, etha- metsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, ethyl-[(3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluormethyl)-3,6-dihydropyrimidin-l(2H)- yl]phenoxy}pyridin-2-yl)oxy]acetat, F-9960, F-5231, i.e. N-{2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-5- oxo-4, 5-dihydro-lH-tetrazol-l-yl]phenyl}ethanesulfonamide, F-7967, i. e. 3-[7-chloro-5-fluoro-2- (trifluoromethyl)-lH-benzimidazol-4-yl]-l-methyl-6-(trifluoromethyl)pyrimidine-2,4(lH,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, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, fluro- chloridone, 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, -isopropyl ammonium, -diammonium, -dimethylammonium, -potassium, -sodium, and -trimesium, H-9201, i.e. O- (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. 1- (dimethoxyphosphoryl) ethyl-(2,4-dichlorophenoxy)acetate, 4-hydroxy- 1 -methoxy-5 -methyl-3- [4-
(trifluormethyl)pyridine-2-yl]imidazolidine-2-on, 4-hydroxy-l-methyl-3-[4-(trifluormethyl)pyridine-2- yl]imidazolidine-2-on, (5-hydroxy-l-methyl-lH-pyrazol-4-yl)(3,3,4-trimethyl-l,l-dioxido-2,3-dihydro- 1 -benzothiophen-5 -yl)methanon, 6-[(2-hydroxy-6-oxocyclohex- 1 -en- 1 -yl)carbonyl] - 1 ,5 -dimethyl-3 -(2- methylphenyl)chinazolin-2,4(lH,3H)-dion, 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)-l-methyl-3-(trifluoromethyl)-lH-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, -ethy,l 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, 2-({2-[(2- methoxyethoxy)methyl]-6-(trifluormethyl)pyridin-3-yl}carbonyl)cyclohexan-l,3-dion, methyl isothiocyanate, l-methyl-4-[(3,3,4-trimethyl-l,l-dioxido-2,3-dihydro-l-benzothiophen-5-yl)carbonyl]- lH-pyrazol-5-ylpropan-l-sulfonat, 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-011, napropamide, NC- 310, i.e. [5-(benzyloxy)-l-methyl-lH-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, QYM-201, QYR-301, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrion, sulfentrazone, sulfometuron, sulfometuron- methyl, sulfosulfuron, SYN-523, SYP-249, i.e. l-ethoxy-3-methyl-l-oxobut-3-en-2-yl 5-[2-chloro-4- (trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. l-[7-fluoro-3-oxo-4-(prop-2-yn-l-yl)-3,4- dihydro-2H- 1 ,4-benzoxazin-6-yl] -3 -propyl-2-thioxoimidazolidine-4,5 -dione, 2,3 ,6-TB A, TCA
(trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazin, terbutryn, tetflupyrolimet, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, topra- mezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vemolate, ZJ-0862, i.e. 3,4-dichloro-N-{2-[(4,6- dimethoxypyrimidin-2-yl)oxy]benzyl}aniline.
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, gibberelbc 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-(l-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.
Examples of safeners which could be mixed with the compound and the composition of the invention 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}- sulphonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-l-oxa-4-azaspiro[4.5]decane (CAS 71526- 07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-l,3-oxazolidine (CAS 52836-31-4).
Examples of nitrification inhibitors which can be mixed with the compound and the composition of the invention are selected from the group consisting of 2-(3, 4-dimethyl- 1 H-pyrazol-1 -yl)succinic acid, 2- (4,5-dimethyl-l H-pyrazol-1 -yl)succinic acid, 3,4-dimethyl pyrazolium glycolate, 3,4-dimethyl pyrazolium citrate, 3,4-dimethyl pyrazolium lactate, 3,4-dimethyl pyrazolium mandelate, 1 ,2,4-triazole, 4-Chloro-3-methylpyrazole, N-((3(5)-methyl-lH-pyrazole-l-yl)methyl)acetamide, N-((3(5)-methyl-l H- pyrazole-l-yl)methyl)formamide, N-((3(5),4-dimethylpyrazole-l-yl)methyl)formamide, N-((4-chloro- 3(5)-methyl-pyrazole-l-yl)methyl)formamide; reaction adducts of dicyandiamide, urea and formaldehyde, triazonyl- formaldehyde-dicyandiamide adducts, 2-cyano- l-((4-oxo- 1,3, 5 -triazinan-1- yl)methyl)guanidine, l-((2-cyanoguanidino)methyl)urea, 2-cyano- 1 -((2 -cyanoguanidino)methyl)- guanidine, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide, 3,4-dimethyl pyrazole phosphate, 4,5-dimethyl pyrazole phosphate, 3,4-dimethylpyrazole, 4,5-dimethyl pyrazole, ammoniumthiosulfate, neem, products based on ingredients of neem, linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate, karanjin, brachialacton, p- benzoquinone sorgoleone, 4-amino- 1,2, 4-triazole hydrochloride, l-amido-2 -thiourea, 2-amino-4-chloro- 6-methylpyrimidine, 2-mercapto-benzothiazole, 5 -ethoxy-3 -trichloromethyl- 1 ,2,4-thiodiazole (terrazole, etridiazole), 2-sulfanilamidothiazole, 3-methylpyrazol, 1,2,4-triazol thiourea, cyan amide, melamine, zeolite powder, catechol, benzoquinone, sodium tetraborate, allylthiourea, chlorate salts, and zinc sulfate.
The compound and the composition of the invention may be combined with one or more agriculturally beneficial agents.
Examples of agriculturally beneficial agents include biostimulants, plant growth regulators, plant signal molecules, growth enhancers, microbial stimulating molecules, biomolecules, soil amendments, nutrients, plant nutrient enhancers, etc., such as lipo-chitooligosaccharides (LCO), chitooligosaccharides (CO), chitinous compounds, flavonoids, jasmonic acid or derivatives thereof (e.g., jasmonates), cytokinins, auxins, gibberellins, absiscic acid, ethylene, brassinosteroids, salicylates, macro- and micro-nutrients, linoleic acid or derivatives thereof, linolenic acid or derivatives thereof, karrikins, and beneficial microorganisms (e.g., Rhizobium spp., Bradyrhizobium spp., Sinorhizobium spp., Azorhizobium spp., Glomus spp., Gigaspora spp., Hymenoscyphous spp., Oidiodendron spp., Laccaria spp., Pisolithus spp., Rhizopogon spp., Scleroderma spp., Rhizoctonia spp., Acinetobacter spp.. Arlhrobacler spp., Arthrobotrys spp., Aspergillus spp., Azospirillum spp., Bacillus spp., Burkholderia spp., Candida spp., Chryseomonas spp., Enterobacter spp., Eupenicillium spp., Exiguobacterium spp., Klebsiella spp., Kluyvera spp., Microbacterium spp., Mucor spp., Paecilomyces spp., Paenibacillus spp., Penicillium spp., Pseudomonas spp., Serratia spp., Stenotrophomonas spp., Streptomyces spp., Streptosporangium spp., Swaminathania spp., Thiobacillus spp., Torulospora spp., Vibrio spp., Xanthobacter spp., Xanthomonas spp., etc.), and combinations thereof.
Methods and uses
The compound and the composition of the invention have potent microbicidal activity and/or plant defense modulating potential. They can be used for controlling unwanted microorganisms, such as unwanted fungi and bacteria, on plants. 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 compound and the composition of the invention 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 compound and the composition of the invention 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.
The compound and the composition of the invention may also be used as antibacterial agent. In particular, they may be used in crop protection, for example for the control of unwanted bacteria, such as Pseudomonadaceae, Rhizobiaceae, Xanthomonadaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae .
The compound and the composition of the invention may also be used as antiviral agent in crop protection. For example the compound and the composition of the invention may have effects on diseases from plant viruses, such as the tobacco mosaic virus (TMV), tobacco rattle virus, tobacco stunt virus (TStuV), tobacco leaf curl virus (VLCV), tobacco nervilia mosaic virus (TVBMV), tobacco necrotic dwarf virus (TNDV), tobacco streak virus (TSV), potato virus X (PVX), potato viruses Y, S, M, and A, potato acuba mosaic virus (PAMV), potato mop-top virus (PMTV), potato leaf-roll virus (PLRV), alfalfa mosaic virus (AMV), cucumber mosaic virus (CMV), cucumber green mottlemosaic virus (CGMMV), cucumber yellows virus (CuYV), watermelon mosaic virus (WMV), tomato spotted wilt virus (TSWV), tomato ringspot virus (TomRSV), sugarcane mosaic virus (SCMV), rice drawf virus, rice stripe virus, rice black- streaked drawf virus, strawberry mottle virus (SMoV), strawberry vein banding virus (SVBV), strawberry mild yellow edge virus (SMYEV), strawberry crinkle virus (SCrV), broad beanwilt virus (BBWV), and melon necrotic spot virus (MNSV).
The present invention also relates to a method for controlling unwanted microorganisms, such as unwanted fungi, oomycetes and bacteria, on plants comprising the step of applying at least one compound of the invention or at least one composition of the invention 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 compound and the composition of the invention 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 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.
Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoots, leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, 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.
Plants and plant cultivars which may 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 may 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 may be treated by the above disclosed methods include those plants characterized by enhanced yield characteristics. Increased yield in said plants may 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 may 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, intemode 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 may 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.
Transgenic plants, seed treatment and integration events
The compound according to the invention can be advantageously used to treat transgenic plants, plant cultivars or plant parts that received genetic material which imparts advantageous and/or useful properties (traits) to these plants, plant cultivars or plant parts. Therefore, it is contemplated that the present invention may be combined with one or more recombinant traits or transgenic event(s) or a combination thereof. For the purposes of this application, a transgenic event is created by the insertion of a specific recombinant DNA molecule into a specific position (locus) within the chromosome of the plant genome. The insertion creates a novel DNA sequence referred to as an “event” and is characterized by the inserted recombinant DNA molecule and some amount of genomic DNA immediately adjacent to/flanking both ends of the inserted DNA. Such trait(s) or transgenic event(s) include, but are not limited to, pest resistance, water use efficiency, yield performance, drought tolerance, seed quality, improved nutritional quality, hybrid seed production, and herbicide tolerance, in which the trait is measured with respect to a plant lacking such trait or transgenic event. Concrete examples of such advantageous and/or useful properties (traits) are better plant growth, vigor, stress tolerance, standability, lodging resistance, nutrient uptake, plant nutrition, and/or yield, in particular improved growth, increased tolerance to high or low temperatures, increased tolerance to drought or to levels of water or soil salinity, enhanced flowering performance, easier harvesting, accelerated ripening, higher yields, higher quality and/or a higher nutritional value of the harvested products, better storage life and/or processability of the harvested products, and increased resistance against animal and microbial pests, such as against insects, arachnids, nematodes, mites, slugs and snails.
Among DNA sequences encoding proteins which confer properties of tolerance to such animal and microbial pests, in particular insects, mention will particularly be made of the genetic material from Bacillus thuringiensis encoding the Bt proteins widely described in the literature and well known to those skilled in the art. Mention will also be made of proteins extracted from bacteria such as Photorhabdus (W097/17432 and WO98/08932). In particular, mention will be made of the Bt Cry or VIP proteins which include the CrylA, CrylAb, CrylAc, CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF proteins or toxic fragments thereof and also hybrids or combinations thereof, especially the CrylF protein or hybrids derived from a CrylF protein (e.g. hybrid CrylA-CrylF proteins or toxic fragments thereof), the CrylA-type proteins or toxic fragments thereof, preferably the CrylAc protein or hybrids derived from the CrylAc protein (e.g. hybrid CrylAb-CrylAc proteins) or the CrylAb or Bt2 protein or toxic fragments thereof, the Cry2Ae, Cry2Af or Cry2Ag proteins or toxic fragments thereof, the CrylA.105 protein or a toxic fragment thereof, the VIP3Aal9 protein, the VIP3Aa20 protein, the VIP3A proteins produced in the COT202 or COT203 cotton events, the VIP3Aa protein ora toxic fragment thereof as described in Estruch et al. (1996), Proc Natl Acad Sci US A. 28;93(11):5389-94, the Cry proteins as described in WO2001/47952, the insecticidal proteins from Xenorhabdus (as described in WO98/50427), Serratia (particularly from S. entomophila) or Photorhabdus species strains, such as Tc-proteins from Photorhabdus as described in WO98/08932. Also any variants or mutants of any one of these proteins differing in some amino acids (1-10, preferably 1-5) from any of the above named sequences, particularly the sequence of their toxic fragment, or which are fused to a transit peptide, such as a plastid transit peptide, or another protein or peptide, is included herein.
Another and particularly emphasized example of such properties is conferred tolerance to one or more herbicides, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin. Among DNA sequences encoding proteins which confer properties of tolerance to certain herbicides on the transformed plant cells and plants, mention will be particularly be made to the bar or PAT gene or the Streptomyces coelicolor gene described in WO2009/152359 which confers tolerance to glufosinate herbicides, a gene encoding a suitable EPSPS (5-Enolp\Tuv\lshikimat-3-phosphat- nthasc) which confers tolerance to
Figure imgf000080_0001
herbicides having EPSPS as a target, especially herbicides such as glyphosate and its salts, a gene encoding glyphosate-n-acetyltransferase, or a gene encoding glyphosate oxidoreductase. Further suitable herbicide tolerance traits include at least one ALS (acetolactate synthase) inhibitor (e.g. W02007/024782), a mutated Arabidopsis ALS/AHAS gene (e.g. U.S. Patent 6,855,533), genes encoding 2,4-D- monooxygenases conferring tolerance to 2,4-D (2,4- dichlorophenoxyacetic acid) and genes encoding Dicamba monooxygenases conferring tolerance to dicamba (3,6-dichloro-2- methoxybenzoic acid).
Yet another example of such properties is resistance to one or more phytopathogenic fungi, for example Asian Soybean Rust. Among DNA sequences encoding proteins which confer properties of resistance to such diseases, mention will particularly be made of the genetic material from glycine tomentella, for example from any one of publically available accession lines PI441001 , PI483224, PI583970, PI446958, PI499939, PI505220, PI499933, PI441008, PI505256 or PI446961 as described in W02019/103918.
Further and particularly emphasized examples of such properties are increased resistance against bacteria and/or viruses owing, for example, to systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and also resistance genes and correspondingly expressed proteins and toxins.
Particularly useful transgenic events in transgenic plants or plant cultivars which can be treated with preference in accordance with the invention include Event 531/ PV-GHBK04 (cotton, insect control, described in W02002/040677), Event 1143-14A (cotton, insect control, not deposited, described in WO2006/128569); Event 1143-5 IB (cotton, insect control, not deposited, described in W02006/128570); Event 1445 (cotton, herbicide tolerance, not deposited, described in US-A 2002- 120964 or W02002/034946); Event 17053 (rice, herbicide tolerance, deposited as PTA-9843, described in WO2010/117737); Event 17314 (rice, herbicide tolerance, deposited as PTA-9844, described in WO2010/117735); Event 281-24-236 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in W02005/103266 or US-A 2005-216969); Event 3006-210-23 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in US-A 2007-143876 orW02005/103266); Event 3272 (com, quality trait, deposited as PTA-9972, described in W02006/098952 or US-A 2006-230473); Event 33391 (wheat, herbicide tolerance, deposited as PTA-2347, described in W02002/027004), Event 40416 (com, insect control - herbicide tolerance, deposited as ATCC PTA-11508, described in WO 11/075593); Event 43A47 (com, insect control - herbicide tolerance, deposited as ATCC PTA-11509, described in WO2011/075595); Event 5307 (com, insect control, deposited as ATCC PTA-9561, described in W02010/077816); Event ASR- 368 (bent grass, herbicide tolerance, deposited as ATCC PTA-4816, described in US-A 2006-162007 or W02004/053062); Event B16 (com, herbicide tolerance, not deposited, described in US-A 2003- 126634); Event BPS-CV127- 9 (soybean, herbicide tolerance, deposited as NCIMB No. 41603, described in W02010/080829); Event BLR1 (oilseed rape, restoration of male sterility, deposited as NCIMB 41193, described in W02005/074671), Event CE43-67B (cotton, insect control, deposited as DSM ACC2724, described in US-A 2009-217423 or WO2006/128573); Event CE44-69D (cotton, insect control, not deposited, described in US-A 2010- 0024077); Event CE44-69D (cotton, insect control, not deposited, described in WO2006/128571); Event CE46-02A (cotton, insect control, not deposited, described in WO2006/128572); Event COT102 (cotton, insect control, not deposited, described in US-A 2006-130175 or W02004/039986); Event COT202 (cotton, insect control, not deposited, described in US-A 2007-067868 or W02005/054479); Event COT203 (cotton, insect control, not deposited, described in W02005/054480); ); Event DAS21606-3 / 1606 (soybean, herbicide tolerance, deposited as PTA-11028, described in WO2012/033794), Event DAS40278 (com, herbicide tolerance, deposited as ATCC PTA-10244, described in WO2011/022469); Event DAS-44406-6 / pDAB8264.44.06.1 (soybean, herbicide tolerance, deposited as PTA-11336, described in WO2012/075426), Event DAS-14536-7 /pDAB8291.45.36.2 (soybean, herbicide tolerance, deposited as PTA-11335, described in WO2012/075429), Event DAS-59122-7 (com, insect control - herbicide tolerance, deposited as ATCC PTA 11384, described in US-A 2006- 070139); Event DAS-59132 (com, insect control - herbicide tolerance, not deposited, described in W02009/100188); Event DAS68416 (soybean, herbicide tolerance, deposited as ATCC PTA-10442, described in WO2011/066384 or WO2011/066360); Event DP-098140-6 (com, herbicide tolerance, deposited as ATCC PTA-8296, described in US-A 2009- 137395 orWO 08/112019); Event DP- 305423-1 (soybean, quality trait, not deposited, described in US-A 2008-312082 or W02008/054747); Event DP-32138-1 (com, hybridization system, deposited as ATCC PTA-9158, described in US-A 2009-0210970 or W02009/103049); Event DP-356043-5 (soybean, herbicide tolerance, deposited as ATCC PTA-8287, described in US-A 2010-0184079 or W02008/002872); EventEE-I (brinjal, insect control, not deposited, described in WO 07/091277); Event Fil 17 (com, herbicide tolerance, deposited as ATCC 209031, described in US-A 2006-059581 or WO 98/044140); Event FG72 (soybean, herbicide tolerance, deposited as PTA- 11041, described in WO2011/063413), Event GA21 (com, herbicide tolerance, deposited as ATCC 209033, described in US-A 2005-086719 or WO 98/044140); Event GG25 (com, herbicide tolerance, deposited as ATCC 209032, described in US-A 2005-188434 orW098/044140); Event GHB119 (cotton, insect control - herbicide tolerance, deposited as ATCC PTA-8398, described in W02008/151780); Event GHB614 (cotton, herbicide tolerance, deposited as ATCC PTA-6878, described in US-A 2010-050282 or W02007/017186); Event GJ11 (com, herbicide tolerance, deposited as ATCC 209030, described in US-A 2005-188434 or W098/044140); Event GM RZ13 (sugar beet, vims resistance, deposited as NCIMB-41601, described in W02010/076212); Event H7-1 (sugar beet, herbicide tolerance, deposited as NCIMB 41158 or NCIMB 41159, described in US-A 2004-172669 or WO 2004/074492); Event JOPLIN1 (wheat, disease tolerance, not deposited, described in US-A 2008-064032); Event LL27 (soybean, herbicide tolerance, deposited as NCIMB41658, described in W02006/108674 or US-A 2008- 320616); Event LL55 (soybean, herbicide tolerance, deposited as NCIMB 41660, described in WO 2006/108675 or US-A 2008-196127); Event LLcotton25 (cotton, herbicide tolerance, deposited as ATCC PTA-3343, described in W02003/013224 or US- A 2003-097687); Event LLRICE06 (rice, herbicide tolerance, deposited as ATCC 203353, described in US 6,468,747 or W02000/026345); Event LLRice62 ( rice, herbicide tolerance, deposited as ATCC 203352, described in W02000/026345), Event LLRICE601 (rice, herbicide tolerance, deposited as ATCC PTA-2600, described in US-A 2008-2289060 or W02000/026356); Event LY038 (com, quality trait, deposited as ATCC PTA-5623, described in US-A 2007-028322 or W02005/061720); Event MIR162 (com, insect control, deposited as PTA-8166, described in US-A 2009-300784 or W02007/142840); Event MIR604 (com, insect control, not deposited, described in US-A 2008-167456 orW02005/103301); Event MON15985 (cotton, insect control, deposited as ATCC PTA-2516, described in US-A 2004- 250317 or W02002/100163); Event MON810 (com, insect control, not deposited, described in US- A 2002-102582); Event MON863 (com, insect control, deposited as ATCC PTA-2605, described in W02004/011601 or US-A 2006-095986); Event MON87427 (com, pollination control, deposited as ATCC PTA-7899, described in WO2011/062904); Event MON87460 (com, stress tolerance, deposited as ATCC PTA-8910, described in W02009/111263 or US-A 2011-0138504); Event MON87701 (soybean, insect control, deposited as ATCC PTA- 8194, described in US-A 2009- 130071 or W02009/064652); Event MON87705 (soybean, quality trait - herbicide tolerance, deposited as ATCC PTA-9241, described in US-A 2010-0080887 or W02010/037016); Event MON87708 (soybean, herbicide tolerance, deposited as ATCC PTA-9670, described in WO2011/034704); Event MON87712 (soybean, yield, deposited as PTA-10296, described in W02012/051199), Event MON87754 (soybean, quality trait, deposited as ATCC PTA-9385, described in W02010/024976); Event MON87769 (soybean, quality trait, deposited as ATCC PTA- 8911, described in US-A 2011-0067141 orW02009/102873); Event MON88017 (com, insect control - herbicide tolerance, deposited as ATCC PTA-5582, described in US-A 2008-028482 or W02005/059103); Event MON88913 (cotton, herbicide tolerance, deposited as ATCC PTA-4854, described in W02004/072235 or US-A 2006-059590); Event MON88302 (oilseed rape, herbicide tolerance, deposited as PTA-10955, described in WO2011/153186), Event MON88701 (cotton, herbicide tolerance, deposited as PTA-11754, described in WO2012/134808), Event MON89034 (com, insect control, deposited as ATCC PTA-7455, described in WO 07/140256 or US-A 2008- 260932); Event MON89788 (soybean, herbicide tolerance, deposited as ATCC PTA-6708, described in US-A 2006-282915 or W02006/130436); Event MSI 1 (oilseed rape, pollination control - herbicide tolerance, deposited as ATCC PTA-850 or PTA-2485, described in W02001/031042); Event MS8 (oilseed rape, pollination control - herbicide tolerance, deposited as ATCC PTA-730, described in W02001/041558 or US-A 2003-188347); Event NK603 (com, herbicide tolerance, deposited as ATCC PTA-2478, described in US-A 2007-292854); Event PE-7 (rice, insect control, not deposited, described in W02008/114282); Event RF3 (oilseed rape, pollination control - herbicide tolerance, deposited as ATCC PTA-730, described in W02001/041558 or US-A 2003-188347); Event RT73 (oilseed rape, herbicide tolerance, not deposited, described in W02002/036831 or US-A 2008- 070260); Event SYHT0H2 /SYN-000H2-5 (soybean, herbicide tolerance, deposited as PTA-11226, described in WO2012/082548), Event T227-1 (sugar beet, herbicide tolerance, not deposited, described in W02002/44407 or US-A 2009-265817); Event T25 (com, herbicide tolerance, not deposited, described in US-A 2001-029014 or W02001/051654); Event T304-40 (cotton, insect control - herbicide tolerance, deposited as ATCC PTA-8171, described in US-A 2010-077501 or W02008/122406); Event T342-142 (cotton, insect control, not deposited, described in WO2006/128568); Event TC1507 (com, insect control - herbicide tolerance, not deposited, described in US-A 2005-039226 or W02004/099447); Event VIP1034 (com, insect control - herbicide tolerance, deposited as ATCC PTA-3925, described in W02003/052073), Event 32316 (com, insect control-herbicide tolerance, deposited as PTA-11507, described in WO2011/084632), Event 4114 (com, insect control-herbicide tolerance, deposited as PTA-11506, described in W02011/084621), event EE-GM3 / FG72 (soybean, herbicide tolerance, ATCC Accession N° PTA-11041) optionally stacked with event EE-GM1/LL27 or event EE-GM2/LL55 (WO2011/063413A2), event DAS- 68416-4 (soybean, herbicide tolerance, ATCC Accession N° PTA-10442, W02011/066360A1), event DAS-68416-4 (soybean, herbicide tolerance, ATCC Accession N° PTA-10442,
WO2011/066384A1), event DP-040416-8 (com, insect control, ATCC Accession N° PTA-11508, WO2011/075593A1), event DP-043A47-3 (com, insect control, ATCC Accession N° PTA-11509, WO2011/075595A1), event DP- 004114-3 (com, insect control, ATCC Accession N° PTA-11506, WO2011/084621A1), event DP-032316-8 (com, insect control, ATCC Accession N° PTA-11507, WO2011/084632A1), event MON-88302-9 (oilseed rape, herbicide tolerance, ATCC Accession N° PTA-10955, WO2011/153186A1), event DAS-21606-3 (soybean, herbicide tolerance, ATCC Accession No. PTA-11028, WO2012/033794A2), event MON-87712-4 (soybean, quality trait, ATCC Accession N°. PTA-10296, WO2012/051199A2), event DAS-44406-6 (soybean, stacked herbicide tolerance, ATCC Accession N°. PTA-11336, WO2012/075426A1), event DAS-14536-7 (soybean, stacked herbicide tolerance, ATCC Accession N°. PTA-11335, WO2012/075429A1), event SYN-000H2-5 (soybean, herbicide tolerance, ATCC Accession N°. PTA-11226,
WO2012/082548A2), event DP-061061-7 (oilseed rape, herbicide tolerance, no deposit N° available, W02012071039A1), event DP-073496-4 (oilseed rape, herbicide tolerance, no deposit N° available, US2012131692), event 8264.44.06.1 (soybean, stacked herbicide tolerance, Accession N° PTA- 11336, WO2012075426A2), event 8291.45.36.2 (soybean, stacked herbicide tolerance, Accession N°. PTA-11335, WO2012075429A2), event SYHT0H2 (soybean, ATCC Accession N°. PTA-11226, WO2012/082548A2), event MON88701 (cotton, ATCC Accession N° PTA-11754,
WO2012/134808A1), event KK179-2 (alfalfa, ATCC Accession N° PTA-11833,
W02013/003558A1), event pDAB8264.42.32.1 (soybean, stacked herbicide tolerance, ATCC Accession N° PTA-11993, W02013/010094A1), event MZDT09Y (com, ATCC Accession N° PTA- 13025, WO2013/012775A1).
Further, a list of such transgenic event(s) is provided by the United States Department of Agriculture’s (USDA) Animal and Plant Health Inspection Service (APHIS) and can be found on their website on the world wide web at anhis.usda.gov. For this application, the status of such list as it is/was on the fding date of this application, is relevant.
The genes/events which impart the desired traits in question may also be present in combinations with one another in the transgenic plants. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice, triticale, barley, rye, oats), maize, soya beans, potatoes, sugar beet, sugar cane, tomatoes, peas and other types of vegetable, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), with particular emphasis being given to maize, soya beans, wheat, rice, potatoes, cotton, sugar cane, tobacco and oilseed rape. Traits which are particularly emphasized are the increased resistance of the plants to insects, arachnids, nematodes and slugs and snails, as well as the increased resistance of the plants to one or more herbicides.
Commercially available examples of such plants, plant parts or plant seeds that may be treated with preference in accordance with the invention include commercial products, such as plant seeds, sold or distributed under the GENUITY®, DROUGHTGARD®, SMARTSTAX®, RIB COMPLETE®, ROUNDUP READY®, VT DOUBLE PRO®, VT TRIPLE PRO®, BOLLGARD II®, ROUNDUP READY 2 YIELD®, YIELDGARD®, ROUNDUP READY® 2 XTEN°™, INTACTA RR2 PRO®, VISTIVE GOLD®, and/or XTENDFLEX™ trade names.
Pathogens
Non-limiting examples of pathogens of fungal diseases which may be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis, Podosphaera species, for example Podosphaera leucotricha Sphaerotheca species, for example Sphaerotheca fuliginea ; Uncinula species, for example Uncinula necator ; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae Hemileia species, for example Hemileia vastatrix Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striiformis ; Uromyces species, for example Uromyces appendiculatus ; diseases caused by pathogens from the group of the Oomycetes, for example Albugo species, for example Albugo Candida ; Bremia species, for example Bremia lactucae; Peronospora species, for example Peronospora pisi or P. brassicae; Phytophthora species, for example Phytophthora infestans; Plasmopara species, for example Plasmopara viticola; Pseudoperonospora species, for example Pseudoperonospora humuli ox Pseudoperonospora cubensis; Pythium species, for example Pythium ultimum ; leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species, for example Alternaria solani; Cercospora species, for example Cercospora beticola ; Cladiosporium species, for example Cladiosporium cucumerinum ; Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium) or Cochliobolus miyabeanus; Colletotrichum species, for example Colletotrichum lindemuthanium ; Corynespora species, for example Corynespora cassiicola; Cycloconium species, for example Cycloconium oleaginum; Diaporthe species, for example Diaporthe citri Elsinoe species, for example Elsinoe fawcettii ; Gloeosporium species, for example Gloeosporium laeticolor; Glomerella species, for example Glomerella cingulata; Guignardia species, for example Guignardia bidwelli; Leptosphaeria species, for example Leptosphaeria maculans;Magnaporthe species, for example Magnaporthe grisea; Microdochium species, for example Microdochium nivale ; Mycosphaerella species, for example Mycosphaerella graminicola, Mycosphaerella arachidicola or Mycosphaerella fijiensis ; Phaeosphaeria species, for example Phaeosphaeria nodorum; Pyrenophora species, for example Pyrenophora teres or Pyrenophora tritici repentis; Ramularia species, for example Ramularia collo-cygni or Ramularia areola ; Rhynchosporium species, for example Rhynchosporium secalis Septoria species, for example Septoria apii or Septoria lycopersici; Stagonospora species, for example Stagonospora nodorum ; Typhula species, for example Typhula incarnata; Venturia species, for example Venturia inaequalis; root and stem diseases caused, for example, by Corticium species, for example Corticium graminearum ; Fusarium species, for example Fusarium oxysporum; Gaeumannomyces species, for example Gaeumannomyces graminis; Plasmodiophora species, for example Plasmodiophora brassicae, Rhizoctonia species, for example Rhizoctonia solani, Sarocladium species, for example Sarocladium oryzae, Sclerotium species, for example Sclerotium oryzae, Tapesia species, for example Tapesia acuformis, Thielaviopsis species, for example Thielaviopsis basicola; ear and panicle diseases (including com cobs) caused, for example, by Alternaria species, for example Alternaria spp.; Aspergillus species, for example Aspergillus flavus, Cladosporium species, for example Cladosporium cladosporioides; Claviceps species, for example Claviceps purpurea, Fusarium species, for example Fusarium culmorum, Gibberella species, for example Gibberella zeae, Monographella species, for example Monographella nivalis; Stagnospora species, for example Stagnospora nodorum; diseases caused by smut fungi, for example Sphacelotheca species, for example Sphacelotheca reiliana; Tilletia species, for example Tilletia caries or Tilletia controversa Urocystis species, for example Urocystis occulta ; Ustilago species, for example Ustilago nuda; fruit rot caused, for example, by Aspergillus species, for example Aspergillus flavus ; Botrytis species, for example Botrytis cinerea ; Monilinia species, for example Monilinia laxa; Penicillium species, for example Penicillium expansum or Penicillium purpurogenum ; Rhizopus species, for example Rhizopus stolonifer ; Sclerotinia species, for example Sclerotinia sclerotiorum Verticilium species, for example Verticilium alboatrum ; seed- and soil-bome rot and wilt diseases, and also diseases of seedlings, caused, for example, by Alternaria species, for example Alternaria brassicicola ; Aphanomyces species, for example Aphanomyces euteiches; Ascochyta species, for example Ascochyta lends ; Aspergillus species, for example Aspergillus flavus ; Cladosporium species, for example Cladosporium herbarum ; Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, Bipolaris Syn: Helminthosporium), Colletotrichum species, for example Colletotrichum coccodes Fusarium species, for example Fusarium culmorum ; Gibberella species, for example Gibberella zeae ; Macrophomina species, for example Macrophomina phaseolina Microdochium species, for example Microdochium nivale ; Monographella species, for example Mon o graph e lla nivalis ; Penicillium species, for example Penicillium expansum ; Phoma species, for example Phoma lingam ; Phomopsis species, for example Phomopsis sojae ; Phytophthora species, for example Phytophthora cactorum Pyrenophora species, for example Pyrenophora graminea Pyricularia species, for example Pyricularia oryzae ; Pythium species, for example Pythium ultimum ; Rhizoctonia species, for example Rhizoctonia solani, Rhizopus species, for example Rhizopus oryzae ; Sclerotium species, for example Sclerotium rolfsii, Septoria species, for example Septoria nodorum Typhula species, for example Typhula incarnata Verticillium species, for example Verticillium dahliae cancers, galls and witches’ broom caused, for example, by Nectria species, for example Nectria galligena ; wilt diseases caused, for example, by Verticillium species, for example Verticillium longisporum Fusarium species, for example Fusarium oxysporum deformations of leaves, flowers and fruits caused, for example, by Exobasidium species, for example Exobasidium vexans Taphrina species, for example Taphrina deformans ; degenerative diseases in woody plants, caused, for example, by Esca species, for example Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranean Ganoderma species, for example Ganoderma boninense ; diseases of plant tubers caused, for example, by Rhizoctonia species, for example Rhizoctonia solani, Helminthosporium species, for example Helminthosporium solani, diseases caused by bacterial pathogens, for example Xanthomonas species, for example Xanthomonas campestris pv. oryzae ; Pseudomonas species, for example Pseudomonas syringae pv. lachrymans; Erwinia species, for example Erwinia amylovora; Liberibacter species, for example Liberibacter asiaticus; Xyella species, for example Xylella fastidiosa ; Ralstonia species, for example Ralstonia solanacearum; Dickeya species, for example Dickeya solani, Clavibacter species, for example Clavibacter michiganensis; Streptomyces species, for example Streptomyces scabies. diseases of soya beans:
Fungal diseases on leaves, stems, pods and seeds caused, for example, by Alternaria leaf spot ( Altemaria spec atrans tenuissima), Anthracnose ( Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cercospora leaf spot and blight ( Cercospora kikuchii), choanephora leaf blight ( Choanephora infundibulifera trispora ( Syn .)), dactuliophora leaf spot ( Dactuliophora glycines), downy mildew ( Peronospora manshurica), drechslera blight ( Drechslera glycini), ffogeye leaf spot ( Cercospora sojina), leptosphaerulina leaf spot ( Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), pod and stem blight ( Phomopsis sojae), powdery mildew ( Microsphaera diffusa), pyrenochaeta leaf spot ( Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight ( Rhizoctonia solani), rust ( Phakopsora pachyrhizi, Phakopsora meibomiae), scab ( Sphaceloma glycines), stemphylium leaf blight ( Stemphylium botryosum), sudden death syndrome ( Fusarium virguliforme), target spot ( Corynespora cassiicola).
Fungal diseases on roots and the stem base caused, for example, by black root rot ( Calonectria crotalariae), charcoal rot ( Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot ( Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot ( Mycoleptodiscus terrestris), neocosmospora ( Neocosmospora vasinfecta), pod and stem blight ( Diaporthe phaseolorum), stem canker (. Diaporthe phaseolorum var. caulivora), phytophthora rot ( Phytophthora megasperma), brown stem rot ( Phialophora gregata), pythium rot ( Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (. Rhizoctonia solani), sclerotinia stem decay ( Sclerotinia sclerotiorum), sclerotinia southern blight ( Sclerotinia rolfsii), thielaviopsis root rot ( Thielaviopsis basicola).
Mycotoxins
In addition, the compound and the composition of the invention may reduce the mycotoxin content in the harvested material and the foods and feeds prepared therefrom. Mycotoxins include particularly, but not exclusively, the following: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2- toxin, fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol (DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins which can be produced, for example, by the following fungi: Fusarium spec., such as F. acuminatum, F. asiaticum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum ( Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F. proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides, and also by Aspergillus spec., such a A.flavus, A. parasiticus, A. nomius,A. ochraceus, A. clavatus,A. terreus,A. versicolor, Penicillium spec., such asP. verrucosum,P. viridicatum,P. citrinum, P. expansum, P. claviforme, P. roqueforti, Claviceps spec., such as C. purpurea, C. fusiformis, C. paspali, C. africana, Stachybotrys spec and others.
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 phytopathogenic fungi.
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 signalling 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 Alternaria 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.
Seed Treatment
The compound and the composition of the invention may also be used to protect seeds from unwanted microorganisms, such as phytopathogenic microorganisms, for instance phytopathogenic fungi or phytopathogenic oomycetes. The term seedfsf as used herein include dormant seeds, primed seeds, pregerminated seeds and seeds with emerged roots and leaves.
Thus, the present invention also relates to a method for protecting seeds from unwanted microorganisms which comprises the step of treating the seeds with the compound or the composition of the invention.
The treatment of seeds with the compound or the composition of the invention protects the seeds from phytopathogenic microorganisms, but also protects the germinating seeds, the emerging seedlings and the plants after emergence from the treated seeds. Therefore, the present invention also relates to a method for protecting seeds, germinating seeds and emerging seedlings.
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 the compound or the composition of the invention, the seeds and the compound or the composition of the invention are mixed until an homogeneous distribution on seeds is achieved. If appropriate, the seeds may then be dried.
The invention also relates to seeds coated with the compound or the composition of the invention.
Preferably, the seeds are 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 the compound or the composition of the invention applied to the seeds 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 compound of the invention 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 the compound of the invention to be applied to the seed in order to achieve optimum seed and germinating plant protection with a minimum amount of compound being employed.
The compound of the invention can be applied as such, directly to the seeds, i.e. without the use of any other components and without having been diluted. Also the composition of the invention can be applied to the seeds.
The compound and the composition of the invention are suitable for protecting seeds of any plant variety. Preferred seeds are 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. More preferred are seeds of wheat, soybean, oilseed rape, maize and rice.
The compound and the composition of the invention may be used for treating transgenic seeds, in particular seeds of plants capable of expressing a polypeptide or protein which acts against pests, herbicidal damage or abiotic stress, thereby increasing the protective effect. Seeds of plants capable of expressing a polypeptide or protein which acts against pests, herbicidal damage or abiotic stress may contain at least one heterologous gene which allows the expression of said polypeptide or protein. These heterologous genes in transgenic seeds may originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. These heterologous genes preferably originate from Bacillus sp., in which case the gene product is effective against the European com borer and/or the Western com rootworm. Particularly preferably, the heterologous genes originate from Bacillus thuringiensis.
Application
The compound of the invention 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 the invention, synthetic substances impregnated with the compound of the invention, fertilizers or microencapsulations in polymeric substances.
Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming or spreading -on. It is also possible to deploy the compound of the invention by the ultra-low volume method, via a drip irrigation system or drench application, to apply it in-furrow or to inject it into the soil stem or trunk. It is further possible to apply the compound of the invention by means of a wound seal, paint or other wound dressing.
The effective and plant-compatible amount of the compound of the invention 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 the invention 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.
The compound and the composition of the invention can be used in combination with models e.g. embedded in computer programs for site specific crop management, satellite farming, precision farming or precision agriculture. Such models support the site specific management of agricultural sites with data from various sources such as soils, weather, crops (e.g. type, growth stage, plant health), weeds (e.g. type, growth stage), diseases, pests, nutrients, water, moisture, biomass, satellite data, yield etc. with the purpose to optimize profitability, sustainability and protection of the environment. In particular, such models can help to optimize agronomical decisions, control the precision of pesticide applications and record the work performed.
As an example, the compound of the invention can be applied to a crop plant according to appropriate dose regime if a model models the development of a fungal disease and calculates that a threshold has been reached for which it is recommendable to apply the compound of the invention to the crop plant.
Commercially available systems which include agronomic models are e.g. FieldScripts™ from The Climate Corporation, Xarvio™ from BASF, AGLogic™ from John Deere, etc.
The compound of the invention can also be used in combination with smart spraying equipment such as e.g. spot spraying or precision spraying equipment attached to or housed within a farm vehicle such as a tractor, robot, helicopter, airplane, unmanned aerial vehicle (UAV) such as a drone, etc. Such an equipment usually includes input sensors (such as e.g. a camera) and a processing unit configured to analyze the input data and configured to provide a decision based on the analysis of the input data to apply the compound of the invention to the crop plants (respectively the weeds) in a specific and precise manner. The use of such smart spraying equipment usually also requires positions systems (e.g. GPS receivers) to localize recorded data and to guide or to control farm vehicles; geographic information systems (GIS) to represent the information on intelligible maps, and appropriate farm vehicles to perform the required farm action such as the spraying.
In an example, fungal diseases can be detected from imagery acquired by a camera. In an example, fungal diseases can be identified and/or classified based on that imagery. Such identification and/ classification can make use of image processing algorithms. Such image processing algorithms can utilize machine learning algorithms, such as trained neutral networks, decision trees and utilize artificial intelligence algorithms. In this manner, the compounds described herein can be applied only where needed.
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
Generality
Measurement of LogP values
Measurement of LogP values as provided herein 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:
[aI 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).
|b| 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).
[cI 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
'H-NMR data
'H-NMR data of selected examples as provided herein are written in form of 'H-N R-pcak lists. To each signal peak are listed the d-value in ppm and the signal intensity in round brackets. Between the d-value - signal intensity pairs are semicolons as delimiters.
The peak list of an example has therefore the form: di (intensityi); d2 (intensity2); . ; dί (intensity ; . ; dh (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 'H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in dimethyl sulfoxide (DMSO). Therefore in NMR peak lists, tetramethylsilane peak can occur but not necessarily.
The 1H-NMR peak lists are similar to classical 1H-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation.
Additionally they can show like classical 1H-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 '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-fmgerprints”.
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 '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.
The following examples illustrate in a non-limiting manner the preparation and biological activity of the compounds of formula (I) according to the invention.
SYNTHESIS OF COMPOUNDS OF FORMULA (I)
Table 1 illustrates in a non-limiting manner examples of compounds of formula (I) according to the invention:
Figure imgf000094_0001
The compounds of formula (I) which are mentioned in table 1 herein below were prepared in accordance with the procedures detailed herein below in connection with specific examples and with the general description of the processes herein disclosed.
In table 1, the logP values were determined according to method [a]. Table 1 :
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Table 2 provides the NMR data ( 1H) of a selected number of compounds from table 1 .
Table 2: NMR peak lists
Figure imgf000097_0002
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
PREPARATION EXAMPLES 3 -G5 -(Difluoromethyl)- 1.3.4-oxadiazol-2-yll -6-l(2-fluorophenyl)methyl -7H-pyrrolo G 3.]-b]pyridin-5 - one (1-001)
Figure imgf000107_0002
Step 1:
A solution of 3, 5 -diethyl 2-(chloromethyl)pyridine-3,5-dicarboxylate (1.00 g, 3.68 mmol, 1 eq.), l-(2- fluorophenyl)methanamine (0.46 g, 4 mmol, 1 eq.) and triethylamine (1.12 g, 11 mmol, 3 eq.) in C¾CN (10 mL) was stirred for 2 hours at 90°C under nitrogen atmosphere. The resulting mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography, eluted with petroleum ether/ethyl acetate (1: 1) to afford ethyl 6-[(2-fluorophenyl)methyl]-5-oxo-7H- pyrrolo[3,4-b]pyridine-3-carboxylate (700 mg, 60.5%) as a yellow solid. Step 2:
A mixture of ethyl 6-[(2-fluorophenyl)methyl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carboxylate (320 mg, 1.02 mmol, 1 eq.) and NH2NH2.H2O (520 mg, 10.2 mmol, 10 eq., 98%) in ethanol (10 mL) was stirred for overnight at 85°C. The resulting mixture was concentrated under reduced pressure. The crude product was purified by reverse phase chromatography with the following conditions (column, C18 silica gel; mobile phase, CH3CN in water, 3% to 100% gradient in 30 minutes; detector, UV 254 nm) to afford 6-[(2- fluorophenyl)methyl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carbohydrazide (400 mg, 84%) as a yellow solid.
Step 3 :
A mixture of 6-[(2-fluorophenyl)methyl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carbohydrazide (250 mg, 0.83 mmol, 1 eq.), 2,2-difluoroacetic anhydride (217 mg, 1.25 mmol, 1.5 eq.), triethylamine (253 mg, 2.5 mmol, 3 eq.) and 4-(dimethylamino)pyridine (2.03 mg, 0.017 mmol, 0.02 eq.) in tetrahydrofuran (10 mL) was stirred for 2 hours at room temperature under nitrogen atmosphere. The reaction was quenched by the addition of water. The resulting mixture was extracted with ethyl acetate (3 x 20mL). The combined organic layers were washed with brine (1x20 mL), dried over anhydrous Na2S04. After filtration, the filtrate was concentrated under reduced pressure. The residue/crude product was purified by reverse phase chromatography with the following conditions (column, Cl 8 silica gel; mobile phase, CH3CN in water, 3% to 100% gradient in 30 minutes; detector, UV 254 nm.) to afford N-(2,2-difluoroacetyl)-6-[(2- fluorophenyl)methyl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carbohydrazide (140 mg, 44.5%) as a white solid.
Step 4:
Into a sealed tube were added N-(2,2-difluoroacetyl)-6-[(2-fluorophenyl)methyl]-5-oxo-7H-pyrrolo[3,4- b]pyridine-3-carbohydrazide (110 mg, 0.29 mmol, 1 eq.), Burgess reagent (416 mg, 1.75 mmol, 6 eq.) and tetrahydrofuran (5 mL) at room temperature. The reaction mixture was irradiated with microwave radiation for 2 hours at 120°C. The reaction was quenched with water at room temperature. The resulting mixture was extracted with ethyl acetate (3 x 20mL). The combined organic layers were washed with brine (1x10 mL), dried over anhydrous Na2SO4. After filtration, the filtrate was concentrated under reduced pressure. The crude product was purified by preparative HPLC with the following conditions (Column: Sunfire prep C18 column, 30* 150, 5um; Mobile Phase A: Water (0.1% HCOOH), Mobile Phase B: CH3CN; Flow rate:60 mL/min) to afford the title compound (60 mg, 57%) as a white solid.
3-15-(Difluoromethyl)-1.3.4-oxadiazol-2-yll-6-(2-phenylphenyl)-7H-pyrrolol3.4-blpyridin-5-one (1-007)
Figure imgf000108_0001
Step 1 :
A mixture of 3,5-diethyl 2-(chloromethyl)pyridine-3,5-dicarboxylate (2.5 g, 9.2 mmol, 1 eq.) and 2- aminobiphenyl (1.71 g, 10 mmol, 1.1 eq.) in dimethyl formamide (5 mL) was stirred for 1 hour at 180°C under nitrogen atmosphere in microwave. The reaction was quenched with water at room temperature. The resulting mixture was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine (1x20 mL), dried over anhydrous Na2SO4. After filtration, the filtrate was concentrated under reduced pressure. The residue was purified by reverse phase chromatography with the following conditions (column, C18 silica gel; mobile phase, CH3CN in water, detector, UV 254 nm.) to afford ethyl 6-[[l,l-biphenyl]-2-yl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carboxylate (550 mg, 16.7%) as a white solid.
Step 2:
A mixture of ethyl 6-[[l,l-biphenyl]-2-yl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carboxylate (500 mg, 1.4 mmol, 1 eq.) and NH2NH2.H2O (350 mg, 7.0 mmol, 5 eq.) in ethanol (5 mL) was stirred overnight at 90°C under nitrogen atmosphere. The resulting mixture was concentrated under reduced pressure to afford 6- [[l,l-biphenyl]-2-yl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carbohydrazide (450 mg, 94%) as a white solid.
Step 3 :
A mixture of 6-[[l,l-biphenyl]-2-yl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carbohydrazide (400 mg, 1.16 mmol, 1 eq.), 2,2-difluoroacetic anhydride (303 mg, 1.7 mmol, 1.5 eq.), triethylamine (352 mg, 3.5 mmol, 3 eq.) and 4-(dimethylamino)pyridine (7.1 mg, 0.058 mmol, 0.05 eq.) in tetrahydrofuran (5 mL) was stirred for 2 hours at room temperature under nitrogen atmosphere. The resulting mixture was concentrated under reduced pressure. The residue was purified by reverse phase chromatography with the following conditions (column, C18 silica gel; mobile phase, CLLCN in water; detector, UV 254 nm) to afford 6- [[1,1 -biphenyl] -2-yl] -N-(2,2-difluoroacetyl)-5 -oxo-7H-pyrrolo [3 ,4-b]pyridine-3 -carbohydrazide (450 mg, 9%) as a white solid.
Step 4:
Into a sealed tube were added 6-[[l,l-biphenyl]-2-yl]-N-(2,2-difluoroacetyl)-5-oxo-7H-pyrrolo[3,4- b]pyridine-3-carbohydrazide (300 mg, 0.71 mmol, 1 eq.), Burgess reagent (846 mg, 3.5 mmol, 5 eq.) and tetrahydrofuran (5 mL) at room temperature. The final reaction mixture was irradiated with microwave radiation for 2 hours at 120°C. The reaction was quenched with water at room temperature. The resulting mixture was extracted with ethyl acetate (3 x 30 mL). The combined organic layers were washed with brine (1x20 mL), dried over anhydrous Na2SO4. After filtration, the filtrate was concentrated under reduced pressure. The crude product was purified by Prep-HPLC to afford the title compound (150 mg, 52%) as a white solid. 6-l5-(Difluoromethyl)- 1.3.4-o\adiazol-2-yl l-2-(2-phenylphcnyl)-3H-isoindol- 1-onc (1-008)
Figure imgf000110_0001
Step 1:
A mixture of 1,3-dimethyl 4-(bromomethyl)benzene-l,3-dicarboxylate (2.5 g, 8.7 mmol, 1 eq.), 2- aminobiphenyl (1.62 g, 10 mmol, 1.1 eq.) and K2CO3 (2.41 g, 17 mmol, 2 eq.) in C1¾CN (10 mL) was stirred for 1 hour at 120°C in microwave under nitrogen atmosphere. The reaction was quenched with water at room temperature. The resulting mixture was extracted with ethyl acetate (2 x 50mL). The combined organic layers were washed with brine (1x20 mL), dried over anhydrous Na2SO4. After filtration, the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography, eluted with petroleum ether/ethyl acetate (2:1) to afford methyl 2-[[l,l- biphenyl]-2-yl]-3-oxo-lH-isoindole-5-carboxylate (2.5 g, 84%) as a white solid.
Step 2:
A mixture of methyl 2-[[l,l-biphenyl]-2-yl]-3-oxo-lH-isoindole-5-carboxylate (1.00 g, 2.9 mmol, 1 eq.) and NH2NH2.H2O (0.73 g, 15 mmol, 5 eq.) in ethanol (5 mL) was stirred overnight at 90°C under nitrogen atmosphere. The resulting mixture was concentrated under reduced pressure to afford 2-[[l,l-biphenyl]- 2-yl]-3-oxo-lH-isoindole-5-carbohydrazide (1 g, 100%) as a white solid.
Step 3 :
A mixture of 2-[[l,l-biphenyl]-2-yl]-3-oxo-lH-isoindole-5-carbohydrazide (600.00 mg, 1.7 mmol, 1 eq.), 2,2-difluoroacetic anhydride (608 mg, 3.5 mmol, 2 eq.), triethylamine (530 mg, 5.2 mmol, 3 eq.) and 4- (dimethylamino)pyridine (10.6 mg, 0.087 mmol, 0.05 eq.) in tetrahydrofuran (10 mL) was stirred for 2 hours at room temperature under nitrogen atmosphere. The resulting mixture was concentrated under reduced pressure. The residue was purified by reverse phase chromatography with the following conditions (column, C18 silica gel; mobile phase, CH3CN in water; detector, UV 254 nm) to afford 2- [[l,l-biphenyl]-2-yl]-N-(2,2-difluoroacetyl)-3-oxo-lH-isoindole-5-carbohydrazide (600 mg, 81.5%) as a white solid.
Step 4:
Into a sealed tube were added 2-[[l,l-biphenyl]-2-yl]-N-(2,2-difluoroacetyl)-3-oxo-lH-isoindole-5- carbohydrazide (300 mg, 0.71 mmol, 1 eq.), Burgess reagent (848 mg, 3.6 mmol, 5 eq.) and tetrahydrofuran (5 mL) at room temperature. The reaction mixture was irradiated with microwave radiation for 2 hours at 120°C. The reaction was quenched with water at room temperature. The resulting mixture was extracted with ethyl acetate (3 x 30mL). The combined organic layers were washed with brine (1x20 mL), dried over anhydrous Na2SO4. After filtration, the filtrate was concentrated under reduced pressure. The crude product was purified by preparative HPLC to afford the title compound (160 mg, 56%) as a white solid.
3 -G5 -(difluoromethyl) - 1 3.4-oxadiazol-2-yl] -6-[ 1 -(2.6-difluorophenYl)cYclopropyl l-7H-pyrrolo G3 4- blpyridin-5-one (1.018)
Figure imgf000111_0001
Step 1:
In a 100 mL 2-neck round bottom flask, ethyl 5-cyano-2-methyl-pyridine-3-carboxylate (2.0 g, 10.5 mmol) was dissolved in chlorobenzene (20 mL) under Argon, N-bromosuccinimide (2.8 g, 15.7 mmol) was added, followed by azobisisobutyronitrile (259 mg, 1.57 mmol). The reaction was heated to 100°C and maintained for 2 hours. The reaction was allowed to cool, partitioned between saturated aqueous NaHCC3 solution and ethyl acetate. The phases were separated, the aqueous layer was extracted with ethyl acetate (2 x 40 mL). The organic phases were combined, washed with brine, dried and the solvent was evaporated. The residue was purified by silica gel chromatography, eluted with dichloromethane, to afford ethyl 2-(bromomethyl)-5-cyano-pyridine-3-carboxylate (900 mg, 31.8%) as a colourless oil.
Step 2:
In an oven dried Radleys tube, ethyl 2-(bromomethyl)-5-cyano-pyridine-3-carboxylate (257 mg, 0.95 mmol) and l-(2,6-difluorophenyl)cyclopropanamine (161 mg, 0.95 mmol) were dissolved in acetonitrile (5 mL). K2CO3 (395 mg, 2.86 mmol) was added and the reaction was heated to 65°C and maintained for 2 hours. After cooling, the solid was filtered, washed with acetonitrile. The filtrate was evaporated to dryness, to afford ethyl 5-cyano-2-[[[l-(2,6-difluorophenyl)cyclopropyl]amino]methyl]pyridine-3- carboxylate (350 mg, 84%), as an orange oil, which was used directly in the next step.
Step 3 :
In a Radleys tube, ethyl 5-cyano-2-[[[l-(2,6-difluorophenyl)cyclopropyl]amino]methyl]pyridine-3- carboxylate (341.3 mg, 0.95 mmol) was dissolved in acetic acid (2 mL). The solution was heated to 65°C and maintained for 2 hours. After cooling, the reaction was evaporated to dryness and the residue was purified by silica gel chromatography (eluted with 0-5% ethyl acetate/dichloromethane) to afford 6-[l- (2,6-difluorophenyl)cyclopropyl]-5-oxo-7H-pynOlo[3,4-b]pyridine-3-carbonitrile (170mg, 54%) as an orange solid. Step 4:
In an oven dried Radleys tube, 6-[l-(2,6-difluorophenyl)cyclopropyl]-5-oxo-7H-pyrrolo[3,4-b]pyridine- 3-carbonitrile (150 mg, 0.48 mmol) was dissolved in dimethyl formamide (2 mL) under Argon, NaN3 (40.7 mg, 0.62 mmol) was added followed by NH4CI (38.7 mg, 0.72 mmol). The reaction was heated to 100°C and maintained for 6 hours.
After cooling, the reaction mixture was added to water with stirring, pH was adjusted to 3 with 1M aqueous solution of hydrochloric acid. The yellow solid was filtered, washed with water and dried, affording 6-[l- (2,6-difluorophenyl)cyclopropyl]-3-(lH-tetrazol-5-yl)-7H-pyrrolo[3,4-b]pyridin-5-one (120mg, 68.9%) which was used directly in the next step.
Step 5 :
In an oven dried Radleys tube 6-[l-(2,6-difluorophenyl)cyclopropyl]-3-(lH-tetrazol-5-yl)-7H- pyrrolo[3,4-b]pyridin-5-one (105 mg, 0.29 mmol) was suspended in dichloromethane (2 mL) under Argon. (2,2-Difluoroacetyl) 2,2-difluoroacetate (206 mg, 1.18 mmol) was added at 0°C, the reaction was allowed to warm to room temperature and was stirred for 30 minutes, then heated to 40°C for 20 hours. The reaction mixture was evaporated to dryness, the residue was purified by silica gel chromatography, eluted with 0-5% ethyl acetate/dichloromethane to afford 3-[5-(difluoromethyl)-l,3,4-oxadiazol-2-yl]-6- [l-(2,6-difluorophenyl)cyclopropyl]-7H-pyrrolo[3,4-b]pyridin-5-one (45mg, 33.8%) as acolourless solid.
3 -15 -Idifluoromethyll- 1 3.4-oxadiazol-2-yll -6-l2-(2.6-difluorophenyl)phenyl I -7H-pyrrolo 13.4-blpyridin-
5 -one
Figure imgf000112_0001
Step 1:
In an oven dried Radleys tube, ethyl 2-(bromomethyl)-5-cyano-pyridine-3-carboxylate (200 mg, 0.74 mmol) was dissolved in dimethyl formamide (3 mL), 2-(2,6-difluorophenyl)aniline (167.7 mg, 0.81 mmol) was added and the reaction was stirred at room temperature for 35 hours. The reaction mixture was poured into water and stirred for 1 hour, the yellow solid was filtered, washed with water and dried. Purification by silica gel chromatography, eluted with 0-10% ethyl acetate/heptane, to afford ethyl 5- cyano-2-[[2-(2,6-difluorophenyl)anilino]methyl]pyridine-3-carboxylate (230 mg, 78.7%) as a yellow solid.
Step 2: In a 25 mL 2-neck round bottom flask, ethyl 5-cyano-2-[[2-(2,6-difluorophenyl)anilino]methyl]pyridine- 3-carboxylate (200 mg, 0.5 mmol) was suspended in 6N aqueous solution of hydrochloric acid (12 mL), heated to 80°C and maintained for 23 hrs. The reaction was allowed to cool, diluted with water, extracted with ethyl acetate (3 x 50 mL) The organics were combined, washed with brine, dried and the solvent evaporated to afford 6-[2-(2,6-difluorophenyl)phenyl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3-carbonitrile (65 mg, 35%) as a yellow solid.
Step 3 :
In an oven dried Radleys tube, 6-[2-(2,6-difluorophenyl)phenyl]-5-oxo-7H-pyrrolo[3,4-b]pyridine-3- carbonitrile (65 mg, 0.18 mmol) was dissolved in dimethyl formamide (1.5 mL) under Argon, NaN3 (15.8 mg, 0.24 mmol) was added followed by NLLCl (15 mg, 0.28 mmol). The reaction was heated to 100°C and maintained for 72 hours, monitoring by LC/MS.
The reaction mixture was allowed to cool, added to ice/water with stirring, pH adjusted to 2 with 1M aqueous solution of hydrochloric acid. The solids were filtered, washed with water and dried, to afford 6- [2-(2,6-difluorophenyl)phenyl]-3-(lH-tetrazol-5-yl)-7H-pyrrolo[3,4-b]pyridin-5-one (55mg, 68%) as a yellow solid.
Step 4:
In an oven dried Radleys tube, 6-[2-(2,6-difluorophenyl)phenyl]-3-(lH-tetrazol-5-yl)-7H-pyrrolo[3,4- b]pyridin-5-one (40.1 mg, 0.1 mmol) was suspended in dichloromethane (3 mL). (2,2-difluoroacetyl) 2,2- difluoroacetate ( 89.4 mg, 0.51 mmol) was added dropwise at 0°C, the reaction was allowed to warm slowly to room temperature and was stirred for 1 hr at which point a colourless homogeneous solution was observed. The reaction was heated to 40°C and maintained for 25 hours. After cooling, the reaction mixture was evaporated to dryness and the residue purified by silica gel chromatography, eluted with 0- 5% ethyl acetate/dichloromethane, to afford 3-[5-(difluoromethyl)-l,3,4-oxadiazol-2-yl]-6-[2-(2,6- difluorophenyl)phenyl]-7H-pyrrolo[3,4-b]pyridin-5-one (25mg, 55%) as a colourless solid.
7-[5 -(difluoromethyl)- 1.3.4-oxadiazol-2-yll -2-phenyl-3.4-dihvdroisoquinolin- 1 -one (1.033)
Figure imgf000113_0001
Step 1:
In a Radleys tube, l-oxo-3,4-dihydro-2H-isoquinoline-7-carboxylic acid (200 mg, 1.04 mmol) was suspended in dimethyl sulfoxide (5 mL) under Argon, iodobenzene (426.8 mg, 2.08 mmol) was added followed by K3PO4 (666.2 mg, 3.13 mmol) and Cul (19.9 mg, 0.1 mmol). The reaction was heated at 100°C for 18 hours, cooled, added to ice water and acidified with 1M aqueous solution of hydrochloric acid. The precipitate was filtered, washed with water and dried to afford l-oxo-2-phenyl-3,4- dihydroisoquinoline-7-carboxylic acid (250 mg, 84.9%) as a beige solid.
Step 2:
In a Radleys tube, l-oxo-2-phenyl-3,4-dihydroisoquinoline-7-carboxylic acid (250 mg, 0.93 mmol) was suspended in ethanol (6 mL), 4 drops of concentrated sulfuric acid were added and the reaction was heated to reflux for 5 hours. After cooling, the solvent was evaporated, reaction partitioned between ethyl acetate and water, organic phase was separated, dried over anhydrous MgSCL and solvent evaporated to afford ethyl l-oxo-2 -phenyl-3, 4-dihydroisoquinoline-7-carboxylate (240 mg, 82.5%) as a brown solid.
Step 3 :
In a Radleys tube, ethyl l-oxo-2 -phenyl-3, 4-dihydroisoquinoline-7-carboxylate (220 mg, 0.74 mmol) was dissolved in methanol (6 mL), hydrazine hydrate (372.9 mg, 7.44 mmol) was added, and the reaction mixture was heated to reflux for 6 hours then allowed to cool and stand for 18 hours. This process was repeated 3 times, after which the reaction was evaporated to dryness, toluene (5 mL) was added and residue re-evaporated to dryness to afford l-oxo-2-phenyl-3,4-dihydroisoquinoline-7-carbohydrazide (210 mg, 95%) as a brown solid.
Step 4:
In a 50 mL round bottom flask, l-oxo-2-phenyl-3,4-dihydroisoquinoline-7-carbohydrazide (210 mg, 0.74 mmol) was suspended in tetrahydrofuran (5 mL) under Argon. The suspension was cooled to 0°C, N,N- diisopropylethylamine was added followed by (2,2-difluoroacetyl) 2,2-difluoroacetate (259.9 mg, 1.49 mmol). The reaction was stirred at 0°C for 15 minutes, then allowed to warm to room temperature and stirred for 2 hours. The reaction was evaporated to dryness to afford crude N'-(2,2-difluoroacetyl)-l-oxo- 2 -phenyl-3, 4-dihydroisoquinoline-7-carbohydrazide (295mg, 99%) which was used directly in next step.
Step 5 :
In a 25 mL round bottom flask, N'-(2,2-difluoroacetyl)- l-oxo-2 -phenyl-3, 4-dihydroisoquinoline-7- carbohydrazide (268.2 mg, 0.74 mmol) was suspended in tetrahydrofuran (5 mL) under Argon. The suspension was cooled to 0°C, N, N-d i i s o p ro p y l c th y l am i n c (289.45 mg, 2.24 mmol) was added followed by addition of p-tosylchloride (355.8 mg, 1.86 mmol). The reaction mixture was stirred at 0°C for 15 minutes, then allowed to warm to room temperature and stirred for 6 hours. The reaction was diluted with ethyl acetate (20 mL), washed with water, the organic layer was dried over anhydrous MgSCL and the solvent evaporated. The residue was purified by silica gel chromatography, eluted with 0-10% ethyl acetate/heptane, followed by trituration with water, to afford 7-[5-(difluoromethyl)-l,3,4-oxadiazol-2-yl]- 2-phenyl-3,4-dihydroisoquinolin-l-one (60 mg, 22.4%) as a colourless solid. BIOLOGICAL EXAMPLES
Example: in vivo preventive test on Puccinia recondita Thrown rust on wheat)
Solvent: 5% by volume of Dimethyl sulfoxide
10% by volume of Acetone
Emulsifier: 1 mΐ of polyoxyethylene sorbitan monooleate (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 500 ppm of active ingredient: 1.007
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 500 ppm of active ingredient: 1.001; 1.004
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: 1.006
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: 1.023; 1.024
Example: in vivo preventive test on Phakospora pachyrhizi (soybean rust)
Solvent: 5% by volume of Dimethyl sulfoxide
10% by volume of Acetone
Emulsifier: Imΐ of polyoxyethylene sorbitan monooleate (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 11 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 500 ppm of active ingredient: 1.001
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 500 ppm of active ingredient: 1.008; 1.011
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: 1.007
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: 1.036
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: 1.018; 1.024
Example: in vivo preventive test on Phakovsora 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 Phakovsora 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 longlasting activity test on Phakovsora 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

Claims
1. Use of a compound of formula (I) for controlling harmful microorganisms in crop protection:
Figure imgf000119_0001
wherein
X is hydrogen or fluorine; W1, W2 and W3 are independently CH, CF or N, wherein W1 and W3 cannot both be N; n is 1 or 2, wherein if n is 2, the two [CR2R3] groups may be the same or different; m is 0, 1 or 2, wherein if m is 2, the two [CR4R5] groups may be the same or different;
R1 is aryl, heteroaryl, C3-C10-carbocyclyl or 3- to 10-membered-heterocyclyl, each of which may be substituted with one or more R1c substituents;
R2 and R3 are independently selected from the group consisting of hydrogen, halogen atom and C1 - C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R2a substituents, or R2 and R3 form, together with the carbon atom to which they are linked, a C=0 group, or
R2 and R3 form, together with the carbon atom to which they are linked, a C3-C6 -cycloalkyl wherein said C3-C6-cycloalkyl may be substituted with one or more R2c substituents;
R4and R5 are independently selected from the group consisting of hydrogen, C1 -C8-haloalkyl and C1 -C8-alkyl, wherein the C1 -C8-alkyl may be substituted with one or more R4a substituents, R1c substituents are independently selected from the group consisting of halogen, cyano, hydroxyl, carboxyl, formyl, carbamoyl, carbamate, sulfanyl, sulfmyl, sulfonyl, amino, nitro, pentafluoro-l6- sulfanyl, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-hydroxyalkyl, C1 -C6-cyanoalkyl, C1 -C6-alkoxy, C1 - C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1 -C6-alkylsulfanyl, C1 -C6-haloalkylsulfanyl, arylsulfanyl, C1 -C6-alkylsulfinyl, C1 -C6-haloalkylsulfinyl, arylsulfmyl, C3-C10-carbocyclyl, C3- C10-halocarbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, aryl-C1 -C6-alkyl, 3- to 10- membered-heterocyclyl-C1 -C6 -alkyl, heteroaryl-C1 -C6-alkyl, C3-C10-carbocyclyl-C1 -C6-alkyl, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6-alkyl)2, -C(=0)R21, -C(=0)OR21, -C(=0)N(R21)2,
-C(=0)N(0R21)R21, -C(=0)NR21N(R21)2, -C(=S)N(R21)2, -C(=NR21)R21,
-C(=NR21)N(R21)2, -C(=NOR21)R21, -N(R21)2, -NR21C(=0)0R21, -N(0R21)C(=0)0R21,
-NR21C(=0)N(R21)2, -NR21C(=0)R21, -N(0R21)C(=0)R21, -NR21C(=S)R21,
-NR21C(=S)N(R21)2, -NR21C(=NR21)R21, -OR21, -OC(=0)R21, -0C(=0)N(R21)2,
-NR21S(=0)2R21, -N=CR21-N(R21)2, -S(=0)2R21, -S(=0)2N(R21)2 and -P(=0)(0R21)2, wherein the C1 -C6 -alkyl, C1 -C6-alkoxy, C2-C6 -alkenyl and C2-C6-alkynyl may be substituted with one or more Ra substituents; wherein the C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl, heteroaryl, arylsulfanyl and arylsulfmyl may be substituted with one or more Rc substituents;
R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl, C3-C10-carbocyclyl, 3- to 10-membered-heterocyclyl, aryl and heteroaryl; wherein the C1 -C6-alkyl may be substituted with one or more Ra substituents and wherein the C3-C10-carbocyclyl, 3- to 10- membered-heterocyclyl, aryl and heteroaryl may be substituted with one or more Rc substituents; R2a , R4a and Ra are independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8-halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6- alkyl)amino, -Si(C1 -C6-alkylG -Si (aryl )( C1 -C6-alkyl)2, C1 -C6-alkoxy. C1 -C6-haloalkoxy. C1 -C6- alkylsulfanyl, C1 -C6-alkylcarbonyl. C1 -C6-haloalkylcarbonyl. C 1 -C6-alkylcarbamoyl. di-(C1 -C6- alkyl)carbamoyl, C 1 -C6-alkoxycarbonyl. C 1 -C6-haloalkoxycarbonyl. aryloxy, C1 -C6- alkylcarbonyloxy, C1 -C6-alkylcarbonylamino. C1 -C6-haloalkylcarbonylamino. C 1 -C8- alkylsulfanyl, C1 -C8-alkylsulfinyl. C1 -C8-alkylsulfonyl, C1 -C8-alkylsulfonylamino, C 1 -C8- haloalkylsulfonylamino, C 1 -C8-alkylsiilfamoyl and di-(C1 -C8-alkyl)sulfamoyl;
R2c and Rc are independently selected from the group consisting of C1 -C6-alkyl, C1 -C6-haloalkyl, C2- C6-alkenyl, C2-C6-alkynyl, halogen atom, nitro, hydroxyl, cyano, carboxyl, amino, sulfanyl, pentafluoro-λ6-sulfanyl, formyl, carbamoyl, carbamate, sulfamoyl, C3-C7-cycloalkyl, C3-C8- halocycloalkyl, C1 -C6-alkylamino, di-(C1 -C6-alkyl)amino, -Si(C1 -C6-alkyl)3, -Si(aryl)(C1 -C6- alkyl)2, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C1 -C6-alkylsulfanyl, C1 -C6-alkylcarbonyl, C1 -C6- haloalkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxycarbonyl, C1 - C6-haloalkoxycarbonyl, aryloxy, C1 -C6-alkylcarbonyloxy, C1 -C6-alkylcarbonylamino, C1 -C6- haloalkylcarbonylamino, C1 -C8-alkylsulfanyl. C 1 -C8-alky l sulfiny l . C1 -C8-alkylsulfonyl, C1 -C8- alkylsulfonylamino, C1 -C8-haloalkylsulfonylamino, C1 -C8-alkylsulfamoyl and di-(C1 -C8- alkyl)sulfamoyl; or a salt, N-oxide or solvate thereof.
2. The use of the compound of formula (I) according to claim 1 or a salt, N-oxide or solvate thereof, wherein W1 is N, CH or CF, and W2 and W3 are independently selected from CH and CF.
3. The use of the compound of formula (I) according to claim 1 or 2, or a salt, N-oxide or solvate thereof, wherein R2 and R3 are hydrogen.
4. The use of the compound of formula (I) according to any of the preceding claims, or a salt, N- oxide or solvate thereof, wherein X is hydrogen.
5. The use of the compound of formula (I) according to any of the preceding claims, or a salt, N- oxide or solvate thereof, wherein n is i.
6. The use of the compound of formula (I) according to any of the preceding claims, or a salt, N- oxide or solvate thereof, wherein m is 0 or 1.
7. The use of the compound of formula (I) according to any of the preceding claims, or a salt, N- oxide or solvate thereof, wherein R1 is an aryl selected from phenyl and naphthyl, a heteroaryl selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, quinolinyl and isoquinolinyl, a C3-C7-cycloalkyl or a 3- to 7-membered heterocyclyl selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2-oxazinanyl, oxathianyl and thiomorpholinyl, wherein the aryl, heteroaryl, C3-C7- cycloalkyl and 3- to 7-membered heterocyclyl may be substituted with one to three R1c substituents.
8. The use of the compound of formula (I) according to any of the preceding claims or a salt, N- oxide or solvate thereof, wherein the R1c substituents are selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C3-C6-cycloalkyl, phenyl, 5- to 6- membered heteroaryl selected from the group consisting of ftiryl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, oxadiazolyl, isothiazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl, 3- to 7-membered heterocyclyl selected from the group consisting of tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, triazolidinyl, isoxazolidinyl, oxazolidinyl, oxadiazolidinyl, thiazolidinyl, isothiazolidinyl, thiadiazolidinyl, piperidinyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl, triazinanyl, hexahydrotriazinyl, tetrahydropyranyl, dioxanyl, tetrahydrothiopyranyl, dithianyl, morpholinyl, 1,2- oxazinanyl, oxathianyl and thiomorpholinyl, -NR21C(=0)0R21, -NR21C(=0)R21, -C(=0)OR21,
-C(=0)N(R21)2 and -0C(=0)N(R21)2, wherein the C3-C6-cycloalkyl, 3- to 7-membered-heterocyclyl, phenyl and heteroaryl may be substituted with one to three Rc substituents; and wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl and C3-C6- cycloalkyl.
9. The use of the compound of formula (I) according to any of the preceding claims, or a salt, N- oxide or solvate thereof, wherein R1 is phenyl or C3-C7-cycloalkyl, wherein the phenyl and C3-C7- cycloalkyl may be substituted with one to three R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy, C3-C6-cycloalkyl, phenyl, -NR21C(=0)0R21 and -NR21C(=0)R21, wherein the C3-C6-cycloalkyl and phenyl may be substituted with one to three Rc substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7- cycloalkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6-alkoxycarbonyl and wherein each R21 is independently selected from the group consisting of hydrogen, C1 -C6-alkyl, C1 -C6-haloalkyl and C3-C6-cycloalkyl.
10. The use of the compound of formula (I) according to any of claims 1 to 8 or a salt, N-oxide or solvate thereof, wherein R1 is selected from aryl, heteroaryl, C3-C7-cycloalkyl and 3- to 7-membered heterocyclyl, wherein the aryl, heteroaryl, C3-C7-cycloalkyl and 3- to 7-membered heterocyclyl is substituted with one cyclic R1c substituent selected from the group consisting of C3-C7-cycloalkyl, aryl, heteroaryl and 3- to 7-membered heterocyclyl and may additionally be substituted with one or two non- cyclic R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy and C1 -C6-haloalkoxy, and wherein the C3-C7-cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three Rc substituents.
11. The use of the compound of formula (I) according to any of claims 1 to 8 or a salt, N-oxide or solvate thereof, wherein R1 is phenyl, which is substituted with one R1c substituent selected from the group consisting of C3-C7-cycloalkyl, aryl, heteroaryl and 3- to 7-membered heterocyclyl and may additionally be substituted with one or two further R1c substituents selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy and C1 -C6-haloalkoxy, wherein the C3-C7-cycloalkyl, 3- to 7-membered-heterocyclyl, aryl and heteroaryl may be substituted with one to three Rc substituents.
12. The use of the compound of formula (I) according to any of the preceding claims or a salt, N- oxide or solvate thereof, wherein the Rc substituents are selected from the group consisting of halogen, cyano, C1 -C6-alkyl, C3-C7-cycloalkyl, C1 -C6-haloalkyl, C1 -C6-alkoxy, C1 -C6-haloalkoxy and C1 -C6- alkoxy carbonyl.
13. The use of the compound of formula (I) according to any of the preceding claims or a salt, N- oxide or solvate thereof, wherein R4 and R5 are independently selected from the group consisting of hydrogen, C1 -Ct-haloalkyl and C1 -Ct-alkyl, wherein the C1 -Ct-alkyl may be substituted with one to three R4a substituents selected from the group consisting of halogen atom, cyano, carboxyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C1 -C6-alkylcarbonyl, C1 -C6-alkylcarbamoyl, di-(C1 -C6-alkyl)carbamoyl, C1 -C6-alkoxy carbonyl and C1 -C6-haloalkoxy carbonyl.
14. A method for controlling harmful microorganisms in crop protection which comprises the step of applying at least one compound of formula (I) according to any of claims 1 to 13 to the harmful microorganisms and/or their habitat.
15. A composition for controlling phytopathogenic harmful fungi comprising at least one compound of formula (I) according to any one of claims 1 to 13 in a fungicidally effective amount.
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