WO2024126407A1 - Dérivés benzimidazoles - Google Patents

Dérivés benzimidazoles Download PDF

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Publication number
WO2024126407A1
WO2024126407A1 PCT/EP2023/085193 EP2023085193W WO2024126407A1 WO 2024126407 A1 WO2024126407 A1 WO 2024126407A1 EP 2023085193 W EP2023085193 W EP 2023085193W WO 2024126407 A1 WO2024126407 A1 WO 2024126407A1
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6alkyl
6alkoxy
methyl
formula
ch2och3
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PCT/EP2023/085193
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English (en)
Inventor
Martin Pouliot
Damien BONVALOT
Nicolas Germain
Federico DAPIAGGI
Daria GROSHEVA
Stephane André Marie JEANMART
Camille LE CHAPELAIN
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Syngenta Crop Protection Ag
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Publication of WO2024126407A1 publication Critical patent/WO2024126407A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D471/02—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 two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D473/00—Heterocyclic compounds containing purine ring systems

Definitions

  • the present invention relates to microbiocidal benzimidazole derivatives, e.g. as active ingredients, which have microbiocidal activity, in particular fungicidal activity, more particularly activity against oomycetes.
  • the invention also relates to preparation of these benzimidazole derivatives, to intermediates useful in the preparation of these benzimidazole derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of the benzimidazole derivatives, to preparation of these compositions and to the use of the benzimidazole derivatives or compositions in agriculture or horticulture for combating, controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi, more particularly oomycetes. It has now surprisingly been found that certain novel benzimidazole derivatives have favourable fungicidal properties, in particular against oomycetes.
  • the present invention provides compounds of formula (I) wherein Z is O or S, and preferably Z is O;
  • A is CH or N;
  • a 1 are independently N or CR 1 ; with the proviso that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 is N, and more preferably the four A 1 are CR 1 ;
  • R 1 are independently selected from hydrogen, hydroxy, halogen, CN, C1-6alkyl, C3-6cycloalkyl, C1- 6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1-4alkyl, C1-6alkylsulfanyl, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-6alkoxy, amino, and NHC(O)C1-6alkyl;
  • a 2 are independently CR 2 or N, with the proviso that no more than three A 2 are N, preferably no more than two A 2 are N, preferably
  • the present invention provides an agrochemical composition comprising a compound of formula (I), and more particularly an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I).
  • Said composition can further comprise at least one compound selected among an additional active ingredient, an appropriate formulation inert, a carrier, an adjuvant, and any mixtures thereof.
  • Compounds of formula (I) may be used to control phytopathogenic microorganisms.
  • a compound of formula (I), or a composition comprising a compound of formula (I) according to the invention may be applied directly to the phytopathogen, to the locus of a phytopathogen, in particular to a plant susceptible to attack by phytopathogens, or to a propagation material of a plant.
  • the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to combat, prevent or control a phytopathogen.
  • the present invention provides a method of combating, preventing or controlling phytopathogens, comprising applying a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to said phytopathogen, to the locus of said phytopathogen, in particular to a plant susceptible to attack by a phytopathogen, or to a propagation material of a plant.
  • Compounds of formula (I) are particularly effective in combating, preventing or controlling phytopathogenic fungi, in particular oomycetes.
  • the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to control phytopathogenic fungi, in particular oomycetes.
  • the present invention provides a method of combating, preventing or controlling phytopathogenic disease, such as phytopathogenic fungi, comprising applying a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to said phytopathogenic fungi, or to the locus of said phytopathogenic fungi, in particular to a plant susceptible to attack by phytopathogenic fungi, in particular oomycetes, or to a propagation material of a plant.
  • a group is indicated as being substituted, e.g. alkyl, this includes those groups that are part of other groups, e.g. the alkyl in alkylthio.
  • halogen refers to fluorine (fluoro or F), chlorine (chloro or Cl), bromine (bromo or Br) or iodine (iodo or I), preferably fluorine, chlorine or bromine.
  • Alkyl as used herein- in isolation or as part of a chemical group – represents straight-chain or branched hydrocarbons, preferably with 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2- dimethylpropyl, 1,1 -dimethylpropyl, 2,2- dimethylpropyl, 1 -ethylpropyl, hexyl, 1 -methylpentyl, 2- methylpentyl, 3-methylpentyl, 4- methylpentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl, 1,1- dimethylbutyl, 2,2-dimethylbut
  • Alkyl groups with 1 to 4 carbon atoms are preferred, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl.
  • Alkenyl in isolation or as part of a chemical group - represents straight-chain or branched hydrocarbons, preferably with 2 to 6 carbon atoms and at least one double bond, for example vinyl, 2- propenyl, 2-butenyl, 3-butenyl, 1- methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4- pentenyl, 1-methyl-2-butenyl, 2- methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3- butenyl, 3-methyl-3-butenyl, 1,1 - dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1 -ethyl-2-propenyl, 2- hexenyl, 3-hexenyl, 4- hexenyl, 5-hexenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 2-methyl-2-penten
  • Alkenyl groups with 2 to 4 carbon atoms are preferred, for example 2-propenyl, 2-butenyl or 1-methyl-2-propenyl.
  • the term "Alkynyl" - in isolation or as part of a chemical group - represents straight-chain or branched hydrocarbons, preferably with 2 to 6 carbon atoms and at least one triple bond, for example 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2- propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2- methyl-3-butynyl, 1-methyl-2- butynyl, 1,1 -dimethyl-2-propynyl, 1 -ethyl-2-propynyl, 2-hexynyl, 3- hexynyl, 4-hexynyl, 5-hexynyl, 1- methyl-2-pentyn
  • Alkynyls with 2 to 4 carbon atoms are preferred, for example ethynyl, 2- propynyl or 2-butynyl-2-propenyl.
  • cycloalkyl in isolation or as part of a chemical group - represents saturated or partially unsaturated mono-, bi- or tricyclic hydrocarbons, preferably with 3 to 10 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl.
  • alkoxy refers to a radical of the formula -ORa wherein Ra is an alkyl radical as generally defined above. Examples of alkoxy include, but are not limited to methoxy, ethoxy, propoxy, iso-propoxy, and tert-butoxy.
  • alkylsulfanyl refers to a radical of the formula -SRa wherein Ra is an alkyl radical as generally defined above.
  • alkylsulfinyl refers to a radical of the formula -S(O)Ra wherein Ra is an alkyl radical as generally defined above.
  • alkylsulfonyl refers to a radical of the formula -S(O)2Ra wherein Ra is an alkyl radical as generally defined above.
  • alkoxycarbonyl refers to a radical of the formula RaOC(O)-, wherein Ra is an alkyl radical as generally defined above.
  • alkylaminocarbonyl refers to a radical of the formula RaNHC(O)- wherein Ra is an alkyl radical as generally defined above.
  • - Hydroxyl or hydroxy stands for a –OH group.
  • the term "effective amount” refers to the amount of the compound, a salt, or N-oxide thereof, which, upon single or multiple applications provides the desired effect. An effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances.
  • Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C 1 -C 4 alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid
  • Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, die
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the compounds of formula (I) according to the invention also include hydrates, which may be formed during salt formation.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
  • a compound of formula (I) according to the present invention wherein the four A 1 are CR 1 .
  • a compound of formula (I) according to the present invention wherein two A 1 are CR 1 and two A 1 are N.
  • a compound of formula (I) according to the present invention wherein three A 1 are CR 1 and one A 1 is N.
  • a compound of formula (I) according to the present invention wherein R 1 are independently selected from hydrogen, hydroxy, halogen, CN, C1-6alkyl, C3-6cycloalkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 1-6 alkoxy, amino, and NHC(O)C 1-6 alkyl, and preferably R 1 are independently selected from hydrogen and C1-6alkyl.
  • R 1 are independently selected from hydrogen, hydroxy, halogen, CN, C1-6alkyl, C3-6cycloalkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 1-6 alkoxy, amino, and NHC(O)C 1-6 alkyl, and preferably R 1 are independently selected from hydrogen and C1-6alkyl.
  • R 1 are independently selected from hydrogen, hydroxy, halogen, CN, C1-6alkyl, C3-6cycloalkyl
  • R 2 are independently selected from hydrogen, hydroxy, halogen, CN, C1-6alkyl, C1-6alkoxy, C1- 6alkoxy-C1-6alkyl, and C1-6alkoxy-C1-6alkoxy, C1-6alkoxycarbonyl, C1-6alkylaminocarbonyl, diC1- 6 alkylaminocarbonyl, and C 1-6 alkylcarbonyl, wherein each of the C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1- 6alkyl, C1-6alkoxy-C1-6alkoxy, C1-6alkoxycarbonyl, C1-6alkylaminocarbonyl, diC1-6alkylaminocarbonyl, and C1-6alkylcarbonyl groups is optionally substituted with one to three substituents independently selected from halogen, hydroxy, and CN; and preferably R 2 are independently selected from hydrogen, halogen,
  • R 3 are independently selected from hydrogen, hydroxy, halogen, CN, C1-6alkyl, C1-6alkoxy, C1- 6alkoxy-C1-6alkyl, C1-6alkoxy-C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, amino, C1-6alkylamino, diC1-6-alkylamino, and C3-6cycloalkylamino, wherein each of the C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1- 6alkyl, C1-6alkoxy-C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, amino, C1-6alkylamino, diC1-6- alkylamino and C3-6cycloalkylamino groups is optionally substituted with one to three substituents independently selected from halogen, hydroxy, and CN.
  • R 3 can be hydrogen.
  • a compound of formula (I) according to the present invention wherein four A 2 are CR 2 and A 3 is N.
  • a compound of formula (I) according to the present invention wherein , and preferably the three A 2 are CR 2 and A 3 is CR 3 .
  • a compound of formula (I) according to the present invention wherein preferably the three A 2 are CR 2 and A 3 is CR 3 .
  • R 2 is as defined in the present invention; preferably R 2 are independently selected from hydrogen, hydroxy, halogen, CN, C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy-C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1-6alkoxycarbonyl, C1-6alkylaminocarbonyl, diC1-6alkylaminocarbonyl, and C1-6alkylcarbonyl, wherein each of the C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy-C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1- 6alkoxycarbonyl, C1-6alkylaminocarbonyl, diC1-6alkylaminocarbonyl, and C1-6alkylcarbonyl groups is optionally substituted with one to three substitu
  • R 4 is selected from C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 2- 6alkenyl, C2-6alkynyl, and C1-6alkoxy, wherein each of the C1-6alkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-4alkyl, C2-6alkenyl, C2-6alkynyl, and C1-6alkoxy groups is optionally substituted with one to three substituents independently selected from halogen and CN; preferably and R 4 is selected from C1-6alkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-4alkyl, and C1-6alkoxy, wherein each of the C1-6
  • a compound of formula (I) according to the present invention, wherein A 3 is CR 3 and wherein R 3 and R 4 taken together form a ring, preferably a 5-8-membered heterocycle, preferably a 6-membered heterocycle, and more preferably one of the rings W1, W2 or W3 as described in the compounds of the formula (I) below:
  • the carbon and/or the nitrogen atoms forming said ring (W1, W2 or W3) can be substituted according to the R 3 and R 4 groups as defined in the present invention, and more preferably can be substituted by a R 3’ group, wherein R 3’ is selected from hydrogen, C1-6alkyl, and C3-6cycloalkyl, wherein each of the C1- 6alkyl and C3-6cycloalkyl groups is optionally substituted with one to three substituents independently selected from halogen and CN.
  • the compounds of the formula (I-W3) can be as follows:
  • the compounds of the formula (I-W1), (I-W2) and (I-W3) can be as described below:
  • the carbon and/or the nitrogen atoms forming said ring (W1, W2 or W3) can be substituted, especially by a R 3’ group, wherein R 3’ is selected from hydrogen, C1-6alkyl, and C3-6cycloalkyl, wherein each of the C1-6alkyl and C3-6cycloalkyl groups is optionally substituted with one to three substituents independently selected from halogen and CN.
  • the compounds of the formula (I-W3) can be as follows:
  • R 5 is selected from C1-6alkyl, C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, and C1- 6alkoxyC1-6alkyl, wherein each of said groups is optionally substituted with one to three substituents independently selected from halogen and CN.
  • a compound of formula (I) wherein Z is O; A is N; the four A 1 are CR 1 with R 1 being independently selected from hydrogen, hydroxy, halogen, CN, C1- 6alkyl, C3-6cycloalkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1-4alkyl, C1-6alkylsulfanyl, C1-6alkylsulfinyl, C1- 6alkylsulfonyl and C1-6alkoxy; and preferably , the four A 2 are CR 2 ; with R 2 being independently selected from hydrogen, hydroxy, halogen, CN, C1- 6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy-C1-6alkoxy, C2-6alkenyl, C2-6alkynyl, C3-6cycloalkyl, C3- 6 cycloalkyl-C
  • R 2 is as defined in the present invention; preferably R 2 are independently selected from hydrogen, hydroxy, halogen, CN, C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy-C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1-6alkoxycarbonyl, C1-6alkylaminocarbonyl, diC1-6alkylaminocarbonyl, and C1-6alkylcarbonyl, wherein each of the C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy-C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1- 6alkoxycarbonyl, C1-6alkylaminocarbonyl, diC1-6alkylaminocarbonyl, and C1-6alkylcarbonyl groups is optionally substituted with one to
  • R 2 is as defined in the present invention; preferably R 2 is selected from hydroxy, halogen, CN, C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1- 6alkoxy-C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1-6alkoxycarbonyl, C1-6alkylaminocarbonyl, diC1-6alkylaminocarbonyl, and C1-6alkylcarbonyl, wherein each of the C1-6alkyl, C1-6alkoxy, C1-6alkoxy- C1-6alkyl, C1-6alkoxy-C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1-6alkoxycarbonyl, C1- 6alkylaminocarbonyl, diC1-6alkylaminocarbonyl, and C1-6alkylcarbonyl groups is optionally substituted with one to three
  • the compound according to the present invention is selected from: methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-4-(methoxymethyl)benzimidazol-1-yl]- 2-pyridyl]carbamate; methyl N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxy-phenyl)carbamoyl]-4-methyl-benzimidazol-1-yl]-2- pyridyl]carbamate; methyl N-[5-[4-ethyl-6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]benzimidazol-1-yl]-2- pyridyl]carbamate; methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-(methoxymethyl)carb
  • the method according to the present invention has advantageous properties for protecting plants against pathogenic, such as phytopathogenic, especially fungi such as oomycetes, attack or infestation, which result in a disease and damage to the plant; particularly in instance of plants, the present invention can control, limit or prevent pathogenic damage on plant, parts of plant, plant propagation material and/or plant grown.
  • Tables 1.1 to 1.132 below illustrate the compounds of the invention.
  • Table 1.1 provides 700 compounds E1.1 to E1.700 of formula (Ia) wherein A is CH, R 2 is H, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.3 provides 700 compounds E3.1 to E3.700 of formula (Ia) wherein A is CH, R 2 is H, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.4 provides 700 compounds E4.1 to E4.700 of formula (Ia) wherein A is CH, R 2 is H, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.5 provides 700 compounds E5.1 to E5.700 of formula (Ia) wherein A is CH, R 2 is H, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.6 provides 700 compounds E6.1 to E6.700 of formula (Ia) wherein A is CH, R 2 is H, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.7 provides 700 compounds E7.1 to E7.700 of formula (Ia) wherein A is CH, R 2 is CH3, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.8 provides 700 compounds E8.1 to E8.700 of formula (Ia) wherein A is CH, R 2 is CH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.9 provides 700 compounds E9.1 to E9.700 of formula (Ia) wherein A is CH, R 2 is CH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.10 provides 700 compounds E10.1 to E10.700 of formula (Ia) wherein A is CH, R 2 is CH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.11 provides 700 compounds E11.1 to E11.700 of formula (Ia) wherein A is CH, R 2 is CH3, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.12 provides 700 compounds E12.1 to E12.700 of formula (Ia) wherein A is CH, R 2 is CH3, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.13 provides 700 compounds E13.1 to E13.700 of formula (Ia) wherein A is CH, R 2 is CH2CH3, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.14 provides 700 compounds E14.1 to E14.700 of formula (Ia) wherein A is CH, R 2 is CH2CH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.15 provides 700 compounds E15.1 to E15.700 of formula (Ia) wherein A is CH, R 2 is CH2CH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.16 provides 700 compounds E16.1 to E16.700 of formula (Ia) wherein A is CH, R 2 is CH2CH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.17 provides 700 compounds E17.1 to E17.700 of formula (Ia) wherein A is CH, R 2 is CH2CH3, are as defined in table Z.
  • Table 1.18 provides 700 compounds E18.1 to E18.700 of formula (Ia) wherein A is CH, R 2 is CH2CH3, are as defined in table Z.
  • Table 1.19 provides 700 compounds E19.1 to E19.700 of formula (Ia) wherein A is CH, R 2 is F, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.20 provides 700 compounds E20.1 to E20.700 of formula (Ia) wherein A is CH, R 2 is F, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.21 provides 700 compounds E21.1 to E21.700 of formula (Ia) wherein A is CH, R 2 is F, R 5 is OCH 3 , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.22 provides 700 compounds E22.1 to E22.700 of formula (Ia) wherein A is CH, R 2 is F, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.23 provides 700 compounds E23.1 to E23.700 of formula (Ia) wherein A is CH, R 2 is F, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.24 provides 700 compounds E24.1 to E24.700 of formula (Ia) wherein A is CH, R 2 is F, R 5 R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.25 provides 700 compounds E25.1 to E25.700 of formula (Ia) wherein A is CH, R 2 is Cl, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.26 provides 700 compounds E26.1 to E26.700 of formula (Ia) wherein A is CH, R 2 R 2 is Cl, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.27 provides 700 compounds E27.1 to E27.700 of formula (Ia) wherein A is CH, R 2 is Cl, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.28 provides 700 compounds E28.1 to E28.700 of formula (Ia) wherein A is CH, R 2 is Cl, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.29 provides 700 compounds E29.1 to E29.700 of formula (Ia) wherein A is CH, R 2 is Cl, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.30 provides 700 compounds E30.1 to E30.700 of formula (Ia) wherein A is CH, R 2 is Cl, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.31 provides 700 compounds E31.1 to E31.700 of formula (Ia) wherein A is CH, R 2 is Br, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.32 provides 700 compounds E32.1 to E32.700 of formula (Ia) wherein A is CH, R 2 is Br, R 5 is CH 3 , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.33 provides 700 compounds E33.1 to E33.700 of formula (Ia) wherein A is CH, R 2 is Br, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.34 provides 700 compounds E34.1 to E34.700 of formula (Ia) wherein A is CH, R 2 is Br, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.35 provides 700 compounds E35.1 to E35.700 of formula (Ia) wherein A is CH, R 2 is Br, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.36 provides 700 compounds E36.1 to E36.700 of formula (Ia) wherein A is CH, R 2 is Br, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.37 provides 700 compounds E37.1 to E37.700 of formula (Ia) wherein A is CH, R 2 is CN, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.38 provides 700 compounds E38.1 to E38.700 of formula (Ia) wherein A is CH, R 2 is CN, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.39 provides 700 compounds E39.1 to E39.700 of formula (Ia) wherein A is CH, R 2 is CN, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.40 provides 700 compounds E40.1 to E40.700 of formula (Ia) wherein A is CH, R 2 is CN, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.41 provides 700 compounds E41.1 to E41.700 of formula (Ia) wherein A is CH, R 2 is CN, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.42 provides 700 compounds E42.1 to E42.700 of formula (Ia) wherein A is CH, R 2 is CN, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.43 provides 700 compounds E43.1 to E43.700 of formula (Ia) wherein A is CH, R 2 is OCH3, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.44 provides 700 compounds E44.1 to E44.700 of formula (Ia) wherein A is CH, R 2 is OCH3, R5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.45 provides 700 compounds E45.1 to E45.700 of formula (Ia) wherein A is CH, R 2 is OCH3, R5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.46 provides 700 compounds E46.1 to E46.700 of formula (Ia) wherein A is CH, R 2 is OCH3, R5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.47 provides 700 compounds E47.1 to E47.700 of formula (Ia) wherein A is CH, R 2 is OCH3, R5 are as defined in table Z.
  • Table 1.48 provides 700 compounds E48.1 to E48.700 of formula (Ia) wherein A is CH, R 2 is OCH3, R 5 are as defined in table Z.
  • Table 1.49 provides 700 compounds E49.1 to E49.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH3, R 5 R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.50 provides 700 compounds E50.1 to E50.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.51 provides 700 compounds E51.1 to E51.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.52 provides 700 compounds E52.1 to E52.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.53 provides 700 compounds E53.1 to E53.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH3, are as defined in table Z.
  • Table 1.54 provides 700 compounds E54.1 to E54.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH3, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.55 provides 700 compounds E55.1 to E55.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH2OCH3, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.56 provides 700 compounds E56.1 to E56.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH2OCH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.57 provides 700 compounds E57.1 to E57.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH2OCH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.58 provides 700 compounds E58.1 to E58.700 of formula (Ia) wherein A is CH, R 2 is OCH2CH2OCH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.59 provides 700 compounds E59.1 to E59.700 of formula (Ia) wherein A is CH, R 2 is are as defined in table Z.
  • Table 1.60 provides 700 compounds E60.1 to E60.700 of formula (Ia) wherein A is CH, R 2 is are as defined in table Z.
  • Table 1.61 provides 700 compounds E61.1 to E61.700 of formula (Ia) wherein A is CH, R 2 is OH, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.62 provides 700 compounds E62.1 to E62.700 of formula (Ia) wherein A is CH, R 2 is OH, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.63 provides 700 compounds E63.1 to E63.700 of formula (Ia) wherein A is CH, R 2 is OH, R 5 is OCH 3 , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.64 provides 700 compounds E64.1 to E64.700 of formula (Ia) wherein A is CH, R 2 is OH, R 5 R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.65 provides 700 compounds E65.1 to E65.700 of formula (Ia) wherein A is CH, R 2 is OH, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.66 provides 700 compounds E66.1 to E66.700 of formula (Ia) wherein A is CH, R 2 is OH, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.67 provides 700 compounds E67.1 to E67.700 of formula (Ia) wherein A is N, R 2 is H, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.68 provides 700 compounds E68.1 to E68.700 of formula (Ia) wherein A is N, R 2 is H, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.69 provides 700 compounds E69.1 to E69.700 of formula (Ia) wherein A is N, R 2 is H, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.70 provides 700 compounds E70.1 to E70.700 of formula (Ia) wherein A is N, R 2 is H, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.71 provides 700 compounds E71.1 to E71.700 of formula (Ia) wherein A is N, R 2 is H, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.72 provides 700 compounds E72.1 to E72.700 of formula (Ia) wherein A is N, R 2 is H, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.73 provides 700 compounds E73.1 to E73.700 of formula (Ia) wherein A is N, R 2 is CH3, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.74 provides 700 compounds E74.1 to E74.700 of formula (Ia) wherein A is N, R 2 is CH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.75 provides 700 compounds E75.1 to E75.700 of formula (Ia) wherein A is N, R 2 is CH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.76 provides 700 compounds E76.1 to E76.700 of formula (Ia) wherein A is N, R 2 is CH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.77 provides 700 compounds E77.1 to E77.700 of formula (Ia) wherein A is N, R 2 is CH 3 , R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.78 provides 700 compounds E78.1 to E78.700 of formula (Ia) wherein A is N, R 2 is CH3, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.79 provides 700 compounds E79.1 to E79.700 of formula (Ia) wherein A is N, R 2 is CH2CH3, R5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.80 provides 700 compounds E80.1 to E80.700 of formula (Ia) wherein A is N, R 2 is CH2CH3, R 5 R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.81 provides 700 compounds E81.1 to E81.700 of formula (Ia) wherein A is N, R 2 is CH2CH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.82 provides 700 compounds E82.1 to E82.700 of formula (Ia) wherein A is N, R 2 is CH2CH3, R5 is OCH 3 , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.83 provides 700 compounds E83.1 to E83.700 of formula (Ia) wherein A is N, R 2 is CH2CH3, R5 are as defined in table Z.
  • Table 1.84 provides 700 compounds E84.1 to E84.700 of formula (Ia) wherein A is N, R 2 is CH2CH3, R5 are as defined in table Z.
  • Table 1.85 provides 700 compounds E85.1 to E85.700 of formula (Ia) wherein A is N, R 2 is F, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.86 provides 700 compounds E86.1 to E86.700 of formula (Ia) wherein A is N, R 2 is F, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.87 provides 700 compounds E87.1 to E87.700 of formula (Ia) wherein A is N, R 2 is F, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.88 provides 700 compounds E88.1 to E88.700 of formula (Ia) wherein A is N, R 2 is F, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.89 provides 700 compounds E89.1 to E89.700 of formula (Ia) wherein A is N, R 2 is F, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.90 provides 700 compounds E90.1 to E90.700 of formula (Ia) wherein A is N, R 2 is F, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.91 provides 700 compounds E91.1 to E91.700 of formula (Ia) wherein A is N, R 2 is Cl, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.92 provides 700 compounds E92.1 to E92.700 of formula (Ia) wherein A is N, R 2 is Cl, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.93 provides 700 compounds E93.1 to E93.700 of formula (Ia) wherein A is N, R 2 is Cl, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.94 provides 700 compounds E94.1 to E94.700 of formula (Ia) wherein A is N, R 2 is Cl, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.95 provides 700 compounds E95.1 to E95.700 of formula (Ia) wherein A is N, R 2 is Cl, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.96 provides 700 compounds E96.1 to E96.700 of formula (Ia) wherein A is N, R 2 is Cl, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.97 provides 700 compounds E97.1 to E97.700 of formula (Ia) wherein A is N, R 2 is Br, R 5 is CH 3 , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.98 provides 700 compounds E98.1 to E98.700 of formula (Ia) wherein A is N, R 2 is Br, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.99 provides 700 compounds E99.1 to E99.700 of formula (Ia) wherein A is N, R 2 is Br, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.100 provides 700 compounds E100.1 to E100.700 of formula (Ia) wherein A is N, R 2 is Br, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.101 provides 700 compounds E101.1 to E101.700 of formula (Ia) wherein A is N, R 2 is Br, R 5 is , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.102 provides 700 compounds E102.1 to E102.700 of formula (Ia) wherein A is N, R 2 is Br, R 5 is , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.103 provides 700 compounds E103.1 to E103.700 of formula (Ia) wherein A is N, R 2 is CN, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.104 provides 700 compounds E104.1 to E104.700 of formula (Ia) wherein A is N, R 2 is CN, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.105 provides 700 compounds E105.1 to E105.700 of formula (Ia) wherein A is N, R 2 is CN, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.106 provides 700 compounds E106.1 to E106.700 of formula (Ia) wherein A is N, R 2 is CN, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.107 provides 700 compounds E107.1 to E107.700 of formula (Ia) wherein A is N, R 2 is CN, R 5 are as defined in table Z.
  • Table 1.108 provides 700 compounds E108.1 to E108.700 of formula (Ia) wherein A is N, R 2 is CN, R 5 are as defined in table Z.
  • Table 1.109 provides 700 compounds E109.1 to E109.700 of formula (Ia) wherein A is N, R 2 is OCH3, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.110 provides 700 compounds E110.1 to E110.700 of formula (Ia) wherein A is N, R 2 is OCH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.111 provides 700 compounds E111.1 to E111.700 of formula (Ia) wherein A is N, R 2 is OCH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.112 provides 700 compounds E112.1 to E112.700 of formula (Ia) wherein A is N, R 2 is OCH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.113 provides 700 compounds E113.1 to E113.700 of formula (Ia) wherein A is N, R 2 is OCH3, table Z.
  • Table 1.114 provides 700 compounds E114.1 to E114.700 of formula (Ia) wherein A is N, are as defined in table Z.
  • Table 1.115 provides 700 compounds E115.1 to E115.700 of formula (Ia) wherein A is N, R 2 is OCH2CH3, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.116 provides 700 compounds E116.1 to E116.700 of formula (Ia) wherein A is N, R 2 is OCH 2 CH 3 , R 5 is CH 3 , A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.117 provides 700 compounds E117.1 to E117.700 of formula (Ia) wherein A is N, R 2 is OCH2CH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.118 provides 700 compounds E118.1 to E118.700 of formula (Ia) wherein A is N, R 2 is OCH2CH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.119 provides 700 compounds E119.1 to E119.700 of formula (Ia) wherein A is N, R 2 is are as defined in table Z.
  • Table 1.120 provides 700 compounds E120.1 to E120.700 of formula (Ia) wherein A is N, R 2 is are as defined in table Z.
  • Table 1.121 provides 700 compounds E121.1 to E121.700 of formula (Ia) wherein A is N, R 2 is OCH2CH2OCH3, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.122 provides 700 compounds E122.1 to E122.700 of formula (Ia) wherein A is N, R 2 is OCH2CH2OCH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.123 provides 700 compounds E123.1 to E123.700 of formula (Ia) wherein A is N, R 2 is OCH2CH2OCH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.124 provides 700 compounds E124.1 to E124.700 of formula (Ia) wherein A is N, R 2 is OCH2CH2OCH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.125 provides 700 compounds E125.1 to E125.700 of formula (Ia) wherein A is N, R 2 is are as defined in table Z.
  • Table 1.126 provides 700 compounds E126.1 to E126.700 of formula (Ia) wherein A is N, R 2 is are as defined in table Z.
  • Table 1.127 provides 700 compounds E127.1 to E127.700 of formula (Ia) wherein A is N, R 2 is OH, R 5 is CH 3 , A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.128 provides 700 compounds E128.1 to E128.700 of formula (Ia) wherein A is N, R 2 is OH, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.129 provides 700 compounds E129.1 to E129.700 of formula (Ia) wherein A is N, R 2 R 2 is OH, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.130 provides 700 compounds E130.1 to E130.700 of formula (Ia) wherein A is N, R 2 is OH, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 are as defined in table Z.
  • Table 1.131 provides 700 compounds E131.1 to E131.700 of formula (Ia) wherein A is N, R 2 is OH, R 5 are as defined in table Z.
  • Table 1.132 provides 700 compounds E132.1 to E132.700 of formula (Ia) wherein A is N, R 2 is OH, R 5 are as defined in table Z.
  • Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, or increased biodegradability).
  • Compounds according to the invention have particularly advantageous levels of biological activity for protecting plants against oomycetes such as Phytophthora, Plasmopara and Pythium.
  • Compounds of formula (I) can be made as shown in the following schemes 1 to 22, in which, unless otherwise stated, the definition of each variable is as defined in the present invention.
  • Compounds of formula (I) can be prepared by the reaction of a compound of formula (II) with a compound of formula (III), wherein either R 8 is independently from each other hydrogen, C 1 -C 6 alkyl or wherein two R 8 together can form a C3-C8 cycloalkyl, in the presence of a base, such as triethylamine, diisopropylethylamine, pyridine, Cs2CO3, K2CO3, K2HPO4 or NaOtBu, and a suitable catalyst, such as copper(II) acetate, copper(II) carbonate, copper(II) hydroxide, copper oxide, copper(I) iodide or copper(I) bromide, in a suitable solvent, such as dimethylformamide, dimethylacetamide, dioxane, ace
  • the outcome of the reaction can be improved by adding boric acid or molecular sieves to the reaction mixture. It is understood that these transformations are done under air as oxygen is needed as a terminal oxidant. In some cases, the copper species might be used in stochiometric amount. This transformation is depicted in Scheme 1.
  • compounds of formula (I) can be prepared by the reaction of a compound of formula (II) with a compound of formula (IV), wherein X is Cl, Br or I, in the presence of a base, such as Cs2CO3, K2CO3, K2HPO4 or NaOtBu, and a suitable palladium catalyst, such as XPhos Pd G3, t-BuXPhos Pd G3, Me4tBuXPhos Pd G3, JohnPhos Pd G3, RuPhos Pd G3, BrettPhos Pd G3 or tBuBrettPhos Pd G3, in a suitable solvent, such as dimethylformamide, dimethylacetamide, dioxane, tetrahydrofuran or toluene.
  • a base such as Cs2CO3, K2CO3, K2HPO4 or NaOtBu
  • a suitable palladium catalyst such as XPhos Pd G3, t-BuXPhos Pd G3, Me4tBuXPhos Pd G
  • compounds of formula (V) can be used as their analogous lithium or sodium salts.
  • This transformation is depicted in Scheme 3.
  • Scheme 3 compounds of formula (IIa), wherein Z is O, can be prepared by the reaction of a compound of formula (VII), or an hydrogen chloride salt thereof, with a compound of formula (VI) and, optionally, a base such as pyridine, 4-N,N-dimethylaminopyridine, sodium hydroxide, triethylamine, potassium carbonate, in a solvent such as tetrahydrofuran, dioxan, toluene or water.
  • a base such as pyridine, 4-N,N-dimethylaminopyridine, sodium hydroxide, triethylamine, potassium carbonate
  • compounds of formula (IIa) can be prepared by deprotection of compounds of formula (XIV), wherein R 10 is a nitrogen protecting group such as trimethylsilylethoxymethyl (SEM), tert- butoxycarbonyl (Boc) or 2-tertahydropyranyl (THP).
  • R 10 is a nitrogen protecting group such as trimethylsilylethoxymethyl (SEM), tert- butoxycarbonyl (Boc) or 2-tertahydropyranyl (THP).
  • SEM trimethylsilylethoxymethyl
  • Boc tert- butoxycarbonyl
  • THP 2-tertahydropyranyl
  • Compounds of formula (XIV) can be obtained by reaction of compounds of formula (XV), wherein X is Cl, Br or I and R 10 is a nitrogen protecting group such as trimethylsilylethoxymethyl, tert-butoxycarbonyl or 2-tertahydropyranyl, with amines of formula (VI) and carbon monoxide in the presence of a catalyst such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) or bis(benzonitrile)palladium chloride, optionally in the presence of a ligand such as 4,5- bis(diphenylphosphino)-9,9-dimethylxanthene and, optionally, a base such as triethylamine.
  • a catalyst such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) or bis(benzonitrile)palladium chloride, optionally in the presence of
  • compounds of formula (Ia), wherein Z is O can be prepared by the reaction of a compound of formula (XVI) with a compound of formula (VI) and a coupling agent, such as N,N'- dicyclohexylcarbodiimide, bis(2-oxo-3-oxazolidinyl)phosphinic chloride, 2-(1H-benzotriazole-1-yl)- 1,1,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, propylphosphonic anhydride or cyanuric chloride, and, optionally, a base such, as triethylamine, ethyldiisopropylamine or N-methylmorpholine in a suitable solvent such ethyl acetate, dimethylformamide, tetrahydrofuran or dichloromethane.
  • a coupling agent such as N
  • compounds of formula (XVI) can be used as their analogous lithium or sodium salts. This transformation is depicted in Scheme 11.
  • Compounds of formula (XVI) can be prepared by the saponification of compounds of formula (XVII), wherein R 9 is a C1-C6 alkyl, using a base, such as NaOH or LiOH, in a suitable solvent such as methanol, ethanol or water at temperature between room temperature and reflux.
  • a suitable solvent such as methanol, ethanol or water at temperature between room temperature and reflux.
  • compounds of formula (XVII) can be isolated as their sodium or lithium salt. This transformation is depicted in Scheme 12.
  • compounds of formula (Ia), wherein Z is O can be prepared, can be obtained from compounds of formula (Ia) can be obtained by reaction of a compound of formula (XVIII), wherein X is Cl, Br or I, with an amine of formula (VI) in the presence of carbon monoxide and in the presence of a catalyst such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) or bis(benzonitrile)palladium chloride, optionally in the presence of a ligand such as 4,5- bis(diphenylphosphino)-9,9-dimethylxanthene and, optionally, a base such as triethylamine.
  • a catalyst such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) or bis(benzonitrile)palladium chloride, optionally in the presence of a ligand such as 4,5- bis(dipheny
  • the outcome of the reaction can be improved by adding boric acid or molecular sieves to the reaction mixture. It is understood that these transformations are done under air as oxygen is needed as a terminal oxidant. In some cases, the copper species might be used in stochiometric amount. This transformation is depicted in Scheme 15.
  • compounds of formula (XVII), wherein R 9 is a C1-C6 alkyl can be prepared by reductive cyclization of a compound of formula (XXIII), wherein R 9 is a C1-C6 alkyl, with a reagent such as formic acid or methanol in the presence of a reducing agent such as Fe(0) or sodium dithionite, in a protic solvent such as methanol or propan-2-ol, eventually in the presence of an additive such as ammonium chloride.
  • a reagent such as formic acid or methanol
  • a reducing agent such as Fe(0) or sodium dithionite
  • a protic solvent such as methanol or propan-2-ol
  • compounds of formula (I) can be prepared by acylation of compounds of formula (XXV) with an acylation agent of formula (XXVI), wherein X is Cl or Br in the presence of a base such as triethylamine or potassium carbonate.
  • Compounds of formula (XXV) can be obtained by the reaction of a compound of formula (II) with a compound of formula (XXVII), wherein either R 8 is independently from each other hydrogen, C1-C6 alkyl or wherein two R 8 together can form a C3-C8 cycloalkyl, in the presence of a base, such as triethylamine, diisopropylethylamine, pyridine, Cs2CO3, K2CO3, K2HPO4 or NaOtBu, and a suitable catalyst, such as copper(II) acetate, copper(II) carbonate, copper(II) hydroxide, copper oxide, copper(I) iodide or copper(I) bromide, in a suitable solvent, such as dimethylformamide, dimethylacetamide, dioxane, acetonitrile, tetrahydrofuran or toluene.
  • a base such as triethylamine, diisopropy
  • the outcome of the reaction can be improved by adding boric acid or molecular sieves to the reaction mixture. It is understood that these transformations are done under air as oxygen is needed as a terminal oxidant. In some cases, the copper species might be used in stochiometric amount.
  • This transformation is depicted in Scheme 20.
  • Scheme 20 Compounds of formula (Ib), wherein Z is S, can be prepared by the reaction of a compound of formula (Ia), wherein Z is O, with phosphorus pentasulfide or Lawesson’s reagent (CAS: 19172-47-5) in a suitable solvent such as toluene, xylene or dichloromethane. This transformation is depicted in Scheme 21.
  • a compound according to the present invention can be converted in a manner known per se into another compound according to the present invention by replacing one or more substituents of the starting compound according to the present invention in the customary manner by (an)other substituent(s) according to the invention.
  • substituents of the starting compound according to the present invention in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of the compounds according to the present invention can be prepared in a manner known per se.
  • acid addition salts of the compounds according to the present invention are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds the compounds according to the present invention can be converted in the customary manner into the free compounds, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of the compounds according to the present invention can be converted in a manner known per se into other salts of the compounds according to the present invention, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • an acid for example with silver acetate
  • a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • the compounds according to the present invention, which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds according to the present invention and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the stereoisomers which are possible or as a mixture of these, for example in the form of pure stereoisomers, such as antipodes and/or diastereomers, or as stereoisomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure stereoisomers and also to all stereoisomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of the compounds according to the present invention in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the
  • N-oxides can be prepared by reacting a compound according to the present invention with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • stereoisomer for example enantiomer or diastereomer, or stereoisomer mixture, for example enantiomer mixture or diastereomer mixture
  • the individual components have a different biological activity.
  • the compounds according to the present invention and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the following Examples illustrate, but do not limit, the invention.
  • the present invention also provides intermediates useful for the preparation of compounds according to the present invention. The below intermediates form a further aspect of the invention.
  • the compounds of formula (I) as defined in the present invention can be used in the agricultural sector and related fields of use e.g. as active ingredients for controlling plant pathogens or on non-living materials for control of spoilage microorganisms or organisms potentially harmful to man.
  • the novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and may be used for protecting numerous cultivated plants.
  • the compounds of formula (I) as defined in the present invention can be used to inhibit or destroy the pathogens that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
  • compounds of formula (I) as defined in the present invention as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • plant propagation material e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example rice)
  • the propagation material can be treated with a composition comprising a compound of formula (I) as defined in the present invention before planting: seed, for example, can be dressed before being sown.
  • the compounds of formula (I) as defined in the present invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • the compounds of formula (I) as defined in the present invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
  • the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
  • Compounds of formula (I) as defined in the present invention and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens.
  • fungi and fungal vectors of disease are for example: Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A.
  • Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. contributing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C.
  • capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P.
  • leucotricha Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P.
  • compounds of formula (I) as defined in the present invention and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes. More particularly, the compounds of formula (I) as defined in the present invention may be used to conrol oomycetes.
  • pathogens may include: Oomycetes, including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare, Pythium sylvaticum and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubens
  • Ascomycetes including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bi
  • Gerlachia nivale Gibberella fujikuroi
  • Gibberella zeae Gibberella zeae
  • Gliocladium spp. Myrothecium verrucaria
  • Nectria ramulariae Trichoderma viride
  • Trichothecium roseum Trichothecium roseum
  • Verticillium theobromae Myrothecium verrucaria
  • Basidiomycetes including smuts for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp.
  • Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae
  • rusts for example those caused by Pucciniales such as Cerotelium fici, Chr
  • Puccinia striiformis f.sp. Secalis Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Tha
  • Blastocladiomycetes such as Physoderma maydis. Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus. As well as diseases caused by other species and genera closely related to those listed above.
  • the compounds and compositions comprising compounds of formula (I) as defined in the present invention may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
  • target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
  • perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
  • cereals for example barley, maize (corn), millet, oats
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
  • legumes for example beans, lentils, peas and soya beans
  • the useful plants and / or target crops in accordance with the invention include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. and VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties.
  • suitable genetically enhanced or engineered crop varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.
  • useful plants and/or “target crops” is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5- enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • EPSPS 5- enol-pyrovyl-shikimate-3-phosphate-synthase
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxidase
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.
  • the term "useful plants" and/or “target crops” is to be understood as including those which naturally are or have been rendered resistant to harmful insects.
  • toxins which can be expressed include ⁇ -endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.
  • An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut ⁇ (Syngenta Seeds).
  • VipCot ⁇ Surgera Seeds
  • Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification).
  • a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I ⁇ (Dow AgroSciences, Pioneer Hi-Bred International).
  • useful plants and/or “target crops” is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0392225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0392225, WO 95/33818, and EP-A-0353191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ - endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae such as ⁇ - endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome- inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • ⁇ -endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated Cry1Ab, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO03/018810).
  • More examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0374753, WO93/07278, WO95/34656, EP-A-0427529, EP-A-451878 and WO03/052073.
  • transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0367 474, EP-A-0401979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard ⁇ (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm ⁇ (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus ⁇ (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink ⁇ (maize variety that expresses a Cry9C toxin); Herculex I ⁇ (maize variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B ⁇ (cotton variety that expresses a Cry1Ac toxin); Bollgard I
  • transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St.
  • This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence.
  • the preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.
  • MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5.
  • NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • locus as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes.
  • seeds in the strict sense
  • Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion.
  • plant propagation material is understood to denote seeds.
  • Pesticidal agents referred to herein using their common name are known, for example, from "The Pesticide Manual", 19th Ed., British Crop Protection Council 2021.
  • the compounds of formula (I) as defined in the present invention may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
  • compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and/or adjuvants e.g. for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
  • Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended.
  • Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor.
  • these concentrates are diluted in water and normally applied as a spray to the area to be treated.
  • the amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix.
  • Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids.
  • Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated.
  • the amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
  • Typical carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter.
  • Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide,
  • Water is generally the carrier of choice for the dilution of concentrates.
  • suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation.
  • Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub.
  • soaps such as sodium stearate
  • alkylnaphthalenesulfonate salts such as sodium dibutylnaphthalenesulfonate
  • dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl) sulfosuccinate
  • sorbitol esters such as sorbitol oleate
  • quaternary amines such as lauryl trimethylammonium chloride
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
  • block copolymers of ethylene oxide and propylene oxide and salts of mono and dialkyl phosphate esters.
  • compositions of the invention include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti- foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention.
  • these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank.
  • These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, plant growth regulators, and/or biologicals.
  • TX means “one compound selected from the compounds defined in the Tables 1.1 to 1.132 and Table A): an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX; abamectin + TX, acequinocyl + TX, acetamiprid + TX, acetoprole + TX, acrinathrin + TX, acynonapyr + TX, afidopyropen + TX, afoxolaner + TX, alanycarb + TX, allethrin + TX, alpha-cypermethrin + TX, alphamethrin + TX, amidoflumet + TX, aminocarb + TX, azocyclotin + TX, bensultap + TX, benzoximate + TX, benzpyrimo
  • TX Neem tree based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococc
  • TX Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp.
  • the compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3- pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1- yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO 2016/156
  • TX Aureobasidium pullulans + TX, Azospirillum (MicroAZ®, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (e.g, BiostartTM, formerly Rhizoboost®) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®, VOTiVO®) + TX,
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain QST 713 (CEASE®, Serenade®, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var.
  • amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX,
  • TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.
  • TX Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reuêtii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
  • Pasteuria spp. Econem® + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.
  • TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Ps
  • Rhodosporidium diobovatum + TX Rhodosporidium toruloides + TX, Rhodotorula spp.
  • Trichoderma asperellum T34 Biocontrol®
  • Trichoderma gamsii TX
  • Trichoderma atroviride Plantmate®
  • Trichoderma harzianum rifai Mycostar®
  • Trichoderma harzianum T-22 Trianum-P®, PlantShield HC®, RootShield®, Trianum-G®) + TX
  • Trichoderma harzianum T-39 Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp.
  • LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL- 21) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp.
  • TX Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal®, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv.
  • Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X®) + TX, Botanical IGR (Neemazad®, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®
  • TX Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX
  • TX Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; other biologicals including: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeospor
  • NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX
  • Bacillus pumilus in particular strain BU F-33, having NRRL Accession No.50185 (CARTISSA® from BASF, EPA Reg. No.71840-19) + TX
  • Bacillus subtilis in particular strain QST713/AQ713 (SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661, U.S.
  • Patent No.6,060,051 + TX
  • Bacillus subtilis strain BU1814 (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX
  • Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX
  • Bacillus subtilis CX-9060 from Certis USA LLC + TX
  • Bacillus sp. in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No.
  • Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX; Paenibacillus polymyxa, in particular strain AC- 1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX; Pantoea agglomerans, in particular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICALTM FD BIOPESTICIDE from Northwest Agri Products) + TX; Pseudomonas proradix (e.g.
  • PRORADIX® from Sourcon Padena) + TX; and (1.2) fungi, examples of which are Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX; Pseudozyma aphidis (as disclosed in WO2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX; Saccharomyces cerevisiae, in particular strains CNCM No.
  • CNCM No.1-3937, CNCM No.1-3938 or CNCM No.1-3939 (as disclosed in WO 2010/086790 from Lesaffre et Compagnie, FR) + TX;
  • biological fungicides selected from the group of: (2.1) bacteria, examples of which are Agrobacterium radiobacter strain K84 (e.g. GALLTROL-A® from AgBioChem, CA) + TX; Agrobacterium radiobacter strain K1026 (e.g. NOGALLTM from BASF SE) + TX; Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No.
  • DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5)) + TX; 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.7,094,592) + TX; Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No. B-50768, WO 2014/028521) (STARGUS® from Marrone Bio Innovations) + TX; Bacillus amyloliquefaciens strain FZB42, Accession No.
  • DSM 23117 available as RHIZOVITAL® from ABiTEP, DE
  • TX Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREENTM from University of Pretoria) + TX
  • Bacillus licheniformis in particular strain SB3086, having Accession No.
  • ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAFTM from Novozymes) + TX; Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX; Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology) + TX; Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX; Bacillus mycoides, isolate, having Accession No.
  • 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) + TX
  • Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) + TX
  • Bacillus pumilus, in particular strain BU F-33 having NRRL Accession No. 50185 (available as part of the CARTISSA product from BASF, EPA Reg.
  • 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) + TX; 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) + TX; Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF SE), having Accession Number NRRL B-50595, U.S.
  • Patent No.5,061,495 + TX Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE) + TX; Bacillus subtilis strain BU1814, (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX; Bacillus subtilis CX-9060 from Certis USA LLC + TX; Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) + TX; Bacillus subtilis IAB/BS03 (AVIVTM from STK Bio-Ag Technologies, PORTENTO® from Idai Nature) + TX; 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) + TX; Paenibacillus epiphyticus (WO 2016/020371) from BASF SE + TX; Paen
  • CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert TX
  • Pseudomonas fluorescens strain A506 e.g. BLIGHTBAN® A506 by NuFarm
  • Pseudomonas proradix e.g. PRORADIX® from Sourcon Padena
  • Streptomyces griseoviridis strain K61 also known as Streptomyces galbus strain K61
  • DSM 7206 Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession No. DSM 7206) (MYCOSTOP® from Verdera, PREFENCE® from BioWorks, cf.
  • Streptomyces lydicus strain WYEC108 also known as Streptomyces lydicus strain WYCD108US
  • ACTINO-IRON® and ACTINOVATE® from Novozymes + TX
  • fungi examples of which are Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia) + TX
  • Ampelomyces quisqualis strain AQ10 having Accession No.
  • CNCM 1-807 e.g., AQ 10® by IntrachemBio Italia
  • TX Aspergillus flavus strain NRRL 21882 (products known as AFLA-GUARD® from Syngenta/ChemChina) + TX
  • Aureobasidium pullulans in particular blastospores of strain DSM14940 + TX
  • Aureobasidium pullulans in particular blastospores of strain DSM 14941 + TX
  • Aureobasidium pullulans in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. Botector® by bio-ferm, CH) + TX
  • Chaetomium cupreum accesion No.
  • CABI 353812 e.g. BIOKUPRUMTM by AgriLife
  • TX Chaetomium globosum (available as RIVADIOM® by Rivale) + TX
  • Coniothyrium minitans, in particular strain CON/M/91-8 accesion No. DSM9660, e.g.
  • Prestop ® by Lallemand + TX; Gliocladium roseum (also known as Clonostachys rosea f rosea), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue A.G (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can. J. Plant Sci.2003, 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 fungal antagonist Clonostachys rosea strain ’IK726’, Australasian Plant Pathol.
  • Trichoderma asperellum in particular, strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX; 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 + TX; Trichoderma atroviride, in particular strain SC1 (Accession No. CBS 122089, WO 2009/116106 and U.S.
  • Patent No.8,431,120 from Bi-PA
  • strain 77B T77 from Andermatt Biocontrol
  • strain LU132 e.g. Sentinel from Agrimm Technologies Limited
  • Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX
  • Trichoderma atroviride strain no. V08/002387 + TX
  • Trichoderma atroviride strain NMI no. V08/002388 + TX
  • Trichoderma atroviride strain NMI no. V08/002389 + TX
  • Trichoderma atroviride strain NMI no.
  • Trichoderma atroviride Trichoderma atroviride, strain LC52 (e.g. Tenet by Agrimm Technologies Limited) + TX; Trichoderma atroviride, strain ATCC 20476 (IMI 206040) + TX; Trichoderma atroviride, strain T11 (IMI352941/ CECT20498) + TX; Trichoderma atroviride, strain SKT-1 (FERM P-16510), JP Patent Publication (Kokai) 11-253151 A + TX; Trichoderma atroviride, strain SKT-2 (FERM P-16511), JP Patent Publication (Kokai) 11-253151 A + TX; Trichoderma atroviride, strain SKT-3 (FERM P-17021), JP Patent Publication (Kokai) 11-253151 A + TX; Trichoderma fertile (e.g.
  • TrichoPlus from BASF + TX
  • Trichoderma gamsii (formerly T. viride), strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.) + TX
  • Trichoderma gamsii (formerly T. viride), strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S.A. DE C.V.) + TX
  • Trichoderma harmatum having Accession No. ATCC 28012 + TX
  • Trichoderma harzianum strain T-22 e.g.
  • Trianum-P from Andermatt Biocontrol or Koppert or strain Cepa SimbT5 (from Simbiose Agro) + TX; Trichoderma harzianum + TX; Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US) + TX; Trichoderma harzianum, strain ITEM 908 (e.g. Trianum-P from Koppert) + TX; Trichoderma harzianum, strain TH35 (e.g.
  • Trichoderma harzianum strain DB 103 (available as T-GRO® 7456 by Dagutat Biolab) + TX
  • Trichoderma polysporum strain IMI 206039 (e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden) + TX
  • Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX
  • Trichoderma virens also known as Gliocladium virens
  • strain GL-21 e.g.
  • 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) + TX; Trichoderma viride, strain TV1(e.g. Trianum-P by Koppert) + TX; Trichoderma viride, in particular strain B35 (Pietr et al., 1993, Zesz. Nauk.
  • NM 99/06216 e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.
  • Verticillium albo-atrum previously V. dahliae
  • strain WCS850 having Accession No.
  • WCS850 deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations) + TX; Verticillium chlamydosporium + TX; (3) biological control agents having an effect for improving plant growth and/or plant health selected from the group of: (3.1) bacteria, examples of which are Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX; Azospirillum lipoferum (e.g., VERTEX-IFTM from TerraMax, Inc.) + TX; Azorhizobium caulinodans, in particular strain ZB-SK-5 + TX; Azotobacter chroococcum, in particular strain H23 + TX; Azotobacter vinelandii, in particular strain ATCC 12837 + TX; a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos)
  • Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX; Bacillus pumilus, in particular strain GB34 (e.g.
  • Bacillus subtilis strain BU1814 (available as TEQUALIS® from BASF SE), Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX; Bacillus thuringiensis BT013A (NRRL No. B-50924) also known as Bacillus thuringiensis 4Q7 + TX; a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation) + TX; Bacillus subtilis, in particular strain MBI 600 (e.g.
  • SUBTILEX® from BASF SE + TX
  • Bacillus tequilensis in particular strain NII-0943 + TX
  • Bradyrhizobium japonicum e.g. OPTIMIZE® from Novozymes
  • Delftia acidovorans in particular strain RAY209 (e.g. BIOBOOST® from Brett Young Seeds) + TX
  • Mesorhizobium cicer e.g., NODULATOR from BASF SE
  • Lactobacillus sp. e.g.
  • Trichoderma atroviride strain CNCM 1-1237 e.g. Esquive® WP from Agrauxine, FR
  • Trichoderma viride e.g. strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX; Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g.
  • Bacillus sphaericus in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. VECTOLEX® from Valent BioSciences, US) + TX; Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX; Bacillus thuringiensis subsp. aizawai, in particular serotype H-7 (e.g.
  • israeltaki strain EG 7841 (CRYMAX® from Certis, US) + TX; Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g. NOVODOR® FC from BioFa DE) + TX; Brevibacillus laterosporus (LATERAL® from Ecolibrium Biologicals) + TX; 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.
  • MBI206 TGAI and ZELTO® from Marrone Bio Innovations + TX
  • Chromobacterium subtsugae in particular strain PRAA4-1T (e.g. MBI-203; e.g. GRANDEVO® from Marrone Bio Innovations) + TX
  • Lecanicillium muscarium Ve6 MYCOTAL from Koppert
  • Paenibacillus popilliae (formerly Bacillus popilliae + TX; e.g. MILKY SPORE POWDERTM or MILKY SPORE GRANULARTM from St.
  • compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer).
  • SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
  • the compounds of formula (I) as defined in the present invention are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants.
  • They can also be selective herbicides or non- selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • the compounds of formula (I) as defined in the present invention may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) as defined in any one of embodiments 1 to 43 or of at least one preferred individual compound as above-defined, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
  • the invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) as defined in the present invention, an agriculturally acceptable carrier and optionally an adjuvant.
  • An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art.
  • composition may comprise at least one or more pesticidally active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I) as defined in the present invention.
  • a further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g.
  • Controlling or preventing means reducing infestation by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
  • a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, which comprises the application of a compound of formula (I) as defined in the present invention, or an agrochemical composition which contains at least one of said compounds, is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect.
  • the compounds of formula (I) as defined in the present invention can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula (I) as defined in any the present invention may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation e.g. a composition containing the compound of formula (I) as defined in the present invention, and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I) as defined in the present invention, may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • compositions that is the methods of controlling pathogens of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pathogens of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is preferably 1g to 2000 g of active ingredient per hectare, more preferably 10 to 1000 g/ha, most preferably 10 to 600 g/ha.
  • a composition comprising a compound of formula (I) as defined in the present invention according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
  • compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK
  • compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
  • appropriate formulation inerts diiluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
  • conventional slow release formulations may be employed where long lasting efficacy is intended.
  • Particularly formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
  • a seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • suitable seed dressing formulation form e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • seed dressing formulations are known in the art.
  • Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g.
  • the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula (I) as defined in the present invention together with component (B) and (C), and optionally other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent.
  • Compounds of Formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
  • advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
  • temperatures are given in degrees Celsius (°C) and “MP” means melting point.
  • LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the methods are described below.
  • Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether - 2 % - (7-8 mol of ethylene oxide) highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % -
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for dry seed treatment a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - Kaolin 65 % 40 % - Talcum - 20%
  • active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsifiable concentrate active ingredient [compound of formula (I)] 10 % octylphenol polyethylene glycol ether 3 % (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Coated granules Active ingredient [compound of formula (I)] 8 % polyethylene glycol (mol. wt.200) 3 % Kaolin 89 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • Suspension concentrate active ingredient [compound of formula (I)] 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % tristyrenephenole with 10-20 moles EO 2 % 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Method B Spectra were recorded on a Mass Spectrometer from Waters (Acquity QDa Mass Spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8 kV, Cone range: 25 V, Extractor: V (No extractor voltage for QDa detector) Source Temperature: 120°C, Desolvation Temperature: 600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment , diode-array detector.
  • Method C Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 110 to 950 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment, diode- array detector and ELSD.
  • Step 2 Preparation of N-(4-chlorophenyl)-N-methyl-4-(methylamino)benzamide
  • dichloromethane 21.0 mL
  • trifluoroacetic acid 1.44 mL, 18.5 mmol, 15.0 eq.
  • Step 3 Preparation of tert-butyl N-[3-bromo-4-[(E)-[4-[(4-chlorophenyl)-methyl-carbamoyl]-N-methyl- anilino]azo]phenyl]carbamate
  • a solution of tert-butyl N-(4-amino-3-bromo-phenyl)carbamate (CAS 1554844-65-3, prepared as described in WO2014140075A1) (260 mg, 0.860 mmol) in acetonitrile (2.60 mL) at 0 °C was added aqueous HCl 32% (0.422 mL, 4.30 mmol, 5.00 eq.).
  • reaction mixture was stirred at -10 °C for an additional 2 hours and then slowly warmed to room temperature, then it was diluted with ethyl acetate and quenched with water. The aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • Step 4 Preparation of tert-butyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl]benzotriazol-1- yl]phenyl]carbamate
  • tert-butyl N-[3-bromo-4-[(E)-[4-[(4-chlorophenyl)-methyl-carbamoyl]-N-methyl- anilino]azo]phenyl]carbamate 150 mg, 0.249 mmol
  • diemthylformamide 3.00 mL
  • potassium acetate 29.6 mg, 0.298 mmol, 1.20 eq.
  • Step 5 Preparation of 3-(4-aminophenyl)-N-(4-chlorophenyl)-N-methyl-benzotriazole-5-carboxamide
  • tert-butyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl]benzotriazol-1- yl]phenyl]carbamate 84.0 mg, 0.162 mmol
  • dichloromethane (4.00 mL) at 0 °C under argon
  • trifluoroacetic acid (0.189 mL, 2.43 mmol, 15.0 eq.
  • Step 6 Preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl]benzotriazol-1- yl]phenyl]carbamate (Compound 69)
  • 3-(4-aminophenyl)-N-(4-chlorophenyl)-N-methyl-benzotriazole-5-carboxamide 30.0 mg, 0.0731 mmol
  • pyridine 0.018 mL, 0.22 mmol, 3.00 eq.
  • dichloromethane (1.00 mL
  • methyl chloroformate 0.014 mL, 0.18 mmol, 2.5 eq.
  • Example 2 Preparation of methyl N-[4-[2-[(4-chlorophenyl)-methyl-carbamoyl]purin-9- yl]phenyl]carbamate (compound 66) (Compound 66) Step 1: Preparation of tert-butyl N-[4-[(5-amino-2-chloro-pyrimidin-4-yl)amino]phenyl]carbamate To a solution of 5-amino-2,4-dichloropyrimidine (2.00 g, 11.8 mmol) in toluene (80.0 mL) were added t- butyl (4-aminophenyl)carbamate (5.03 g, 23.7 mmol, 2.00 eq.) and triethylamine (5.00 mL, 35.5 mmol, 3.00 eq.).
  • Step 2 Preparation of tert-butyl N-[4-(2-chloropurin-9-yl)phenyl]carbamate
  • acetic acid 15.6 mL
  • triethyl orthoformate 17.6 mL, 105 mmol, 15.0 eq.
  • Step 3 Preparation of methyl 9-[4-(tert-butoxycarbonylamino)phenyl]purine-2-carboxylate
  • 1,1'-bis(diphenylphosphino)ferrocene 35 mg, 0.061 mmol, 0.04 eq.
  • bis(benzonitrile) palladium(II) chloride (12 mg, 0.031 mmol, 0.02 eq.)
  • methanol 22.0 mL
  • tert-butyl N-[4-(2-chloropurin-9-yl)phenyl]carbamate 567 mg, 1.52 mmol
  • triethylamine 0.279 mL, 1.98 mmol, 1.30 eq.
  • reaction mixture was purged with argon for 5 minutes, then it was stirred overnight at 80 °C under 10 bar of CO. After cooling and purging the CO, the mixture was directly taken up on isolute and purified by flash chromatography over silica gel (ethyl acetate/methanol) to afford methyl 9-[4-(tert-butoxycarbonylamino)phenyl]purine-2-carboxylate as a light red solid.
  • Step 4 Preparation of 9-[4-(tert-butoxycarbonylamino)phenyl]purine-2-carboxylic acid
  • tetrahydrofuran/water 3:1, 14.0 mL
  • lithium hydroxide 89.6 mg, 2.09 mmol, 1.50 eq.
  • the resulting aqueous mixture was extracted with tert-butyl methyl ether, the aqueous layer was then acidified with 1N HCl to pH 3 and extracted with ethyl acetate. The combined ethyl acetate layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford the crude 9-[4-(tert-butoxycarbonylamino)phenyl]purine-2-carboxylic acid as beige crystals. The product was used in the next step without further purification.
  • Step 5 Preparation of tert-butyl N-[4-[2-[(4-chlorophenyl)-methyl-carbamoyl]purin-9- yl]phenyl]carbamate
  • reaction mixture was diluted with additional dichloromethane, quenched with water.
  • organic layer was separated and washed successively with water and brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure.
  • the crude residue was purified by flash chromatography over silica gel (ethyl acetate/methanol) to afford tert-butyl N-[4-[2-[(4-chlorophenyl)-methyl-carbamoyl]purin-9- yl]phenyl]carbamate as colorless gum.
  • Step 6 Preparation of 9-(4-aminophenyl)-N-(4-chlorophenyl)-N-methyl-purine-2-carboxamide
  • a solution of tert-butyl N-[4-[2-[(4-chlorophenyl)-methyl-carbamoyl]purin-9-yl]phenyl]carbamate (410 mg, 0.788 mmol) in methanol (10.0 mL) at 0 °C was added HCl (4 M in dioxane, 2.00 mL, 7.88 mmol, 10.0 eq.) dropwise.
  • the reaction mixture was stirred at room temperature for 72 hours, then it was concentrated under reduced pressure, the residue was stirred in a mixture of water and ethyl acetate and basic layer was basified with NaOH to pH 9-10.
  • the mixture was extracted with ethyl acetate and the combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • the crude residue was purified by flash chromatography over silica gel (ethyl acetate/methanol) to afford 9-(4-aminophenyl)-N-(4-chlorophenyl)-N-methyl-purine-2- carboxamide as a beige solid.
  • Step 7 Preparation of methyl N-[4-[2-[(4-chlorophenyl)-methyl-carbamoyl]purin-9-yl]phenyl]carbamate (Compound 66) To a solution of 9-(4-aminophenyl)-N-(4-chlorophenyl)-N-methyl-purine-2-carboxamide (66.0 mg, 0.166 mmol) and pyridine (0.041 mL, 0.50 mmol, 3.0 eq.) in dichloromethane (3.00 mL) at 10 °C was added methyl chloroformate (0. mL, 0.41 mmol, 2.5 eq.) dropwise.
  • reaction mixture was then allowed to warm to room temperature and stirred for an additional 2 hours.
  • the reaction mixture was then diluted with dichloromethane, quenched with aqueous NaHCO3, and extracted with dichloromethane.
  • the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • the crude residue was purified by flash chromatography over silica gel (cyclohexane/ethyl acetate) to afford methyl N-[4-[2-[(4-chlorophenyl)-methyl-carbamoyl]purin-9- yl]phenyl]carbamate as a white solid.
  • Example 3 Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-4- methyl-benzimidazol-1-yl]-2-pyridyl]carbamate (compound 26) (Compound 26) Step 1: Preparation of 3-tert-butoxycarbonyl-7-methyl-benzimidazole-5-carboxylic acid To a yellow suspension of 7-methyl-3H-benzimidazole-5-carboxylic acid (CAS: 398452-96-5; 7.0 g, 40 mmol) in acetonitrile (160 mL) and water (1.50 mL) was added triethylamine (11.0 mL, 79.0 mmol, 2.00 eq.) followed by 4-dimethylaminopyridine (490 mg, 4.00 mmol, 0.10 eq.) and a portion wise addition of di-tert-butyl dicarbonate (11.0
  • reaction mixture was stirred at room temperature for 2 hours, then it was diluted with ethyl acetate and water.
  • the aqueous layer was acidified with HCl 2M to pH 1 and the mixture was extracted with ethyl acetate.
  • the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford 3-tert-butoxycarbonyl-7-methyl-benzimidazole-5-carboxylic acid as a pale yellow solid.
  • Step 2 Preparation of tert-butyl 6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-4-methyl- benzimidazole-1-carboxylate
  • 4-fluoro-3-methoxy-N-methylaniline 320 mg, 1.96 mmol, 1.05 eq.
  • N,N- diisopropylethylamine (0.96 mL, 5.60 mmol, 3.0 eq.)
  • 3-tert-butoxycarbonyl-7-methyl-benzimidazole- 5-carboxylic acid 516 mg, 1.87 mmol) in ethyl acetate (7.5 mL) was added propylphosphonic anhydride solution (50 wt% in ethyl acetate, 2.0 mL, 3.36 mmol, 1.8 eq.), portionwise.
  • reaction mixture was allowed to stir at room temperature for 4 hours, then it was poured into water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography (cyclohexane/ethyl acetate) to afford tert-butyl 6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-4- methyl-benzimidazole-1-carboxylate as a brown gum.
  • Step 3 Preparation of N-(4-fluoro-3-methoxy-phenyl)-N,7-dimethyl-3H-benzimidazole-5-carboxamide
  • a mixture of tert-butyl 6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-4-methyl-benzimidazole-1- carboxylate (795 mg g, 1.92 mmol), toluene (5.8 mL) and trifluoroacetic acid (1.03 mL, 13.5 mmol, 7.00 eq.) was stirred overnight at room temperature, after which it was concentrated under reduced pressure and taken up in water.
  • Step 4 Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-4-methyl- benzimidazol-1-yl]-2-pyridyl]carbamate (Compound 26)
  • N-(4-fluoro-3-methoxy-phenyl)-N,7-dimethyl-3H-benzimidazole-5-carboxamide 100 mg, 0.319 mmol
  • boric acid 60 mg, 0.958 mmol, 3.0 eq.
  • copper (II) acetate 174 mg, 0.958 mmol, 3.0 eq.
  • N,N-diisopropylethylamine 0.170 mL, 0.958 mmol, 3.0 eq.
  • Step 2 Preparation of methyl N-[5-[(5-amino-2-chloro-4-pyridyl)amino]-2-pyridyl]carbamate
  • a solution of methyl N-[5-[(2-chloro-5-nitro-4-pyridyl)amino]-2-pyridyl]carbamate 250 mg, 0.734 mmol
  • iron 81.9 mg, 1.47 mmol, 2.00 eq.
  • ammonia hydrochloride 392 mg, 7.34 mmol, 10.0 eq.
  • the reaction mixture was stirred at 100 °C for 2 hours, then it was filtered through a pad of celite and washed with an excess of ethyl acetate.
  • the filtrate was concentrated under reduced pressure, diluted with water, and extracted with ethyl acetate.
  • the combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to afford methyl N-[5-[(5-amino-2-chloro-4-pyridyl)amino]-2-pyridyl]carbamate as a solid.
  • the product was used in the next step without further purification.
  • Step 3 Preparation of methyl N-[5-(6-chloroimidazo[4,5-c]pyridin-1-yl)-2-pyridyl]carbamate
  • methyl N-[5-[(5-amino-2-chloro-4-pyridyl)amino]-2-pyridyl]carbamate 5.00 g, 16.2 mmol
  • diethoxymethoxyethane 25.0 mL
  • hydrogen chloride 36 mass %, 1.64 g, 16.2 mmol, 1.00 eq.
  • Step 4 Preparation of methyl 1-[6-(methoxycarbonylamino)-3-pyridyl]imidazo[4,5-c]pyridine-6- carboxylate
  • methyl N-[5-(6-chloroimidazo[4,5-c]pyridin-1-yl)-2-pyridyl]carbamate (3.00 g, 9.38 mmol) and sodium acetate (2.31 g, 28.2 mmol, 3.00 eq.) were dissolved in methanol (100 mL), and the mixture was degassed with argon for 10 minutes.
  • Step 5 Preparation of lithium 1-[6-(methoxycarbonylamino)-3-pyridyl]imidazo[4,5-c]pyridine-6- carboxylate
  • methyl 1-[6-(methoxycarbonylamino)-3-pyridyl]imidazo[4,5-c]pyridine-6-carboxylate 800 mg, 2.20 mmol
  • methanol 10.0 mL
  • water 10.0 mL
  • lithium hydroxide hydride 369 mg, 8.80 mmol, 4.00 eq.
  • Step 6 Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]imidazo[4,5- c]pyridin-1-yl]-2-pyridyl]carbamate (Compound 24) To a solution of lithium 1-[6-(methoxycarbonylamino)-3-pyridyl]imidazo[4,5-c]pyridine-6-carboxylate (250 mg, 0.744 mmol) and 4-fluoro-3-methoxy-N-methyl-aniline (173 mg, 1.12 mmol, 1.50 eq.) in N,N- dimethylformamide (10.0 mL) was added diisopropylethylamine (0.401 mL, 2.23 mmol, 3.00 eq.) and 1- [bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hex
  • Example 5 Preparation of methyl N-[5-[6-[(4-fluorophenyl)-methyl-carbamoyl]benzimidazol-1- yl]-2-pyridyl]carbamate (compound 22) butoxycarbonylbenzimidazole-5-carboxylic acid
  • 3H-benzimidazole-5-carboxylic acid (1.00 g, 6.04 mmol) and sodium carbonate (1.54 g, 14.5 mmol) in water (15.1 mL) at room temperature was added dropwise a solution of di-tert-butyl pyrocarbonate (2.66 g, 12.1 mmol) in dioxane (9.0 mL).
  • reaction mixture was stirred at room temperature overnight and then poured in water.
  • the mixture was extracted with diethylether, the aqueous layer was acidified with HCl 2M until pH 1, and the aqueous layer extracted again with ethyl acetate.
  • the combined organic layers were washed with brine, dried over sodium sulfate and concentrated under reduced pressure to yield a mixture of 1-tert-butoxycarbonylbenzimidazole-5- carboxylic acid and 3-tert-butoxycarbonylbenzimidazole-5-carboxylic acid isomers which were used in the next step without further purification.
  • Step 4 Preparation of methyl N-[5-[6-[(4-fluorophenyl)-methyl-carbamoyl]benzimidazol-1-yl]-2- pyridyl]carbamate (Compound 22)
  • N-(4-fluorophenyl)-N-methyl-3H-benzimidazole-5-carboxamide 210 mg, 0.780 mmol
  • boric acid 97.4 mg, 1.56 mmol, 2.00 eq.
  • copper(II) acetate 212.5 mg, 1.17 mmol, 1.50 eq.
  • N,N-diisopropylethylamine 0.277 mL, 1.56 mmol, 2.00 eq.
  • the reaction mixture was stirred at 60 °C under an atmosphere of air for 2.5 hours.
  • the reaction mixture was cooled to room temperature and poured into water.
  • the aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure.
  • the crude residue was purified over a preparative HPLC column (CO2/methanol) to afford methyl N-[5-[6-[(4-fluorophenyl)-methyl- carbamoyl]benzimidazol-1-yl]-2-pyridyl]carbamate as a pale pink solid.
  • Example 6 Preparation of methyl N-[5-[6-(7-fluoro-2,3-dihydro-1,4-benzoxazine-4-carbonyl)-4- methyl-benzimidazol-1-yl]-2-pyridyl]carbamate (compound 64) (Compound 64) Step 1: Preparation of (7-fluoro-2,3-dihydro-1,4-benzoxazin-4-yl)-(7-methyl-3H-benzimidazol-5- yl)methanone To a solution of 7-methyl-3H-benzimidazole-5-carboxylic acid (CAS 398452-96-5, commercially available and can be prepared according to WO2009144554A1) (500 mg, 2.84 mmol) in N,N- dimethylformamide (7.00 mL) was added 1-methylimidazole (699 mg, 8.51 mmol, 3.00 eq.), N,N,N',N'- tetramethylchlor
  • reaction mixture was stirred at room temperature for 4 hours, then it was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel (ethyl acetate/petroleum ether) to afford (7-fluoro-2,3-dihydro-1,4-benzoxazin-4-yl)-(7-methyl- 3H-benzimidazol-5-yl)methanone as a yellow solid.
  • Example 7 This example illustrates the preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy- phenyl)-methyl-carbamoyl]-4-(methoxymethyl)benzimidazol-1-yl]-2-pyridyl]carbamate (Compound 1) (Compound 1) Step 1: Preparation of methyl 6-bromo-1-(2-trimethylsilylethoxymethyl)benzimidazole-4-carboxylate At 0 °C under nitrogen atmosphere added sodium hydride 60% (2.82 g, 70.6 mmol, 1.20 eq.) was added to a solution of methyl 6-bromo-1H-benzimidazole-4-carboxylate [CAS 1806519-50-9] (15.0 g, 58.8 mmol) in dry DMF (400 mL).
  • the bomb was then flushed with carbon monoxide, sealed, and pressurized to 2.5 MPa with carbon monoxide.
  • the reaction mixture was stirred at 100 °C for 36 hours before the vessel was cooled to room temperature and the pressure released.
  • the reaction mixture was concentrated to dryness and purified by silica gel column chromatography over silica gel (petroleum ether/ethyl acetate) to obtain methyl 7-(methoxymethyl)-3-(2- trimethylsilylethoxymethyl)benzimidazole-5-carboxylate as a brown oil.
  • reaction mixture was stirred for 8 hours at room temperature.
  • the reaction mixture was adjusted to pH 9 with saturated aqueous NaHCO3 solution, then partitioned between dichloromethane (150 mL) and aqueous NaHCO3.
  • the separated organic layer was evaporated to dryness and purified by silica gel column chromatography over silica gel (dichloromethane/methanol) to give N-(4-fluoro-3-methoxy-phenyl)-7- (methoxymethyl)-N-methyl-3H-benzimidazole-5-carboxamide as a light yellow solid.
  • reaction mixture was stirred at 35 °C for 24 hours under oxygen atmosphere. Then the mixture was filtered through celite. The filtrate was concentrated under reduces pressure to give the crude which was purified by column chromatography on silica gel (methanol/dichloromethane).
  • reaction mixture was allowed to premix for 30min, then a solution of prop-2-enenitrile [CAS 107-13-1] (2.26 g, 42.5 mmol, 2.0 eq.) in toluene (10 mL) was added to the reaction mixture.
  • the resulting reaction mixture was stirred at room temperature for 3 hours before it was quenched with saturated aqueous solution of NH4Cl and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo.
  • reaction mixture was stirred at 75 °C for 8 hours before the resulting reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether) to give N-(2-cyanoethyl)-N-(4-fluoro-3-methoxy- phenyl)-7-methyl-3H-benzimidazole-5-carboxamide as a brown solid.
  • reaction mixture was stirred at 35 °C for 24 hours under oxygen atmosphere. Then the mixture was filtered through celite and the filtrate was concentrated under reduced pressure to give the crude which was purified by column chromatography on silica gel (dichloromethane/methanol). It was further purified by trituration in diethylether to afford qualified methyl N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxy-phenyl)carbamoyl]-4-methyl-benzimidazol- 1-yl]-2-pyridyl]carbamate as an off-white powder.
  • reaction mixture was stirred at 80 °C for 8 hours under nitrogen atmosphere. Then the resulting mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (methanol/dichloromethane) to give methyl 7-vinyl-3H- benzimidazole-5-carboxylate as a yellow solid.
  • reaction mixture was stirred at room temperature for 2 hours before it was adjusted to pH ⁇ 7 with NaHCO3 solution.
  • the resulting mixture was diluted with water and extracted with ethyl acetate.
  • the combined organic phases were washed with brine, dried over sodium sulfate, concentrated under reduced pressure and purified by reversed phase chromatography (acetonitrile/water containing 0.1% formic acid) to afford 7-ethyl-N-(4-fluoro-3-methoxy-phenyl)-N-methyl-3H-benzimidazole-5-carboxamide as a yellow solid.
  • reaction mixture was stirred at 35 °C for 8 hours under oxygen atmosphere before it was filtered.
  • the filtrate was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (methanol/dichloromethane). It was further purified by trituration with methyl tert-butyl ether/acetonitrile (1:1) to obtain methyl N-[5-[4-ethyl- 6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]benzimidazol-1-yl]-2-pyridyl]carbamate as a white solid.
  • reaction mixture was heated at 80°C under nitrogen atmosphere for 7 hours. Then the reaction mixture was concentrated in reduced pressure and the residue was purified by reversed phase chromatography (C18 column, eluting with acetonitrile/water containing 0.1% formic acid) to afford 2-(4-fluoro-3-methoxy-anilino)acetonitrile as a brown solid.
  • reaction mixture was stirred at 35 °C for 16 hours under oxygen atmosphere. Then the mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (methynol/dichloromethane). It was further purified by trituration with methyl tert-butyl ether/acetonitrile (20:1) to obtain methyl N-[5-[6-[cyanomethyl-(4-fluoro-3-methoxy-phenyl)carbamoyl]-4-methyl- benzimidazol-1-yl]-2-pyridyl]carbamate as a yellow solid.
  • reaction mixture was stirred at 80 °C for 4 hours under nitrogen atmosphere, then it was diluted with ethyl acetate, washed with water and brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure.
  • the residue was purified by silica gel column chromatography (dichloromethane/methanol) to obtain 4-fluoro-3-methoxy-N-(2-methoxyethyl)aniline as a brown oil.
  • reaction mixture was stirred at 35 °C for 8 hours under oxygen atmosphere before it was filtered.
  • the filtrate was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (methanol/dichloromethane). It was further purified by trituration with acetonitrile to obtain methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-(2- methoxyethyl)carbamoyl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate as an off-white solid.
  • Example 14 Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)- (methoxymethyl)carbamoyl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate (Compound 23) (Compound 23) Step 1: Preparation of 2-[(6-bromo-4-methyl-benzimidazol-1-yl)methoxy]ethyl-trimethyl-silane 6-bromo-4-methyl-1H-benzimidazole (CAS 255064-10-9, 2.00 g, 9.48 mmol) was dissolved in tetrahydrofuran (30 mL) and the solution was cooled down to 0 °C.
  • Step 3 preparation of N-(4-fluoro-3-methoxy-phenyl)-N-(methoxymethyl)-7-methyl-3-(2- trimethylsilylethoxymethyl)benzimidazole-5-carboxamide
  • N-(4-fluoro-3-methoxy-phenyl)-7-methyl-3-(2-trimethylsilylethoxymethyl)benzimidazole-5- carboxamide 100 mg, 0.232 mmol
  • tetrahydrofuran 1.0 mL
  • Sodium hydride (18.6 mg, 0.466 mmol, 2.00 equiv, 60 mass% in oil) was added portionwise.
  • chloromethyl methyl ether (0.026 mL, 0.349 mmol, 1.50 eq.) was added to the reaction mixture slowly.
  • the resulting reaction mixture was stirred at room temperature overnight.
  • the reaction was quenched by addition of saturated aqueous ammonium chloride solution at 0 °C.
  • the aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with water then brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 4 preparation of N-(4-fluoro-3-methoxy-phenyl)-N-(methoxymethyl)-7-methyl-3H-benzimidazole- 5-carboxamide (Intermediate I-3) (Intermediate I-3) Tetramethylethylenediamine (0.095 mL, 0.633 mmol, 3.00 equiv) and tetrabutylammonium fluoride (1 M in tetrahydrofuran, 0.633 mL, 0.633 mmol, 3.00 eq.) were added to a solution of N-(4-fluoro-3-methoxy- phenyl)-N-(methoxymethyl)-7-methyl-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxamide (0.100 g, 0.211 mmol, 1.00 eq.) in dimethylformamide (1.00 mL).
  • Step 5 Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-(methoxymethyl)carbamoyl]-4- methyl-benzimidazol-1-yl]-2-pyridyl]carbamate (Compound 23) Boric acid (0.036 g, 0.58 mmol, 2.
  • N,N- diisopropylethylamine (0.104 mL, 0.582 mmol, 2.00 eq.) was added followed by methyl N-[5-(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.162 g, 0.582 mmol, 2.00 eq.)
  • the reaction was stirred at 65 °C for 12 hours.
  • the reaction mixture was poured into water.
  • the aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with water then brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • N,N- diisopropylethylamine (0.197 mL, 1.107 mmol, 2.00 eq.) was added followed by methyl N-[5-(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.146 g, 0.664 mmol, 1.20 eq.).
  • the reaction mixture was purged with oxygen for 10 minutes.
  • the reaction was stirred at room temperature for 12 hours.
  • the reaction mixture was poured into water.
  • the aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with water then brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 2 Preparation of 3-(6-acetamido-3-pyridyl)-N-(4-fluoro-3-methoxy-phenyl)-N-(methoxymethyl)-7- methyl-benzimidazole-5-carboxamide
  • Compound 94 Pyridine (0.015 mL, 0.184 mmol, 2.00 eq.) and dimethylaminopyridine (5.8 mg, 0.046 mmol, 0.50 eq.) were added to a solution of 3-(6-amino-3-pyridyl)-N-(4-fluoro-3-methoxy-phenyl)-N-(methoxymethyl)-7- methyl-benzimidazole-5-carboxamide (40.0 mg, 0.0919 mmol) in dichloromethane (0.40 mL).
  • Acetyl chloride (10.8 mg, 0.138 mmol, 1.50 eq.) was added portionwise. The mixture was stirred at room temperature for 20 hours. The reaction was then quenched by addition of saturated aqueous sodium bicarbonate solution. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Example 17 Preparation of methyl N-[5-[5-[(4-fluoro-3-methoxy-phenyl)-methyl- carbamoyl]imidazo[4,5-b]pyridin-3-yl]-2-pyridyl]carbamate (Compound 12) (Compound 12) Step 1: Preparation of N-(4-fluoro-3-methoxy-phenyl)-N-methyl-3H-imidazo[4,5-b]pyridine-5- carboxamide To a solution of 3H-imidazo[4,5-b]pyridine-5-carboxylic acid (CAS 1019108-05-4, 0.410 g, 2.51 mmol, 1.32 eq.) and 4-fluoro-3-methoxy-N-methyl-aniline (0.300 g, 1.93 mmol) in pyridine (6.00 mL) was added propanephosphonic acid anhydride (50.0 %, 3.69 g, 5.80 mmol, 3.00 eq.).
  • Step 2 Preparation of methyl N-[5-[5-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]imidazo[4,5- b]pyridin-3-yl]-2-pyridyl]carbamate (Compound 12)
  • N-(4-fluoro-3-methoxy-phenyl)-N-methyl-3H-imidazo[4,5-b] pyridine-5-carboxamide (0.280 g, 0.932 mmol)
  • methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl] carbamate 0.389 g, 1.40 mmol, 1.50 eq.
  • MeOH 5.00 mL
  • cupriooxycopper 0.400 g, 2.80 mmol, 3.00 eq.
  • Example 18 Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl- carbamoyl]imidazo[4,5-b]pyridin-1-yl]-2-pyridyl]carbamate (Compound 37) (Compound 37) Step 1: Preparation of N-(4-fluoro-3-methoxy-phenyl)-N-methyl-1H-imidazo[4,5-b]pyridine-6- carboxamide To a solution of 1H-imidazo[4,5-b] pyridine-6-carboxylic acid (CAS 24638-31-1, 0.400 g, 2.45 mmol) and 4-fluoro-3-methoxy-N-methyl-aniline (0.457 g, 2.94 mmol, 1.18 eq.) in pyridine (6.00 mL) was added propanephosphonic acid anhydride (50.0 %, 4.68 g, 7.36 mmol, 2.50 equiv).
  • Step 2 Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]imidazo[4,5- b]pyridin-1-yl]-2-pyridyl]carbamate (Compound 37)
  • N-(4-fluoro-3-methoxy-phenyl)-N-methyl-1H-imidazo[4,5-b] pyridine-6-carboxamide (0.360 g, 1.20 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl] carbamate (0.500 g, 1.80 mmol, 1.50 eq.) in methanol (6.00 mL) was added cupriooxycopper (0.515 g, 3.60 mmol, 3.00 eq.).
  • Example 20 Preparation of methyl N-[5-[6-[(4-fluorophenyl)-methyl-carbamoyl]imidazo[4,5- c]pyridin-1-yl]-2-pyridyl]carbamate (Compound 42) (Compound 42) Step 1: Preparation of methyl N-[5-[(2-chloro-5-nitro-4-pyridyl)amino]-2-pyridyl]carbamate.
  • Step 2 Preparation of methyl N-[5-[(5-amino-2-chloro-4-pyridyl)amino]-2-pyridyl]carbamate Iron (9.01 g, 161 mmol, 5.00 eq.) was added to a solution of methyl N-[5-[(2-chloro-5-nitro-4- pyridyl)amino]-2-pyridyl]carbamate (11.0 g, 32.3 mmol) in ethanol (1000 mL) and H2O (120 mL), followed by ammonium chloride (1
  • Step 3 Preparation of methyl N-[5-(6-chloroimidazo[4,5-c]pyridin-1-yl)-2-pyridyl]carbamate
  • a solution of methyl N-[5-[(5-amino-2-chloro-4-pyridyl)amino]-2-pyridyl]carbamate (2.00 g, 6.47 mmol) in diethoxymethoxyethane (10.0 mL) was charged with hydrogen chloride (36.0 %, 0.655 g, 6.47 mmol, 1.00 eq.) and stirred at 100 °C for 1 hour. The reaction mixture was concentrated under reduced pressure.
  • Step 4 Preparation of methyl 1-[6-(methoxycarbonylamino)-3-pyridyl]imidazo[4,5-c]pyridine-6- carboxylate
  • Step 5 Preparation of [1-[6-(methoxycarbonylamino)-3-pyridyl]imidazo[4,5-c]pyridine-6- carbonyl]oxylithium Lithium hydroxide hydrate (369 mg, 8.80 mmol, 4.00 equiv) was added to a solution of methyl 1-[6- (methoxycarbonylamino)-3-pyridyl]imidazo[4,5-c]pyridine-6-carboxylate (800 mg, 2.20 mmol) in THF (15.0 mL)/methanol (10.0 mL)/H2O (10.0 mL).
  • Example 20 Preparation of methyl N-[5-[6-[(4-chlorophenyl)-methyl-carbamothioyl]-4-methyl- benzimidazol-1-yl]-2-pyridyl]carbamate (Compound 98) (Compound 98) Step 1: Preparation of methyl N-[5-(6-bromo-4-methyl-benzimidazol-1-yl)-2-pyridyl]carbamate Boric acid (0.200 g, 3.00 mmol, 2.00 eq.) and copper(II) acetate (0.400 g, 2.00 mmol, 1.5 eq.) were added to a solution of 6-bromo-4-methyl-1H-benzimidazole (0.300 g, 1.00 mmol) in acetonitrile (10 mL).
  • N,N-diisopropylethylamine (0.500 mL, 2.00 mmol, 2.00 eq.) was added followed by methyl N-[5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.800 g, 3.00 mmol, 2.00 eq.).
  • the reaction was stirred at 65 °C for 12 hours.
  • the reaction mixture was poured into water.
  • the aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with water then brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • the reaction was heated at 100 °C for 6 hours.
  • the reaction mixture was filtered on celite using methanol, and the filtrate was concentrated under reduced pressure.
  • the crude residue was purified by column chromatography on silica gel (cyclohexane/ethylacetate) to afford methyl N-[5-[6-[(4-chlorophenyl)-methyl-carbamoyl]-4- methyl-benzimidazol-1-yl]-2-pyridyl]carbamate as a white solid.
  • Step 3 Preparation of methyl N-[5-[6-[(4-chlorophenyl)-methyl-carbamothioyl]-4-methyl-benzimidazol- 1-yl]-2-pyridyl]carbamate (Compound 98)
  • a suspension of methyl N-[4-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-4-methyl- benzimidazol-1-yl]phenyl]carbamate (25.0 mg, 0.0556 mmol) and Lawesson's reagent (CAS 19172-47- 5, 0.0162 g, 0.70 eq.) in toluene (0.83 mL) was heated to 110 °C for 2.5 hours.
  • fungicidal activity of the compounds of the invention have been tested as follows: Phytophthora infestans / tomato / leaf disc preventative (late blight) Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated leaf disks are incubated at 16 °C and 75% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
  • the following compounds gave at least 80% control of Phytophthora infestans at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 71, 72, 94, 96, 97 Plasmopara viticola / grape / leaf disc preventative (late blight) Grape vine leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated leaf disks are incubated at 19 °C and 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application).
  • test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 2-3 days after application.
  • the following compounds gave at least 80% control of Pythium ultimum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 34, 38, 39, 40, 42, 44, 45, 54, 55, 61, 65, 66, 72, 78, 79, 82, 88, 93, 94, 95, 96, 97

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Plant Pathology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Agronomy & Crop Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Mycology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des composés de formule (I) dans laquelle les substituants sont tels que définis dans la revendication 1, des processus et des procédés de préparation de composés de formule (I), des compositions agrochimiques comprenant des composés de formule (I) tels que définis dans la revendication 1, la préparation de ces compositions et l'utilisation des composés ou compositions en agriculture ou horticulture pour combattre, prévenir ou lutter contre l'infestation de plantes, de cultures vivrières récoltées, de graines ou de matériaux non vivants par des micro-organismes phytopathogènes, en particulier des champignons.
PCT/EP2023/085193 2022-12-16 2023-12-11 Dérivés benzimidazoles WO2024126407A1 (fr)

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WO2017025510A1 (fr) 2015-08-12 2017-02-16 Syngenta Participations Ag Dérivés hétérobicycliques microbiocides
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