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WO2025233384A1 - Microbiocidal pyrazole compounds - Google Patents

Microbiocidal pyrazole compounds

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Publication number
WO2025233384A1
WO2025233384A1 PCT/EP2025/062451 EP2025062451W WO2025233384A1 WO 2025233384 A1 WO2025233384 A1 WO 2025233384A1 EP 2025062451 W EP2025062451 W EP 2025062451W WO 2025233384 A1 WO2025233384 A1 WO 2025233384A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
alkoxy
cyano
formula
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/062451
Other languages
French (fr)
Inventor
Christopher Charles SCARBOROUGH
Andrew Edmunds
Atul Mahajan
Matthias Weiss
Dorothée HENRYON
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Crop Protection AG Switzerland
Original Assignee
Syngenta Crop Protection AG Switzerland
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Crop Protection AG Switzerland filed Critical Syngenta Crop Protection AG Switzerland
Publication of WO2025233384A1 publication Critical patent/WO2025233384A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides

Definitions

  • the present invention relates to microbiocidal pyrazole derivatives, e.g. as active ingredients, which have microbiocidal activity, in particular fungicidal activity.
  • the invention also relates to preparation of these pyrazole derivatives, to intermediates useful in the preparation of these pyrazole derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of the pyrazole derivatives, to preparation of these compositions and to the use of the pyrazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.
  • R 1 is selected from hydrogen, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or Cs-Ce-cycloalkyl;
  • R 2 is selected from cyano, hydroxy, amino, Ci-C4-alkoxy, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, C1-C4- haloalkoxy, Ci-C4-haloalkylsulfanyl, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Cs-Ce-cycloalkyloxy, C1-C4- alkoxy-Ci-C4-alkyl, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, or Ci-C4-alkylsulfonyl;
  • R 3 is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl;
  • R 4 is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, or Cs-Ce-cycloalkyl;
  • B 1 is selected from CR 7 , or N;
  • B 2 is selected from CR 8 , or N;
  • B 3 is selected from CR 9 , or N;
  • R 5 , R 6 , R 7 , R 8 and R 9 are independently selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, C3-C6- alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4- alkylcarbonyl, Ci-C4-alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, C1-C4- alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl,
  • Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from cyano, nitro, carboxy, hydroxy, Ci-C4-alkyl, C2-C4-alkenyl, C2- C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, C3-C6- haloalkenyloxy, Cs-Ce-cycloalkyloxy, C3-C6-cycloalkyl-Ci-C4-alkoxy, C3-C6-halocycloalkyl-Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4
  • an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to the invention.
  • Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
  • a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms wherein a fungicidally effective amount of a compound of formula (I) according to the invention, or a composition comprising the compound of formula (I), is applied to the plants, to parts thereof or the locus thereof.
  • a compound of formula (I) according to the invention as a fungicide.
  • the use may exclude methods for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.
  • the compounds of formula (I) or the intermediate compounds of formula (III) according to the invention 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, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C4-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, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci- C4-alkane- or arylsulfonic acids which are un
  • the compounds of formula (I) or the intermediate compounds of formula (III) according to the invention 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-
  • asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also, atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula (I) is intended to include all those possible isomeric forms and mixtures thereof.
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I) according to the invention.
  • a compound of formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present.
  • the present invention includes all possible tautomeric forms for a compound of formula (I) according to the invention.
  • 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.
  • N-oxides can be prepared by reacting a compound of formula (I) with a suitable oxidizing agent, for example the HzOz/urea adduct, in the presence of an acid anhydride, e.g., trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the HzOz/urea adduct
  • an acid anhydride e.g., trifluoroacetic anhydride.
  • the compounds of formula (I) according to the invention also include hydrates, which may be formed during salt formation.
  • halogen refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine, or bromine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.
  • amino means a -NHz group.
  • cyano means a -CN group.
  • hydroxyl or “hydroxy” means an -OH group.
  • carboxylic acid means a -COOH group.
  • Ci-Cn-alkyl refers to a saturated straight- or branched hydrocarbon chain having 1 to n carbon atoms. Examples include but are not limited to methyl, ethyl, n-propyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, n-pentyl, 1 ,1 -dimethylpropyl, 1 ,2- dimethylpropyl.
  • Cz-Cn-alkenyl refers to an unsaturated straight or branched hydrocarbon chain having from two to n carbon atoms and comprising at least one double bond that can be of either the (Z) or (E) configuration. Examples include but are not limited to ethenyl (or vinyl), prop-1 -enyl, prop-2-enyl (or allyl), prop-1 -en-2-yl (or isopropenyl), or but-2-enyl.
  • Cs-Cn-alkenyl refers to an unsaturated straight or branched hydrocarbon chain having from three to n carbon atoms.
  • Cz-Cn-alkynyl refers to a straight or branched hydrocarbon chain having from two to n carbon atoms and comprising at least one triple bond. Examples include but are not limited to ethynyl, prop-2-ynyl (or propargyl), or but-3-ynyl. Analogously, the term “Cs-Cn-alkynyl” as used herein refers to an unsaturated straight or branched hydrocarbon chain having from three to n carbon atoms.
  • Cs-Cn-cycloalkyl refers to a saturated, monovalent, monocylic hydrocarbon ring which contains 3 to n carbon atoms. Examples include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Ci-Cn-haloalkyl refers to a "Ci-Cn-alkyl” as defined herein, in which one or more hydrogen atoms may be replaced with one or more halogen atoms that may be the same or different.
  • Examples include but are not limited to chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2- trichloroethyl.
  • Ci-Cn-haloalkoxy refers to an Ci-Cn-alkoxyl group as defined herein substituted with one or more halogen atoms which may be the same or different.
  • Cz-Cn-haloalkenyl refers to a Cz-Cn-alkenyl radical respectively substituted with one or more halogen atoms which may be the same or different.
  • C3- Cn-halocycloalkyl or “Ci-Cn-haloalkoxy” as used herein refers to a Cs-Cn-cycloalkyl radical or Ci-Cn- alkoxyl radical respectively substituted with one or more halogen atoms which may be the same or different.
  • cyano-Ci-Cn-alkyl refers to Ci-Cn-alkyl as defined herein, in which at least one hydrogen atom is replaced with a cyano group, for example, cyano-methyl, 2-cyano-ethyl, 2-cyano- propyl, 3-cyano-propyl, 1 -(cyano-methyl)-2-ethyl, 1 -(methyl)-2-cyano-ethyl, 4-cyanobutyl.
  • Ci-Cn-alkoxy refers to groups of the formula -O-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein. Examples include but are not limited to methoxy, ethoxy, n-propoxy, 1 - methylethoxy, n-butoxy, 1 -methylpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
  • Cs-Ce-cycloalkyloxy refers to groups of the formula -O-(C3-Cn-cycloalkyl), in which the term “Cs-Cn-cycloalkyl” is as defined herein.
  • Cs-Cn-alkenyloxy refers to groups of the formula -O-(C3-Cn-alkenyl), in which the term “Cs-Cn-alkenyl” is as defined herein.
  • Cs-Cn-alkynyloxy refers to groups of the formula -O-(C3-Cn-alkynyl), in which the term “Cs-Cn-alkynyl” is as defined herein.
  • Ci-Cn-alkoxy-Ci-Cn-alkyl refers to a group of the formula -(Ci-Cn-alkyl)-O-(Ci- Cn-alkyl), in which the term Ci-Cn-alkyl is as defined herein. Examples include, but are not limited to methoxymethyl, methoxyethyl, ethoxymethyl or propoxymethyl.
  • Ci-Cn-alkyl-Ci-Cn-alkoxy refers to a radical of the formula -R a -ORt>, where R a is a “Ci-Cn-alkyl” group as defined above, and Rb refers to an “Ci-Cn-alkyl” group as defined above.
  • Ci-Cn-alkoxy-Ci-Cn-alkoxy refers to a group of the formula -O-(Ci-Cn-alkyl)-O- (Ci-Cn-alkyl), in which the term Ci-Cn-alkyl is as defined herein.
  • Ci-Cn-alkyl-Ci-Cn-alkoxy-Ci-Cn-alkoxy refers to a radical of the formula -R a - ORb-ORc, where R a is a “Ci-Cn-alkyl” group as defined herein, and Rb and R c refer to an “Ci-Cn-alkyl” group as defined herein.
  • Ci-Cn-alkylthio“ or “Ci-Cn-alkylsulfanyl“ refers to a group of the formula -S-(Ci- Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein, and wherein the group is linked through the sulfur atom.
  • Cs-Cn-cycloalkyl-Ci-Cn-alkyl refer a “Ci-Cn-alkyl” as defined herein, wherein one hydrogen atom is replaced with a “Cs-Cn-cycloalkyl” group as defined herein. Examples include but are not limited to cyclopropylmethyl, cyclopropylethyl.
  • Cs-Cn-halocycloalkyl-Ci-Cn- alkyl refers to “Ci-Cn-alkyl” as defined herein, wherein one hydrogen atom is replaced with a “Cs-Cn- cycloalkyl” group as defined herein, wherein the “Cs-Cn-cycloalkyl” group is substituted by one or more of the same or different halogen atoms. Examples are 3,3-difluorobutylmethyl and 1 - chlorocyclopropylmethyl.
  • Cs-Cn-cycloalkyl-Ci-Cn-alkoxy refer a “Ci-Cn-alkoxy” group as defined herein, wherein one hydrogen atom is replaced with a “Cs-Cn-cycloalkyl” group as defined herein.
  • Ci-Cn-alkylsulfonyl-Ci-Cn-alkyl refer a “Ci-Cn-alkyl” as defined herein, wherein one hydrogen atom is replaced with a “Ci-Cn-alkylsulfonyl” group as defined herein.
  • Ci-Cn-haloalkoxycarbonyl refers to a “Ci-Cn-alkoxycarbonyl” group as defined herein, in which one or more hydrogen atoms may be replaced with one or more halogen atoms that may be the same or different.
  • N-Ci-Cn-alkylamino refers to a group of the formula -NH-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein.
  • N,N-di(Ci-Cn-alkyl)amino refers to a group of the formula -N-(Ci-Cn-alkyl)2, in which each term “Ci-Cn-alkyl”, which may be the same or different, is as defined herein.
  • 4-, 5-, or 6-membered heterocycle refers to a 4-, 5-, or 6-membered monocyclic ring-system containing 1 , 2 or 3 heteroatoms independently selected from oxygen (O), nitrogen (N) and sulfur (S), where the ring system is saturated or unsaturated, but not aromatic.
  • O oxygen
  • N nitrogen
  • S sulfur
  • the "4-, 5-, or 6-membered heterocycle” can be connected to the rest of the molecule through any carbon atom or nitrogen atom contained in the heterocycle.
  • saturated 3- to 6-membered heterocyclyl groups include but are not limited to 4-membered rings such as azetidinyl, oxetanyl, thietanyl, 5-membered rings such as tetrahydrofuranyl, 1 ,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, and 6-membered rings such as piperidinyl, piperazinyl, and morpholinyl.
  • 4-membered rings such as azetidinyl, oxetanyl, thietanyl, 5-membered rings such as tetrahydrofuranyl, 1 ,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, and 6-membered rings such as piperidinyl
  • unsaturated 4- to 6-membered heterocycles include but are not limited to 5-membered rings such as dihydrofuranyl, 1 ,3-dioxolyl, pyrrolinyl, and 6-membered rings such as pyranyl, and thiopyranyl.
  • 5- or 6-membered heteroaryl refers to a 5- or 6-membered monocyclic, aromatic ring system containing 1 , 2, or 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur.
  • the heteroatom ring members can only be nitrogen atoms.
  • 5-membered heteroaryl include but are not limited to furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, isooxazolyl.
  • 6-membered heteroaryl include but are not limited to pyridyl (or pyridinyl), pyridazinyl, pyrimidinyl.
  • Ci-Cn-alkoxycarbonyl-Ci-Cn-alkyl refers a “Ci-Cn-alkyl” as defined herein, wherein one hydrogen atom is replaced with a Ci-Cn-alkoxycarbonyl, Ci-Cn-alkylcarbonyloxy, Ci-Cn-alkylcarbonylamino, N,N- di(Ci-Cn-alkyl)amino
  • substituents refers to a number of substituents that ranges from one to (n) number of substituents possible based on the number of available bonding sites, provided that the conditions of stability and chemical feasibility are met.
  • controlling refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced.
  • pest refers to insects, and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain, and timber); and those pests associated with the damage of man-made structures.
  • the term pest encompasses all stages in the life cycle of the pest.
  • the term "effective amount” refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.
  • an effective amount is readily determined by the skilled person in the art, using known techniques and by observing results obtained under analogous circumstances. In determining the effective amount, a number of factors are considered including, but not limited to the type of plant or derived product to be applied; the pest to be controlled and its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.
  • room temperature or “RT” or “rt” or “ambient temperature” refer to a temperature of about 15°C to about 35°C.
  • rt can refer to a temperature of about 20°C to about 30°C.
  • R 1 is selected from hydrogen, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, or Cs-Ce-cycloalkyl.
  • R 1 is selected from Ci-Cs-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or cyclopropyl.
  • R 1 is Ci-C4-alkyl.
  • R 1 is Ci-Cs-alkyl. More preferably R 1 is methyl, ethyl, or isopropyl. Even more preferably R 1 is methyl.
  • R 2 is selected from cyano, hydroxy, amino, Ci-C4-alkoxy, C1-C4- alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-haloalkoxy, Ci-C4-haloalkylsulfanyl, Cs-Ce-alkenyloxy, C3-C6- alkynyloxy, Cs-Ce-cycloalkyloxy, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, or C1- C4-alkylsulfonyl.
  • R 2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2- alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, C1-C2- haloalkoxy, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or C1- C2-alkylsulfonyl.
  • R 2 is selected from cyano, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C3- Ce-cycloalkyloxy, or Ci-C4-alkoxy-Ci-C2-alkyl.
  • R 2 is cyano, Ci-Cs-alkoxy, Ci-Cz-haloalkoxy, C3- Ce-cycloalkyloxy, or Ci-C2-alkoxy-Ci-C2-alkyl. More preferably R 2 is cyano, methoxy, difluoromethoxy, or methoxymethyl.
  • R 2 is cyano, Ci-Cs-alkoxy, or Ci-C2-alkylsulfanyl.
  • R 2 is cyano, methoxy, or methylsulfanyl.
  • R 3 is selected from hydrogen, halogen, Ci-C4-alkyl, or C1-C4- haloalkyl.
  • R 3 is hydrogen, halogen, Ci-Cs-alkyl, or Ci-C2-haloalkyl.
  • R 3 is selected from hydrogen, halogen, or Ci-Cs-alkyl.
  • R 3 is hydrogen, fluorine, chlorine, or methyl. More preferably R 3 is hydrogen or methyl. Even more preferably R 3 is hydrogen.
  • R 3 is hydrogen or Ci-Cs-alkyl.
  • R 4 is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, or Cs-Ce-cycloalkyl.
  • R 4 is hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-haloalkyl, or cyclopropyl. More preferably R 4 is hydrogen, chlorine, bromine, fluorine, methyl, ethyl, trifluoromethyl, difluoromethyl, or cyclopropyl.
  • R 4 is selected from hydrogen, halogen, or C1-C4- alkyl.
  • R 4 is hydrogen, halogen, or Ci-Cs-alkyl. More preferably R 4 is hydrogen, chlorine, bromine, or methyl. Most preferably R 4 is hydrogen.
  • R 5 , R 6 , R 7 , R 8 and R 9 are independently selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C1-C4- alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, C1-C4- dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4-alkyl)a
  • R 5 and R 6 are independently selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce- alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci- C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, C1- C4-alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano-Ci-
  • R 5 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N
  • R 5 is hydrogen, halogen, Ci-C4-alkyl, or cyano. More preferably R 5 is hydrogen, fluorine, chlorine, bromine, methyl, or cyano. Even more preferably R 5 is hydrogen, fluorine, methyl, or cyano. Still more preferably R 5 is hydrogen or cyano. Most preferably R 5 is hydrogen.
  • R 6 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N
  • R 6 is hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4- alkoxycarbonyl, Ci-C4-alkylcarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, C1-C4- haloalkyl, or Ci-C4-alkoxy.
  • R 6 is hydrogen, chlorine, bromine, fluorine, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2,2-trifluoroethoxy, 2,2-difluoroethoxy, methoxy, ethoxy, methoxymethoxy, 2-methoxyethoxy, methoxycarbonyl, hydroxy, cyano, cyclopropyl, cyanocyclopropyl, or methylcyclopropyl.
  • R 6 is hydrogen, chlorine, bromine, fluorine, methyl, difluoromethyl, difluoromethoxy, 2,2,2-trifluoroethoxy, 2,2-difluoroethoxy, methoxy, 2- methoxyethoxy, methoxycarbonyl, hydroxy, cyano, or cyclopropyl. Still more preferably R 6 is hydrogen, chlorine, bromine, fluorine, methyl, cyano, or cyclopropyl. Still even more preferably R 6 is hydrogen, cyano, or cyclopropyl. Still even more preferably R 6 is hydrogen or cyano. Most preferably R 6 is hydrogen.
  • R 6 is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci- C4-haloalkyl, Ci-C4-haloalkoxy, or Ci-C4-alkoxy.
  • R 6 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cz-haloalkyl, Ci-Cz-haloalkoxy, or Ci-Cs-alkoxy. More preferably R 6 is hydrogen, or Ci-Cs-alkyl.
  • B 1 is selected from CR 7 , or N. In another embodiment B 1 is CR 7 . In another embodiment B 1 is N. Preferably B 1 is CR 7 .
  • B 2 is selected from CR 8 , or N. In another embodiment B 2 is CR 8 . In another embodiment B 2 is N. Preferably B 2 is CR 8 .
  • R 7 , R 8 and R 9 are independently selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce- alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci- C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, C1- C4-alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano
  • R 7 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N
  • R 7 is hydrogen, halogen, hydroxy, cyano, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy Ci-Cs-haloalkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-alkylcarbonyl, or Cs-Ce-cycloalkyl; wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C3- alkyl, Ci-Cz-haloalkyl, or Ci-Cs-alkoxy.
  • R 7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci- Cs-haloalkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkoxycarbonyl, C1-C3- alkylcarbonyl, or Cs-Ce-cycloalkyl; wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, or Ci-Cs-alkyl.
  • R 7 is hydrogen, chlorine, bromine, fluorine, cyano, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2,2- trifluoroethoxy, 2,2-difluoroethoxy, methoxy, ethoxy, methoxymethyl, 2-methoxyethyl, methoxycarbonyl, ethoxycarbonyl, cyclopropyl, cyanocyclopropyl, or methylcyclopropyl.
  • R 7 is hydrogen, halogen, cyano, Ci -Cs-alkyl, Ci-Cs-alkoxy, C1-C3- alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or Cs-Ce-cycloalkyl; wherein said C3-C6- cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, or Ci-Cs-alkyl.
  • R 7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, C1-C3- alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl. More preferably hydrogen, chlorine, bromine, fluorine, cyano, methyl, ethyl, isopropyl, methoxy, ethoxy, methoxymethyl, 2-methoxyethyl, methoxycarbonyl, ethoxycarbonyl, or cyclopropyl.
  • R 8 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N
  • R 8 is hydrogen, halogen, hydroxy, cyano, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or Cs-Ce-cycloalkyl; wherein said C3-C6- cycloalkyl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, Ci-Cs-alkyl, Ci-Cz-haloalkyl, or Ci-Cs-alkoxy.
  • R 8 is hydrogen, halogen, cyano, Ci- Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or Cs-Ce-cycloalkyl; wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, or Ci-Cs-alkyl.
  • R 8 is hydrogen, chlorine, bromine, fluorine, cyano, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2,2-trifluoroethoxy, 2,2-difluoroethoxy, methoxy, ethoxy, methoxymethyl, 2- methoxyethyl, methoxycarbonyl, ethoxycarbonyl, cyclopropyl, cyanocyclopropyl, or methylcyclopropyl.
  • R 8 is hydrogen, halogen, cyano, Ci -Cs-alkyl, Ci-Cs-alkoxy, C1-C3- alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or Cs-Ce-cycloalkyl; wherein said Cs-Ce- cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, or Ci-Cs-alkyl.
  • R 8 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, C1-C3- alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl. More preferably hydrogen, chlorine, bromine, fluorine, cyano, methyl, ethyl, isopropyl, methoxy, ethoxy, methoxymethyl, 2-methoxyethyl, methoxycarbonyl, ethoxycarbonyl, or cyclopropyl.
  • R 9 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N
  • R 9 is hydrogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Cs-Ce-cycloalkyl. More preferably R 9 is hydrogen, halogen, methyl, cyano, difluoromethyl, or cyclopropyl. Even more preferably R 9 is hydrogen, chlorine, bromine, methyl, cyano, difluoromethyl, or cyclopropyl. Most preferably R 9 is hydrogen or cyano. Still even more preferably R 9 is hydrogen.
  • Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from cyano, nitro, carboxy, hydroxy, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C3- Ce-alkenyloxy, Cs-Ce-alkynyloxy, Cs-Ce-haloalkenyloxy, Cs-Ce-cycloalkyloxy, C3-C6-cycloalkyl-Ci-C4- alkoxy, C3-C6-halocycloalkyl-Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl,
  • Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-C4-alkyl, Ci-Cs-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, phenyl, 5 to 6 membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said 4-, 5- or 6-membered saturated, partially saturated or aromatic heterocycle contains 1 , 2 or 3 heteroatoms selected from O, S or N, with the proviso that no more than one is O or S, wherein any of said phenyl and 5- or 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen,
  • Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cz-haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or C3-C6- cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl.
  • Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkyl, C1-C2- haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2- haloalkyl.
  • Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, C1-C2- haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl.
  • Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-C2-haloalkyl, C1-C2- haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or cyclopropyl.
  • the present invention accordingly, makes available a compound of formula (I) having R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 , B 2 , B 3 and Z 1 as defined above in all combinations / each permutation.
  • Embodiments according to the invention are provided as set out below.
  • the compound of formula (I) may be a compound of formula (l-A) wherein R 1 is methyl; R 3 is hydrogen; and w are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 , and R 6 are hydrogen; and R 2 , R 7 , R 8 , R 9 , B 1 , B 2 , B 3 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 , and R 6 are hydrogen;
  • R 7 , R 8 and R 9 are independently selected from hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci- Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl;
  • R 2 , B 1 , B 2 , B 3 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 , and R 6 are hydrogen; B 1 is CR 7 or N; B 2 is CR 8 or N; B 3 is N; R 7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs- alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; R 8 is hydrogen, halogen, cyano, C1-C3- alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with
  • R 2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2-alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or Ci-C2-alkylsulfonyl;
  • R 4 , R 5 , and R 6 are hydrogen;
  • B 1 is CR 7 or N;
  • B 2 is CR 8 or N;
  • B 3 is N;
  • R 7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs- alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkyl
  • the compound of formula (I) may be a compound of formula (I-A1 ), wherein R 1 is methyl; R 3 is hydrogen; B 1 is CR 7 ; B 2 is CR 8 ; and B 3 is N; and wherein R 2 , R 4 , R 5 , R 6 , R 7 , R 8 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 , and R 6 are hydrogen; and R 2 , R 7 , R 8 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 and R 6 are hydrogen;
  • R 7 and R 8 are independently selected from hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs- alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl;
  • R 2 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 , and R 6 are hydrogen;
  • R 7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci- Cs-alkoxycarbonyl, or cyclopropyl;
  • R 8 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, C1-C3- alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl;
  • Z 1 is selected from Ci-Ce- alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-
  • R 2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2-alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or Ci-C2-alkylsulfonyl;
  • R 4 , R 5 , and R 6 are hydrogen;
  • R 7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs- alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cycloprop
  • the compound of formula (I) may be a compound of formula (I-A2), wherein R 1 is methyl; R 3 is hydrogen; B 1 is CR 7 ; B 2 is CR 8 ; and B 3 is CR 9 ; and w are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 , and R 6 are hydrogen; and R 2 , R 7 , R 8 , R 9 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 , and R 6 are hydrogen; R 7 , R 8 and R 8 are independently selected from hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci- Cs-alkyl, Ci-C3-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; and R 2 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2-alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or Ci-C2-alkylsulfonyl;
  • R 4 , R 5 , and R 6 are hydrogen;
  • R 7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, C1-C3- alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropy
  • the compound of formula (I) may be a compound of formula (I-A3), wherein R 1 is methyl, R 3 is hydrogen, B 1 , B 2 and B 3 are N and (I-A3) wherein R 2 , R 4 , R 5 , R 6 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 , and R 6 are hydrogen; and R 2 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 4 , R 5 , and R 6 are hydrogen;
  • Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cz-haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl; and R 2 is as defined for the compounds of formula (I) according to the present invention.
  • R 2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2-alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or Ci-C2-alkylsulfonyl; R 4 , R 5 , and R 6 are hydrogen; Z 1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkyl, Ci
  • the presence of one or more possible asymmetric carbon atoms in any of the compounds selected from compounds of formula (I), (l-A), (I-A1 ), (I-A2) and (I-A3), or compounds selected from compounds listed in Tables B-1 to B-32, or Table P (below), according to the invention means that the compounds may occur in chiral isomeric forms, i.e. , enantiomeric or diastereomeric forms.
  • the compound of formula (I) according to the invention is selected from compounds listed in any one of Tables B-1 to B-32.
  • the compound of formula (I) according to the invention is selected from 8-cyano-N- (2-ethoxyethyl)-4-(5-methoxy-1 -methyl-pyrazol-4-yl)quinoline-2-carboxamide; 8-cyano-4-(5-methoxy-1 - methyl-pyrazol-4-yl)-N-pentyl-quinoline-2-carboxamide; 8-cyano-4-(5-cyano-1 -methyl-pyrazol-4-yl)-N- pentyl-quinoline-2-carboxamide; 8-bromo-4-(5-cyano-1 -methyl-pyrazol-4-yl)-N-pentyl-quinoline-2- carboxamide; 4-(5-cyano-1 -methyl-pyrazol-4-yl)-N-pentyl-quinoline-2-carboxamide; 4-(5-ethoxy-1 -methyl- pyrazol-4-yl)-N-pentyl-quinoline-2-carboxamide
  • compounds of formula (I) may be prepared by a person skilled in the art following known methods. More specifically, compounds of formula (I) may be prepared from compounds of formula (III) or a salt thereof, wherein Z 1 as defined above for the compound of formula (I) by reaction with a compound of formula (II), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 5 , R 6 , B 1 , B 2 , and B 3 , are as defined above for the compound of formula (I). This reaction is shown in Scheme 1 .
  • compounds of formula (Ila), where X° is halogen are formed by treatment of compounds of formula (II) with, for example, oxalyl chloride or thionyl chloride in the presence of catalytic quantities of N,N-dimethylformamide (DMF) in inert solvents such as dichloromethane (DCM) or tetrahydrofuran (THF) at temperatures between 20°C to 100°C, preferably 25°C.
  • DMF dichloromethane
  • THF tetrahydrofuran
  • compounds of formula (I) may be prepared by treatment of compounds of formula (II) with dicyclohexyl carbodiimide (DCC), 1 -ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 1 - [bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) to give the activated compound of formula (lib), wherein G° is G 01 , G 02 or G 03 as set forth below, in an inert solvent, e.g.
  • a compound of formula (II) can also be activated by reaction with a coupling reagent such as propanephosphonic acid anhydride (T3P) to provide compounds of formula (Ila), wherein G° is G 04 as set forth below, as described for example in Synthesis 2013, 45, 1569. Further reaction with an amine (or a salt thereof) of the compound of formula (III) leads to compounds of formula (I).
  • a coupling reagent such as propanephosphonic acid anhydride (T3P) to provide compounds of formula (Ila), wherein G° is G 04 as set forth below, as described for example in Synthesis 2013, 45, 1569.
  • Compounds of formula (II) can be prepared from compounds of formula (lie), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 and B 3 are as described in formula (I), and R 01 is Ci-C4-alkyl, by ester hydrolysis.
  • a variety of conditions can be used, as for example aqueous sodium hydroxide or lithium hydroxide, and an organic water miscible solvent like THF, dimethoxyethane, methanol, or ethanol.
  • ester hydrolyses are well known to those skilled in the art.
  • a further method to prepare compounds of formula (I) involves amino carbonylation of compounds of formula (III) with compounds of formula (IV), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 5 , R 6 , B 1 , B 2 , and B 3 , are as defined in compounds of formula (I), and X° is halogen, preferably Cl, Br or iodine.
  • Such amino carbonylation’s involve treatment of compounds of formula (III) with compounds of formula (IV) under a carbon monoxide atmosphere between 1 -10 bar, in the presence of a palladium catalyst, for example [1 ,3- Bis(diphenylphosphino)propane] palladium ⁇ I) chloride in an inert solvent such as methyl-THF or THF and a base such as triethyl amine.
  • a palladium catalyst for example [1 ,3- Bis(diphenylphosphino)propane] palladium ⁇ I) chloride in an inert solvent such as methyl-THF or THF and a base such as triethyl amine.
  • Compound of formula (V), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 and B 2 are as defined above for the compound of formula (I), may be prepared by reacting compounds of formula (VI) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 and B 2 are as defined above for the compound of formula (I) with a oxidizing agent such as hydrogen peroxide in acetic acid or m-chloroperbenzoic acid in a presence of solvent. Similar reactions have been described in W004/052370 or Adv. Synth. Cat. 2020, 362(24), 5777-5782. Such oxidations can also be performed in presence of oxygen using ruthenium as catalyst as described in Chem. Comm. 2002, (10), 1040-1041 . This reaction is shown in Scheme 4.
  • Suzuki-Miyaura cross-coupling reactions between compounds of formula (VII) and compounds of formula (VIII) are well known to a person skilled in the art and are usually carried out in the presence of a palladium catalyst, such as tetrakis(triphenylphosphine)-palladium(0) or [1 ,1 '-bis(diphenyl- phosphino)ferrocene]palladium(ll) dichloride dichloromethane complex, and a base, such as sodium or potassium carbonate, in a solvent, such as N,N-dimethylformamide, dioxane or dioxane-water mixtures, at temperatures between room temperature and 160°C, optionally under microwave heating conditions, and preferably under inert atmosphere.
  • a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(0) or [1 ,1 '-bis(diphenyl- phosphino)ferrocene]palladium
  • reaction can be performed by reacting a compound of formula (X), wherein R 1 , R 2 and R 3 are as defined above for the compound of formula (I), with a compound of formula (IX), wherein, R 4 , R 5 , R 6 , R 7 , B 1 and B 2 are as defined above for the compound of formula (I) and X° is halogen, preferably chlorine, bromine or iodine, to provide a compound of formula (VI), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 and B 2 are as defined above for the compound of formula (I).
  • This reaction is shown in Scheme 6.
  • a further cross-coupling chemistry namely C-H activation, can also be used to prepare compounds of formula (VI), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 and B 2 are as defined above for the compound of formula (I) (Scheme 7).
  • Compounds of formula (XIX) can be converted to compounds of formula (XX), wherein R 5 , R 6 , B 1 , B 2 , and R 01 are as previously defined, and X° is halogen, by halogenation with for example POX°3, e.g. phosphoryl chloride or phosphoryl bromide, under conditions know to those skilled in the art and described for example in Bio. Med. Chem. Lett. 2010, 20(3), 954-957, and J. Med. Chem. 2006, 49(21 ), 6351 -6363.
  • Compounds of formula (XX) can then be reacted with compounds of formula (X) using the Suzuki-Miyaura reaction conditions described in scheme 6, to give compounds of formula (lid).
  • compounds of formula (XX) can be treated with organic zinc compounds of formula (XXI), readily obtained by zincation of compounds of formula (VIII), in the presence of nickel or palladium catalysts to give compounds of formula (lid).
  • organo zinc coupling reactions (Negishi reactions) are well known to those skilled in the art and conditions using Ni and Pd catalysts have been reported (see: “Recent developments in the chemistry of Negishi coupling: a review” Chem. Pap. 2024, pp 1 -32, https://doi.Org/10.1007/s1 1696-024-03369-7 and references cited therein).
  • Yet another coupling, namely C-H activation of compounds of formula (XII) with compounds of formula (XX) using conditions described vide infra (scheme 7) also leads to compounds of formula (lid).
  • the compounds of formula (I) 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 compounds of formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • the compounds of formula (I) according to the invention can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the 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 can be used for protecting numerous cultivated plants.
  • the compounds of formula (I) can be used to inhibit or destroy the pests 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 also protecting those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
  • the present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of formula (I) according to the invention is applied to the plants, to parts thereof or the locus thereof.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount where used 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) may also be possible to use compounds of formula (I) according to the invention as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown.
  • the active compounds of formula (I) 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) according to the 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.
  • the compounds of formula (I) according to the invention are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
  • These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example: Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. including A. f/avus, A. fumigatus, A. nidulans, A. niger, A. terras, Aureobasidium spp. including A.
  • Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. including 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.
  • arachidicola Cercosporidium personatum, Cladosporium spp., Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., Colletotrichum spp. including C. musae, Corynespora spp. including Corynespora cassiicola, Cryptococcus neoformans, Diaporthe spp.
  • Diaporthe miriciae also known as Diaporthe ueckeri or Diaporthe ueckerae
  • Didymella spp. Drechslera spp.
  • Elsinoe spp. Epidermophyton spp.
  • Erwinia amylovora Erysiphe spp. including E. cichoracearum
  • Eutypa lata Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F.
  • 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.
  • the compounds of formula (I) according to the invention may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees, or evergreens, for example conifers, as well as for tree injection, pest management and the like.
  • 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
  • useful plants is to be understood as also including 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
  • ALS inhibitors for example primisulfuron, prosulfuron and trifloxysulfuron
  • EPSPS (5-enol-pyrovyl-shikimate-3- phosphate-synthase) inhibitors
  • GS glutamine synthetase
  • PPO pro
  • 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®.
  • useful plants is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricin N- acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety
  • crops is to be understood as including also crop plants which have been so transformed using recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as deltaendotoxins, e.g., Cryl Ab, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp.
  • deltaendotoxins e.g., Cryl Ab, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C
  • Vip vegetative insecticidal proteins
  • Vip1 , Vip2, Vip3 or Vip3A or
  • 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
  • ribosomeinactivating 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, ecdy
  • delta-endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins, and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, W002/15701 ).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements 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 W02003/018810).
  • Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-0374753, WO93/07278, WO95/34656, EP0427529, EP0451878 and WG03/052073.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • 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 CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in W02003/018810.
  • 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.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B 1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x 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 CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • the compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi, especially phytopathogenic fungi on soybean plants.
  • phytopathogenic diseases especially phytopathogenic fungi, especially phytopathogenic fungi on soybean plants.
  • soybean plants are genetically modified soybean plants.
  • the genetically modified plants are soybean plants.
  • Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), lntacta®2 XtendTM, Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Roundup ReadyTM 2 XtendTM, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, PlenishTM.
  • Transgenic soybean plants expressing toxins for example insecticidal proteins such as delta-endotoxins, e.g., CrylAc (Cryl Ac Bt protein). Accordingly, this may include transgenic soybean plants comprising event MON87701 (disclosed in W02009/064652), event MON87701 x MON89788 (disclosed in WO2014/170327, e.g.
  • event MON87751 (disclosed in WO2014/201235)
  • event DAS-44406-6 e.g., commercially available as Enlist E3TM, DAS- 44406-6, disclosed in WO2012/075426
  • event DAS-81419-2 (described in WO2013/016527, e.g., commercially available as ConkestaTM soybean); event DAS-81419-2 x DAS-44406-6 (e.g., commercially available as ConkestaTM Enlist E3TM Soybean).
  • transgenic events are provided by the United States Department of Agriculture's (USDA) Animal and Plant Health Inspection Service (APHIS) and can be found on their website on the World Wide Web at aphis.usda.gov.
  • USDA United States Department of Agriculture's
  • APIS Animal and Plant Health Inspection Service
  • the compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi such as Alternaria spp. in fruits, vegetables and potatoes; Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes; Rhizoctonia solani in potatoes and vegetables; Uncinula necator in grapes; Cladosporium cucumerinum, Didymella bryoniae, Sphaerotheca fuliginea and Glomerella lagenarium in cucurbits; Leveillula taurica in cucurbits and solanaceous crops; Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymoseptoria spp. in cereals.
  • phytopathogenic diseases especially phytopathogenic fungi such as Alternaria spp. in fruits, vegetables and potatoes; Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes; Rhizoctonia solani in potatoes
  • the compounds of formula (I) and compositions comprising said compounds are suitable for controlling the following fungal diseases on soybeans and genetically modified soybeans, for example Bt soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (leaf spots), e.g. C. sojina or C. kikuchii; Colletotrichum spp. (teleomorph: Glomerella) (anthracnose), e.g. C. truncation or C.
  • Diaporthe spp. e.g. Diaporthe miriciae (also known as Diaporthe ueckeri or Diaporthe ueckerae) (damping off); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot), e.g. F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans; Macrophomina phaseolina (syn.
  • phaseoli root and stem rot
  • Microsphaera diffusa prowdery mildew
  • Peronospora spp. downy mildew
  • Phialophora spp. e.g. P. gregata (brown stem rot)
  • Phialophora spp. e.g. P. gregata (brown stem rot)
  • Phomopsis spp. e.g. P. phaseoli (teleomorph: Diaporthe phaseolorum); Pythium spp. (damping-off); Phytophthora spp. (wilt, root, leaf, fruit and stem root), e.g. P.
  • megasperma (syn. P. sojae); Rhizoctonia spp., e.g. R. solan! (root and stem rot); Sclerotinia spp. (stem rot or white mold); Septoria spp., e.g. S. glycines (brown spot); S. rolfsii (syn. Athelia rolfsii); Thielaviopsis spp. (black root rot).
  • locus 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.
  • vegetative material such as cuttings or tubers, for example potatoes.
  • seeds in the strict sense
  • roots in the strict sense
  • fruits in the tubers
  • bulbs rhizomes
  • parts of plants may also be mentioned.
  • 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 can be protected before transplantation by a total or partial treatment by immersion.
  • plant propagation material is understood to denote seeds.
  • the compounds of formula (I) according to the 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. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating, or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The 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 adjuvants 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.
  • Such carriers are for example described in WO1997/33890.
  • 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. In use, 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 sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate 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
  • 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.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions 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.
  • Pressurized sprayers wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, may also be used.
  • Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to a person skilled in the art.
  • 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, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenz
  • 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. They can be anionic, cationic, non-ionic, or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
  • Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; 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.
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming 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.
  • biocidal 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. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • Pesticidal agents are referred to herein using their common name are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.
  • 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) according to the invention are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • 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) according to the 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) or of at least one preferred individual compound as defined herein, in free form or in agrochemical 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) according to the 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.
  • said composition may comprise at least one or more pesticidal-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I).
  • the compound of formula (I) according to the invention may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide, or plant growth regulator where appropriate.
  • An additional active ingredient may, in some cases, result in unexpected synergistic activities.
  • Suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fung
  • lecontei NPV niclosamide-olamine
  • nicotine nicotine sulfate, nikkomycins, nitenpyram, nithiazine, nitrapyrin, nitrilacarb, nitrothal-isopropyl, norbormide, nornicotine, novaluron, noviflumuron, nuarimol, 0,0, O', O' -tetrapropyl dithiopyrophosphate, octadeca-2,13-dien-1 -yl acetate, octadeca-2,13-dien-1 -yl acetate, octhilinone, ofurace, oleic acid, omethoate, orfralure, Orius spp., orysastrobin, osthol, ostramone, oxadixyl, oxamate, oxamyl, oxantel pamoate, oxa
  • the active ingredient mixture of the compound selected from compounds of formula (I), (l-A), (I-A1 ), (I- A2), or (I-A3), or compounds selected from compounds listed in Tables B-1 to B-32, or compounds listed in Table P (below), is preferably in a mixing ratio of from 100:1 to 1 :100, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, and still more especially from 5:1 to 1 :5 Those mixing ratios are by weight.
  • the mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound selected from compounds of formula (I), (l-A), (I-A1 ), (I-A2), or (I- A3), or compounds selected from compounds listed in Tables B-1 to B-32, or compounds listed in Table P (below), and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides, or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematoc
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • Another aspect of the invention is related to the use of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein, of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, or of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g., seeds, harvested crops, e.g., harvested food crops, or non-living materials by insects, or by phytopathogenic microorganisms, preferably fungal organisms.
  • useful plants such as crop plants, propagation material thereof, e.g., seeds, harvested crops, e.g., harvested food crops, or non-living materials by insects, or by phytopathogenic microorganisms, preferably fungal organisms.
  • 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., harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
  • useful plants such as crop plants, propagation material thereof, e.g., seeds, harvested crops, e.g., harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms
  • a compound of formula (I) according to the invention or of a preferred individual compound as defined herein as active ingredient to the plants
  • 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, or insects which comprises the application of a compound of formula (I) according to the invention, or an agrochemical composition which contains at least one compound of formula (I), 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) according to the 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).
  • Such granulates can be applied to the flooded rice field.
  • the compounds of formula (I) 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) according to the invention and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I), 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).
  • extenders for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to I kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient dosages are from 10mg to 1g of active substance per kg of seeds.
  • g a.i./ha refers to the application rate given in gram [g] of active ingredient [a.i.] per unit of surface [ha].
  • the unit hectare symbol ha is the metric unit of area that equals a square with 100 m side (1 hm 2 ) or 10,000 square meters. Hectare is a commonly used unit of area in the metric system.
  • rates of 0.001 to 50 g of a compound of formula (I) per kg of seed preferably from 0.01 to 10g per kg of seed are generally sufficient.
  • composition comprising a compound of formula (I) 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 (EG), 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). Also, 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., the condensation product of formaldehyde with naphthalene sulfonate, an alkyl aryl sulfonate, a lignin sulfonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.
  • surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g., the condensation product of formaldehyde with naphthalene sulfonate, an alkyl aryl sulfonate, a lignin sulfonate
  • 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., as slow-release capsules or microcapsules.
  • 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) according to the invention optionally together with other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 to 80%, preferably between about 5 to 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. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %)
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • Table A This table discloses X substituent definitions Z 1 of compounds of the formula (la) according to the invention: wherein Z 1 according to compounds of Formula (I) of the invention is are as defined below:
  • Table B-2 This table provides 34 compounds (B-2.01 ) to (B-2.34) of formula (la), wherein R 4 , R 5 , and R 6 are H; R 2 is OCH3, B 1 , B 2 are CH, B 3 is N, and Z 1 substituents are as defined in Table A.
  • compound (B-2.09) has the following structure:
  • Table B-3 This table provides 34 compounds (B-3.01 ) to (B-3.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is CH, B 2 is C-CN, B 3 is N, and Z 1 substituents are as defined in Table A.
  • compound (B-3.13) has the following structure: compound B-3.13
  • Table B-4 This table provides 34 compounds (B-4.01 ) to (B-4.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is CH, B 2 is C-CH3, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-5 This table provides 34 compounds (B-5.01 ) to (B-5.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 , is OCH3, B 1 is CH, B 2 is C-F, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-6 This table provides 34 compounds (B-6.01 ) to (B-6.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is CH, B 2 is C-CI, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-7 This table provides 34 compounds (B-7.01 ) to (B-7.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is CH, B 2 is C-Br, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-8 This table provides 34 compounds (B-8.01 ) to (B-8.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is CH, B 2 is C-OCH3, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-9 This table provides 34 compounds (B-9.01 ) to (B-9.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is CH, B 2 is C-SCH3, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-10 This table provides 34 compounds (B-10.01 ) to (B-10.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is CH, B 2 is C-CO2CH3, B 3 is N, and Z 1 substituents are as defined in Table A.
  • compound (B-10.30) has the following structure: compound B-10.30
  • Table B-1 1 This table provides 34 compounds (B-1 1 .01 ) to (B-1 1 .34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is CH, B 2 is C-OH, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-12 This table provides 34 compounds (B-12.01 to (B-12.34) of formula (la), wherein R 4 , R 5 , and
  • R 6 are H, R 2 is OCH3, B 1 is C-OCH3, B 2 is C-CN, B 3 is N, and Z 1 substituents are as defined in Table A.
  • compound (B-12.32) has the following structure: compound B-12.32
  • Table B-13 This table provides 34 compounds (B-13.01 ) to (B-13.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is C-OCH3, B 2 is C-CH3, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-14 This table provides 34 compounds (B-14.01 to (B-14.34) of formula (la), wherein R 4 , R 5 , and
  • R 6 are H, R 2 is OCH3, B 1 is C-OCH3, B 2 is C-Br, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-15 This table provides 34 compounds (B-15.01 to (B-15.34) of formula (la), wherein R 4 , R 5 , and
  • R 6 are H, R 2 is OCH3, B 1 is C-OCH3, B 2 is C-CI, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-16 This table provides 34 compounds (B-16.01 ) to (B-16.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is C-OCH3, B 2 is C-CO2CH3, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-17 This table provides 34 compounds (B-17.01 to (B-17.34) of formula (la), wherein R 4 , R 5 , and
  • R 6 are H, R 2 is OCH3, B 1 and B 2 are C-CN, B 3 is N, and Z 1 substituents are as defined in Table A.
  • compound (B-17.01 ) has the following structure: compound B-17.01
  • Table B-18 This table provides 34 compounds (B-18.01 ) to (B-18.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is C-CN, B 2 is C-CH3, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-19 This table provides 34 compounds (B-19.01 ) to (B-19.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 ,is OCH3, B 1 is C-CN, B 2 is C-Br, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-20 This table provides 34 compounds (B-20.01 ) to (B-20.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is C-CN, B 2 is C-CI, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-21 This table provides 34 compounds (B-21 .01 ) to (B-21 .34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is OCH3, B 1 is C-CN, B 2 is C-CO2CH3, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-22 This table provides 34 compounds (B-22.01 ) to (B-22.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is SCH3, B 1 , B 2 are CH, B 3 is N, and Z 1 substituents are as defined in Table A.
  • compound (B-22.18) has the following structure: compound B-22.18
  • Table B-23 This table provides 34 compounds (B-23.01 ) to (B-23.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is SCH3, B 1 is CH, B 2 is C-CN, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-24 This table provides 34 compounds (B-24.01 ) to (B-24.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R, is NHCH3, B 1 , B 2 are CH, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-25 This table provides 34 compounds (B-25.01 ) to (B-25.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is NHCH3, B 1 is CH, B 2 is C-CN, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-26 This table provides 34 compounds (B-26.01 ) to (B-26.34) of formula (la), wherein R 4 , R 5 , and R 6 are H, R 2 is CN, B 1 , B 2 are CH, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-27 This table provides 34 compounds (B-27.01 to (B-27.34) of formula (la), wherein R 4 , R 5 , and
  • R 6 are H, R 2 is CN, B 1 is CH, B 2 is C-CN, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-28 This table provides 34 compounds (B-28.01 to (B-28.34) of formula (la), wherein R 4 , R 5 , and
  • R 6 are H, R 2 is OCHF2, B 1 , B 2 are CH, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-29 This table provides 34 compounds (B-27.01 to (B-27.34) of formula (la), wherein R 4 , R 5 , and
  • R 6 are H, R 2 is OCHF2, B 1 is CH, B 2 is C-CN, B 3 is N, and Z 1 substituents are as defined in Table A.
  • R 5 , and R 6 are H, R 2 is OCH3, B 1 , B 2 are CH, B 3 is N, and Z 1 substituents are as defined in Table A.
  • Table B-31 This table provides 34 compounds (B-31 .01 to (B-31 .34) of formula (la), wherein R 4 , R 5 , are
  • R 6 is CH3, R 2 is OCH3, B 1 , B 2 are CH, B 3 is N, and Z 1 substituents are as defined in Table A.
  • compound (B-31 .24) has the following structure:
  • Table B-32 This table provides 34 compounds (B-32.01 ) to (B-32.34) of formula (la), wherein R 4 , R 5 , and R 6 are H; R 2 is OCH3; B 1 is CH; B 2 is C-CO2CH2CH3; B 3 is N; and Z 1 substituents are as defined in Table A.
  • the compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by a person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 60 ppm, 20 ppm or 2 ppm.
  • 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 physicochemical properties, or increased biodegradability).
  • Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) 2 % highly dispersed silicic acid 5 % 10 % 10 %
  • the combination 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 ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % Kaolin 65 % 40 % -
  • the combination 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 ingredients 10 % octylphenol polyethylene glycol ether (4 to 5 mol of ethylene oxide) 3 % calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 %
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • Suspension concentrates active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • the finely ground combination 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 suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • 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 ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a flowable concentrate from which solutions of any desired dilution can be obtained by dilution with water, that can be used directly for seed treatment.
  • solutions of any desired dilution can be obtained by dilution with water, that can be used directly for seed treatment.
  • dilutions living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Slow Release
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • 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.
  • Formulation types include 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 (EG), 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), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo- emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • DABCO 1 ,4-diazabicyclo[2.2.2]octane also known as triethylenediamine or TEDA
  • the compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.
  • LC/MS Liquid Chromatography Mass Spectroscopy and the description of the apparatus, and the methods is as follows.
  • Step 1 Preparation of 5-ethoxy-1 -methyl-pyrazole
  • Step 2 Preparation of methyl 4-(5-ethoxy-1 -methyl-pyrazol-4-yl)cuinoline-2-carboxylate
  • Step 1 Preparation of dimethyl (Z)-2-(2-cvanoanilino)but-2-enedioate
  • Step 5 Preparation of 5-methoxy-1 -methyl-4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)pyrazole
  • Step 6 Preparation of methyl 8-cvano-4-(5-methoxy-1 -methyl-Dyrazol-4-yl)guinoline-2-carboxylate
  • Step 6 Preparation of 8-cvano-4-(5-methoxy-1 -methyl-pyrazol-4-yl)-A/-pentyl-guinoline-2-carboxamide (compound P-2, Table P)
  • Step 3 Preparation of methyl 4-(5-cvano-1 -methyl-pyrazol-4-yl)auinoline-2-carboxylate
  • step 2 by reaction of methyl 4-bromoquinoline-2-carboxylate (140 mg, 0.53 mmol) and 2-methylpyrazole-3-carbonitrile (84 mg, 0.79 mmol) in the presence of potassium acetate (104 mg, 1 .05 mmol) and palladium(ll)acetate (6.2 mg, 0.026 mmol) in N,N-Dimethylacetamide (1 .4 mL) at 140°C. This gave the title compound after purification.
  • Step 4 Preparation of lithium;4-(5-cyano-1 -methyl-pyrazol-4-yl)quinoline-2-carboxylate 66
  • Step 5 Preparation of 4-(5-cvano-1 -methyl-pyrazol-4-yl)-A/-pentyl-guinoline-2-carboxamide (compound P- 5, Table P)
  • Example B1 Alternaria so/an/7 tomato / (early blight)
  • Tomato leaf disks cv. Baby are placed on 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 2 days after application.
  • the inoculated leaf disks are incubated at 23°C I 21 °C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) 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 on untreated check disk leaf disks (5 to 7 days after application).
  • Example B2 Botryotinia fuckeliana (Botrytis cinerea) / (Gray mould)
  • Example B3 Glomerella lagenarium (Colletotrichum lagenarium) I (Anthracnose)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-5, P-6, P-10, P-11 , P-12
  • Example B4 Fusarium culmorum I (Head blight)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-5, P-6, P-11 , P-12
  • Example B5 Phaeosphaeria nodorum (Septoria nodorum) I wheat I (Glume blotch)
  • Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (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 2 days after application.
  • the inoculated test leaf disks are incubated at 20°C and 75% 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 (5 to 7 days after application).
  • Example B6 Monographella nivalis (Microdochium nivale) I (foot rot cereals)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-5, P-6, P-10, P-11 , P-12 Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth).
  • test compound After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application.
  • the following compounds gave at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-4, P-5, P-6, P-10, P-11 , P-12, P-13, P-14
  • Example B8 Magnaporthe cirisea (Pyricularia oryzae) / (Rice Blast)
  • Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segments are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf segments are incubated at 20°C and 65% 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 disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 to 7 days after application).
  • Example B10 Thanatephorus cucumeris (Rhizoctonia solani) / (foot rot, damping-off)
  • Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO-solution of the test compounds into a microtiter plate (96- well format), the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Thanatephorus cucumeris at 20ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-3, P- 5, P-6, P-10, P-11 , P-12
  • Example B11 Mycosphaerella graminicola (Septaria tritici) / liquid culture (Septaria blotch)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-4, P-5, P-6, P-10, P-11 , P-12, P-13, P-14
  • Example B12 Cercospora soiina (froqeve leaf spot of soybean)
  • Example B14 Blumeria oraminis f. so. tritici (Erysiphe oraminis f. so. tritici) / wheat / (Powdery mildew on wheat)
  • Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application.
  • the inoculated leaf disks are incubated at 20 °C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 to 8 days after application).
  • the following compounds gave at least 80% control of Blumeria graminis f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-10, P-11 , P-12
  • Example B15 Fusarium culmorum / wheat / (Head blight)
  • Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the spikelets are inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated spikelets are incubated at 20 °C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 to 8 days after application).
  • the following compounds gave at least 80% control of Fusarium culmorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-3, P-11 , P-12
  • Example B16 Gibberella zeae (Fusarium araminearum) I wheat I (Head blight)
  • Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the spikelets are inoculated with a spore suspension of the fungus.
  • the inoculated test leaf disks are incubated at 20 °C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber, the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 to 8 days after application).
  • the following compounds gave at least 80% control of Gibberella zeae at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-6, P-12
  • Example B17 Sclerotinia sclerotiorum / liquid culture (cottony rot)
  • Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-11 , P-12

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Abstract

A compound of formula (I), wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, or N-oxides of those compounds, which can be used as fungicides.

Description

MICROBIOCIDAL PYRAZOLE COMPOUNDS
The present invention relates to microbiocidal pyrazole derivatives, e.g. as active ingredients, which have microbiocidal activity, in particular fungicidal activity. The invention also relates to preparation of these pyrazole derivatives, to intermediates useful in the preparation of these pyrazole derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of the pyrazole derivatives, to preparation of these compositions and to the use of the pyrazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.
According to a first aspect of the present invention, there is provided a compound of formula (I): wherein
R1 is selected from hydrogen, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or Cs-Ce-cycloalkyl;
R2 is selected from cyano, hydroxy, amino, Ci-C4-alkoxy, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, C1-C4- haloalkoxy, Ci-C4-haloalkylsulfanyl, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Cs-Ce-cycloalkyloxy, C1-C4- alkoxy-Ci-C4-alkyl, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, or Ci-C4-alkylsulfonyl;
R3 is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl;
R4 is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, or Cs-Ce-cycloalkyl;
B1 is selected from CR7, or N;
B2 is selected from CR8, or N;
B3 is selected from CR9, or N;
R5, R6, R7, R8 and R9 are independently selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, C3-C6- alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4- alkylcarbonyl, Ci-C4-alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, C1-C4- alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci ^-alkylcarbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6- membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, C1-C4- haloalkyl, or Ci-C4-alkoxy, and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy; and
Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from cyano, nitro, carboxy, hydroxy, Ci-C4-alkyl, C2-C4-alkenyl, C2- C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, C3-C6- haloalkenyloxy, Cs-Ce-cycloalkyloxy, C3-C6-cycloalkyl-Ci-C4-alkoxy, C3-C6-halocycloalkyl-Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, Cs-Ce-cycloalkyloxycarbonyl, C3-C6-cycloalkyl-Ci-C4-alkyloxycarbonyl, C3-C6- halocycloalkyl-Ci-C4-alkyloxycarbonyl, Ci-C4-haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, C3-C6- cycloalkycarbonyloxy, N-Ci-C4-alkoxy-C-Ci-C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci ^-alkylcarbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said 4-, 5- or 6-membered saturated, partially saturated or aromatic heterocycle contains 1 , 2 or 3 heteroatoms selected from O, S or N, with the proviso that no more than one is O or S, wherein any of said phenyl and said 5- to 6-membered saturated, partially saturated or aromatic heterocycle, are unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy, and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy; or an agrochemically acceptable salt, or N-oxide thereof.
Surprisingly, it has been found that the compounds of formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
According to a second aspect of the invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to the invention. Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
According to a third aspect of the invention, there is provided a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to the invention, or a composition comprising the compound of formula (I), is applied to the plants, to parts thereof or the locus thereof.
According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) according to the invention as a fungicide. According to this particular aspect of the invention, the use may exclude methods for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.
The compounds of formula (I) or the intermediate compounds of formula (III) according to the invention, 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, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C4-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, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci- C4-alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid.
The compounds of formula (I) or the intermediate compounds of formula (III) according to the invention, 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.
The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also, atropisomers may occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I) according to the invention. Likewise, a compound of formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present. The present invention includes all possible tautomeric forms for a compound of formula (I) according to the invention.
In each case, 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. N-oxides can be prepared by reacting a compound of formula (I) with a suitable oxidizing agent, for example the HzOz/urea adduct, in the presence of an acid anhydride, e.g., trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem. 1989, 32 (12), 2561 -73, or W02000/15615. The compounds of formula (I) according to the invention also include hydrates, which may be formed during salt formation.
As used herein, the term "halogen" or “halo” refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine, or bromine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.
As used herein, amino means a -NHz group. As used herein, cyano means a -CN group.
As used herein, the term “hydroxyl” or “hydroxy” means an -OH group.
As used herein, the term “carboxylic acid” means a -COOH group.
As used herein, the term "Ci-Cn-alkyl” refers to a saturated straight- or branched hydrocarbon chain having 1 to n carbon atoms. Examples include but are not limited to methyl, ethyl, n-propyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, n-pentyl, 1 ,1 -dimethylpropyl, 1 ,2- dimethylpropyl.
As used herein, the term “Cz-Cn-alkenyl” refers to an unsaturated straight or branched hydrocarbon chain having from two to n carbon atoms and comprising at least one double bond that can be of either the (Z) or (E) configuration. Examples include but are not limited to ethenyl (or vinyl), prop-1 -enyl, prop-2-enyl (or allyl), prop-1 -en-2-yl (or isopropenyl), or but-2-enyl. Analogously, the term “Cs-Cn-alkenyl” as used herein refers to an unsaturated straight or branched hydrocarbon chain having from three to n carbon atoms.
As used herein, the term “Cz-Cn-alkynyl” refers to a straight or branched hydrocarbon chain having from two to n carbon atoms and comprising at least one triple bond. Examples include but are not limited to ethynyl, prop-2-ynyl (or propargyl), or but-3-ynyl. Analogously, the term “Cs-Cn-alkynyl” as used herein refers to an unsaturated straight or branched hydrocarbon chain having from three to n carbon atoms.
As used herein, the term “Cs-Cn-cycloalkyl” refers to a saturated, monovalent, monocylic hydrocarbon ring which contains 3 to n carbon atoms. Examples include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
As used herein, the term "Ci-Cn-haloalkyl" refers to a "Ci-Cn-alkyl” as defined herein, in which one or more hydrogen atoms may be replaced with one or more halogen atoms that may be the same or different. Examples include but are not limited to chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2- trichloroethyl. Similarly, the term “Ci-Cn-haloalkoxy” as used herein refers to an Ci-Cn-alkoxyl group as defined herein substituted with one or more halogen atoms which may be the same or different.
Similarly, the term “Cz-Cn-haloalkenyl” as used herein refers to a Cz-Cn-alkenyl radical respectively substituted with one or more halogen atoms which may be the same or different. Similarly, the term “C3- Cn-halocycloalkyl” or “Ci-Cn-haloalkoxy” as used herein refers to a Cs-Cn-cycloalkyl radical or Ci-Cn- alkoxyl radical respectively substituted with one or more halogen atoms which may be the same or different. As used herein, the term “cyano-Ci-Cn-alkyl” refers to Ci-Cn-alkyl as defined herein, in which at least one hydrogen atom is replaced with a cyano group, for example, cyano-methyl, 2-cyano-ethyl, 2-cyano- propyl, 3-cyano-propyl, 1 -(cyano-methyl)-2-ethyl, 1 -(methyl)-2-cyano-ethyl, 4-cyanobutyl.
As used herein, the term "Ci-Cn-alkoxy" refers to groups of the formula -O-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein. Examples include but are not limited to methoxy, ethoxy, n-propoxy, 1 - methylethoxy, n-butoxy, 1 -methylpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
As used herein, the term “Cs-Ce-cycloalkyloxy” refers to groups of the formula -O-(C3-Cn-cycloalkyl), in which the term “Cs-Cn-cycloalkyl” is as defined herein.As used herein, the term “Cs-Cn-alkenyloxy” refers to groups of the formula -O-(C3-Cn-alkenyl), in which the term “Cs-Cn-alkenyl” is as defined herein.
As used herein, the term "Cs-Cn-alkynyloxy" refers to groups of the formula -O-(C3-Cn-alkynyl), in which the term “Cs-Cn-alkynyl” is as defined herein.
As used herein, the term “Ci-Cn-alkoxy-Ci-Cn-alkyl” refers to a group of the formula -(Ci-Cn-alkyl)-O-(Ci- Cn-alkyl), in which the term Ci-Cn-alkyl is as defined herein. Examples include, but are not limited to methoxymethyl, methoxyethyl, ethoxymethyl or propoxymethyl. This term can be used interchangeably with the term “Ci-Cn-alkyl-Ci-Cn-alkoxy” which refers to a radical of the formula -Ra-ORt>, where Ra is a “Ci-Cn-alkyl” group as defined above, and Rb refers to an “Ci-Cn-alkyl” group as defined above.
As used herein, the term “Ci-Cn-alkoxy-Ci-Cn-alkoxy” refers to a group of the formula -O-(Ci-Cn-alkyl)-O- (Ci-Cn-alkyl), in which the term Ci-Cn-alkyl is as defined herein.
As used herein, the term “Ci-Cn-alkyl-Ci-Cn-alkoxy-Ci-Cn-alkoxy” refers to a radical of the formula -Ra- ORb-ORc, where Ra is a “Ci-Cn-alkyl” group as defined herein, and Rb and Rc refer to an “Ci-Cn-alkyl” group as defined herein.
As used herein, the term “Ci-Cn-alkylthio“ or “Ci-Cn-alkylsulfanyl“ refers to a group of the formula -S-(Ci- Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein, and wherein the group is linked through the sulfur atom.
As used herein, the term “Ci-Cn-alkylsulfinyl“ refers to a group of the formula -S(=O)-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein, and wherein the group is linked through the sulfur atom.
As used herein, the term “Ci-Cn-alkylsulfonyl“ refers to a a group of the formula -S(=O)2-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein, and wherein the group is linked through the sulfur atom.
As used herein, the term “Cs-Cn-cycloalkyl-Ci-Cn-alkyl” refer a “Ci-Cn-alkyl” as defined herein, wherein one hydrogen atom is replaced with a “Cs-Cn-cycloalkyl” group as defined herein. Examples include but are not limited to cyclopropylmethyl, cyclopropylethyl. Similarly, the term “Cs-Cn-halocycloalkyl-Ci-Cn- alkyl” refers to “Ci-Cn-alkyl” as defined herein, wherein one hydrogen atom is replaced with a “Cs-Cn- cycloalkyl” group as defined herein, wherein the “Cs-Cn-cycloalkyl” group is substituted by one or more of the same or different halogen atoms. Examples are 3,3-difluorobutylmethyl and 1 - chlorocyclopropylmethyl.
As used herein, the term “Cs-Cn-cycloalkyl-Ci-Cn-alkoxy” refer a “Ci-Cn-alkoxy” group as defined herein, wherein one hydrogen atom is replaced with a “Cs-Cn-cycloalkyl” group as defined herein.
As used herein, the term “Ci-Cn-alkylsulfonyl-Ci-Cn-alkyl” refer a “Ci-Cn-alkyl” as defined herein, wherein one hydrogen atom is replaced with a “Ci-Cn-alkylsulfonyl” group as defined herein.
As used herein, the term “Ci-Cn-alkylcarbonyl” refers to a group of the formula -C(=O)-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein.
As used herein, the term “Cs-Cn-cycloalkylcarbonyl” refers to a group of the formula -C(=O)-(C3-Cn- cycloalkyl), in which the term “Cs-Cn-cycloalkyl” is as defined herein.
As used herein, the term “Cs-Cn-cycloalkyloxycarbonyl” refers to a group of the formula -C(=O)-(O-C3-Cn- cycloalkyl), in which the term “Cs-Cn-cycloalkyl” is as defined herein.
As used herein, the term “Ci-Cn-alkylcarbonyloxy” refers to a group of the formula -O-C(=O)-(Ci-Cn-alkyl), in which the term Ci-Cn-alkyl is as defined herein.
As used herein, the term “Ci-Cn-alkoxycarbonyl” refers to a group of the formula -C(=O)-O-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein.
As used herein, the term “Ci-Cn-alkoxycarbonyl-Ci-C4-alkyl” refers to a group of the formula -(Ci-Cn- alkyl)-C(=O)-O-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein.
As used herein, the term “Ci-Cn-haloalkoxycarbonyl” refers to a “Ci-Cn-alkoxycarbonyl” group as defined herein, in which one or more hydrogen atoms may be replaced with one or more halogen atoms that may be the same or different.
As used herein, the term “Cz-Cn-alkenyloxycarbonyl” refers to a group of the formula -C(=O)-O-(C2-Cn- alkenyl), in which the term “Cz-Cn-alkenyl” is as defined herein. Analogously, the term “Cs-Cn- alkenyloxycarbonyl” as used herein to a group of the formula -C(=O)-O-(C3-Cn-alkenyl), in which the term “Cs-Cn-alkenyl” is as defined herein.
As used herein, the term “Ci-Cn-alkylcarbonyloxy-Ci-Cn-alkyl” refers to a group of the formula -(Ci-Cn- alkyl)-C-O-C(=O)-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein.
As used herein, the term “N-Ci-Cn-alkylamino” refers to a group of the formula -NH-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein.
As used herein, the term "N,N-di(Ci-Cn-alkyl)amino" refers to a group of the formula -N-(Ci-Cn-alkyl)2, in which each term “Ci-Cn-alkyl”, which may be the same or different, is as defined herein.
As used herein, the term “Ci-Cn-alkylaminocarbonyl” refers to a group of the formula -C(=O)-NH-(Ci-Cn- alkyl), in which the term “Ci-Cn-alkyl” is as defined herein. As used herein, the term “aminocarbonyl-Ci-Cn-alkyl” refers to a group of the formula -(Ci-Cn-alkyl)- C(=O)-NH2, in which the term “Ci-Cn-alkyl” is as defined herein.
As used herein, the term “Ci-Cn-alkylaminocarbonyl-Ci-Cn-alkyl” refers to a group of the formula -(Ci-Cn- alkyl)-C(=O)-NH-(Ci-Cn-alkyl), in which the term “Ci-Cn-alkyl” is as defined herein.
As used herein, the term “carbamoyl” refers to a group of the formula -C(=O)-NH2.
As used herein, the term “N-Ci-Cn-alkoxy-C-Ci-Cn-alkyl-carbonimidoyl” refers to a group of the formula - C(Ra)=NO(Rb), wherein Ra is a “Ci-Cn-alkyl” group as defined herein, and Rb is a “Ci-Cn-alkyl” group as defined herein.
As used herein the term “N-hydroxy-C-Ci-Cn-alkyl-carbonimidoyl” refers to a group of the formula - C(Ra)=NOH, wherein Ra is a “Ci-Cn-alkyl” group as defined herein.
As used herein the term "4-, 5-, or 6-membered heterocycle” refers to a 4-, 5-, or 6-membered monocyclic ring-system containing 1 , 2 or 3 heteroatoms independently selected from oxygen (O), nitrogen (N) and sulfur (S), where the ring system is saturated or unsaturated, but not aromatic. Unless stated otherwise, the "4-, 5-, or 6-membered heterocycle” can be connected to the rest of the molecule through any carbon atom or nitrogen atom contained in the heterocycle. Examples of saturated 3- to 6-membered heterocyclyl groups include but are not limited to 4-membered rings such as azetidinyl, oxetanyl, thietanyl, 5-membered rings such as tetrahydrofuranyl, 1 ,3-dioxolanyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, and 6-membered rings such as piperidinyl, piperazinyl, and morpholinyl. Examples of unsaturated 4- to 6-membered heterocycles include but are not limited to 5-membered rings such as dihydrofuranyl, 1 ,3-dioxolyl, pyrrolinyl, and 6-membered rings such as pyranyl, and thiopyranyl.
As used herein the term “5- or 6-membered heteroaryl” refers to a 5- or 6-membered monocyclic, aromatic ring system containing 1 , 2, or 3 heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulfur. In the 6-membered heteroaryl rings the heteroatom ring members can only be nitrogen atoms. Examples of 5-membered heteroaryl include but are not limited to furyl (furanyl), thienyl, pyrrolyl, pyrazolyl, imidazolyl, isooxazolyl. Examples of 6-membered heteroaryl include but are not limited to pyridyl (or pyridinyl), pyridazinyl, pyrimidinyl.
Unless defined otherwise, the definitions for collective terms also apply to these collective terms in composite moieties. For example, the terms “Ci-Cn-alkoxycarbonyl-Ci-Cn-alkyl”, “Ci-Cn-alkylcarbonyloxy- Ci-Cn-alkyl”, “Ci-Cn-alkylcarbonylamino-Ci-Cn-alkyl”, “N,N-di(Ci-Cn-alkyl)amino-Ci-Cn-alkyl” and “N-(Ci- Cn-alkyl)amino-Ci-Cn-alkyl” as used herein refer a “Ci-Cn-alkyl” as defined herein, wherein one hydrogen atom is replaced with a Ci-Cn-alkoxycarbonyl, Ci-Cn-alkylcarbonyloxy, Ci-Cn-alkylcarbonylamino, N,N- di(Ci-Cn-alkyl)amino or N-(Ci-C4-alkyl)amino group as defined herein respectively. As used herein the expression “one, two, or (n) substituents” refers to a number of substituents that ranges from one to (n) number of substituents possible based on the number of available bonding sites, provided that the conditions of stability and chemical feasibility are met.
As used herein, the term "controlling" refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced.
As used herein, the term "pest" refers to insects, and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain, and timber); and those pests associated with the damage of man-made structures. The term pest encompasses all stages in the life cycle of the pest.
As used herein, the term "effective amount" refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.
An effective amount is readily determined by the skilled person in the art, using known techniques and by observing results obtained under analogous circumstances. In determining the effective amount, a number of factors are considered including, but not limited to the type of plant or derived product to be applied; the pest to be controlled and its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.
As used herein, the term “room temperature” or “RT” or “rt” or “ambient temperature” refer to a temperature of about 15°C to about 35°C. For example, rt can refer to a temperature of about 20°C to about 30°C.
The following list provides definitions, including preferred definitions, for substituents R1, R2, R3, R4, R5, R5, R6, B1, B2, B3, and Z1 with reference to the compounds of formula (I) of the present invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.
In one embodiment of the invention, R1 is selected from hydrogen, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, or Cs-Ce-cycloalkyl. Preferably R1 is selected from Ci-Cs-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or cyclopropyl. In another embodiment of the invention, R1 is Ci-C4-alkyl. Preferably R1 is Ci-Cs-alkyl. More preferably R1 is methyl, ethyl, or isopropyl. Even more preferably R1 is methyl.
In one embodiment of the invention, R2 is selected from cyano, hydroxy, amino, Ci-C4-alkoxy, C1-C4- alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-haloalkoxy, Ci-C4-haloalkylsulfanyl, Cs-Ce-alkenyloxy, C3-C6- alkynyloxy, Cs-Ce-cycloalkyloxy, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, or C1- C4-alkylsulfonyl. Preferably R2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2- alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, C1-C2- haloalkoxy, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or C1- C2-alkylsulfonyl. In another embodiment of the invention, R2 is selected from cyano, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C3- Ce-cycloalkyloxy, or Ci-C4-alkoxy-Ci-C2-alkyl. Preferably R2 is cyano, Ci-Cs-alkoxy, Ci-Cz-haloalkoxy, C3- Ce-cycloalkyloxy, or Ci-C2-alkoxy-Ci-C2-alkyl. More preferably R2 is cyano, methoxy, difluoromethoxy, or methoxymethyl.
In another embodiment of the invention, R2 is cyano, Ci-Cs-alkoxy, or Ci-C2-alkylsulfanyl. Preferably R2 is cyano, methoxy, or methylsulfanyl.
In one embodiment of the invention, R3 is selected from hydrogen, halogen, Ci-C4-alkyl, or C1-C4- haloalkyl. Preferably R3 is hydrogen, halogen, Ci-Cs-alkyl, or Ci-C2-haloalkyl. In another embodiment R3 is selected from hydrogen, halogen, or Ci-Cs-alkyl. Preferably R3 is hydrogen, fluorine, chlorine, or methyl. More preferably R3 is hydrogen or methyl. Even more preferably R3 is hydrogen. In another embodiment, R3 is hydrogen or Ci-Cs-alkyl.
In one embodiment of the invention, R4 is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, or Cs-Ce-cycloalkyl. Preferably R4 is hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-haloalkyl, or cyclopropyl. More preferably R4 is hydrogen, chlorine, bromine, fluorine, methyl, ethyl, trifluoromethyl, difluoromethyl, or cyclopropyl. In another embodiment of the invention, R4 is selected from hydrogen, halogen, or C1-C4- alkyl. Preferably R4 is hydrogen, halogen, or Ci-Cs-alkyl. More preferably R4 is hydrogen, chlorine, bromine, or methyl. Most preferably R4 is hydrogen.
In one embodiment of the invention, R5, R6, R7, R8 and R9 are independently selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C1-C4- alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, C1-C4- dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy- C-Ci-C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, C1- C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy, and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, C1-C4- haloalkyl, or Ci-C4-alkoxy.
In one embodiment of the invention, R5 and R6 are independently selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce- alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci- C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, C1- C4-alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci ^-alkylcarbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6- membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, C1-C4- haloalkyl, or Ci-C4-alkoxy, and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy.
In one embodiment R5 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci-C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4- alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy, and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy.
Preferably R5 is hydrogen, halogen, Ci-C4-alkyl, or cyano. More preferably R5 is hydrogen, fluorine, chlorine, bromine, methyl, or cyano. Even more preferably R5 is hydrogen, fluorine, methyl, or cyano. Still more preferably R5 is hydrogen or cyano. Most preferably R5 is hydrogen.
In one embodiment R6 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci-C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4- alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy, and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy. Preferably R6 is hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4- alkoxycarbonyl, Ci-C4-alkylcarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, C1-C4- haloalkyl, or Ci-C4-alkoxy. More preferably R6 is hydrogen, chlorine, bromine, fluorine, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2,2-trifluoroethoxy, 2,2-difluoroethoxy, methoxy, ethoxy, methoxymethoxy, 2-methoxyethoxy, methoxycarbonyl, hydroxy, cyano, cyclopropyl, cyanocyclopropyl, or methylcyclopropyl. Even more preferably R6 is hydrogen, chlorine, bromine, fluorine, methyl, difluoromethyl, difluoromethoxy, 2,2,2-trifluoroethoxy, 2,2-difluoroethoxy, methoxy, 2- methoxyethoxy, methoxycarbonyl, hydroxy, cyano, or cyclopropyl. Still more preferably R6 is hydrogen, chlorine, bromine, fluorine, methyl, cyano, or cyclopropyl. Still even more preferably R6 is hydrogen, cyano, or cyclopropyl. Still even more preferably R6 is hydrogen or cyano. Most preferably R6 is hydrogen.
In another embodiment of the invention, R6 is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci- C4-haloalkyl, Ci-C4-haloalkoxy, or Ci-C4-alkoxy. Preferably R6 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cz-haloalkyl, Ci-Cz-haloalkoxy, or Ci-Cs-alkoxy. More preferably R6 is hydrogen, or Ci-Cs-alkyl.
In one embodiment of the invention, B1 is selected from CR7, or N. In another embodiment B1 is CR7. In another embodiment B1 is N. Preferably B1 is CR7.
In one embodiment of the invention, B2 is selected from CR8, or N. In another embodiment B2 is CR8. In another embodiment B2 is N. Preferably B2 is CR8.
In one embodiment of the invention, R7, R8 and R9 are independently selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce- alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci- C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, C1- C4-alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci ^-alkylcarbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6- membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, C1-C4- haloalkyl, or Ci-C4-alkoxy, and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy.
In one embodiment R7 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci-C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4- alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy, and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy. Preferably R7 is hydrogen, halogen, hydroxy, cyano, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy Ci-Cs-haloalkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-alkylcarbonyl, or Cs-Ce-cycloalkyl; wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C3- alkyl, Ci-Cz-haloalkyl, or Ci-Cs-alkoxy. More preferably R7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci- Cs-haloalkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkoxycarbonyl, C1-C3- alkylcarbonyl, or Cs-Ce-cycloalkyl; wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, or Ci-Cs-alkyl. Still more preferably R7 is hydrogen, chlorine, bromine, fluorine, cyano, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2,2- trifluoroethoxy, 2,2-difluoroethoxy, methoxy, ethoxy, methoxymethyl, 2-methoxyethyl, methoxycarbonyl, ethoxycarbonyl, cyclopropyl, cyanocyclopropyl, or methylcyclopropyl.
In another embodiment of the invention, R7 is hydrogen, halogen, cyano, Ci -Cs-alkyl, Ci-Cs-alkoxy, C1-C3- alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or Cs-Ce-cycloalkyl; wherein said C3-C6- cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, or Ci-Cs-alkyl. Preferably R7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, C1-C3- alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl. More preferably hydrogen, chlorine, bromine, fluorine, cyano, methyl, ethyl, isopropyl, methoxy, ethoxy, methoxymethyl, 2-methoxyethyl, methoxycarbonyl, ethoxycarbonyl, or cyclopropyl.
In one embodiment R8 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci-C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4- alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy. Preferably R8 is hydrogen, halogen, hydroxy, cyano, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci- Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or Cs-Ce-cycloalkyl; wherein said C3-C6- cycloalkyl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, Ci-Cs-alkyl, Ci-Cz-haloalkyl, or Ci-Cs-alkoxy. More preferably R8 is hydrogen, halogen, cyano, Ci- Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or Cs-Ce-cycloalkyl; wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, or Ci-Cs-alkyl. Still more preferably R8 is hydrogen, chlorine, bromine, fluorine, cyano, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2,2-trifluoroethoxy, 2,2-difluoroethoxy, methoxy, ethoxy, methoxymethyl, 2- methoxyethyl, methoxycarbonyl, ethoxycarbonyl, cyclopropyl, cyanocyclopropyl, or methylcyclopropyl.
In another embodiment of the invention, R8 is hydrogen, halogen, cyano, Ci -Cs-alkyl, Ci-Cs-alkoxy, C1-C3- alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or Cs-Ce-cycloalkyl; wherein said Cs-Ce- cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, or Ci-Cs-alkyl. Preferably R8 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, C1-C3- alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl. More preferably hydrogen, chlorine, bromine, fluorine, cyano, methyl, ethyl, isopropyl, methoxy, ethoxy, methoxymethyl, 2-methoxyethyl, methoxycarbonyl, ethoxycarbonyl, or cyclopropyl.
In one embodiment R9 is selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, Ci-C4-alkylaminocarbonyl, di(Ci-C4- alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci-C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4- alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy. Preferably R9 is hydrogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Cs-Ce-cycloalkyl. More preferably R9 is hydrogen, halogen, methyl, cyano, difluoromethyl, or cyclopropyl. Even more preferably R9 is hydrogen, chlorine, bromine, methyl, cyano, difluoromethyl, or cyclopropyl. Most preferably R9 is hydrogen or cyano. Still even more preferably R9 is hydrogen.
In one embodiment of the invention, Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from cyano, nitro, carboxy, hydroxy, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C3- Ce-alkenyloxy, Cs-Ce-alkynyloxy, Cs-Ce-haloalkenyloxy, Cs-Ce-cycloalkyloxy, C3-C6-cycloalkyl-Ci-C4- alkoxy, C3-C6-halocycloalkyl-Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C1- C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, Cs-Ce-cycloalkyloxycarbonyl, C3-C6- cycloalkyl-Ci-C4-alkyloxycarbonyl, C3-C6-halocycloalkyl-Ci-C4-alkyloxycarbonyl, C1-C4- haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, Cs-Ce-cycloalkycarbonyloxy, N-Ci-C4-alkoxy-C-Ci ^-alkylcarbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6- membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said 4-, 5- or 6-membered saturated, partially saturated or aromatic heterocycle contains 1 , 2 or 3 heteroatoms selected from O, S or N, with the proviso that no more than one is O or S, wherein any of said phenyl and said 5- to 6-membered saturated, partially saturated or aromatic heterocycle, are unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, C1- C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy, and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, C1-C4- haloalkyl, or Ci-C4-alkoxy. Preferably Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-C4-alkyl, Ci-Cs-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, phenyl, 5 to 6 membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said 4-, 5- or 6-membered saturated, partially saturated or aromatic heterocycle contains 1 , 2 or 3 heteroatoms selected from O, S or N, with the proviso that no more than one is O or S, wherein any of said phenyl and 5- or 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci- C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy; and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, or C1-C4- haloalkyl.
In another embodiment of the invention, Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cz-haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or C3-C6- cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl. Preferably Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkyl, C1-C2- haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2- haloalkyl. Even more preferably Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, C1-C2- haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl. Still even more preferably Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-C2-haloalkyl, C1-C2- haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or cyclopropyl.
The present invention, accordingly, makes available a compound of formula (I) having R1, R2, R3, R4, R5, R6, R7, R8, R9, B1, B2, B3 and Z1 as defined above in all combinations / each permutation.
Embodiments according to the invention are provided as set out below.
In an embodiment of the invention, the compound of formula (I) may be a compound of formula (l-A) wherein R1 is methyl; R3 is hydrogen; and w are as defined for the compounds of formula (I) according to the present invention. Preferably in the compound of formula (l-A) of the invention, R4, R5, and R6 are hydrogen; and R2, R7, R8, R9, B1, B2, B3 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (l-A) of the invention, R4, R5, and R6 are hydrogen; R7, R8 and R9 are independently selected from hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci- Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; and R2, B1 , B2, B3 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (l-A) of the invention, R4, R5, and R6 are hydrogen; B1 is CR7 or N; B2 is CR8 or N; B3 is N; R7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs- alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; R8 is hydrogen, halogen, cyano, C1-C3- alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cz-haloalkyl, C1-C2- haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2- haloalkyl; and R2 is as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (l-A) of the invention, R2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2-alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or Ci-C2-alkylsulfonyl; R4, R5, and R6 are hydrogen; B1 is CR7 or N; B2 is CR8 or N; B3 is N; R7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs- alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; R8 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci- Cs-alkoxycarbonyl, or cyclopropyl; and Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or C3-C6- cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl.
In an embodiment of the invention, the compound of formula (I) may be a compound of formula (I-A1 ), wherein R1 is methyl; R3 is hydrogen; B1 is CR7; B2 is CR8; and B3 is N; and wherein R2, R4, R5, R6, R7, R8 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A1 ) of the invention, R4, R5, and R6 are hydrogen; and R2, R7, R8 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A1 ) of the invention, R4, R5 and R6 are hydrogen; R7 and R8 are independently selected from hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs- alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; and R2 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A1 ) of the invention, R4, R5, and R6 are hydrogen; R7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci- Cs-alkoxycarbonyl, or cyclopropyl; R8 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, C1-C3- alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; Z1 is selected from Ci-Ce- alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cz-haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl; and R2 is as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A1 ) of the invention, R2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2-alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or Ci-C2-alkylsulfonyl; R4, R5, and R6 are hydrogen; R7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs- alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; R8 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs- alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; and Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkyl, C1-C2- haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2- haloalkyl.
In an embodiment of the invention, the compound of formula (I) may be a compound of formula (I-A2), wherein R1 is methyl; R3 is hydrogen; B1 is CR7; B2 is CR8; and B3 is CR9; and w are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A2) of the invention, R4, R5, and R6 are hydrogen; and R2, R7, R8, R9 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A2) of the invention, R4, R5, and R6 are hydrogen; R7, R8 and R8 are independently selected from hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci- Cs-alkyl, Ci-C3-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; and R2 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A2) of the invention, R2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2-alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or Ci-C2-alkylsulfonyl; R4, R5, and R6 are hydrogen; R7 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, C1-C3- alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; R8 is hydrogen, halogen, cyano, Ci-Cs-alkyl, C1-C3- alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; R9 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci- Cs-alkoxycarbonyl, or cyclopropyl; and Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or C3-C6- cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl.
In an embodiment of the invention, the compound of formula (I) may be a compound of formula (I-A3), wherein R1 is methyl, R3 is hydrogen, B1, B2 and B3 are N and (I-A3) wherein R2, R4, R5, R6 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A3) of the invention, R4, R5, and R6 are hydrogen; and R2 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A3) of the invention, R4, R5, and R6 are hydrogen; Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cz-haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl; and R2 is as defined for the compounds of formula (I) according to the present invention.
Preferably in the compound of formula (I-A3) of the invention, R2 is cyano, hydroxy, amino, Ci-Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2-alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, Cs-Ce-cycloalkyloxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or Ci-C2-alkylsulfonyl; R4, R5, and R6 are hydrogen; Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkyl, Ci- C2-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl, wherein said C3-C6- cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl.
The presence of one or more possible asymmetric carbon atoms in any of the compounds selected from compounds of formula (I), (l-A), (I-A1 ), (I-A2) and (I-A3), or compounds selected from compounds listed in Tables B-1 to B-32, or Table P (below), according to the invention means that the compounds may occur in chiral isomeric forms, i.e. , enantiomeric or diastereomeric forms.
More preferably the compound of formula (I) according to the invention is selected from compounds listed in any one of Tables B-1 to B-32.
Even more preferably the compound of formula (I) according to the invention is selected from compounds listed in Table P (below).
Even more preferably the compound of formula (I) according to the invention is selected from 8-cyano-N- (2-ethoxyethyl)-4-(5-methoxy-1 -methyl-pyrazol-4-yl)quinoline-2-carboxamide; 8-cyano-4-(5-methoxy-1 - methyl-pyrazol-4-yl)-N-pentyl-quinoline-2-carboxamide; 8-cyano-4-(5-cyano-1 -methyl-pyrazol-4-yl)-N- pentyl-quinoline-2-carboxamide; 8-bromo-4-(5-cyano-1 -methyl-pyrazol-4-yl)-N-pentyl-quinoline-2- carboxamide; 4-(5-cyano-1 -methyl-pyrazol-4-yl)-N-pentyl-quinoline-2-carboxamide; 4-(5-ethoxy-1 -methyl- pyrazol-4-yl)-N-pentyl-quinoline-2-carboxamide; 8-cyano-4-(5-hydroxy-1 -methyl-pyrazol-4-yl)-N-pentyl- quinoline-2-carboxamide; 8-bromo-4-(5-hydroxy-1 -methyl-pyrazol-4-yl)-N-pentyl-quinoline-2-carboxamide; 8-chloro-4-(5-hydroxy-1 -methyl-pyrazol-4-yl)-N-pentyl-quinoline-2-carboxamide; 8-cyano-4-(1 -methyl-5- prop-2-ynoxy-pyrazol-4-yl)-N-pentyl-quinoline-2-carboxamide; 8-chloro-4-(5-methoxy-1 -methyl-pyrazol-4- yl)-N-pentyl-quinoline-2-carboxamide; 8-cyano-4-(5-ethoxy-1 -methyl-pyrazol-4-yl)-N-pentyl-quinoline-2- carboxamide; ethyl 4-(5-cyano-1 -methyl-pyrazol-4-yl)-2-(pentylcarbamoyl)quinoline-8-carboxylate; or methyl 4-(5-cyano-1 -methyl-pyrazol-4-yl)-2-(pentylcarbamoyl)quinoline-8-carboxylate.
The compounds of formula (I) according to the present invention can be made as shown in the following Schemes 1 to 13, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).
In particular, compounds of formula (I), wherein R1, R2, R3, R4, R5, R5, R6, B1, B2, B3, and Z1 are as described under formula (I) in can be prepared as described in Schemes 1 to 13, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I). In any of the Schemes 1 to 13 below, the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e. , enantiomeric or diastereomeric forms.
Compounds of formula (I) may be prepared by a person skilled in the art following known methods. More specifically, compounds of formula (I) may be prepared from compounds of formula (III) or a salt thereof, wherein Z1 as defined above for the compound of formula (I) by reaction with a compound of formula (II), wherein R1 , R2, R3, R4, R5, R5, R6, B1, B2, and B3, are as defined above for the compound of formula (I). This reaction is shown in Scheme 1 .
Scheme 1
In Scheme 1 , compounds of formula (II), wherein R1, R2, R3, R4, R5, R5, R6, B1, B2, and B3, are as defined above for the compound of formula (I) are activated to compounds of formula (Ila) by methods known to a person skilled in the art and described, for example, in Tetrahedron 2005, 61 (46), 10827-10852. For example, compounds of formula (Ila), where X° is halogen, are formed by treatment of compounds of formula (II) with, for example, oxalyl chloride or thionyl chloride in the presence of catalytic quantities of N,N-dimethylformamide (DMF) in inert solvents such as dichloromethane (DCM) or tetrahydrofuran (THF) at temperatures between 20°C to 100°C, preferably 25°C. Treatment of compounds of formula (Ila) with compounds of formula (III), wherein Z1 is as defined above for the compound of formula (I), optionally in the presence of a base, e.g. triethylamine or pyridine, leads to compounds of formula (I). Alternatively, compounds of formula (I) may be prepared by treatment of compounds of formula (II) with dicyclohexyl carbodiimide (DCC), 1 -ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 1 - [bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) to give the activated compound of formula (lib), wherein G° is G01 , G02 or G03 as set forth below, in an inert solvent, e.g. pyridine, DMF, acetonitrile, DCM, or THF, optionally in the presence of a base, e.g. triethylamine, at temperatures between 30°C and 180°C. Finally, a compound of formula (II) can also be activated by reaction with a coupling reagent such as propanephosphonic acid anhydride (T3P) to provide compounds of formula (Ila), wherein G° is G04 as set forth below, as described for example in Synthesis 2013, 45, 1569. Further reaction with an amine (or a salt thereof) of the compound of formula (III) leads to compounds of formula (I).
Compounds of formula (II) can be prepared from compounds of formula (lie), wherein R1, R2, R3, R4, R5, R6, B1, B2 and B3 are as described in formula (I), and R01 is Ci-C4-alkyl, by ester hydrolysis. A variety of conditions can be used, as for example aqueous sodium hydroxide or lithium hydroxide, and an organic water miscible solvent like THF, dimethoxyethane, methanol, or ethanol. Such ester hydrolyses are well known to those skilled in the art. Compounds of formula (lie) can also be directly converted to compounds of formula (I) by reacting compounds of formula (He) with compounds of formula (III) in the presence of trimethyl aluminum, or trimethyl aluminum-DABCO complex in an inert solvent such as toluene or DCM. Such reactions have been reported in the literature (see Tetrahedron Lett. 1977, 4171 -4174, and Tetrahedron Lett. 2006, 5767-5769, and references cited therein). A further method to prepare compounds of formula (I) involves amino carbonylation of compounds of formula (III) with compounds of formula (IV), wherein R1 , R2, R3, R4, R5, R5, R6, B1, B2, and B3, are as defined in compounds of formula (I), and X° is halogen, preferably Cl, Br or iodine. Such amino carbonylation’s involve treatment of compounds of formula (III) with compounds of formula (IV) under a carbon monoxide atmosphere between 1 -10 bar, in the presence of a palladium catalyst, for example [1 ,3- Bis(diphenylphosphino)propane] palladium^ I) chloride in an inert solvent such as methyl-THF or THF and a base such as triethyl amine. Such amino carbonylation reactions are well known to those skilled in the art and similar reactions have been reported in for example Org. Lett. 2007, 9, 4575-4578, or Org. Lett. 2015, 17, 3236-3239.
Scheme 2 Compounds of formula (Ila), wherein R1 , R2, R3, R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I), B3 is N, and R01 is Ci-C4-alkyl, namely compounds of formula (llaa), may be prepared by reacting compounds of formula (IVa) wherein R1 , R2, R3, R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I), and B3 is N, namely compounds of formula (IVaa), in a high- pressure reactor typically under a carbon monoxide atmosphere between 1 -10 bar using palladium- catalyzed conditions analogously to conditions described in US20150218102 or WO98/04557. This reaction is carried out in the presence of an alcohol R01-OH, wherein R01 is Ci-C4-alkyl, and a base, for example triethylamine, to give the corresponding ester wherein R01 is Ci-C4-alkyl. This reaction is shown in Scheme 2. Compounds of formula (IVaa), wherein R1 , R2, R3, R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I), and B3 is nitrogen, may be prepared by reacting compounds of formula (V), wherein R1 , R2, R3, R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I), and wherein B3 is N+-O_ (N-oxide), with a chlorinating agent such as phosphorus oxychloride, oxalyl chloride or thionyl chloride, neat or in a presence of an inert solvent. Similar reactions have been described for example in Tetrahedron Lett. 2014, 55(51 ), 7130-7132. This reaction is shown in Scheme 3.
Scheme 3
Compound of formula (V), wherein R1, R2, R3, R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I), may be prepared by reacting compounds of formula (VI) wherein R1 , R2, R3, R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I) with a oxidizing agent such as hydrogen peroxide in acetic acid or m-chloroperbenzoic acid in a presence of solvent. Similar reactions have been described in W004/052370 or Adv. Synth. Cat. 2020, 362(24), 5777-5782. Such oxidations can also be performed in presence of oxygen using ruthenium as catalyst as described in Chem. Comm. 2002, (10), 1040-1041 . This reaction is shown in Scheme 4.
Scheme 4 Compounds of formula (VI), wherein R1 , R2, R3, R4, R5, R6, B1 , and B2 are as defined above for the compound of formula (I), may be prepared by reacting compounds of formula (VIII), wherein R1 , R2 and R3 are as defined above for the compound of formula (I) and X° is halogen, preferably chlorine, bromine or iodine, with compounds of formula (VII), wherein R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I), by means of a C-C bond formation reaction typically under palladium-catalyzed (alternatively nickel-catalyzed) cross-coupling conditions. This reaction is shown in Scheme 5.
Scheme 5
Suzuki-Miyaura cross-coupling reactions between compounds of formula (VII) and compounds of formula (VIII) are well known to a person skilled in the art and are usually carried out in the presence of a palladium catalyst, such as tetrakis(triphenylphosphine)-palladium(0) or [1 ,1 '-bis(diphenyl- phosphino)ferrocene]palladium(ll) dichloride dichloromethane complex, and a base, such as sodium or potassium carbonate, in a solvent, such as N,N-dimethylformamide, dioxane or dioxane-water mixtures, at temperatures between room temperature and 160°C, optionally under microwave heating conditions, and preferably under inert atmosphere. Such reactions have been reviewed for example in J. Organomet. Chem. 1999, 576, 147-168. A person skilled in the art will also recognize that the reaction can be performed by reacting a compound of formula (X), wherein R1, R2 and R3 are as defined above for the compound of formula (I), with a compound of formula (IX), wherein, R4, R5, R6, R7, B1 and B2 are as defined above for the compound of formula (I) and X° is halogen, preferably chlorine, bromine or iodine, to provide a compound of formula (VI), wherein R1 , R2, R3, R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I). This reaction is shown in Scheme 6.
Scheme 6
A further cross-coupling chemistry, namely C-H activation, can also be used to prepare compounds of formula (VI), wherein R1 , R2, R3, R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I) (Scheme 7).
Scheme 7
As shown in Scheme 7, compounds of formula (XI), wherein R4, R5, R6, B1 and B2 are as defined above for the compound of formula (I) and X° is halogen, preferably chlorine, bromine or iodine, are reacted with compounds of formula (XII), wherein R1 , R2 and R3 are as defined above for the compound of formula (I), in the presence of a palladium catalyst, typically palladium acetate Pd(OAc)2, a suitable ligand, for example 1 ,10-phenanthroline, in the presence of a base such as cesium carbonate or potassium carbonate, in inert solvents such as chlorobenzene, toluene or xylene at temperatures between room temperature and 180°C, optionally under microwave heating conditions, preferably under inert atmosphere. Similar reactions have been reported in the literature for example in Chem. Sci. 2013, 4, 2374-2379.
An alternative synthesis of compounds of formula (I) wherein R1 , R2, R3, R5, R6, B1 , B2 and Z1 are as described in formula (I), B3 is nitrogen, and R4 is hydrogen, namely compounds of formula (la), is shown in scheme 9.
Scheme 9
As shown in scheme 9, a compound of formula (XIII), wherein R1 , R2 and R3 are as previously described for formula (I) are treated with a compound of formula (XIV) wherein R5, R6, B1 , and B2 are as previously defined, and compounds of formula (XV), wherein R01 is Ci-C4-alkyl, under silver/triflic acid catalysis conditions, in an inert solvent such as methanol, to yield compounds of formula (lid) wherein R1 , R2, R3 R5, R6, B1 , B2 and R01 are as previously defined. Compounds of formula (lid) are converted to compounds of formula (la) using the methods described in scheme 1 . Such reactions have been described in for example in J. Org. Chem. 2009, 74, 15, 5476-5480. A very similar type of reaction can be used to produce compounds of formula (lid) as shown in scheme 10.
Scheme 10 In this case, an acetyl compound of formula (XVI) is reacted with compound (XVa) and the catalyst system is Cu(ll)triflate/triflic acid, in acetonitrile under air (see Org. Chem. Front. 2018, 5, 1713-1718). Compounds of formula (XIII) and (XVI) can be readily prepared from compounds of formula (XVII), wherein R1, R2 and R3 are as previously defined and X° is halogen, preferably chlorine, bromine or iodine, by a palladium catalysed Sonogashira and Stille couplings, respectively, which are well known to those skilled in the art (scheme
Scheme 1 1
Reactions similar to those described above can be performed in a stepwise manner as shown in scheme 12.
As shown in scheme 12, compounds of formula (XIV) upon reaction with compounds of formula (XVa) in an organic solvent such as methanol, toluene, THF and the like lead to compounds of formula (XVIII). Compounds of formula (XVIII) can be cyclized to compounds of formula (XIX) by, for example, by heating at temperatures between 200-250°C neat, or in an organic solvent such as diphenyl ether or 1 ,2- dichlorbenzene. Such reactions have been described (see for example Dalton Transactions 2012, 41 (31 ), 9373-9381 , or Molecules 2019, 24(19), 3502). Compounds of formula (XIX) can be converted to compounds of formula (XX), wherein R5, R6, B1, B2, and R01 are as previously defined, and X° is halogen, by halogenation with for example POX°3, e.g. phosphoryl chloride or phosphoryl bromide, under conditions know to those skilled in the art and described for example in Bio. Med. Chem. Lett. 2010, 20(3), 954-957, and J. Med. Chem. 2006, 49(21 ), 6351 -6363. Compounds of formula (XX) can then be reacted with compounds of formula (X) using the Suzuki-Miyaura reaction conditions described in scheme 6, to give compounds of formula (lid). Alternatively, compounds of formula (XX) can be treated with organic zinc compounds of formula (XXI), readily obtained by zincation of compounds of formula (VIII), in the presence of nickel or palladium catalysts to give compounds of formula (lid). Such organo zinc coupling reactions (Negishi reactions) are well known to those skilled in the art and conditions using Ni and Pd catalysts have been reported (see: “Recent developments in the chemistry of Negishi coupling: a review” Chem. Pap. 2024, pp 1 -32, https://doi.Org/10.1007/s1 1696-024-03369-7 and references cited therein). Yet another coupling, namely C-H activation of compounds of formula (XII) with compounds of formula (XX) using conditions described vide infra (scheme 7), also leads to compounds of formula (lid). These transformations are summarized in scheme 13.
Scheme 13
Compounds of formula (lid) are converted to compounds of formula (I) as described above. All other compounds noted in schemes 1 to 13 but not specifically described, can be prepared according to methods known to those skilled in that art, or are commercially available.
The compounds of formula (I) 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. As already indicated, surprisingly, it has now been found that the compounds of formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
The compounds of formula (I) according to the invention can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the 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 can be used for protecting numerous cultivated plants. The compounds of formula (I) can be used to inhibit or destroy the pests 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 also protecting those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of formula (I) according to the invention is applied to the plants, to parts thereof or the locus thereof.
It is also possible to use a compound of formula (I) according to the invention as a fungicide. The term “fungicide” as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term “fungicidally effective amount” where used 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.
It may also be possible to use compounds of formula (I) according to the invention as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown. The active compounds of formula (I) 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.
Furthermore, the compounds of formula (I) according to the 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.
In addition, the invention could be used to protect non-living materials from fungal attack, e.g., lumber, wall boards, and paint.
The compounds of formula (I) according to the invention are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses. These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example: Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. including A. f/avus, A. fumigatus, A. nidulans, A. niger, A. terras, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. including 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. arachidicola, Cercosporidium personatum, Cladosporium spp., Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., Colletotrichum spp. including C. musae, Corynespora spp. including Corynespora cassiicola, Cryptococcus neoformans, Diaporthe spp. including Diaporthe miriciae (also known as Diaporthe ueckeri or Diaporthe ueckerae), Didymella spp., Drechslera spp., Elsinoe spp., Epidermophyton spp., Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., Histoplasma spp. including H. 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. philippinensis and P. sorghi, Peronospora spp., Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp., Phoma spp., Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including 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. ultimum, Ramularia spp., Rhizoctonia spp., Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp., Scedosporium spp. including S. apiospermum and S. profit leans, Schizothyrium pomi, Sclerotinia spp., Sclerotium spp., Septoria spp., including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp., Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp., Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp., Typhula spp., Uncinula necator, Urocystis spp., Ustilago spp., Venturia spp. including V. inaequalis, Verticillium spp., and Xanthomonas spp..
The compounds of formula (I) according to the invention may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees, or evergreens, for example conifers, as well as for tree injection, pest management and the like.
Within the scope of present invention, 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. 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.
The term "useful plants" is to be understood as also including 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. 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). Examples of 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" is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricin N- acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature- Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.
The term "crops" is to be understood as including also crop plants which have been so transformed using recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus. Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as deltaendotoxins, e.g., Cryl Ab, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or 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; ribosomeinactivating 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, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
Further, in the context of the present invention there are to be understood by delta-endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, W002/15701 ). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, 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 W02003/018810).
Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-0374753, WO93/07278, WO95/34656, EP0427529, EP0451878 and WG03/052073.
The processes for the preparation of such transgenic plants are generally known to a person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO95/34656, EP0367474, EP0401979 and WO90/13651.
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 CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a Cryl Ac toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are:
1 . Bt11 Maize from Syngenta Seeds SAS, Chemin de I'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 Cryl Ab 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 I'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 CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in W02003/018810.
4. 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. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B 1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x 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 CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
The compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi, especially phytopathogenic fungi on soybean plants. In one embodiment such soybean plants are genetically modified soybean plants.
In one embodiment the genetically modified plants are soybean plants. Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), lntacta®2 Xtend™, Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™.
Transgenic soybean plants expressing toxins, for example insecticidal proteins such as delta-endotoxins, e.g., CrylAc (Cryl Ac Bt protein). Accordingly, this may include transgenic soybean plants comprising event MON87701 (disclosed in W02009/064652), event MON87701 x MON89788 (disclosed in WO2014/170327, e.g. commercially available as Intacta RR2 PRO® soybean), event MON87751 (disclosed in WO2014/201235), event DAS-44406-6 (e.g., commercially available as Enlist E3™, DAS- 44406-6, disclosed in WO2012/075426), or event DAS-81419-2 (described in WO2013/016527, e.g., commercially available as Conkesta™ soybean); event DAS-81419-2 x DAS-44406-6 (e.g., commercially available as Conkesta™ Enlist E3™ Soybean).
Furthermore, such a list of transgenic events is provided by the United States Department of Agriculture's (USDA) Animal and Plant Health Inspection Service (APHIS) and can be found on their website on the World Wide Web at aphis.usda.gov.
The compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi such as Alternaria spp. in fruits, vegetables and potatoes; Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes; Rhizoctonia solani in potatoes and vegetables; Uncinula necator in grapes; Cladosporium cucumerinum, Didymella bryoniae, Sphaerotheca fuliginea and Glomerella lagenarium in cucurbits; Leveillula taurica in cucurbits and solanaceous crops; Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymoseptoria spp. in cereals.
The compounds of formula (I) and compositions comprising said compounds, are suitable for controlling the following fungal diseases on soybeans and genetically modified soybeans, for example Bt soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (leaf spots), e.g. C. sojina or C. kikuchii; Colletotrichum spp. (teleomorph: Glomerella) (anthracnose), e.g. C. truncation or C. g/oeosporioides; Corynespora cassiicola (leaf spots); Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot); Diaporthe spp., e.g. Diaporthe miriciae (also known as Diaporthe ueckeri or Diaporthe ueckerae) (damping off); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot), e.g. F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans; Macrophomina phaseolina (syn. phaseoli) (root and stem rot); Microsphaera diffusa (powdery mildew); Peronospora spp. (downy mildew), e.g. P. manshurica; Phakopsora pachyrhizi and P. meibomiae (soybean rust); Phialophora spp., e.g. P. gregata (brown stem rot); Phomopsis spp., e.g. P. phaseoli (teleomorph: Diaporthe phaseolorum); Pythium spp. (damping-off); Phytophthora spp. (wilt, root, leaf, fruit and stem root), e.g. P. megasperma (syn. P. sojae); Rhizoctonia spp., e.g. R. solan! (root and stem rot); Sclerotinia spp. (stem rot or white mold); Septoria spp., e.g. S. glycines (brown spot); S. rolfsii (syn. Athelia rolfsii); Thielaviopsis spp. (black root rot).
The term “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.
The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
The term “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. There can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of plants. 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 can be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.
The compounds of formula (I) according to the 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. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating, or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The 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 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. Such carriers are for example described in WO1997/33890.
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. In use, 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 sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate 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. Pressurized sprayers, wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, may also be used.
Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to a person skilled in the art.
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, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 ,1 ,1 -trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N- methyl-2-pyrrolidinone. 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. They can be anionic, cationic, non-ionic, or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; 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. 16 ethoxylate; 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.
Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming 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.
In addition, further, other biocidal 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. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.
In addition, the 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) according to the invention are normally used in the form of agrochemical 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) according to the 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) or of at least one preferred individual compound as defined herein, in free form or in agrochemical 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) according to the 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. Preferably said composition may comprise at least one or more pesticidal-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I).
The compound of formula (I) according to the invention may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide, or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities.
Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorous fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.
The following mixtures of the compounds of formula (I), or compounds selected from compounds listed in Tables B-1 to B-32, or compounds listed in Table P (below), with active ingredients are preferred: (4E,10Z)-tetradeca-4, 10-dienyl acetate, (7E,9Z)-dodeca-7,9-dien-1 -yl acetate, (E)-6-methylhept-2-en-4-ol, (E)-dec-5-en-1 -yl acetate with (E)-dec-5-en-1 -ol, (E)-tridec-4-en-1 -yl acetate, (S)-bioallethrin, (Z)-dodec-7- en-1 -yl acetate, (Z)-hexadec-l 1 -en-1 -yl acetate, (Z)-hexadec-l 1 -enal, (Z)-hexadec-13-en-11 -yn-1 -yl acetate, (Z)-icos-13-en-10-one, (Z)-tetradec-7-en-1 -al, (Z)-tetradec-9-en-1 -ol, (Z)-tetradec-9-en-1 -yl acetate, 1 ,1 -bis(4-chlorophenyl)-2-ethoxyethanol, 1 -(2-chlorophenyl)-3,3-dimethyl-2-(1 ,2,4-triazol-1 - ylmethyl)butan-2-ol, 1 -(5-bromo-2-pyridyl)-2-(2,4-difluorophenyl)-1 ,1 -difluoro-3-(1 ,2,4-triazol-1 -yl)propan- 2-ol, 1 -hydroxy-1 H-pyridine-2-thione, 1 -methylcyclopropene, 1 -naphthaleneacetamide, 1 -naphthylacetic acid, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2,4-D, 2,4-DB, 2,6-dichloro-N-(4- trifluormethylbenzyl)benzamide, 2-(1 ,3-dith iolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl piperonylate, 2-(4,5-dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(difluoromethyl)-N-((3R)-1 ,1 ,3- trimethylindan-4-yl) pyridine-3-carboxamide, 2-(octylthio)-ethanol, 2-bromo-2-bromomethyl- pentanedinitrile, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3-(4-chlorophenyl)-5-methylrhodanine, 3-(difluoromethyl)-1 - methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 3-(difluoromethyl)-N-(7-fluoro-1 ,1 ,3,3-tetra- methyl-indan-4-yl)-1 -methyl-pyrazole-4-carboxamide, 3-(difluoro-methyl)-N-(7-fluoro-1 ,1 ,3,3-tetramethyl- indan-4-yl)-1 -methyl-pyrazole-4-carboxamide, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl) pyridazine, 3-methyl-1 -phenylpyrazol-5-yldimethyl-carbamate, 3-phenylphenol, 4,5-dich lorodithiol-3-one,
4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, 4-(2-bromo-4-fluoro-phenyl)-N-(2- chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(quinoxalin-2-ylamino)benzene sulfonamide, 4- [[6-[2-(2,4-difluorophenyl)-1 ,1 -difluoro-2-hydroxy-3-(1 ,2,4-triazol-1 -yl)propyl]-3-pyridyl]oxy] benzonitrile, 4- chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, 4-CPA, 4-methyl(prop- 2-ynyl)amino-3,5-xylyl methylcarbamate, 4-methylnonan-5-ol with 4-methylnonan-5-one, 4-phenylphenol,
5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, 5-amino-1 ,3,4-thiadiazole-2-thiol, 5-fluoro-2-(p- tolylmethoxy)pyrimidin-4-amine, 5-hydroxy-6-methyl-4-(((E)-pyridin-3-ylmethylene)amino)-4,5-dihydro- 1 ,2,4-triazin-3(2H)-one, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid, 8-hydroxyquinoline sulfate, 11 -ethyl-10, 12-dioxo-2,5,8-trithia-4, 11 -diazatricyclo[7.3.0.03,7]dodeca-1 (9),3,6-triene-6-carbonitrile, 14- methyl octadec-1 -ene, [(9Z,11 E)-tetradeca-9,11 -dienyl] acetate, [(Z)-dodec-9-enyl] acetate, abamectin, acephate, acequinocyl, acetamiprid, acethion, acetoprole, acibenzolar, acibenzolar-S-methyl, acrinathrin, Adoxophyes orana GV, Agrobacterium radiobacter, alanycarb, albendazole, aldicarb, allethrin, allosamidin, allyl alcohol, allyxycarb, alpha-ecdysone, alpha-multistriatin, Amblyseius spp., ametoctradin, amidithion, amidoflumet, amidothioate, aminocarb, amisulbrom, amiton, amiton hydrogen oxalate, amitraz, anabasine, Anagrapha falcifera NPV, Anagrus atomus, ancymidol, anilazine, anisiflupurin, anthraquinone, antu, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, athidathion, aureofungin, Autographa californica NPV, avermectin B1 a, azaconazole, azadirachtin A, azafenidin, azamethiphos, azinphos-ethyl, azinphos-methyl, azithiram, azoxystrobin, Bacillus sphaericus (Neide), Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, Bacillus thuringiensis ssp. aizawai, baculovirus, barthrin, Beauveria brongniartii, benalaxyl, benalaxyl-M, benazepril, benclothiaz, benfuracarb, benomyl, bensultap, benthiavalicarb, benzalkonium chloride, benzamorf, benzothiostrobin, benzovindiflupyr, beta-cyfluthrin, beta-cypermethrin, bethoxazin, bifemetstrobin, bifenazate, bifenthrin, binapacryl, bioallethrin, bioethanomethrin, biopermethrin, bioresmethrin, bisthiosemi, bistrifluron, bitertanol, bixafen, blasticidin-S, borax, bordeaux mixture, boscalid, brodifacoum, brofenvalerate, brofluthrinate, bromadiolone, bromfenvinfos, bromophos, bromophos-ethyl, bromuconazole, bufencarb, bupirimate, buprofezin, buserelin, busulfan, but-3-ynyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate, butacarb, butathiofos, butocarboxim, butonate, butopyronoxyl, butoxy(polypropylene glycol), butoxycarboxim, butylamine, cadusafos, calciferol, calcium phosphate, calcium polysulfide, cambendazole, captafol, captan, carbanolate, carbaryl, carbendazim, carbendazim hydrochloride, carbofuran, carbosulfan, carboxin, carprofen, carpropamid, cartap, cartap hydrochloride, cefalexin, cefovecin, cefquinome, ceftiour, cestex, cevadine, chinomethionat, chitosan, chlobenthiazone, chloralose, chlorantraniliprole, chlorbenside, chlordimeform, chlorethephon, chlorethoxyfos, chlorfenapyr, chlorfenazole, chlorfentazine, chlorfenvinphos, chlorfluazuron, chlormephos, chlormequat, chlorodimeform hydrochloride, chloroinconazide, chloromebuform, chloromethiuron, chloroneb, chlorothalonil, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlortetracycline, chlorthiophos, chlozolinate, cholecalciferol, chromafenozide, Chrysoperla carnea, cinerin, cinerin I, cinerin II, cis-jasmone, cis-resmethrin, cismethrin, clenbuterol, climbazole, cloethocarb, clofencet, clorsulon, clothianidin, clozylacon (acetamide), codlelure, copper acetate, copper hydroxide, copper naphthenate, copper octanoate, copper oleate, copper oxide, copper oxychloride, copper silicate, copper sulfate, copper(ll) carbonate, coumachlor, coumafene, coumafuryl, Coumatetralyl, coumethoxystrobin (jiaxiangjunzhi), coumithoate, coumoxystrobin, cryolite, Cryptolaemus montrouzieri, cuelure, cufraneb, cuprous(l) oxide, cyanofenphos, cyanthoate, cyazofamid, cybutryne, cyclafuramid, cyclethrin, cyclobutrifluram, Cydia pomonella GV, cyenopyrafen, cyflufenamid, cyflumetofen, cyfluthrin, cyhalothrin, cymiazole, cymoxanil, cypermethrin (alphametrin), cyphenothrin, cyproconazole, cyprodinil, cyprodinil, cyromazine, cytokinins, D-tetramethrin, Dacnusa sibirica, DAEP, dazomet, DCPM, debacarb, decarbofuran, deltamethrin, demephion-O, demephion-S, demeton-O, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dibutyl adipate, dibutyl phthalate, dibutyl succinate, dicapthon, dichlobentiazox, dichlofluanid, dichlone, dichlorprop, dichlorvos, dichlozoline, diclocymet, diclomezine, dicloran, dicofol, dicresyl, dicrotophos, dicyclanil, dicyclopentadiene, diethofencarb, diethyltoluamide, difenacoum, difenoconazole, difenzoquat, difethialone, diflovidazin, diflubenzuron, diflumetorim, Diglyphus isaea, dimatif, dimefluthrin, dimetan, dimethachlon, dimethipin, dimethirimol, dimethoate, dimethomorph, dimethrin, dimethyl disulfide, dimethyl phthalate, dimetilan, dimoxystrobin, dinactin, diniconazole, diniconazole-M, dinobuton, dinocap, dinocton, dinoseb, dinotefuran, diofenolan, dioxabenzofos, diphenylamine, dipyrithione, disparlure, disulfiram, disulfoton, ditalimfos, dithianon, dithicrofos, dithiocarbamate, dodec-8-en-1 -yl acetate, dodemorph, dodicin, dodine, dofenapyn, dominicalure, doramectin, drazoxolon, DSP, ecdysterone, edifenphos, emamectin benzoate, EMPC, empenthrin, Encarsia formosa, endosulfan, endothal, endothion, enestroburin (enoxastrobin), enrofloxacin, entomopathogenic bacteria, entomopathogenic fungi, entomopathogenic virus, EPBP, epoxiconazole, eprinomectin, Eretmocerus eremicus, esfenvalerate, etaconazole, ethaboxam, ethiofencarb, ethion, ethiprole, ethirimol, ethoate-methyl, ethoprophos, ethoxyquin, ethyl 4- methyloctanoate, ethyl formate, ethyl hexanediol, etofenprox, etoxazole, etridiazole, etrimfos, eugenol, eurax, EXD, exo-brevicomin, famoxadone, famphur, farnesol with nerolidol, febantel, fenamidone, fenaminstrobin, fenamiphos, fenarimol, fenazaquin, fenbendazole, fenbuconazole, fenbutatin oxide, feneptamidoquin, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenitrothion, fenobucarb, fenopyramid, fenothiocarb, fenoxacrim, fenoxanil, fenoxycarb, fenpiclonil, fenpicoxamid, fenpirithrin, fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine, fenpyroximate, fensulfothion, fenthion, fenthion-ethyl, fentin, fentin acetate, fentin chloride, fentin hydroxide, fenvalerate, ferbam, ferimzone, ferric phosphate, fipronil, flocoumafen, flonicamid, florfenicol, florylpicoxamid, fluacrypyrim, fluazinam, fluazuron, flubendazole, flubendiamide, flubeneteram, flubenzimin, flucycloxuron, flucycloxuron, flucythrinate, fludioxonil, fluenetil, flufenerim, flufenoxuron, flufenoxystrobin, flufenprox, fluindapyr, flumetralin, flumetylsulforim, flumorph, fluopicolide, fluopimomide, fluopyram, fluoroimide, fluoxapiprolin, fluoxastrobin, fluoxytioconazole, flupyrazofos, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fonofos, forchlorfenuron, formaldehyde, formetanate, formetanate hydrochloride, formothion, formparanate, fosetyl, fosetyl-aluminium, fosmethilan, fosthiazate, fosthietan, frontalin, fuberidazole, furalaxyl, furametpyr, furathiocarb, furethrin, furfural, gibberellic acid, glyodin, glyphosate, grandlure I, grandlure II, grandlure III, grandlure IV, guazatine triacetate, halfenprox, halofenozide, hemel, heptenophos, Heterorhabditis bacteriophora and H. megidis, hexaconazole, hexadecyl cyclopropanecarboxylate, hexaflumuron, hexalure, hexamide, hexythiazox, Hippodamia convergens, huanjunzuo (rac-(1 S,2S)-1 -(4-chlorophenyl)-2-(1 ,2,4-triazol-1 -yl)cycloheptanol), hydramethylnon, hydrated lime (calcium hydroxide), hymexazol, hyquincarb, icaridin, imanin (hypericin), imazalil, imazalil sulfate, imibenconazole, imidacloprid, iminoctadine, indoxacarb, inpyrfluxam, iodocarb, ipconazole, ipfentrifluconazole, ipflufenoquin, iprobenfos (IBP), iprodione, iprovalicarb, ipsdienol, ipsenol, IPSP, isamidofos, isazofos, isocarbophos, isofetamid, isoflucypram, isolan, isoprocarb, isoprothiolane, isopyrazam, isothioate, isotianil, isoxathion, ivermectin, japonilure, jasmolin I, jasmolin II, juvenile hormone I, juvenile hormone II, juvenile hormone III, kadethrin, kanamycin, kasugamycin, kasugamycin hydrochloride hydrate, kinetin, kinoprene, kresoxim-methyl, kurstaki, lambda-cyhalothrin, Leptomastix dactylopii, leptophos, levamisole, lineatin, lirimfos, looplure, lufenuron, Ivbenmixianan, lythidathion, m- cumenyl methylcarbamate, Macrolophus caliginosus, magnesium phosphide, malathion, maleic hydrazide, malonoben, Mamestra brassicae NPV, mancopper, mancozeb, mandestrobin, mandipropamid, maneb, mazidox, mebendazole, mecarbam, mecarphon, medlure, mefentrifluconazole, megatomoic acid, meloxicam, menazon, mepanipyrim, meperfluthrin, mephosfolan, mepiquat, mepronil, meptyldinocap, mesulfenfos, metaflumizone, metalaxyl, metalaxyl-M, metaldehyde, metam, metam- potassium, metam-sodium, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, metarylpicoxamid, metconazole, methacrifos, methamidophos, methasulfocarb, methidathion, methiocarb, methiotepa, methocrotophos, methomyl, methoprene, methoquin-butyl, methothrin, methoxyfenozide, methyl apholate, methyl eugenol, methyl iodide, methyl neodecanamide, metiram, metofluthrin, metolcarb, metominostrobin, metoxadiazone, metrafenone, metyltetraprole, mevinphos, mexacarbate, MGK 264, milbemycin, milbemycin oxime, monocrotophos, morantel tartrate, morzid, moxidectin, muscalure, myclobutanil, myclozolin, Myrothecium verrucaria composition, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4-carboxamide, N- cyclopropyl-3-(difluoromethyl)-5-fluoro-N-[(2-isopropylphenyl)methyl]-1 -methyl-pyrazole-4-carboxamide, nabam, naled, NC-170, nemadectin, Neodiprion sertifer NPV and N. lecontei NPV, niclosamide-olamine, nicotine, nicotine sulfate, nikkomycins, nitenpyram, nithiazine, nitrapyrin, nitrilacarb, nitrothal-isopropyl, norbormide, nornicotine, novaluron, noviflumuron, nuarimol, 0,0, O', O' -tetrapropyl dithiopyrophosphate, octadeca-2,13-dien-1 -yl acetate, octadeca-2,13-dien-1 -yl acetate, octhilinone, ofurace, oleic acid, omethoate, orfralure, Orius spp., orysastrobin, osthol, ostramone, oxadixyl, oxamate, oxamyl, oxantel pamoate, oxasulfuron, oxathiapiprolin, oxfendazole, oxibendazole, oxine copper, oxolinic acid, oxpoconazole, oxycarboxin, oxydemeton-methyl, oxydeprofos, oxydisulfoton, oxytetracycline, oxytetracycline dihydrate, paclobutrazol, Paecilomyces fumosoroseus, paraoxon, parathion, parathion- methyl, parbendazole, pefurazoate, penconazole, pencycuron, penethamate, penflufen, penthiopyrad, permethrin, petroleum oils, PH 60-38, phenamacril, phenthoate, phorate, phosacetim, phosalone, phosfolan, phosglycin, phosmet, phosnichlor, phosphamidon, phosphocarb, phosphonic acid, phosphorus, phoxim, phoxim-methyl, phthalide, Phytoseiulus persimilis, picarbutrazox, picoxystrobin, pimobendan, pindone, piperalin, piperonyl butoxide, piprotal, pirimetaphos, pirimicarb, pirimiphos-methyl, polycarbamate, polynactin, polyoxin B, polyoxin d, potassium ethylxanthate, potassium hydroxyquinoline sulfate, praziquantel, precocene I, precocene II, precocene III, primidophos, probenazole, prochloraz, procymidone, profenofos, profluthrin, prohexadione, prohexadione-calcium, promacyl, promecarb, propamidine, propamocarb, propaphos, propargite, propetamphos, propiconazole, propineb, propionic acid, propoxur, propyl isomer, proquinazid, prothidathion, prothioconazole, prothiofos, prothoate, protrifenbute, pydiflumetofen, pymetrozine, pyraclofos, pyraclostrobin, pyrafluprole, pyrametostrobin, pyrantel pamoate, pyraoxystrobin, pyrapropoyne, pyraziflumid, pyrazophos, pyrazoxone, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins (natural products), pyrethroids (natural products), pyribencarb, pyridaben, pyridachlometyl, pyridalyl, pyridaphenthion, pyridin-4-amine, pyrifenox, pyrifluquinazon, pyrimethanil, pyrimidifen, pyrimorph, pyriofenone, pyriprole, pyriproxyfen, pyrisoxazole, pyroquilon, quassia, quinalphos, quinalphos-methyl, quinoclamine, quinofumelin, quinonamid, quinothion, quinoxyfen, quintozene, R-1492, R-metalaxyl, Reynoutria sachalinensis extract, ribavirin, rotenone, ryanodine (ryania), sabadilla, schradan, scilliroside, seboctylamine, sedaxane, selamectin, sesamex, sesamolin, siglure, silafluofen, silthiofam, simeconazole, sodium tetrathiocarbonate, sophamide, sordidin, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, spiroxamine, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., streptomycin, streptomycin sesquisulfate, sulcatol, sulcofuron, sulfiram, sulfur, sulprofos, tar oils, tau-fluvalinate, TCMTB, TDE, tebuconazole, tebufenozide, tebufenpyrad, tebufloquin, tebupirimfos, tecnazene, teflubenzuron, tefluthrin, temephos, terallethrin, terbam, terbufos, tetrachlorvinphos, tetraconazole, tetradec-11 -en-1 -yl acetate, tetradifon, tetramethrin, tetramethylfluthrin, tetranactin, thiabendazole, thiacloprid, thiadiazole copper, thiamethoxam, thiapronil, thicrofos, thicyofen, thidiazuron, thifluzamide, thiocarboxime, thiocyclam, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thiometon, thiophanate, thiophanate-methyl, thioquinox, thiosultap, thiosultap- disodium, thiram, thuringiensin, tiadinil, tiamulin, tioxymid, tolclofos-methyl, tolfenpyrad, tolprocarb, tolylfluanid, tralomethrin, transpermethrin, tretamine, triadimefon, triadimenol, triarathene, triazamate, triazophos, triazoxide, tribufos, trichlorfon, trichlormetaphos-3, trichloronat, Trichogramma spp., triclabendazole, triclopyricarb, tricyclazole, tridemorph, trifenmorph, trifloxystrobin, triflumizole, triflumuron, triforine, trimedlure, trimedlure A, trimedlure B1 , trimedlure B2, trimedlure C, trimethacarb, trinactin, trinexapac, trinexapac-ethyl, trioxyflanilide, triprene, triticonazole, trunc-call, tulathromycin, Typhlodromus occidentalis, uniconazole, uredepa, validamycin, valifenalate, vamidothion, vaniliprole, veratridine, veratrine, verbutin, Verticillium lecanii, vinclozolin, XMC, xylenols, zeatin, zeta-cypermethrin, zhongshengmycin, zinc naphthenate, zinc thiazole, zineb, ziram, zolaprofos, zoxamide, 2- (difluoromethyl)-N-[(3S)-3-ethyl-1 ,1 -dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675), methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy- 1 -methyl-2-(1 ,2,4-triazol-1 -ylmethyl)cyclopentanecarboxylate (this compound may be prepared from the methods described in WO 2019/093522), methyl (2R)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy- 3-(1 ,2,4-triazol-1 -yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1 -(2,6-difluorophenyl)cyclopropyl]pyrimidin-2- amine (this compound may be prepared from the methods described in WO 2021/255093), aminopyrifen (this compound may be prepared from the methods described in WO 2014/006945), dipymetitrone (this compound may be prepared from the methods described in WO 201 1/138281 ), 1 -[6-(difluoromethyl)-5- methyl-3-pyridyl]-4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915), 1 -[4-(difluoromethoxy)-2-methyl-phenyl]-2-(1 ,2,4-triazol-1 -yl)-1 - [1 -(trifluoromethyl)cyclopropyl] ethanol (this compound may be prepared from the methods described in WO 2021 /249800), 1 -[2-chloro-4-(difluoromethoxy)phenyl]-2-(1 ,2 ,4-triazol- 1 -yl)-1 -[1 -(trifluoromethyl) cyclopropyl]ethanol (this compound may be prepared from the methods described in WO 2021/249800), 1 -(5,6-dimethyl-3-pyridyl)-4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915), N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]benzenecarbothioamide (this compound may be prepared from the methods described in WO 2015/185485), 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2017/178245), flufenoxadiazam, N- methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide (this compound may be prepared from the methods described in WO 2015/185485), (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2- methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018/153707), (Z,2E)-5-[1 -(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3- dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2013/092224), methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-1 -[4-(trifl u oromethy l)-2-py ridy I] ethylideneamino]oxymethyl]phenyl]acetate (this compound may be prepared from the methods described in WO 2022/033906), (2E)-2-methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-1 -[4-(trifluoromethyl)-2- pyridyl]ethylideneamino]oxymethyl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2022/033906), (2E)-2-[2-[[(E)-[3-(4-fluorophenyl)-1 -methyl-prop-2-ynylidene]amino] oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide (this compound may be prepared from the methods described in WO 2021/249928), methyl (2E)-2-[2-[[(E)-[3-(4-fluorophenyl)-1 -methyl-prop-2- ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (this compound may be prepared from the methods described in WO 2021/249928), 3-[2-(1 -chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)- 2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290), 3-[2-(1 -chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290), 2-[6-(4- bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179), 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3- pyridyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1 -(2-fluorophenyl)ethyl]pyrimidin-2- amine (this compound may be prepared from the methods described in WO 2021/255093), 5-[5- (difluoromethyl)-l ,3,4-oxadiazol-2-yl]-N-[1 -(3,5-difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093), N-[1 -(2-fluorophenyl)cyclopropyl]-5- [5-(trifluoromethyl)-1 ,3,4-oxadiazol-2-yl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1 -(2,6- difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093), 2-(difluoromethyl)-5-[2-[1 -(2,6-difluorophenyl)cyclopropoxy]pyrimidin-5-yl]-1 ,3,4- oxadiazole (this compound may be prepared from the methods described in WO 2021/255093), 5-[5- (difluoromethyl)-l ,3,4-oxadiazol-2-yl]-N-[1 -(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093), 5-[(4-bromo-2-methyl- phenyl)methyl]-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2021 /255070), 3-[3-(3-cyclopropyl- 2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1 ,2,4- oxadiazine (this compound may be prepared from the methods described in WO 2021/255070), N-(2,2,2- trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]oxazole-4-carboxamide (this compound may be prepared from the methods described in WO 2022/1331 14), ethyl 1 -[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl] phenoxy]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2022/1331 14), ethyl 1 -[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop- 1 -enoxy]phenyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021 /183707), ethyl 1 -[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2- yl]methoxy]phenyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021/183707), methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2- methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012), methyl N-[[5-[1 -(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl] carbamate (this compound may be prepared from the methods described in WO 2020/097012), methyl N- [[5-[1 -(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]- carbamate (this compound may be prepared from the methods described in WO 2020/097012), methyl 2-[2-chloro-4-(4- chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1 -yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522), 4,4,5-trifluoro-3,3-dimethyl-1 -(3-quinolyl)isoquinoline, 5- fluoro-3,3,4,4-tetramethyl-1 -(3-quinolyl)isoquinoline, 2-methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-thienyl]methyl] acetamide (this compound may be prepared from the methods described in WO 2020/256113), N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]-2-methyl- propanamide (this compound may be prepared from the methods described in WO 2020/256113), N- [methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]butanamide (this compound may be prepared from the methods described in WO 2020/256113), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1 - dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675), 2-(difluoromethyl)-N-(3-ethyl-1 ,1 -dimethyl-indan-4-yl)pyridine-3- carboxamide (this compound may be prepared from the methods described in WO 2014/095675), 2- (difluoromethyl)-N-(l ,1 ,3-trimethylindan-4-yl)pyridine-3-carboxamide, (5R)-3-[3-(3-chloro-2-fluoro- phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), (5S)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl) methyl]-5,6- dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), 3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4- methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), 2-[(2,6-difluoro-4-pyridyl)-(2- methylpropanoyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511 A1 , WO2021244952A1 ); 2-[(2,6-difluoro-4- pyridyl)-(tetrahydropyran-4-carbonyl)amino]-N-(2,2-dimethyl-cyclobutyl)-5-methyl-thiazole-4-carboxamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511 A1 , WO2021244952A1 ); 2-[cyano- (2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109509A1 ); 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-N- (2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109509A1 ); 2-[(2,6-difluoro-4-pyridyl)-(2-methoxyacetyl) amino]-N-(2,2- dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W0202010951 1 A1 , WO2021244952A1 ); 2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N- spiro[3.4]octan-3-yl-thiazole-4-carboxamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W0202010951 1 A1 , WO2021244952A1 ); N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl] methyl]cyclopropanecarboxamide (this compound may be prepared from the methods described in WO 2017/055473); methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (this compound may be prepared from the methods described in W02020/193387); methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate (this compound may be prepared from the methods described in W02020/193387); N-[(1 R)-1 -benzyl-1 ,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide (this compound may be prepared from the methods described in WO2017/153380); N-[(1 S)-1 -benzyl-1 ,3-dimethylbutyl]-8- fluoroquinoline-3-carboxamide (this compound may be prepared from the methods described in WO2017/153380); 2-[(2,6-difluoro-4-pyridyl)-(oxetane-3-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5- methyl-thiazole-4-carboxamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W0202010951 1 A1 , WO2021244952A1 ); 2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole- 4-carboxamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W0202010951 1 A1 ,
WO2021244952A1 ); N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- propanamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO 2017/055473).
The references in brackets behind the active ingredients, e.g., [3878- 19-1] refer to the Chemical Abstracts Registry number. The above-described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1 ). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "development code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.
The active ingredient mixture of the compound selected from compounds of formula (I), (l-A), (I-A1 ), (I- A2), or (I-A3), or compounds selected from compounds listed in Tables B-1 to B-32, or compounds listed in Table P (below), is preferably in a mixing ratio of from 100:1 to 1 :100, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, and still more especially from 5:1 to 1 :5 Those mixing ratios are by weight.
The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
The mixtures comprising a compound selected from compounds of formula (I), (l-A), (I-A1 ), (I-A2), or (I- A3), or compounds selected from compounds listed in Tables B-1 to B-32, or compounds listed in Table P (below), and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying a compound selected from compounds of formula (I), (l-A), (I-A1 ), (I- A2), or (I-A3), or compounds selected from compounds listed in Tables B-1 to B-32, or compounds listed in Table P (below), and the active ingredient(s) as described above, is not essential for working the present invention.
The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides, or herbicides.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds (I) for the preparation of these compositions are also a subject of the invention.
Another aspect of the invention is related to the use of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein, of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, or of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g., seeds, harvested crops, e.g., harvested food crops, or non-living materials by insects, or by phytopathogenic microorganisms, preferably fungal organisms.
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., harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
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, or insects which comprises the application of a compound of formula (I) according to the invention, or an agrochemical composition which contains at least one compound of formula (I), 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. However, the compounds of formula (I) according to the 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) 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) according to the invention and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I), 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).
Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to I kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1g of active substance per kg of seeds.
The term “g a.i./ha” as used herein refer to the application rate given in gram [g] of active ingredient [a.i.] per unit of surface [ha]. The unit hectare (symbol ha) is the metric unit of area that equals a square with 100 m side (1 hm2) or 10,000 square meters. Hectare is a commonly used unit of area in the metric system.
When the combinations of the present invention are used for treating seed, rates of 0.001 to 50 g of a compound of formula (I) per kg of seed, preferably from 0.01 to 10g per kg of seed are generally sufficient.
Suitably, a composition comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
The 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 (EG), 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), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
Such 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). Also, 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., the condensation product of formaldehyde with naphthalene sulfonate, an alkyl aryl sulfonate, a lignin sulfonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.
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. Such 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., as slow-release capsules or microcapsules.
In general, 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) according to the invention optionally together with other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 to 80%, preferably between about 5 to 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. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline, compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
Preferred formulations can have the following compositions (weight %)
Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules: active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The disclosure in the present application makes available each and every combination of embodiments disclosed herein. The compounds according to the following Tables B-1 to B-32 may be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula (I). In any of Tables B-1 to B-32 below, the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.
Table A: This table discloses X substituent definitions Z1 of compounds of the formula (la) according to the invention: wherein Z1 according to compounds of Formula (I) of the invention is are as defined below:
The following compounds are thus specifically described in Tables B-1 to B-32 with the substituents for Formula (la) Table B-1 This table provides 34 compounds (B-1 .01 to (B-1 .34) of formula (la), wherein R4, R5, and R6 are H; R2 is OCH3, B1, B2 and B3 are CH, and Z1 substituents are as defined in Table A. For example, compound (B-1 .01 ) has the following structure:
Compound B-1 .01
Table B-2: This table provides 34 compounds (B-2.01 ) to (B-2.34) of formula (la), wherein R4, R5, and R6 are H; R2 is OCH3, B1 , B2 are CH, B3 is N, and Z1 substituents are as defined in Table A. For example, compound (B-2.09) has the following structure:
Compound B-2.09
Table B-3: This table provides 34 compounds (B-3.01 ) to (B-3.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is CH, B2 is C-CN, B3 is N, and Z1 substituents are as defined in Table A. For example, compound (B-3.13) has the following structure: compound B-3.13
Table B-4: This table provides 34 compounds (B-4.01 ) to (B-4.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is CH, B2 is C-CH3, B3 is N, and Z1 substituents are as defined in Table A.
Table B-5: This table provides 34 compounds (B-5.01 ) to (B-5.34) of formula (la), wherein R4, R5, and R6 are H, R2, is OCH3, B1 is CH, B2 is C-F, B3 is N, and Z1 substituents are as defined in Table A.
Table B-6: This table provides 34 compounds (B-6.01 ) to (B-6.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is CH, B2 is C-CI, B3 is N, and Z1 substituents are as defined in Table A.
Table B-7: This table provides 34 compounds (B-7.01 ) to (B-7.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is CH, B2 is C-Br, B3 is N, and Z1 substituents are as defined in Table A.
Table B-8: This table provides 34 compounds (B-8.01 ) to (B-8.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is CH, B2 is C-OCH3, B3 is N, and Z1 substituents are as defined in Table A. Table B-9: This table provides 34 compounds (B-9.01 ) to (B-9.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is CH, B2 is C-SCH3, B3 is N, and Z1 substituents are as defined in Table A.
Table B-10: This table provides 34 compounds (B-10.01 ) to (B-10.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is CH, B2 is C-CO2CH3, B3 is N, and Z1 substituents are as defined in Table A. For example, compound (B-10.30) has the following structure: compound B-10.30
Table B-1 1 : This table provides 34 compounds (B-1 1 .01 ) to (B-1 1 .34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is CH, B2 is C-OH, B3 is N, and Z1 substituents are as defined in Table A.
Table B-12 This table provides 34 compounds (B-12.01 to (B-12.34) of formula (la), wherein R4, R5, and
R6 are H, R2 is OCH3, B1 is C-OCH3, B2 is C-CN, B3 is N, and Z1 substituents are as defined in Table A.
For example, compound (B-12.32) has the following structure: compound B-12.32
Table B-13: This table provides 34 compounds (B-13.01 ) to (B-13.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is C-OCH3, B2 is C-CH3, B3 is N, and Z1 substituents are as defined in Table A.
Table B-14 This table provides 34 compounds (B-14.01 to (B-14.34) of formula (la), wherein R4, R5, and
R6 are H, R2 is OCH3, B1 is C-OCH3, B2 is C-Br, B3 is N, and Z1 substituents are as defined in Table A.
Table B-15 This table provides 34 compounds (B-15.01 to (B-15.34) of formula (la), wherein R4, R5, and
R6 are H, R2 is OCH3, B1 is C-OCH3, B2 is C-CI, B3 is N, and Z1 substituents are as defined in Table A.
Table B-16: This table provides 34 compounds (B-16.01 ) to (B-16.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is C-OCH3, B2 is C-CO2CH3, B3 is N, and Z1 substituents are as defined in Table A.
Table B-17 This table provides 34 compounds (B-17.01 to (B-17.34) of formula (la), wherein R4, R5, and
R6 are H, R2 is OCH3, B1 and B2 are C-CN, B3 is N, and Z1 substituents are as defined in Table A. For example, compound (B-17.01 ) has the following structure: compound B-17.01
Table B-18: This table provides 34 compounds (B-18.01 ) to (B-18.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is C-CN, B2 is C-CH3, B3 is N, and Z1 substituents are as defined in Table A.
Table B-19: This table provides 34 compounds (B-19.01 ) to (B-19.34) of formula (la), wherein R4, R5, and R6 are H, R2,is OCH3, B1 is C-CN, B2 is C-Br, B3 is N, and Z1 substituents are as defined in Table A.
Table B-20: This table provides 34 compounds (B-20.01 ) to (B-20.34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is C-CN, B2 is C-CI, B3 is N, and Z1 substituents are as defined in Table A.
Table B-21 : This table provides 34 compounds (B-21 .01 ) to (B-21 .34) of formula (la), wherein R4, R5, and R6 are H, R2 is OCH3, B1 is C-CN, B2 is C-CO2CH3, B3 is N, and Z1 substituents are as defined in Table A.
Table B-22: This table provides 34 compounds (B-22.01 ) to (B-22.34) of formula (la), wherein R4, R5, and R6 are H, R2 is SCH3, B1, B2 are CH, B3 is N, and Z1 substituents are as defined in Table A. For example, compound (B-22.18) has the following structure: compound B-22.18
Table B-23: This table provides 34 compounds (B-23.01 ) to (B-23.34) of formula (la), wherein R4, R5, and R6 are H, R2 is SCH3, B1 is CH, B2 is C-CN, B3 is N, and Z1 substituents are as defined in Table A.
Table B-24: This table provides 34 compounds (B-24.01 ) to (B-24.34) of formula (la), wherein R4, R5, and R6 are H, R, is NHCH3, B1, B2 are CH, B3 is N, and Z1 substituents are as defined in Table A.
Table B-25: This table provides 34 compounds (B-25.01 ) to (B-25.34) of formula (la), wherein R4, R5, and R6 are H, R2 is NHCH3, B1 is CH, B2 is C-CN, B3 is N, and Z1 substituents are as defined in Table A.
Table B-26: This table provides 34 compounds (B-26.01 ) to (B-26.34) of formula (la), wherein R4, R5, and R6 are H, R2 is CN, B1 , B2 are CH, B3 is N, and Z1 substituents are as defined in Table A.
Table B-27 This table provides 34 compounds (B-27.01 to (B-27.34) of formula (la), wherein R4, R5, and
R6 are H, R2 is CN, B1 is CH, B2 is C-CN, B3 is N, and Z1 substituents are as defined in Table A. Table B-28 This table provides 34 compounds (B-28.01 to (B-28.34) of formula (la), wherein R4, R5, and
R6 are H, R2 is OCHF2, B1 , B2 are CH, B3 is N, and Z1 substituents are as defined in Table A.
Table B-29 This table provides 34 compounds (B-27.01 to (B-27.34) of formula (la), wherein R4, R5, and
R6 are H, R2 is OCHF2, B1 is CH, B2 is C-CN, B3 is N, and Z1 substituents are as defined in Table A.
Table B-30 This table provides 34 compounds (B-30.01 to (B-30.34) of formula (la), wherein R4 is CH3,
R5, and R6 are H, R2 is OCH3, B1 , B2 are CH, B3 is N, and Z1 substituents are as defined in Table A.
Table B-31 This table provides 34 compounds (B-31 .01 to (B-31 .34) of formula (la), wherein R4, R5, are
H, R6 is CH3, R2 is OCH3, B1 , B2 are CH, B3 is N, and Z1 substituents are as defined in Table A. For example, compound (B-31 .24) has the following structure:
Compound B-31 .24
Table B-32: This table provides 34 compounds (B-32.01 ) to (B-32.34) of formula (la), wherein R4, R5, and R6 are H; R2 is OCH3; B1 is CH; B2 is C-CO2CH2CH3; B3 is N; and Z1 substituents are as defined in Table A.
EXAMPLES
The Examples which follow serve to illustrate the invention and are not meant in any way to limit the invention.
The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by a person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 60 ppm, 20 ppm or 2 ppm.
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 physicochemical properties, or increased biodegradability).
FORMULATION EXAMPLES
Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) 2 % highly dispersed silicic acid 5 % 10 % 10 %
Kaolin 62 % 27 % -
The combination 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 ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % Kaolin 65 % 40 % -
Talcum 20 %
The combination 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 ingredients 10 % octylphenol polyethylene glycol ether (4 to 5 mol of ethylene oxide) 3 % calcium dodecylbenzene sulfonate 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.
Dusts a) b) c)
Active ingredients 5 % 6 % 4 %
Talcum 95 %
Kaolin - 94 % mineral filler - - 96 %
Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressings for seed.
Extruder granules
Active ingredients 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 %
Kaolin 82 %
The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
Coated granules
Active ingredients 8% polyethylene glycol (mol. wt. 200) 3 %
Kaolin 89 %
The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
Suspension concentrates active ingredients 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 combination 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 ingredients 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 combination is intimately mixed with the adjuvants, giving a flowable concentrate from which solutions of any desired dilution can be obtained by dilution with water, that can be used directly for seed treatment. 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. Slow Release
28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1 ). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion 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.
Formulation types include 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 (EG), 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), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
ABBREVIATIONS
CDCI3 deuterated chloroform
DABCO 1 ,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDA
DCM dichloromethane
DMF dimethylformamide
DMSO dimethyl sulfoxide
DMSO-d6 deuterated Dimethyl sulfoxide
EtOAc ethyl acetate
HCI hydrochloric acid h/hrs hour/hours
LC-MS Liquid Chromatography Mass Spectrometry (LC-MS, LCMS or LC/MS)
MgSO4 magnesium sulphate
Na2SO4 sodium sulphate rh relative humidity rt room temperature
Rt retention time sat. saturated ssp. subspecies
TLC thin layer chromatography THF tetrahydrofuran
PREPARATION EXAMPLES
The compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.
Throughout this description, temperatures are given in degrees Celsius and “m.p.” means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus, and the methods is as follows.
1H NMR and 19F NMR measurements were recorded on a Bruker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS (1H) and CFCI3 (19F) standard. Spectra measured in deuterated solvents as indicated. Either one of the LC-MS methods below was used to characterize the compounds. The characteristic LC-MS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H)+ or (M-H)-.
LCMS Method A 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. Column: Waters UPLC HSS T3, 1.8 pm, 30 x 2.1 mm, Temp: 60°C, DAD Wavelength range (nm): 210 to 400, Runtime: 1.5 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow (ml/min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10-100% B in 1 .0 min, 100% B isocratic for 0.2min, 100-10% B in 0.05min, 10%
B isocratic for 0.05 min.
LCMS Method B: Spectra were recorded on a Mass Spectrometer from Waters (Acquity sdq 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. Column: Acquity UPLC HSS T3 C18, 1 .8 pm, 30 x 2.1 mm, Temp: 40°C, DAD Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.05 % HCOOH: gradient: 0 min 10% B; 0.-0.2 min 10-
50% B; 0.2-0.6 min 50-100% B; 0.6-1 .3 min 100% B; 1.3-1 .4 min 100-10% B; 1.4-1 .6 min 10% B; Flow (mL/min) 0.6.
The compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below. Example Prep-1 : Preparation of 4-(5-ethoxy-1 -methyl-pyrazol-4-yl)-A/-pentyl-guinoline-2-carboxamide
(Compound P-6, table P)
Compound P-6, Table P
Step 1 : Preparation of 5-ethoxy-1 -methyl-pyrazole
A suspension of 2-methylpyrazol-3-ol (5.00 g, 51.0 mmol), and potassium carbonate (14.1 g, 102 mmol) in DMF (25 mL) was treated with iodoethane (8.32 mL, 16.2 g, 102 mmol) at rt and stirred at this temperature, monitoring by LCMS. Upon reaction completion, the reaction mixture was diluted with 50 ml water, and extracted with TBME(3x). The combined organic layers were washed with brine, dried over NazSO, filtered, and concentrated in vacuo. The residue obtained was diluted with water (30 mL) and extracted with pentane (8x3). The combined organic layers were washed with brine, dried over NazSO, filtered, and concentrated in vacuo to give the title compound which was used in the next step without further purification.
LCMS (Method B): Rt 0.54 min; m/z = 127 (M+H); 1H NMR (400 MHz, CDCI3) 5 ppm: 7.28 (d, J=2.13 Hz, 1 H) 5.47 (d, J=2.13 Hz, 1 H) 4.08 (q, J=7.09 Hz, 2 H) 3.64 (s, 3 H) 1 .41 (t, J=7.09 Hz, 3 H)
Step 2: Preparation of methyl 4-(5-ethoxy-1 -methyl-pyrazol-4-yl)cuinoline-2-carboxylate
In a Supelco™ reaction vial, a suspension of methyl 4-bromoquinoline-2-carboxylate (300 mg, 1 .07 mmol, CAS [139896-91 -6]), 5-ethoxy-1 -methyl-pyrazole (0.289 mg, 1.61 mmol) and potassium acetate (212 mg, 2.14 mmol) in N,N-Dimethylacetamide (3 mL) was purged with nitrogen for 10 mins. To this was added Palladium(ll)acetate (13 mg, 0.05mmol), the vial sealed, and the reaction heated at 140°C, monitoring by LCMS. After reaction completion, the reaction mixture was cooled, quenched with water, and extracted with EtOAc (3x). The combined organic layers were washed with brine, dried over NazSO, filtered, and concentrated in vacuo. The crude product was adsorbed over Celite and purified by normal phase column eluting with 60% EtOAc in cyclohexane to give the title compound. LCMS (Method B): Rt 1 .04 min; m/z = 312 (M+H+)
Step 3. Preparation of 4-(5-ethoxy-1 -methyl-pyrazol-4-yl)-A/-pentyl-guinoline-2-carboxamide (Compound P-6, Table P)
In a Supelco™ reaction vial, methyl 4-(5-ethoxy-1 -methyl-pyrazol-4-yl)quinoline-2-carboxylate (20 mg, 0.061 mmol) was treated with pentan-1 -amine (0.01 1 g, 0.12 mmol), the flask sealed and heated at 90°C in the microwave. After reaction completion (monitoring by LCMS), the reaction mixture was diluted with water (50 ml) and extracted with EtOAc (50 ml x 2). The combined organic layers were washed with brine, dried over NazSC , and concentrated in vacuo to obtain the crude product. This was dissolved in EtOAc, adsorbed on celite and purified by reverse phase chromatography (50-60% acetonitrile in water) to afford the title compound as a gummy mass.
LCMS (Method B): Rt 1 .22 min; m/z = 367 (M+H); 1H NMR (400 MHz, CDCI3) 5 ppm: 8.36 - 8.40 (m, 1 H) 8.34 (s, 1 H) 8.1 1 - 8.19 (m, 2 H) 7.80 (t, 1 H) 7.64 - 7.67 (m, 1 H) 7.63 (s, 1 H) 3.84 (s, 3 H) 3.76 (q, 2 H) 3.53 - 3.59 (m, 2 H) 1 .66 - 1 .79 (m, 2H) 1 .38 - 1 .49 (m, 4 H) 1 .13 (t, 3 H) 0.92 - 0.99 (m, 3 H)
Example Prep-2 Preparation 8-cvano-4-(5-methoxy-1 -methyl-pyrazol-4-yl)-A/-pentyl-ouinoline-2- carboxamide (Compound P-2, Table P)
Compound P-2, Table P
Step 1 : Preparation of dimethyl (Z)-2-(2-cvanoanilino)but-2-enedioate
A solution of 2-aminobenzonitrile (17 mmol, 2.0 g) and dimethyl but-2-ynedioate (17 mmol, 2.5 g) in methanol (25 mL) was heated at 80°C, with the reaction being monitored by LCMS. Upon reaction completion, the mixture was cooled and concentrated in vacuo to give the title compound as a white solid that was used in the next step without further purification.
LCMS (Method B): Rt 1 .1 1 min, m/z = 261 (M+H); 1H NMR (400 MHz, CDCI3) 6 ppm: 9.94 (s, 1 H) 7.59 (dd, J=7.75, 1 .50 Hz, 1 H) 7.46 (t, J=7.89 Hz, 1 H) 7.27 (s, 1 H) 7.14 (t, J=7.43 Hz, 1 H) 6.82 (d, J=8.25 Hz, 1 H) 5.73 (s, 1 H), 3.79 (s, 3 H), 3.74 (s, 3 H) Step 3: Preparation of methyl 8-cvano-4-hvdroxy-guinoline-2-carboxylate
A solution of dimethyl (E)-2-(2-cyanoanilino)but-2-enedioate (3 g, 11.5 mmol) in diphenyl ether (15 mL) was heated at 250°C, monitoring by LCMS. Upon reaction completion, the reaction mass was adsorbed over silica and purified by normal phase column chromatography eluting with 0-70% EtOAc in cyclohexane to give the title compound.
LCMS (Method B): Rt 0.88 min, m/z = 229 (M+H)
Step 4: Preparation of methyl 4-bromo-8-cvano-guinoline-2-carboxylate
A sample of methyl 8-cyano-4-hydroxy-quinoline-2-carboxylate (2.5 g, 11 mmol) in acetonitrile (25 mL) was treated with phosphorus oxybromide (6.3 g, 22 mmol) and potassium carbonate (3.9 g, 27 mmol) and the reaction mixture was refluxed at 80°C, monitoring by LCMS. Upon reaction completion, the reaction mixture was cooled, and added slowly added to an ice-cold solution of saturated NazCOs until the pH of the solution was basic. The mixture was diluted with EtOAc, the EtOAc layer decanted, and the aqueous layer back extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo, to give the title compound which was used in the next step without further purification.
LCMS (Method B): Rt 1 .09 min, m/z = 291/293 (M+H)
Step 5: Preparation of 5-methoxy-1 -methyl-4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)pyrazole
In a Supelco™ reaction vial, a suspension of 4-bromo-5-methoxy-1 -methyl-pyrazole (582 mg, 3.05 mmol, CAS [89717-68-0]), 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-1 ,3,2- dioxaborolane (0.947 mg, 3.66 mmol), and potassium carbonate (425 mg, 3.0467076 mmol) in 1 ,4- dioxane (3 mL) was degassed with N2. To this suspension was then added then Palladium(ll)acetate (14.4 mg, 0.061 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (6.0 mg, 0.122 mmol) the vial sealed, and the mixture stirred and heated under N2 at 90°C. Upon reaction completion (monitoring by LCMS) the reaction mixture was diluted with EtOAc and filtered over celite. The filtrate was diluted with water, the organic layer decanted, and the aqueous phase extracted with EtOAc (2x). The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by chromatography over silica gel to afford the title compound.
LC-MS (Method A): Rt 0.91 min, m/z = 239 (M+H).; 1H NMR (400 MHz, CDCI3) 5 ppm: 1.32 (s, 124 H) 3.64 (s, 3 H) 4.13 (s, 3 H) 7.60 (s, 1 H)
Step 6: Preparation of methyl 8-cvano-4-(5-methoxy-1 -methyl-Dyrazol-4-yl)guinoline-2-carboxylate
In a Supelco™ reaction vial, a solution of methyl 4-bromo-8-cyano-quinoline-2-carboxylate (110 mg, 0.38 mmol) and added potassium carbonate (0.104 mg, 0.77 mmol) in 2-methyltetrahydrofuran (1.1 mL) and water (0.1 mL) was flushed with argon for 5 min. To this solution was added 1 ,1'- bis(diphenylphosphino)ferrocene-palladium(ii)dichloride dichloromethane complex (31 mg, 0.038 mmol) and 5-methoxy-1 -methyl-4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)pyrazole (180 mg, 0.45 mmol). The vessel was sealed and heated at 70°C under argon, monitoring by LCMS. After reaction completion, the reaction mixture was cooled rt and diluted with water. The suspension was filtered and the aqueous layer from the filtrate was extracted with EtOAc (3x). The combined organic layers were washed with brine, dried over MgSO4 and concentrated to give the title compound which was used without further purification in the next step.
LCMS (Method A): Rt 0.84 min, m/z = 323 (M+H)
Step 6: Preparation of 8-cvano-4-(5-methoxy-1 -methyl-pyrazol-4-yl)-A/-pentyl-guinoline-2-carboxamide (compound P-2, Table P)
In a Supelco™ reaction vial, a suspension of methyl 8-cyano-4-(5-methoxy-1 -methyl-pyrazol-4- yl)quinoline-2-carboxylate (0.1 g, 0.155 mmol) in toluene (0.8 mL) was treated with 1 ,5,7- triazabicyclo[4.4.0]dec-5-ene (6.6 mg, 0.046 mmol) followed by pentan-1 -amine (20 mg, 0.027 mL, 0.23 mmol). The vial was sealed and heated at 70°C monitoring by LCMS. After reaction completion, the reaction mixture was concentrated in vacuo and the residue obtained was purified by chromatography over silica gel to yield the title compound. LCMS (Method A): Rt 1 .04 min, m/z = 378 [M+H]; 1H NMR (400 MHz, CDCI3) 5 ppm: 8.44 - 8.49 (m, 1 H) 8.41 (br d, J=5.1 Hz, 2 H) 8.22 (d, J=6.5 Hz, 1 H) 7.71 (br s, 1 H) 7.62 (br s, 1 H) 3.86 (s, 3 H) 3.53 - 3.65 (m, 5 H) 1 .75 (br t, J=7.1 Hz, 2 H) 1 .37 - 1 .51 (m, 4 H) 0.93 - 1 .01 (m, 3 H)
Example Prep-3: Preparation of 8-cvano-4-(5-hvdroxy-1 -methyl-pyrazol-4-yl)-A/-pentyl-ouinoline-2- carboxamide (Compound P-7, Table P) Compound P-7, Table P
A solution of 8-cyano-4-(5-methoxy-1 -methyl-pyrazol-4-yl)-A/-pentyl-quinoline-2-carboxamide (7 mg, 0.018 mmol), lithium chloride (0.0023 mg, 0.056) in DMF (0.2 mL) was stirred at 100°C, monitoring by LCMS. Upon reaction completion, the mixture was cooled and dilute with H2O, and extracted with EtOAc. The combined organic layers were washed with brine, dried over NazSO, filtered and concentrated in vacuo. Purification by combiflash chromatography, eluting with EtAOc/EtOH 3:1 in cyclohexane gave the title compound.
LCMS (Method A): Rt 0.87 min, m/z = 364 (M+H); 1H NMR (400 MHz, CDCI3) 5 ppm 9.1 1 (s, 1 H) 8.46 (s, 1 H) 8.33 - 8.41 (m, 2 H) 7.87 - 7.92 (m, 1 H) 7.75 (dd, J=8.5, 7.1 Hz, 1 H) 7.60 (s, 1 H) 3.59 (s, 3 H) 3.47
- 3.53 (m, 2 H) 1 .63 - 1 .78 (m, 2 H) 1 .49 (m, 4 H) 1 .03 (br t, J=6.9 Hz, 3 H)
Example Prep-4: Preparation of 4-(5-cvano-1 -methyl-pyrazol-4-yl)-A/-pentyl-guinoline-2-carboxamide
P-5, Table compound P-5, Table P
Step 1 : Preparation of 2-methylpyrazole-3-carboxamide
A suspension of 2-methylpyrazole-3-carboxylic acid (300 mg, 2.379 mmol) and ammonium carbonate (0.571 mg, 5.947 mmol) in DMF (3 mL) was cooled to 0°C, and treated with N,N-diethylethanamine (1 .34 mL, 972 mg, 9.51 mmol) dropwise, followed by 1 -hydroxybenzotriazole (0.744 mg, 5.233 mmol) and 1 - ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC, 1 .024 g, 5.233 mmol). The resulting reaction mixture was allowed to warm to rt mixture and monitored by LCMS and TLC. Upon completion, the reaction mixture was diluted with water (30 mL) and extracted with EtOAc (20 mlx3). The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. This gave the title compound as an off white solid.
LCMS (Method B): Rt: 0.15 min, m/z 126 (M+H); 1H NMR (400 MHz, DMSO-d6) 6 ppm 7.95 (s, 1 H) 7.48 (br s, 1 H) 7.43 (d, J=2.00 Hz, 1 H) 6.85 (d, J=2.00 Hz, 1 H) 4.04 (s, 3 H)
Step 2: Preparation of 2-methylDyrazole-3-carbonitrile
To a stirred solution of 2-methylpyrazole-3-carboxamide (810 mg, 5.502 mmol) in pyridine (1 1 .0 mL) at 0°C under N2 was added slowly phosphorus oxychloride (0.7771 mL, 1 .28 g, 8.25mmol). The reaction mixture was stirred at rt (monitoring by TLC). Upon completion, the pH of the reaction mixture was adjusted to pH 3 by the dropwise addition of 6N HCI. The mixture was extracted with EtOAc (3x), and the combined organic layers were washed with brine, dried over NazSO and concentrated in vacuo to give the title compound as a brown gum. The compound was used in the next step without further purification.
1H NMR (400 MHz, DMSO-d6) 6 ppm: 7.69 (d, J=2.13 Hz, 1 H) 7.14 (d, J=2.13 Hz, 1 H) 4.01 (s, 3 H)
Step 3: Preparation of methyl 4-(5-cvano-1 -methyl-pyrazol-4-yl)auinoline-2-carboxylate
Carried out analogously to Example 1 , step 2 by reaction of methyl 4-bromoquinoline-2-carboxylate (140 mg, 0.53 mmol) and 2-methylpyrazole-3-carbonitrile (84 mg, 0.79 mmol) in the presence of potassium acetate (104 mg, 1 .05 mmol) and palladium(ll)acetate (6.2 mg, 0.026 mmol) in N,N-Dimethylacetamide (1 .4 mL) at 140°C. This gave the title compound after purification.
LCMS (Method B): Rt 1 .01 min, m/z = 293 (M+H); 1H NMR (400 MHz, CDCI3) 5 ppm 8.42 (d, J=8.38 Hz, 1 H) 8.23 (s, 1 H) 8.00 (d, J=8.38 Hz, 1 H) 7.84 - 7.91 (m, 2 H) 7.73 (dd, 1 H) 4.23 (s, 3 H) 4.12 (s, 3 H)
Step 4: Preparation of lithium;4-(5-cyano-1 -methyl-pyrazol-4-yl)quinoline-2-carboxylate 66
To a solution of methyl 4-(5-cyano-1 -methyl-pyrazol-4-yl)quinoline-2-carboxylate (25 mg, 0.081 mmol) in THF (0.25 mL) and water (0.1 mL) was added lithium hydroxide hydrate (13.6 mg, 0.32 mmol) at rt (monitoring by LCMS). Upon reaction completion, the solvent was removed by concentration in vacuo to give the title compound as a white solid that was used in the following step without further purification. LCMS (Method B): Rt 0.91 min, m/z= 279 (M+H of free acid)
Step 5: Preparation of 4-(5-cvano-1 -methyl-pyrazol-4-yl)-A/-pentyl-guinoline-2-carboxamide (compound P- 5, Table P)
A suspension of lithium;4-(5-cyano-1 -methyl-pyrazol-4-yl)quinoline-2-carboxylate (30 mg, 0.105 mmol) in EtOAc (0.2 mL), was treated with pentan-1 -amine (10 mg, 0.116 mmol), 1 -propanephosphonic anhydride (201 mg, 0.317 mmol), and N,N-diisopropylethylamine (0.0922 mL, 70 mg, 0.528 mmol) at rt. The mixture was monitored by LCMS. Upon reaction completion, the reaction mixture was diluted with water (20 mL) and extracted with EtOAc (2x). The combined organic layers were dried over anhydrous NazSO4, filtered, and concentrated in vacuo to obtain a crude residue which upon reverse phase combiflash purification (eluting with 30-60% acetonitrile in water) yielded the crude title compound as a gummy mass.
LCMS (Method B): Rt 1.19 min; m/z = 348 (M+H)+; 1H NMR (400 MHz, CDCI3) 5 ppm: 8.32 (s, 1 H) 8.28 (br s, 1 H) 8.21 (d, 1 H) 7.96 (d, 1 H) 7.81 - 7.86 (m, 2 H) 7.68 (ddd, 1 H) 4.22 (s, 3 H) 3.51 - 3.60 (m, 2 H) 1 .68 - 1 .78 (m, 2 H) 1 .33 - 1 .53 (m, 4 H) 0.85 - 1 .05 (m, 3 H)
Examples of synthesized compounds are shown in Table P.
Table P: Synthesised compounds and spectral and physical chemical data
BIOLOGICAL EXAMPLES
Example B1 : Alternaria so/an/7 tomato / (early blight)
Tomato leaf disks cv. Baby are placed on 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 2 days after application. The inoculated leaf disks are incubated at 23°C I 21 °C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) 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 on untreated check disk leaf disks (5 to 7 days after application). The following compounds gave at least 80% control of Alternaria solani at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-5, P- 6, P-10, P-11 , P-12, P-14
Example B2: Botryotinia fuckeliana (Botrytis cinerea) / (Gray mould)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-6, P-10, P-11 , P-12
Example B3: Glomerella lagenarium (Colletotrichum lagenarium) I (Anthracnose)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-5, P-6, P-10, P-11 , P-12
Example B4: Fusarium culmorum I (Head blight)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-5, P-6, P-11 , P-12
Example B5: Phaeosphaeria nodorum (Septoria nodorum) I wheat I (Glume blotch)
Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (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 2 days after application. The inoculated test leaf disks are incubated at 20°C and 75% 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 (5 to 7 days after application). The following compounds gave at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-4, P-5, P-6, P-10, P-11 , P-12, P-13, P-14
Example B6: Monographella nivalis (Microdochium nivale) I (foot rot cereals)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-5, P-6, P-10, P-11 , P-12 Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-4, P-5, P-6, P-10, P-11 , P-12, P-13, P-14
Example B8: Magnaporthe cirisea (Pyricularia oryzae) / (Rice Blast)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Magnaporthe grisea at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-4, P-5, P-6, P-10, P-11 , P-12, P-13, P-14
Example B9: Pyrenophora teres / barlev / (Net blotch)
Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 20°C and 65% 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 disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 to 7 days after application). The following compounds gave at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-4, P-5, P-6, P-10, P-11 , P-12, P-13, P-14
Example B10: Thanatephorus cucumeris (Rhizoctonia solani) / (foot rot, damping-off)
Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO-solution of the test compounds into a microtiter plate (96- well format), the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Thanatephorus cucumeris at 20ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-3, P- 5, P-6, P-10, P-11 , P-12
Example B11 : Mycosphaerella graminicola (Septaria tritici) / liquid culture (Septaria blotch)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-3, P-4, P-5, P-6, P-10, P-11 , P-12, P-13, P-14
Example B12: Cercospora soiina (froqeve leaf spot of soybean)
Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). A DMSO solution of the test compounds was placed into a microtiter plate (96-well format) and the nutrient broth containing the fungal spores was added to it. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 3 to 4 days at 620nm. The following compounds gave at least 80% control of Cercospora sojina at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-6, P-10, P-12
Example B13: Corynespora cassiicola (target leaf spot of tomato)
Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). A DMSO solution of the test compounds was placed into a microtiter plate (96-well format) and the nutrient broth containing the fungal spores was added to it. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 3 to 4 days at 620nm. The following compounds gave at least 80% control of Corynespora cassiicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-3, P-4, P-5, P- 6, P-10, P-12
Example B14: Blumeria oraminis f. so. tritici (Erysiphe oraminis f. so. tritici) / wheat / (Powdery mildew on wheat)
Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks are incubated at 20 °C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 to 8 days after application). The following compounds gave at least 80% control of Blumeria graminis f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-2, P-10, P-11 , P-12
Example B15: Fusarium culmorum / wheat / (Head blight)
Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The spikelets are inoculated with a spore suspension of the fungus 1 day after application. The inoculated spikelets are incubated at 20 °C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 to 8 days after application). The following compounds gave at least 80% control of Fusarium culmorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-3, P-11 , P-12
Example B16: Gibberella zeae (Fusarium araminearum) I wheat I (Head blight)
Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application, the spikelets are inoculated with a spore suspension of the fungus. The inoculated test leaf disks are incubated at 20 °C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber, the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 to 8 days after application). The following compounds gave at least 80% control of Gibberella zeae at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-6, P-12
Example B17: Sclerotinia sclerotiorum / liquid culture (cottony rot)
Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-11 , P-12

Claims

1 . A compound of formula (I) wherein
R1 is selected from hydrogen, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or Cs-Ce-cycloalkyl;
R2 is selected from cyano, hydroxy, amino, Ci-C4-alkoxy, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-haloalkoxy, Ci-C4-haloalkylsulfanyl, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, C3-C6- cycloalkyloxy, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, or C1-C4- alkylsulfonyl;
R3 is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl;
R4 is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, or Cs-Ce-cycloalkyl;
B1 is selected from CR7, or N;
B2 is selected from CR8, or N;
B3 is selected from CR9, or N;
R5, R6, R7, R8 and R9 are independently selected from hydrogen, halogen, hydroxy, amino, cyano, carboxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, C3-C6- alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, carbamoyl, Ci-C4-alkylamino, Ci-C4-dialkylamino, C1- C4-alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci-C4- alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heterocycle, or Cs-Ce-cycloalkyl, wherein any of said phenyl and 5- to 6-membered saturated, partially saturated or aromatic heterocycle are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy, and wherein said C3-C6- cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy; and
Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from cyano, nitro, carboxy, hydroxy, Ci-C4-alkyl, C2-C4- alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce-alkenyloxy, C3-C6- alkynyloxy, Cs-Ce-haloalkenyloxy, Cs-Ce-cycloalkyloxy, C3-C6-cycloalkyl-Ci-C4-alkoxy, C3-C6- halocycloalkyl-Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C1-C4- alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, Cs-Ce-cycloalkyloxycarbonyl, Cs- C6-cycloalkyl-Ci-C4-alkyloxycarbonyl, C3-C6-halocycloalkyl-Ci-C4-alkyloxycarbonyl, C1-C4- haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, Cs-Ce-cycloalkycarbonyloxy, N-Ci-C4-alkoxy-C-Ci- C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heterocycle, or C3-C6- cycloalkyl, wherein any of said 4-, 5- or 6-membered saturated, partially saturated or aromatic heterocycle contains 1 , 2 or 3 heteroatoms selected from O, S or N, with the proviso that no more than one is O or S, wherein any of said phenyl and said 5- to 6-membered saturated, partially saturated or aromatic heterocycle, are unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy, and wherein any of said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy; or an agrochemically acceptable salt, or N-oxide thereof.
2. The compound according to claim 1 , wherein R1 is Ci-Cs-alkyl; and R3 is hydrogen or Ci-Cs-alkyl.
3. The compound according to claim 1 or claim 2, wherein R4 is hydrogen; R5 is hydrogen; and R6 is hydrogen or Ci-Cs-alkyl.
4. The compound according to any one of claims 1 to 3, wherein R1 is methyl; and R3 is hydrogen.
5. The compound according to any one of claims 1 to 4, wherein R7, R8, and R9 are independently selected from hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, C1- Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or Cs-Ce-cycloalkyl, and wherein any of said C3-C6- cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, or Ci- Cs-alkyl.
6. The compound according to any one of claims 1 to 5, wherein B1 is CR7; B2 is CR8; and B3 is N.
7. The compound according to claim 6, wherein R7 is hydrogen, halogen, cyano, Ci -Cs-alkyl, C1-C3- alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl; and R8 is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, C1-C3- alkylcarbonyl, Ci-Cs-alkoxycarbonyl, or cyclopropyl.
8. The compound according to any one of claims 1 to 7, wherein R2 is cyano, hydroxy, amino, Ci- Cs-alkoxy, Ci-C2-alkylamino, di(Ci-C2-alkyl)amino, Ci-C2-haloalkoxy, Ci-C2-haloalkylsulfanyl, C3- Ce-cycloalkyloxy, Ci-Cz-alkoxy-Ci-Cz-alkyl, Ci-C2-alkylsulfanyl, Ci-C2-alkylsulfinyl, or C1-C2- alkylsulfonyl.
9. The compound according to claim 8, wherein R2 is cyano, Ci-Cs-alkoxy, or Ci-C2-alkylsulfanyl.
10. The compound according to any one of claims 1 to 9, wherein Z1 is selected from Ci-Ce-alkyl, wherein said Ci-Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkyl, Ci-C2-haloalkoxy, C1-C4- alkylcarbonyl, Ci-C4-alkoxycarbonyl, or Cs-Ce-cycloalkyl, wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, cyano, Ci-C2-alkyl, or C1- C2-haloalkyl.
11. The compound according to claim 10, wherein Z1 is selected from Ci-Ce-alkyl, wherein said Ci- Ce-alkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-C2-haloalkyl, Ci-C2-haloalkoxy, Ci-C4-alkylcarbonyl, C1-C4- alkoxycarbonyl, or cyclopropyl.
12. An agrochemical composition comprising a fungicidally effective amount of a compound as defined in any one of claims 1 to 11 .
13. The agrochemical composition according to claim 12, further comprising at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier
14. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound as defined in any one of claims 1 to 11 , or a composition comprising said compound, is applied to the plants, to parts thereof or the locus thereof.
15. Use of a compound according to any one of claims 1 to 11 as a fungicide.
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