WO2021074309A1 - Dérivés de 1-(3-quinolyl)-3,4-dihydroisoquinoléine utilisés en tant que fongicides pour lutter contre des phytopathogènes spécifiques - Google Patents

Dérivés de 1-(3-quinolyl)-3,4-dihydroisoquinoléine utilisés en tant que fongicides pour lutter contre des phytopathogènes spécifiques Download PDF

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WO2021074309A1
WO2021074309A1 PCT/EP2020/079068 EP2020079068W WO2021074309A1 WO 2021074309 A1 WO2021074309 A1 WO 2021074309A1 EP 2020079068 W EP2020079068 W EP 2020079068W WO 2021074309 A1 WO2021074309 A1 WO 2021074309A1
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methyl
hydrogen
fluoro
cyano
chloro
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PCT/EP2020/079068
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English (en)
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Matthias Weiss
Laura Quaranta
Farhan BOU HAMDAN
Atul Mahajan
Simon Williams
Jagadeesh Prathap KILARU
Indira SEN
Stephane BIERI
Martin Diggelmann
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Syngenta Crop Protection Ag
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Publication of WO2021074309A1 publication Critical patent/WO2021074309A1/fr

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    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • 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

Definitions

  • the present invention relates to microbiocidal dihydroisoquinoline derivatives, eg, as active ingredients, which have microbiocidal activity, in particular fungicidal activity.
  • the invention also relates to the preparation of these dihydroisoquinoline derivatives, to intermediates useful in the preparation of these dihydroisoquinoline derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these dihydroisoquinoline derivatives, and to the preparation of these compositions.
  • the present invention also relates to methods of preventing or controlling the infestation of useful plants by a phytopathogen selected from (i) Mycosphaerella graminicola ( Septoha tritici), (ii) Monographella nivalis ( Microdochium nivale) or (iii) Fusarium culmorum and/or Gibberella zeae ( Fusarium graminearum) on cereals, in particular wheat.
  • a phytopathogen selected from (i) Mycosphaerella graminicola ( Septoha tritici), (ii) Monographella nivalis ( Microdochium nivale) or (iii) Fusarium culmorum and/or Gibberella zeae ( Fusarium graminearum) on cereals, in particular wheat.
  • Monographella nivalis ( Microdochium nivale) is a fungal plant pathogen that attacks cereals during all stages of development, causing various diseases such as, inter alia, seedling blight, snow mold, foot rot, and ear blight.
  • Gibberella zeae (anamorph: Fusarium graminearum) is a fungal plant pathogen which causes fusarium head blight, a devastating disease on wheat and barley.
  • Fusarium culmorum is likewise a fungal plant pathogen and the causal agent of seedling blight, foot rot, ear blight, stalk rot, common root rot and other diseases of cereals, and is a causal agent also of Fusarium head blight.
  • Fusarium head blight (FHB) also known as scab, is a fungal disease of small grain cereals including wheat, barley, oats, rye, corn, triticale, canary seed and some forage grasses.
  • Wheat is a grass cultivated for its seed, a cereal grain which is a worldwide staple food.
  • Septoria tritici blotch is caused by the ascomycete fungus Mycosphaerella graminicola (asexual stage: Septoria tritici) and is one of the most important diseases of wheat - it is one of the most economically damaging diseases of this crop (being currently the most economically relevant disease in Europe).
  • Certain fungicidal quinoline compounds are described in WO 2005/070917 and WO 2018/190326. However, their use controlling or preventing the phytopathogen Mycosphaerella graminicola Monographella nivalis ( Microdochium nivale) and Fusarium culmorum and/or Gibberella zeae ( Fusarium graminearum), has not been demonstrated.
  • R 1 is fluoro, cyano, chloro or methyl
  • R 2 is hydrogen or fluoro
  • R 3 is hydrogen or methyl
  • R 4 is Ci-C 4 alkyl or Ci-C 4 haloalkyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl ring, wherein the ring structure can be substituted with 1 to 4 fluoro atoms;
  • R 6 is hydrogen, hydroxy, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Cs-Cscycloalkoxy, Ci-C 4 haloalkoxy, cyano, or Cs-Cscycloalkyl;
  • R 7 is hydrogen or methyl
  • R 8 is hydrogen or methyl
  • R 9a is hydrogen, Ci-C 4 alkyl or Cs-Cscycloalkyl
  • R 9b is Ci-C 4 alkyl or Cs-Cscycloalkyl; and each R 9c is independently selected from hydrogen, Ci-C 4 alkyl or both R 9c together with the nitrogen atom to which they are connected atom form a 4-, 5- or 6-membered saturated heterocycle; or a salt, enantiomer, tautomer and/or an N-oxide thereof, provided that the compound is not one of the following compounds:
  • an agrochemical composition comprising a fungicidally effective amount of a compound of Formula (I).
  • Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically- acceptable diluent or carrier.
  • a phytopathogen selected from:
  • R 1 is fluoro, cyano, chloro or methyl
  • R 2 is hydrogen or fluoro
  • R 3 is hydrogen or methyl
  • R 4 is Ci-C 4 alkyl or Ci-C 4 haloalkyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl ring, wherein the ring structure can be substituted with 1 to 4 fluoro atoms;
  • R 6 is hydrogen, hydroxy, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Cs-Cscycloalkoxy, Ci-C 4 haloalkoxy, cyano, or Cs-Cscycloalkyl;
  • R 7 is hydrogen or methyl
  • R 8 is hydrogen or methyl
  • R 9a is hydrogen, Ci-C 4 alkyl or Cs-Cscycloalkyl
  • R 9b is Ci-C 4 alkyl or Cs-Cscycloalkyl; and each R 9c is independently selected from hydrogen, Ci-C 4 alkyl or both R 9c together with the nitrogen atom to which they are connected atom form a 4-, 5- or 6-membered saturated heterocycle; or a salt, enantiomer, tautomer and/or an N-oxide thereof.
  • a compound of Formula (I) as a fungicide, including against the phytopathogens (i) Mycosphaerella graminicola, (ii) Monographella nivalis (Microdochium nivaie), or (iii) Fusarium culmorum and/or Gibberella zeae ( Fusarium graminearum).
  • the use may exclude methods for the treatment of the human or animal body by surgery or therapy.
  • substituents are indicated as being optionally substituted, this means that they may or may not carry one or more identical or different substituents, e.g. one to three substituents. Normally not more than three such optional substituents are present at the same time.
  • substituents are indicated as being substituted, e.g. alkyl, this includes those groups that are part of other groups, e.g. the alkyl in alkylthio.
  • halogen refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • Alkyl substituents may be straight-chained or branched. Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, n- propyl, n-butyl, n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl, iso-butyl, sec-butyl, fe/f-butyl or iso-amyl.
  • Alkenyl substituents can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or ⁇ -configuration. Examples are vinyl and allyl.
  • the alkenyl groups are preferably C2-C6, more preferably C 2 -C 4 and most preferably C 2 -C3alkenyl groups.
  • Alkynyl substituents can be in the form of straight or branched chains. Examples are ethynyl and propargyl.
  • the alkynyl groups are preferably C2-C6, more preferably C 2 -C 4 and most preferably C 2 -C3alkynyl groups.
  • Haloalkyl groups may contain one or more identical or different halogen atoms and, for example, may stand for CH2CI, CHCI2, CCI3, CH2F, CHF2, CF 3 , CF2CI, CF3CH2, CH3CF2, CF3CF2 or CCI3CCI2.
  • Haloalkenyl groups are alkenyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, 2,2-difluorovinyl or 1 ,2-dichloro-2-fluoro-vinyl.
  • Alkoxy means a radical -OR, where R is alkyl, e.g. as defined above. Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-methylethoxy, propoxy, butoxy, 1-methylpropoxy and 2- methylpropoxy.
  • Cyano means a -CN group.
  • Nitro means a -NO2 group.
  • Amino means an -NH2 group.
  • Hydroxyl or hydroxy stands for a -OH group.
  • Cycloalkyl may be saturated or partially unsaturated, preferably fully saturated, and is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cyclohexenyl.
  • Aryl groups are aromatic ring systems which can be in mono-, bi- ortricyclic form. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyl and naphthyl, phenyl being most preferred. Where an aryl moiety is said to be substituted, the aryl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
  • Heteroaryl groups are aromatic ring systems containing at least one heteroatom and consisting either of a single ring or of two or more fused rings.
  • single rings will contain up to three heteroatoms and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur.
  • monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g.
  • [1 ,2,4] triazolyl furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl.
  • bicyclic groups include purinyl, quinolinyl, cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiazolyl.
  • Monocyclic heteroaryl groups are preferred, pyridyl being most preferred. Where a heteroaryl moiety is said to be substituted, the heteroaryl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
  • asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in optically 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).
  • formula (I) is intended to include all possible tautomers.
  • the present invention includes all possible tautomeric forms for a compound of formula (I).
  • the compounds of formula (I) are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable 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.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are, in any combination thereof, as set out below:
  • R 1 is fluoro or chloro. Most preferably, R 1 is fluoro.
  • R 2 is fluoro
  • R 1 and R 2 are fluoro. In other preferred embodiments, R 1 is fluoro and R 2 is hydrogen.
  • R 3 is methyl
  • R 4 is Ci-C3alkyl or Ci-C3haloalkyl; or R3 and R4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring, wherein the ring structure can be substituted with 1 to 2 fluoro atoms. More preferably, R 4 is methyl, ethyl or Ci-C2fluoroalkyl; or R3 and R4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring, wherein the ring structure can be substituted with 1 to 2 fluoro atoms. Most preferably, R 4 is methyl or ethyl; or R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring.
  • R 5 is halogen, Ci-C3alkyl, C 2 -C3alkenyl, C 2 -C3alkynyl, Ci-C3alkoxy, Ci-C3haloalkyl, Ci-C3haloalkoxy, cyano, or C3-C 4 cycloalkyl. More preferably, R 5 is fluoro, chloro, bromo, iodo, Ci- C3alkyl, Ci-C3alkoxy, Ci-C3fluoroalkyl, Cifluoroalkoxy, cyano, or cyclopropyl.
  • R 5 is fluoro, chloro, bromo, iodo, methyl, ethyl, methoxy, trifluoromethyl, difluoromethyl, difluoromethoxy, cyano, or cyclopropyl.
  • R 6 is hydrogen, hydroxy, halogen, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3alkoxy, Ci- C3haloalkoxy, cyano, or Cs-Cscycloalkyl. More preferably, R 6 is hydrogen, hydroxy, fluoro, chloro, bromo, methyl, ethyl, Ci-C2fluoroalkyl, Ci-C2alkoxy, Ci-C2fluoroalkoxy, cyano, or cyclopropyl.
  • R 6 is hydrogen, hydroxy, fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, methoxy, cyano, or cyclopropyl. Most preferably, R 6 is hydrogen, fluoro, chloro, bromo, methyl, methoxy or cyano. In certain preferred embodiments, R 6 is Ci-C3alkyl, in particular methyl.
  • R 5 is halogen or cyano and R 6 is Ci-C3alkyl, and preferably, R 5 is chloro, bromo or cyano and R 6 is methyl.
  • R 7 is hydrogen and R 8 is hydrogen or methyl or R 7 is hydrogen or methyl and R 8 is hydrogen. Most preferably, R 7 and R 8 are both hydrogen.
  • the phytopathogen is Mycosphaerella graminicola ( Septoria tritici).
  • the phytopathogen is Monographella nivalis (Microdochium nivale).
  • the phytopathogen is Fusarium culmorum and/or Gibberella zeae ( Fusarium graminearum).
  • a preferred group of compounds of formula (I) for use according to the invention are those of formula (1-1) which are compounds of formula (I) wherein:
  • R 1 is fluoro or chloro
  • R 2 is hydrogen or fluoro
  • R 3 is hydrogen or methyl
  • R 4 is Ci-C3alkyl or Ci-C3haloalkyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring, wherein the ring structure can be substituted with 1 to 2 fluoro atoms;
  • R 5 is halogen, Ci-C3alkyl, C2-C3 alkynyl, C2-C3 alkenyl, Ci-C3alkoxy, Ci-C3haloalkyl, Ci- C3haloalkoxy, cyano, or C3-C 4 cycloalkyl;
  • R 6 is hydrogen, hydroxy, halogen, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3alkoxy, Ci-C3haloalkoxy, cyano, or Cs-Cscycloalkyl;
  • R 7 is hydrogen or methyl
  • R 8 is hydrogen or methyl; or a salt, enantiomer, tautomer and/or an N-oxide thereof.
  • a further preferred group of compounds of formula (I) for use according to the invention are those of formula (I-2) which are compounds of formula (I) wherein:
  • R 1 is fluoro
  • R 2 is hydrogen or fluoro
  • R 3 is hydrogen or methyl
  • R 4 is methyl, ethyl or Ci-C2fluoroalkyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring, wherein the ring structure can be substituted with 1 to 2 fluoro atoms;
  • R 5 is fluoro, chloro, bromo, iodo, Ci-C3alkyl, Ci-C3alkoxy, Ci-C3fluoroalkyl, Cifluoroalkoxy, cyano, or cyclopropyl;
  • R 6 is hydrogen, fluoro, chloro, bromo, methyl, ethyl, Ci-C2fluoroalkyl, Ci-C2alkoxy, Ci- C2fluoroalkoxy, cyano, or cyclopropyl;
  • R 7 is hydrogen and R 8 is hydrogen or methyl or R 7 is hydrogen or methyl and R 8 is hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof.
  • a further preferred group of compounds of formula (I) for use according to the invention are those of formula (I-3) which are compounds of formula (I) wherein:
  • R 1 is fluoro
  • R 2 is hydrogen or fluoro
  • R 3 is methyl
  • R 4 is methyl or ethyl; or R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring;
  • R 5 is fluoro, chloro, bromo, iodo, methyl, ethyl, methoxy, trifluoromethyl, difluoromethyl, difluoromethoxy, cyano, or cyclopropyl;
  • R 6 is hydrogen, fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, methoxy, cyano, or cyclopropyl [most preferably R 6 is hydrogen, fluoro, chloro, bromo, methyl, methoxy or cyano]; and
  • R 7 and R 8 are both hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof.
  • a further preferred group of compounds of formula (I) for use according to the invention are those of formula (I-4) which are compounds of formula (I) wherein:
  • R 1 is fluoro
  • R 2 is hydrogen or fluoro
  • R 3 is methyl and R 4 is methyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclopentyl ring
  • R 5 is chloro, bromo or cyano
  • R 6 is hydrogen or methyl; and R 7 and R 8 are both hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof.
  • Embodiments according to the invention are provided as set out below.
  • Embodiment 1 provides a method of preventing or controlling the infestation of useful plants by a phytopathogen selected from (i) Mycosphaerella graminicola, (ii) Monographella nivalis (Microdochium nivaie), or (iii) Fusarium culmorum and/or Gibberella zeae ( Fusarium graminearum), on cereals, in particular wheat, which comprises applying to the phytopathogen, to the locus of the phytopathogen, or to a plant susceptible to attack by the phytopathogen, or to propagation material thereof, a fungicidally effective amount of a compound of formula (I) or a salt, enantiomer, tautomer and/or an N-oxide thereof, as defined above.
  • a phytopathogen selected from (i) Mycosphaerella graminicola, (ii) Monographella nivalis (Microdochium nivaie), or (iii) Fusarium cul
  • Embodiment 2 provides a method according to embodiment 1 wherein R 1 is fluoro or chloro.
  • Embodiment 3 provides a method according to embodiment 1 or 2 wherein R 3 is methyl.
  • Embodiment 4 provides a method according to any one of embodiments 1 , 2 or 3 wherein R 4 is Ci-C3alkyl or Ci-C3haloalkyl; or R3 and R4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring, wherein the ring structure can be substituted with 1 to 2 fluoro atoms.
  • Embodiment 5 provides a method according to any one of embodiments 1 , 2, 3 or 4 wherein R 5 is halogen, Ci-C3alkyl, C2-C3 alkynyl, C2-C3 alkenyl, Ci-C3alkoxy, Ci-C3haloalkyl, Ci-C3haloalkoxy, cyano, or C3-C 4 cycloalkyl.
  • Embodiment 6 provides a method according to any one of embodiments 1 , 2, 3, 4 or 5 wherein R 6 is hydrogen, halogen, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3alkoxy, Ci-C3haloalkoxy, cyano, or C3- C5cycloalkyl.
  • Embodiment 7 provides a method according to any one of embodiments 1 , 2, 3, 4, 5 or6 wherein R7 is hydrogen and R 8 is hydrogen or methyl or R7 is hydrogen or methyl and Rs is hydrogen .
  • Embodiment 8 provides a method according to any one of embodiments 1 , 2, 3, 4, 5, 6 or 7 wherein R 1 is fluoro.
  • Embodiment 9 provides a method according to any one of embodiments 1 , 2, 3, 4, 5, 6, 7 or 8 wherein R 4 is methyl, ethyl or Ci-C2fluoroalkyl; or R3 and R4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring, wherein the ring structure can be substituted with 1 to 2 fluoro atoms.
  • Embodiment 10 provides a method according to any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8 or 9 wherein R 5 is fluoro, chloro, bromo, iodo, Ci-C3alkyl, Ci-C3alkoxy, Ci-C3fluoroalkyl, Cifluoroalkoxy, cyano, or cyclopropyl.
  • Embodiment 11 provides a method according to any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10 wherein R 6 is hydrogen, fluoro, chloro, bromo, methyl, ethyl, Ci-C2fluoroalkyl, Ci-C2alkoxy, Ci- C2fluoroalkoxy, cyano, or cyclopropyl.
  • Embodiment 12 provides a method according to any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 wherein R 7 and R 8 are both hydrogen.
  • Embodiment 13 provides a method according to any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 wherein R 4 is methyl or ethyl; or R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring.
  • Embodiment 14 provides a method according to any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12 or 13 wherein R 5 is fluoro, chloro, bromo, iodo, methyl, ethyl, methoxy, trifluoromethyl, difluoromethyl, difluoromethoxy, cyano, or cyclopropyl.
  • Embodiment 15 provides a method according to any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13 or 14 wherein R 6 is hydrogen, fluoro, chloro, bromo, methyl, methoxy or cyano.
  • novel compounds of formula (IH) which are compounds of formula (I) wherein,
  • R 1 is fluoro, cyano, chloro or methyl
  • R 2 is hydrogen or fluoro
  • R 3 is hydrogen or methyl;
  • R 4 is Ci-C 4 alkyl or Ci-C 4 haloalkyl; or
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl ring, wherein the ring structure can be substituted with 1 to 4 fluoro atoms;
  • R 6 is hydrogen, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Cs-Cscycloalkoxy, Ci- C 4 haloalkoxy, cyano, or Cs-Cscycloalkyl;
  • R 7 is hydrogen or methyl
  • R 8 is hydrogen or methyl
  • R 9a is hydrogen, Ci-C 4 alkyl or Cs-Cscycloalkyl
  • R 9b is Ci-C 4 alkyl or Cs-Cscycloalkyl; and each R 9c is independently selected from hydrogen, Ci-C 4 alkyl or both R 9c together with the nitrogen atom to which they are connected atom form a 4-, 5- or 6-membered saturated heterocycle; or a salt, enantiomer, tautomer and/or an N-oxide thereof, provided that the compound is not one of the following compounds:
  • the preferred defintions of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined above for compounds of formula (I), whilst taking account of any respective limitations in scope and the provisory clause above for the compounds of formula (IH).
  • Embodiments according to this aspect of the invention are compounds as defined above in any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14 or 15, whilst taking account of any respective limitations in scope and the provisory clause above for the compounds of formula (IH).
  • a preferred novel group of compounds of formula (I) are those of formula (IH-1) which are compounds of formula (IH) wherein
  • R 1 is fluoro or chloro
  • R 2 is hydrogen or fluoro
  • R 3 is hydrogen or methyl
  • R 4 is Ci-C3alkyl or Ci-C3haloalkyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring, wherein the ring structure can be substituted with 1 to 2 fluoro atoms;
  • R 5 is halogen, Ci-C3alkyl, C 2 -C3alkynyl, C 2 -C3alkenyl, Ci-C3alkoxy, Ci-C3haloalkyl, Ci- C3haloalkoxy, cyano, or C3-C 4 cycloalkyl;
  • R 6 is hydrogen, halogen, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3alkoxy, Ci-C3haloalkoxy, cyano, or C3-C5cycloalkyl;
  • R 7 is hydrogen or methyl
  • R 8 is hydrogen or methyl; or a salt, enantiomer, tautomer and/or an N-oxide thereof, provided that the compound is not one of the following compounds:
  • a further preferred novel group of compounds of formula (I) are those of formula (IH-2) which are compounds of formula (IH) wherein R 1 is fluoro;
  • R 2 is hydrogen or fluoro
  • R 3 is hydrogen or methyl
  • R 4 is methyl, ethyl or Ci-C2fluoroalkyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring, wherein the ring structure can be substituted with 1 to 2 fluoro atoms;
  • R 5 is fluoro, chloro, bromo, iodo, Ci-C3alkyl, Ci-C3alkoxy, Ci-C3fluoroalkyl, Cifluoroalkoxy, cyano, or cyclopropyl;
  • R 6 is hydrogen, fluoro, chloro, bromo, methyl, ethyl, Ci-C2fluoroalkyl, Ci-C2alkoxy, Ci- C2fluoroalkoxy, cyano, or cyclopropyl;
  • R 7 is hydrogen and Rs is hydrogen or methyl or R 7 is hydrogen or methyl and R 8 is hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof, provided that the compound is not one of the following compounds:
  • a further preferred novel group of compounds of formula (I) are those of formula (IH-3) which are compounds of formula (IH) wherein:
  • R 1 is fluoro
  • R 2 is hydrogen or fluoro
  • R 3 is methyl
  • R 4 is methyl or ethyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring;
  • R 5 is fluoro, chloro, bromo, iodo, methyl, ethyl, methoxy, trifluoromethyl, difluoromethyl, difluoromethoxy, cyano, or cyclopropyl;
  • R 6 is hydrogen, fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, methoxy, cyano, or cyclopropyl [most preferably R 6 is hydrogen, fluoro, chloro, bromo, methyl, methoxy or cyano]; and
  • R 7 and R 8 are both hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof, provided that the compound is not one of the following compounds:
  • a further preferred novel group of compounds of formula (I) are those of formula (IH-4) which are compounds of formula (IH) wherein: R 1 is fluoro;
  • R 2 is hydrogen or fluoro
  • R 3 is methyl
  • R 4 is methyl or ethyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring;
  • R 5 is fluoro, chloro, bromo, iodo, methyl, ethyl, methoxy, trifluoromethyl, difluoromethyl, difluoromethoxy, cyano, or cyclopropyl;
  • R 6 is hydrogen, fluoro, chloro, bromo, methyl, methoxy or cyano
  • R 7 and R 8 are both hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof, provided that the compound is not one of the following compounds:
  • a further preferred novel group of compounds of formula (I) are those of formula (IH-5) which are compounds of formula (IH) wherein: R 1 is fluoro;
  • R 2 is hydrogen or fluoro
  • R 3 is methyl and R 4 is methyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl ring
  • R 5 is chloro, bromo, methyl or cyano
  • R 6 is hydrogen or methyl
  • R 7 and R 8 are both hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof, provided that the compound is not one of the following compounds:
  • a further preferred novel group of compounds of formula (I) are those of formula (IH-6) which are compounds of formula (IH) wherein:
  • R 1 is fluoro
  • R 2 is hydrogen or fluoro
  • R 3 is methyl and R 4 is methyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl or cyclopentyl ring;
  • R 5 is bromo, methyl, cyano, difluoromethoxy, ethynyl
  • R 6 is halogen or methyl
  • R 7 and R 8 are both hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof.
  • a further preferred novel group of compounds of formula (I) are those of formula (IH-7) which are compounds of formula (IH) wherein
  • R 1 is fluoro
  • R 2 is hydrogen or fluoro
  • R 3 is methyl and R 4 is methyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl ring
  • R 5 is bromo, methyl, cyano, difluoromethoxy, ethynyl
  • R 6 is chloro or methyl
  • R 7 and R 8 are both hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof.
  • a further preferred novel group of compounds of formula (I) are those of formula (IH-8) which are compounds of formula (IH) wherein R 1 is fluoro;
  • R 2 is hydrogen or fluoro
  • R 3 is methyl and R 4 is methyl
  • R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl ring;
  • R 5 is chloro, bromo, methyl or cyano;
  • R 6 is methyl
  • R 7 and R 8 are both hydrogen; or a salt, enantiomer, tautomer and/or an N-oxide thereof.
  • Specific examples of compounds of formula (I) are illustrated in the Tables A1 to A13 below:
  • Table A1 provides 107 compounds of formula (I): wherein R 1 is fluoro, R 2 is H, R 3 and R 4 are methyl, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z below.
  • Table A2 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is fluoro, R 3 and R 4 are methyl, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A3 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is H, R 3 and R 4 are methyl, R 7 is CH 3 and R 8 is H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A4 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is H, R 3 and R 4 are methyl, R 7 is H and R 8 is CH 3, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A5 provides 107 compounds of formula (I) wherein R 1 is chloro, R 2 is H, R 3 and R 4 are methyl, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A6 provides 107 compounds of formula (I) wherein Ri is fluoro, R 2 is H, R 3 is methyl, R 4 is ethyl, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A7 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is fluoro, R 3 is methyl, R 4 is ethyl, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A8 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is H, R 3 is methyl, R 4 is H, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A9 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is fluoro, R 3 is methyl, R 4 is H, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A10 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is H, R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl ring, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A11 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is fluoro, R 3 and R 4 together with the carbon atom to which they are attached form a cyclobutyl ring, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A12 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is H, R 3 and R 4 together with the carbon atom to which they are attached form a cyclopentyl ring, R 7 and R 8 are H, and wherein the values of R 5 and R 6 are as defined in Table Z above.
  • Table A13 provides 107 compounds of formula (I) wherein R 1 is fluoro, R 2 is fluoro, R 3 and R 4 together with the carbon atom to which they are attached form a cyclopentyl ring, R 7 and R 8 are H, and wherein the values of R 5 and R6 are as defined in Table Z above.
  • Compounds of formula (I) may possess any number of additional benefits including, inter alia, advantageous levels of biological activity or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, or increased biodegradability).
  • compounds of general formula (I) can be prepared from compounds of formula (II) and (III) in the presence of a Bronsted acid such as sulphuric acid ortrifluoromethane sulfonic acid, in the presence or absence of an inert solvent such as dichloromethane as described in WO 2013/047751.
  • a Bronsted acid such as sulphuric acid ortrifluoromethane sulfonic acid
  • an inert solvent such as dichloromethane as described in WO 2013/047751.
  • Compounds of formula (III) can be prepared from compounds of formula (lll-a), wherein R 11 is chloro, bromo or iodo, by treatment with a transition metal salt such as palladium(ll) acetate, a phosphine ligand such as 1 ,T-bis(diphenylphosphino)-ferrocene and a cyanide source such as zinc cyanide in a solvent such as N,N-dimethylacetamide at temperatures between 20°C and 150°C.
  • a transition metal salt such as palladium(ll) acetate
  • a phosphine ligand such as 1 ,T-bis(diphenylphosphino)-ferrocene
  • a cyanide source such as zinc cyanide in a solvent such as N,N-dimethylacetamide at temperatures between 20°C and 150°C.
  • compounds of general formula (I) can be prepared from compounds of formula (IV) by treatment with a dehydrating agent such as trifluoromethanesulfonic anhydride or chloromethylene(dimethyl)ammonium chloride and a base such as 2,6-lutidine in an inert solvent such as dichloromethane or chlorobenzene at temperatures between -40°C to 150°C. This is shown in scheme 3.
  • a dehydrating agent such as trifluoromethanesulfonic anhydride or chloromethylene(dimethyl)ammonium chloride
  • a base such as 2,6-lutidine in an inert solvent such as dichloromethane or chlorobenzene
  • Compounds of formula (IV) can be prepared from compounds of formula (IV-b) and compounds of formula (IV-a) in the presence of a dehydrating agent such as propylphosphonic anhydride or phosgene and a base such as triethyl amine in an inert solvent such as toluene.
  • a dehydrating agent such as propylphosphonic anhydride or phosgene
  • a base such as triethyl amine
  • an inert solvent such as toluene.
  • compounds of formula (IV) can be prepared from compounds of formula (lll-a), wherein Rn is chloro, bromo or iodo, and (IV-a) in the presence of a transition metal salt such as palladium(ll)acetate, a phosphine ligand such as 1 ,1'- bis(diphenylphosphino)-ferrocene and a base such as triethyl amine in a solvent such as toluene under carbon monoxide atmosphere.
  • a transition metal salt such as palladium(ll)acetate
  • a phosphine ligand such as 1 ,1'- bis(diphenylphosphino)-ferrocene
  • a base such as triethyl amine
  • Compounds of formula (IV-a) can be prepared from compounds of formula (IV-c), wherein X is - OH, -NH2 or -NHOH, by methods well known to a person skilled in the art and described in ChemMedChem 2018, p. 2351-2373, J. Org. Chem., 2017, p 4044-4049 and Org. Lett., 2010, p. 4644- 4647.
  • compounds of general formula (IV-a) can be prepared from compounds of formula (IV-f) in the presence of a reducing agent such as palladium on carbon under an hydrogen atmosphere in a solvent such as methanol.
  • a reducing agent such as palladium on carbon under an hydrogen atmosphere in a solvent such as methanol.
  • Compounds of formula (IV-f) can be prepared from compounds of formula (IV-d), wherein Rn is chloro or bromo, and nitro compounds of formula (IV-g) as described in J. Am. Chem. Soc. 2012, p. 9942-9945. This is shown in scheme 6.
  • compounds of general formula (I) can be prepared from compounds of formula (V), wherein R 14 is -B(OH) 2 , -B(0C(CH 3 ) 2 C(CH 3 ) 2 0) or -B(0CH 2 C(CH 3 ) 2 CH 2 0), and compounds of formula (VI), wherein R 15 is chloro, bromo, iodo, -OSC>2CF 3 or -OSC>2(CF2) 3 CF 3, in the presence of a transition metal salt such as palladium(ll)acetate, a phosphine ligand such as tri(2-furyl)phosphine and a base such as K 3 PC> 4 in a solvent such as N,N-dimethylformamide at temperature between 20°C and 150°C. This is shown in scheme 7.
  • compounds of formula (I) can be obtained by transformation of another, closely related, compound of formula (I) (or an analogue thereof) using standard synthesis techniques known to the person skilled in the art.
  • Non-exhaustive examples include oxidation reactions, reduction reactions, hydrogenation reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, alkylation reactions, nucleophilic addition reactions and halogenation reactions.
  • the compounds of formula (I) 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 WO 97/33890.
  • 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 sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils
  • 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.
  • Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • 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 those 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
  • 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 sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.
  • 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
  • salts of mono and dialkyl phosphate esters such as 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, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. 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 biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • 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) are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • 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) may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic Mycosphaerella graminicola, Monographella nivalis (Microdochium nivaie), or Fusarium culmorum and/or Gibberella zeae ( Fusarium graminearum), comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as above-defined, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
  • a fungicidal composition of the invention comprising a compound according to Formula (I) or to the uses of such compositions in a method of combating, preventing or controlling the phytopathogen Mycosphaerella graminicola
  • the said composition may comprise a fungicidally effective amount of a compound of formula (I), 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 pesticidally active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula
  • the compound of formula (I) 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: 1 ,2,4-thiadiazoles, 2,6- dinitroanilines, acylalanines, aliphatic nitrogenous compounds, amidines, aminopyrimidinols, anilides, anilino-pyrimidines, anthraquinones, antibiotics, aryl-phenylketones, benzamides, benzene- sulfonamides, benzimidazoles, benzothiazoles, benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles, benzylcarbamates, butylamines, carbamates, carboxamides, carpropamids, chloronitriles, cinnamic acid amides, copper containing compounds, cyanoacetamideoximes, cyanoacrylates, cyanoimidazoles, cyanomethylene-thiazolidines, dicarbonitriles, dicarboxamides, dicarboximi
  • suitable additional active ingredients also include the following: a compound selected from the group of substances consisting of petroleum oils, 1 ,1-bis(4-chlorophenyl)-2- ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4- chlorophenyl phenyl sulfone, acetoprole, aldoxycarb, amidithion, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenous oxide, azobenzene, azothoate, benomyl, benoxafos, benzyl benzoate, bixafen, brofenvalerate, bromo- cyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium poly
  • FMC 1137 formetanate, formetanate hydrochloride, formparanate, gamma-HCH, glyodin, halfenprox, hexadecyl cyclopropanecarboxylate, isocarbophos, jasmolin I, jasmolin II, jodfenphos, lindane, malonoben, mecarbam, mephosfolan, mesulfen, methacrifos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3- one, nifluridide, nikkomycins, nitrilacarb, n
  • Agrobacterium radiobacter Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus a bdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV,
  • Cryptolaemus montrouzieri Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formos a, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis,
  • Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Ne odiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus,
  • XMC zetamethrin, zinc phosphide, zolaprofos, and meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, pyrimorph, trifenmorph, 1 ,2-dibromo-3-chloropropane, 1 ,3-dichloropropene, 3,4- dichlorotetrahydrothiophene 1 ,1 -dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo- 1 ,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, 2-fluoro-N-(3-methoxyphenyl)-9H-purin- 6-amine, benclothiaz, cytokinins, DCIP, fur
  • the compounds of the invention may also be used in combination with anthelmintic agents.
  • anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP- 444964 and EP-594291 .
  • Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO- 9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
  • the compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
  • the compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 96/11945, WO 93/19053, WO 93/25543, EP 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173, and EP 0 503 538.
  • the compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • the compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.
  • Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, me
  • Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
  • Pyrethroids acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1 R)-cis-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a- cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvaler
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
  • antiparasitics acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydr
  • Biological agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
  • Bactericides chlortetracycline, oxytetracycline, streptomycin.
  • TX means one compound selected from the compounds as represented in Tables A1 to A13 (above) or one compound selected from compounds E.001 to E.187 as represented in Table E (below): a compound selected from the group of substances consisting of petroleum oils + TX, 1 ,1-bis(4- chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N- 1-naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxycarb + TX, amidithion + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsen
  • TX Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp.
  • TX (these compounds may be prepared from the methods described in WO2015/155075); N'-[5-bromo- 2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound may be prepared from the methods described in IPCOM000249876D); N-isopropyl-N’-[5-methoxy-2-methyl-4- (2, 2, 2-trifluoro-1 -hydroxy-1 -phenyl-ethyl)phenyl]-N-methyl-formamidine+ TX, N’-[4-(1 -cyclopropyl- 2, 2, 2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine +
  • TX (these compounds may be prepared from the methods described in WO2018/228896); N-ethyl-N’- [5-methoxy-2-methyl-4-[2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N’- [5-methoxy-2-methyl-4-[2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine +
  • TX (these compounds may be prepared from the methods described in WO2019/110427); N-[(1 R)-1- benzyl-3-chloro-1 -methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1 -benzyl-3- chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 R)-1 -benzyl-3, 3, 3-trifluoro-1- methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1 -benzyl-3, 3, 3-trifluoro-1 -methyl- propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 R)-1 -benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro- quinoline-3-carboxamide + TX,
  • the compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4- bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2- fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO 2016
  • the active ingredient mixture of the compounds of formula (I) selected from one compound selected from the compounds as represented in Tables A1 to A13 (above) or one compound selected from compounds E.001 to E.187 as represented in Table E (below) is preferably in a mixing ratio of from 100:1 to 1 :6000, 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, very especially from 5:1 to 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 : 1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1
  • 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 one compound selected from the compounds as represented in Tables A1 to A13 (above) or one compound selected from compounds E.001 to E.187 as represented in Table E (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 useful plants and / or target crops in accordance with the invention include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. and VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties.
  • suitable genetically enhanced or engineered crop varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.
  • useful plants and/or “target crops” is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxidase
  • 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 and/or “target crops” is to be understood as including those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include d-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.
  • Vip vegetative insecticidal proteins
  • insecticidal proteins of bacteria colonising nematodes and toxins produced by scorpions, arachnids, wasps and fungi.
  • An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds).
  • An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds).
  • Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification).
  • a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
  • useful plants and/or “target crops” is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392225, WO 95/33818, and EP-A-0 353 191 .
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 5- endotoxins, e.g. CrylAb, 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 colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae or insecticidal proteins from Bacillus thuringiensis, such as 5- endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or
  • orXenorhabdus 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
  • d-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, WO 02/15701).
  • 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 W003/018810).
  • toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, W095/34656, EP-A-0 427 529, EP-A-451 878 and W003/052073.
  • the processes for the preparation of such transgenic plants are generally known to the 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 WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • 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 Cry1Fa2 toxin and the enzyme phosphinothricine 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
  • 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 WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • 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 c 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 Cry1 Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • 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. There may 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 may be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.
  • Pesticidal agents referred to herein using their common name are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.
  • the compounds of formula (I) 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.
  • the compound of formula (I) 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.
  • 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, nematocides
  • 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) 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 above-defined, or of a fungicidal or insecticidal mixture comprising at least one compound of Formula (I) or at least one preferred individual compound as above-defined, 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) or of a preferred individual compound as above-defined 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.
  • 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
  • a compound of formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or
  • 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), or an agrochemical composition which contains at least one of said compounds, is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect.
  • the compounds of formula (I) 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 granularform (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), 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).
  • surfactants surface active compounds
  • the application methods for the compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is preferably 1g to 2000 g of active ingredient per hectare, more preferably 10 to 1000 g/ha, most preferably 10 to 600 g/ha.
  • convenient dosages are from 10mg to 1g of active substance per kg of seeds.
  • 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 used according to the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical
  • compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
  • appropriate formulation inerts diiluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
  • conventional slow release formulations may be employed where long lasting efficacy is intended.
  • Particularly formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
  • a seed dressing formulation is applied in a manner known per se to the seeds employing the combination ofthe 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) together with component (B) and (C), and optionally other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. 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.
  • Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether 2 %
  • Kaolin 62 % 27 % The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with waterto give suspensions of the desired concentration.
  • Powders for dry seed treatment a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 %
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsifiable concentrate active ingredient [compound of formula (I)] 10 % octylphenol polyethylene glycol ether 3 %
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Active ingredient [compound of formula (I)] 5 % 6 % 4 % talcum 95 %
  • Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • Active ingredient 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 %
  • the active ingredient 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.
  • Active ingredient 8 % polyethylene glycol (mol. wt. 200) 3 %
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • Suspension concentrate active ingredient [compound of formula (I)] 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % tristyrenephenole with 10-20 moles EO 2 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a 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.
  • 28 parts of a combination of the compound of formula (I) 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.
  • 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 the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1 .5 ppm, 0.8 ppm or 0.2 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 physico-chemical properties, or increased biodegradability).
  • Example A1 5-bromo-1-(8-fluoro-3-quinolyl)spiro[4H-isoquinoline-3,1 '-cyclopropane] (compound E.037).
  • Step 1
  • the brown suspension was quenched slowly with an aqueous sodium hydroxide solution (4N, 4 mL) and diluted with methyl fe/f-butyl ether (TBME) before filtration over celite.
  • TBME methyl fe/f-butyl ether
  • the layers were separated, and the aqueous phase was extracted with TBME.
  • the combined organic layers were washed with water, dried over MgSC , filtered and concentrated in vacuo.
  • the residue was purified by flash chromatography (cyclohexane:EtOAc) to give 1-[(2-bromophenyl)methyl]cyclopropanamine as an orange oil.
  • Example A2 Preparation of 5-bromo-1-(8-fluoro-3-quinolyl)-3,3-dimethyl-4H-isoquinoline (compound E.033).
  • Step 1
  • Step 1
  • Example A4 Preparation of enantiomerically enriched 3-[5-chloro-3-methyl-3,4-dihydroisoquinolin-1- yl]-8-fluoro-quinoline (compounds E.126 and E.127).
  • a racemic sample of 3-[5-chloro-3-methyl-3,4-dihydroisoquinolin-1-yl]-8-fluoro-quinoline was separated by preparative SCF (Sepiatec Prep SFC 100) using the following parameters: column: Daicel CHIRALPAK ® OZ, 5um, 1.0 cm x 25cm, mobile phase: A: CO2 B: ACN (isocratic: 30% B in 4 min), backpressure: 150 bar, flow rate: 30 ml/min, GLS pump: 5ml/min EtOAc, detection: UV 240 nm, injection volume: 300ul.
  • Example A5 3-(5-chloro-3-methyl-3,4-dihydroisoquinolin-1-yl)-8-fluoro-quinoline (compound E.068).
  • Step 1 To a solution of 1-(2-chlorophenyl)propan-2-amine hydrochloride (0.23 g, 1.12 mmol) and 8- fluoroquinoline-3-carboxylic acid (0.224 g, 1.17 mmol, 1.05 equiv.) in EtOAc (4.5 mL) were added pyridine (0.35 g, 0.361 mL, 4.46 mmol, 4.0 equiv.) then propylphosphonic anhydride 50% solution in EtOAc (2.13 g, 1.99 mL, 3.35 mmol, 3.0 equiv.). The reaction mixture was stirred at RT for 17h. The solution was quenched with water and then extracted with EtOAc.
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 L/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment , diode-array detector and ELSD detector.
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 L/h , Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment , diode-array detector and ELSD detector.
  • Mass spectra were recorded on a Mass Spectrometer from Agilent (Single quadrupole I mass spectrometer) equipped with an Multimode- Electron Spray and APCI (Polarity: positive and negative ions), Capillary: 4.00 KV, Corona Current 4.0 pA, Charging Voltage, 2.00 kV, Nitrogen Gas Flow: 12.0 L/min, Nebulizer Pressure: 35 psig, Mass range: 100 to 1000 m/z), Dry gas temperature 250°C, Vaporizer temperature 200°C.
  • Agilent Single quadrupole I mass spectrometer
  • APCI Multimode- Electron Spray and APCI
  • HPLC spectra were recorded on HPLC from Agilent: quaternary pump, heated column compartment, diode-array detector.
  • SFC spectra were recorded on a SFC from Waters Acquity UPCVQDa with following parameters: Column: Daicel SFC CHIRALPAK® IA, 3 urn, 0.3 cm x 10 cm, 40°C, mobile phase: A: CO2 B: EtOH gradient: 07% B in 9.8 min, ABPR: 1800 psi, flow rate: 2.0 mL/min, detection: 240 nm, sample concentration: 1 mg/ml_ in acetonitrile/MeOH 1/1 , Injection: 1 uL.
  • Table E Melting point (mp) and/or LC/MS data (retention time (Rt)) for compounds of Formula (I).
  • 2-week old wheat plants cv. Riband are sprayed in a spray chamber with the formulated test compound (10% in emulsifiable concentrate (EC)) diluted in water.
  • the test plants are inoculated by spraying a spore suspension on them one day after application and then kept at 22°C/21 °C (day/night) in a greenhouse. Disease damage is assessed directly when an appropriate level of disease appears on untreated check plants and efficacy was calculated compare to untreated controls (16 - 19 days after application).
  • the following compounds gave at least 80% control of Mycosphaerella graminicola at 60 ppm when compared to untreated control under the same conditions, which showed extensive disease development.
  • Mycosphaerella graminicola (Septoria tritici) on wheat / curative
  • 2-week old wheat plants cv. Riband are sprayed with the formulated test compound (10% in emulsifiable concentrate (EC)) diluted in water 5 days after the test plants have been inoculated by spraying a spore suspension on them.
  • the treated plants are kept in the greenhouse at 20/21 °C (day/night) until an appropriate level of disease appears on untreated check plants. Disease damage is assessed directly and efficacy is calculated compared to untreated controls (14 - 19 days after inoculation).
  • the following compounds gave at least 70% control of Mycosphaerella graminicola at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development.
  • 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 4-5 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:
  • 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 3-4 days after application.
  • nutrient broth PDB potato dextrose broth
  • 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.
  • Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with a (DMSO) solution of the 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 - 8 days after application).
  • Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with a (DMSO) solution of the test compound diluted in water.
  • DMSO DMSO
  • 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 - 8 days after application).
  • Mvcosphaerella graminicola (Septoria tritici) on wheat / preventative 2-week old wheat plants cv. Riband are sprayed in a spray chamber with the formulated test compound (10% in emulsifiable concentrate (EC)) diluted in water.
  • the test plants are inoculated by spraying a spore suspension on them one day after application and then kept at 22°C/21 °C (day/night) in a greenhouse. Disease damage is assessed directly when an appropriate level of disease appears on untreated check plants and efficacy was calculated compared to untreated controls (16 to 19 days after application).

Abstract

La présente invention concerne des dérivés de 1-(3-quinolyl)-3,4-dihydroisoquinoléine de formule (I) ainsi qu'un procédé permettant de combattre, prévenir ou maîtriser des phytopathogènes Mycosphaerella graminicola (Septoria tritici)), Fusarium culmorum, Gibberella zeae (Fusarium graminearum) et Monographella nivalis (Microdochium nivale), qui comprend l'application au phytopathogène, au locus du phytopathogène, ou à une plante susceptible d'être attaquée par le phytopathogène, ou à un matériau de propagation de celui-ci, d'une quantité efficace du point de vue fongicide d'un dérivé de 1-(3-quinolyl)-3,4-dihydroisoquinoléine de formule (I). La présente invention concerne la synthèse d'exemples de composés, d'exemples de formulation, de données biologiques pertinentes (activité antifongique contre Mycosphaerella graminicola (Septoria tritici), Fusarium culmorum, Gibberella zeae (Fusarium graminearum) et Monographella nivalis (Microdochium nivale) lorsqu'elles sont vaporisés sur des plantes), ainsi que des données comparatives contre trois composés de l'art antérieur (par exemple, pages 52 à 85 ; exemples de formulation ; exemples A1 à A3 ; tableau E ; composés E.01 à E.187 ; exemples biologiques). Des composés donnés à titre d'exemples sont par exemple : 5-bromo-1-(8-fluoro-3-quinolyl)spiro[4H-isoquinoléine-3,1'- cyclopropane] (exemple A1) 5-bromo-1-(8-fluoro-3-quinolyl)-3,3-diméthyl-4H-isoquinoléine (exemple A2) 1-(8-fluoro-3-quinolyl)-3,3-diméthyl-4H-isoquinoléine-5-carbonitrile (exemple A3)
PCT/EP2020/079068 2019-10-16 2020-10-15 Dérivés de 1-(3-quinolyl)-3,4-dihydroisoquinoléine utilisés en tant que fongicides pour lutter contre des phytopathogènes spécifiques WO2021074309A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024068656A1 (fr) * 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Compositions fongicides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1736471A1 (fr) * 2004-01-23 2006-12-27 Sankyo Agro Company, Limited 3-(dihydro(tetrahydro)isoquinolin-1-yl)quinolines
EP2103214A1 (fr) * 2006-12-01 2009-09-23 Sankyo Agro Company, Limited Agent de traitement de sols ou de graines comprenant un composé quinoléine ou un sel de celui-ci en tant que substance active, ou procédé pour lutter contre une maladie de plante l'utilisant
WO2018190326A1 (fr) * 2017-04-10 2018-10-18 三井化学アグロ株式会社 Composition de lutte contre les nuisibles contenant un composé pyridone et un composé à base de quinoléine et procédé de lutte contre les nuisibles, et nouveau composé à base de quinoléine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1736471A1 (fr) * 2004-01-23 2006-12-27 Sankyo Agro Company, Limited 3-(dihydro(tetrahydro)isoquinolin-1-yl)quinolines
EP2103214A1 (fr) * 2006-12-01 2009-09-23 Sankyo Agro Company, Limited Agent de traitement de sols ou de graines comprenant un composé quinoléine ou un sel de celui-ci en tant que substance active, ou procédé pour lutter contre une maladie de plante l'utilisant
WO2018190326A1 (fr) * 2017-04-10 2018-10-18 三井化学アグロ株式会社 Composition de lutte contre les nuisibles contenant un composé pyridone et un composé à base de quinoléine et procédé de lutte contre les nuisibles, et nouveau composé à base de quinoléine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024068656A1 (fr) * 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Compositions fongicides

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