WO2016066636A1 - N-(2-halogen-2-phenethyl)carboxamides as fungicides - Google Patents

N-(2-halogen-2-phenethyl)carboxamides as fungicides Download PDF

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WO2016066636A1
WO2016066636A1 PCT/EP2015/074858 EP2015074858W WO2016066636A1 WO 2016066636 A1 WO2016066636 A1 WO 2016066636A1 EP 2015074858 W EP2015074858 W EP 2015074858W WO 2016066636 A1 WO2016066636 A1 WO 2016066636A1
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Prior art keywords
halogen atoms
alkyl
halogen
halogenoalkyl
formula
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PCT/EP2015/074858
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French (fr)
Inventor
Anne Decor
Hans-Georg Schwarz
Jörg GREUL
Pierre-Yves Coqueron
Adeline KÖHLER
Valérie TOQUIN
Philippe Rinolfi
Ulrike Wachendorff-Neumann
Peter Dahmen
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Bayer Cropscience Aktiengesellschaft
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Publication of WO2016066636A1 publication Critical patent/WO2016066636A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
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    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
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    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
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    • 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
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms

Definitions

  • the present invention relates to the use of N-(2-halogen-2-phenethyl)carboxamides for the control of phytopathogenic microorganisms in agriculture, wherein a compound of formula (I) is applied to the phytopathogenic microorganisms, their habitat, the plant, the seed thereof, plant parts, plant propagation material or the soil on which the plants are grown or intended to be grown in an effective amount.
  • the present invention further relates to compositions containing such compounds and methods for the control of phytopathogenic microorganisms on plants, the habitat of such micro organims, the plant, the seed thereof, plant parts, plant propagation material or the soil on which the plants are grown or intended to be grown.
  • Phytopathogenic microorganisms cause a substantial loss in agricultural production including food and industrial crops and are control with compounds having fungicidal activity. To be useful in agriculture these compounds should have a high activity against phytopathogenic microorganisms, a broad spectrum activity against different species of phytopathogenic microorganisms and should be able to be applied in an environmentally safe way.
  • A can represent 4-pyrazoles, 5-thiazoles, 4-pyrroles or 4-triazoles;
  • R 1 , R 2 , R 3 and R 4 can represent hydrogen, halogen, nitro, Ci-Ce-aikyl, Cs-Ce-cycloalkyl, C2-Ce-alkenyl, C2-C6-alkynyl; or R 1 and R 2 represent together a C2-Cs-alkylene group;
  • B can represent substituted phenyl.
  • X and Y can represent halogen atoms, cyano, nitro, G-Ce-alkyl, Ci-C6-haloalkyl etc.
  • R 1 , R 2 , R 3 and R 4 are substituents of an alkandiyl chain, exemplified as hydrogen, alkyl and R 1 + R 2 or R 3 + R 4 forming together a cyclopropyl ring.
  • the document does not exemplify compounds wherein the alkandiyl chain is substituted by halogen, e.g. fluorine.
  • EP-A 1997800 discloses N-2-(hetero)arylethylcarboxamide derivatives as fungi-controlling agents.
  • the references discloses also certain N-(2-halogen-2-phenethyl)carboxamides where the heterocyclyl attached to the carbonyl group represents pyrazines or 3-pyridyls.
  • this document does not disclose evidence of synthesis of such compounds nor corresponding biological efficacy
  • WO-A 2012/168361 discloses insecticidal thiazolyl carboxamides which embrace certain fluorine- containing phenethyl carboxamides, like following examples 1.106 and 1.107, but are not disclosed as
  • WO2014/004064 are disclosed certain N-[(pyrazolylsubstituted-phenyl)-2,2 dihalo-ethyl] carboxamides, such as example 150, in above-mentioned document, with a claimed fungicidal efficacy, however such heterocyclophenethyl carboxamides are not part of the present invention and are only remotely connected to the present invention as they explicitly require the specific presence of an additional heterocycle in their general structure.
  • T oxygen or sulfur
  • n 0, I, 2, 3, 4 or 5;
  • X independently from each other X represents halogen, nitro, cyano, isonitrile, hydroxy, amino, sulfanyl, pentafluoro ⁇ 6 -sulfanyl, formyl, formyloxy, formylamino, (hydroxyimino)-Ci-C8-alkyl, (G- G-alkoxyimino)-G-G-alkyl, (G-G-alkenyloxyimino)-G-G-alkyl, (G-G-alkynyloxyimino)-G-G- alkyl, (benzyloxyimino)-Ci-C8-alkyl, carboxy, carbamoyl, N-hydroxycarbamoyl, carbamate, G-G- alkyl, Ci-Cs-halogenoalkyl having 1 to 9 halogen atoms, C2-Cs-alkenyl, C2-C8-halogenoalkenyl having 1 to 9 hal
  • Z 1 , Z 2 and Z 3 independently represent hydrogen, halogen, cyano, G-Cs-alkyl, G-Cs-halogenoalkyl having 1 to 5 halogen atoms, G-Cs-alkoxy, G-Cs-alkylsulfanyl, or G-Cs-alkoxycarbonyl; or
  • Z 2 and Z 3 form together with the carbon atom to which they are attached a 3- to 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 6 groups Q which can be the same or different;
  • Q represents halogen, cyano, nitro, G-Cs-alkyl, G-Cs-halogenoalkyl having 1 to 9 halogen atoms, G- Cs-alkoxy, G-Cs-halogenoalkoxy having 1 to 9 halogen atoms, G-C8-alkylsulfanyl, Ci-Cs- halogenoalkylsulfanyl having 1 to 9 halogen atoms, tri-(Ci-C8-alkyl)-silyl, tri-(Ci-C8-alkyl)-silyl-Ci- C8-alkyl, Ci-Cs-alkoxyimino-Ci-Cs-alkyl, (benzyloxyimino)-Ci-C8-alkyl;
  • A represents phenyl of formula A 1
  • Y 1 represents halogen, nitro, SH, SF 5 , CHO, OCHO, NHCHO, cyano, G-Cg-alkyl, G-Cg-halogenoalkyl having 1 to 5 halogen atoms, C2-C8-alkenyl, C2-Cs-alkynyl, C3-C6-cycloalkyl, Cs-Ce-halogenocycloalkyl having 1 to 9 halogen atoms, G-G-alkylsulfanyl, -G-G-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-Cs-alkoxy, G-G-halogenoalkoxy having 1 to 5 halogen atoms, G-G-alkoxy-G-G-alkyl, G- Ce-alkenyloxy-Ci-Cg-alkyl, G-G-alkynyloxy-G-G-alkyl, G-G-alkeny
  • Y 2 , Y 3 , Y 4 and Y 5 independently from each other represent hydrogen or Y 1 ;
  • A represents a heterocycle of formula (A 2 )
  • R 1 to R 3 independently from each other represent hydrogen, halogen, G-G-alkyl, G-G-halogenoalkyl comprising 1 to 9 halogen atoms, G-G-alkoxy or G-G-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 3 )
  • R 4 to R 6 independently from each other represent hydrogen, halogen, G-G-alkyl, G-G-halogenoalkyl comprising 1 to 9 halogen atoms, G-G-alkoxy or G-G-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 4 )
  • R 9 to R 11 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, amino, C1-C5- alkoxy, G-Cs-alkylsulfanyl, G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or C1-C5- halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 5 )
  • R and R independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, amino, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms, and
  • R 14 represents hydrogen, halogen, G-Cs-alkyl, G-Cs-alkoxy, amino, G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or G-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 6 )
  • R represents hydrogen or substituted or unsubstitued G-Cs-alkyl, and R 20 to R 22 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 7 )
  • R 23 represents hydrogen, halogen, Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, and
  • R 24 represents hydrogen or Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A 8 )
  • R 25 represents hydrogen, halogen, Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, and
  • R 26 represents hydrogen, Ci-Cs-alkyl or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A 9 )
  • R 29 represents hydrogen, halogen, G-G-alkyl, G-G-alkoxy, G-G-halogenoalkoxy comprising 1 to 9 halogen atoms or G-G-halogenoalkyl comprising 1 to 9 halogen atoms, and
  • R 30 represents hydrogen, halogen, G-G-alkyl, G-G-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms, amino, G-G-alkylamino or di-(G- C5-alkyl)-amino; or
  • A represents a heterocycle of formula (A 10 )
  • R 31 represents hydrogen or G-G-alkyl
  • R 32 represents hydrogen, halogen, G-G-alkyl or G-G-halogenoalkyl comprising 1 to 9 halogen atoms, and
  • R 33 represents hydrogen, halogen, nitro, G-G-alkyl, G-G-alkoxy, G-G-halogenoalkoxy comprising 1 to 9 halogen atoms or G-G-halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 1 : )
  • R and R independently from each other represent hydrogen, halogen, G-Cs-alkyl, G-G halogenoalkyl comprising 1 to 9 halogen atoms, G-G-alkoxy or a G-G-alkylsulfanyl, and
  • R represents hydrogen or G-Cs-alkyl; or A represents a heterocycle of formula (A 12 )
  • R 40 and R 41 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 13 )
  • R 42 and R 43 independently from each other represent hydrogen, halogen, G-Cs-alkyl, C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms or amino; or
  • A represents a heterocycle of formula (A 14 )
  • R 44 and R 45 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 15 )
  • R 47 represents hydrogen, halogen, Ci-Cs-alkyl or G-G-halogenoalkyl comprising 1 to 9 halogen atoms, and
  • R 46 represents hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-Cs-alkylsulfanyl; or
  • A represents a heterocycle of formula (A 16 )
  • R 49 and R 48 independently from each other represent hydrogen, halogen, G-G-alkyl, G-Cs-alkoxy, G- C5-halogenoalkoxy comprising 1 to 9 halogen atoms or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 17 )
  • R 50 and R 51 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, G- G-halogenoalkoxy comprising 1 to 9 halogen atoms or G-G-halogenoalkyl comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A 18 )
  • R 52 represents hydrogen, halogen, G-Cs-alkyl or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 19 )
  • R 53 represents hydrogen, halogen, G-Cs-alkyl or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 20 )
  • R 54 and R 56 independently from each other represent hydrogen, halogen, G-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms, and
  • R 55 represents hydrogen or G-Cs-alkyl; or A represents a heterocycle of formula (A 21 )
  • R 57 and R 59 independently from each other represent hydrogen, halogen, G-Cj-alkyl or C1-C5 halogenoalkyl comprising 1 to 9 halogen atoms, and
  • R 58 represents hydrogen or Ci-Cs-alkyl
  • A represents a heterocycle of formula (A 22 )
  • R 60 and R 61 independently from each other represent hydrogen, halogen, C i-C -alkyl or G-C5 halogenoalkyl comprising 1 to 9 halogen atoms, and
  • R 62 represents a hydrogen atom or G-Cs-alkyl
  • A represents a heterocycle of formula (A 23 )
  • R represents hydrogen, halogen, Ci-Cs-alkyl, cyano, Ci-Cs-alkoxy, Ci-Cs-alkylsulfanyl, C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms, Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms, amino, Ci-Cs-alkylamino or di(Ci-C5-alkyl)amino, and
  • R 64 represents hydrogen or Ci-Cs-alkyl
  • R 65 represents hydrogen, halogen, Ci-Cs-alkyl, Cs-Cs-cycloalkyl, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-Cs-alkoxy, C3-Cs-alkynyloxy or Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 24 )
  • R 66 represents hydrogen, halogen, hydroxy, cyano, Ci-C t-alkyl, Ci-C/i-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms and Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
  • R 67 , R 68 and R 69 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, SCi-C4-alkylsulfinyl and Ci-C4-alkylsulfonyl; or
  • A represents a heterocycle of formula (A 25 )
  • R 70 represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, G-Cs-alkylsulfanyl, C2-C5-alkenylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
  • R 71 , R 72 and R 73 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl; or
  • A represents a heterocycle of formula (A )
  • R 7 , R 75 , R 7 and R 77 independently from each other represent hydrogen, halogen, hydroxy, cyano, Ci- C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl and Ci-C4-alkylsulfonyl; or
  • A represents a heterocycle of formula (A 27 )
  • X 1 represents -S-, -SO-, -SO2- and -CH 2 -, and
  • R represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms
  • R 7 and R independently from each other represent hydrogen and Ci-C4-alkyl
  • A represents a heterocycle of formula (A )
  • R 81 represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
  • A represents a heterocycle of formula (A )
  • R represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
  • A represents a heterocycle of formula (A JU )
  • R represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
  • A is a heterocycle of formula (A 31 )
  • SO represents a sulfoxyde group
  • SO2 represents a sulfone group, an alkyl group, an alkenyl group and an alkynyl group as well as moieties containing these terms, can be linear or branched.
  • aryl also in terms like arylalkyl, arylalkenyl, arylalkynyl, aryloxy means phenyl or naphthyl, wherein phenyl is optionally substituted by 1 to 5 groups Q, and naphtyl is optionally substituted by 1 to 6 groups Q.
  • heterocyclyl means a saturated, partially saturated or unsaturated 4-, 5-, 6-, 7-, 8-, 9-, or 10- membered ring comprising 1 to 4 heteroatoms selected from the list consisting of oxygen (0), nitrogen (N), and sulfur (S).
  • Heteroatom means an atom selected from the group consisting of O, N, and S.
  • halogenated radical like e.g. halogenoalkyl, halogenoalkoxy
  • those halogen atoms can be the same or different.
  • Ci-Ce-alkyl comprises the largest range defined here for an alkyl radical. Specifically, this definition comprises the meanings methyl, ethyl, n , isopropyl, n , iso , sec , tert-butyl, and also in each case all isomeric pentyls, hexyls, heptyls and octyls, such as methyl, ethyl, propyl, 1 -me-thylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1- methylpentyl, 2-methylpentyl, 3-
  • a preferred range is Cl-C4-alkyl, such as methyl, ethyl, n , isopropyl, n , iso , sec , tert-butyl.
  • the definition Cl-C3-alkyl comprises methyl, ethyl, n , isopropyl.
  • the definition halogen comprises fluorine, chlorine, bromine and iodine.
  • Halogen-substituted alkyl - referred to as G-C8-halogenoalkyl - represents, for example, G-Cs-alkyl as defined above substituted by one or more halogen substituents which can be the same or different.
  • G-Cs-haloalkyl represents chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1- fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 1-fluoro-l-methylethyl, 2-fluoro-l,l-dimethylethyl, 2-chloro-l,l-dimethylethyl, 2-fluoro-l -fluoromethyl- 1 -methylethyl, 2- fluoro
  • C2-Cs-alkenyl comprises the largest range defined here for an alkenyl radical. Specifically, this definition comprises the meanings ethenyl, n , isopropenyl, n , iso , sec , tert-butenyl, and also in each case all isomeric pentenyls, hexenyls, heptenyls, octenyls, 1 -methyl- 1-propenyl, 1- ethyl- 1-butenyl, 2,4-dimethyl-l-pentenyl, 2,4-dimethyl-2-pentenyl.
  • Halogen-substituted alkenyl - referred to as C2-C8- halogenoalkenyl - represents, for example, C2-C8-alkenyl as defined above substituted by one or more halogen substituents which can be the same or different.
  • C2-Cs-alkynyl comprises the largest range defined here for an alkynyl radical. Specifically, this definition comprises the meanings ethynyl, n , isopropynyl, n , iso , sec , tert-butynyl, and also in each case all isomeric pentynyls, hexynyls, heptynyls, octynyls.
  • Halogen-substituted alkynyl - referred to as C2-Cs-halogenoalkynyl - represents, for example, C2-C8-alkynyl as defined above substituted by one or more halogen substituents which can be the same or different.
  • C3-C7-cycloalkyl comprises monocyclic saturated hydrocarbyl groups having 3 to 7 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
  • halogen-substituted cycloalkyl and halocycloalkyl comprises monocyclic saturated hydrocarbyl groups having 3 to 7 carbon ring members, such as 1 -fluoro-cyclopropyl, 1-chloro- cyclopropyl, 1-bromo-cyclopropyl, 2,2-dichloro-l-methyl-cyclopropyl, 2,2-dibromo-i-methyl- cyclopropyl, 1 -fluoro-cyclobutyl, 1 -chloro-cyclobutyl, 1 -fluoro-cyclopentyl, 1 -chloro-cyclopentyl, 1- fluoro-cyclohexyl or 1-chloro-cyclohexyl.
  • Compounds of the present invention can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound.
  • the invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term "scalemic” denotes a mixture of enantiomers in different proportions) and to the mixtures of all the possible stereoisomers, in all proportions.
  • the diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se by the man ordinary skilled in the art.
  • Compounds of the present invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound.
  • the invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions.
  • the geometric isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.
  • any of the compounds of formula (I) wherein X represents a hydroxy, a sulfanyl or an amino may be found in its tautomeric form resulting from the shift of the proton of said hydroxy, sulfanyl or amino group.
  • Such tautomeric forms of such compounds are also part of the present invention. More generally speaking, all tautomeric forms of compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group, as well as the tautomeric forms of the compounds which can optionally be used as intermediates in the preparation processes and which will be defined in the description of these processes, are also part of the present invention.
  • Agriculture shall encompass the production of food and feed crops, forestry, the protection of stored products including food, feed but also other materials of plant origin.
  • Preferably agriculture shall encompass the production of food and feed crops, forestry, the protection of stored products being food, feed, and materials of plant origin.
  • Plant product mean any product derived from a plant.
  • control of phytopathogenic microorganisms means a reduction in infestation by phytopathogenic microorganisms, compared with the untreated plant, the seed of a plant, the plant propagation material or the plant product, measured as efficacy, preferably a reduction by 25-50 %, compared with the untreated plant, the seed of a plant, the plant propagation material or the plant product (100 %), more preferably a reduction by 40-79 %, compared with the the untreated plant, the seed of a plant, the plant propagation material or the plant product (100 %); even more preferably, the infection by phytopathogenic microorganisms is entirely suppressed (by 70-100 %).
  • the control may be curative, i.e. for treatment of the plant, the seed of a plant, the plant propagation material or the plant product or protective, for protection of the untreated plant, the seed of a plant, the plant propagation material or the plant product, which have not yet been infected.
  • an “effective amount” means an amount of the inventive compound which is sufficient to control the phytopathogenic microorganism in a satisfactory manner or to eradicate the phytopathogenic microorganism completely, and which, at the same time, does not cause any significant symptoms of phytotoxicity. In general, this application rate may vary within a relatively wide range. It depends on several factors, for example on the phytopathogenic microorganism to be controlled, the plant, the climatic conditions and the ingredients of the inventive compositions.
  • Phytopathogenic microorganisms mean fungi and bacteria capable of infecting a plant, a seed of a plant, a plant propagation material or a plant product.
  • phytopathogenic microorganism means phytopathogenic fungi.
  • Fungi means Plasmodiophoromycetes, Peronosporomycetes (Syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (Syn. Fungi imperfecti).
  • Bacteria means species including Pseudomonadaceae, Rhizobiaceae, Enter obacteriaceae, Corynebacteriaceae and Streptomycetaceae capable of infecting a plant, a seed of a plant, a plant propagation material or a plant product.
  • the present invention provides the use of a compound of formula (I) as defined above
  • T oxygen or sulfur
  • n 0, 1, 2, 3 or 4;
  • X independently from each other X represents halogen, nitro, cyano, isonitrile, hydroxy, amino, sulfanyl, pentafluoro ⁇ 6 -sulfanyl, formyl, formyloxy, formylamino, (hydroxyimino)-Ci-C4-alkyl, (Ci- C4-alkoxyimino)-Ci-C4-alkyl, (C3-C4-alkenyloxyimino)-Ci-C4-alkyl, (C3-C4-alkynyloxyimino)-Ci-C4- alkyl, (benzyloxyimino)-Ci-C4-alkyl, carboxy, carbamoyl, N-hydroxycarbamoyl, carbamate, C1-C4- alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, C2-C4-alkenyl, C2-C4
  • Z 1 , Z 2 and Z 3 independently represent hydrogen, halogen, cyano, G-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, or Ci-C4-alkoxycarbonyl; or
  • Z 2 and Z 3 form together with the carbon atom to which they are attached a 3- to 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 6 groups Q which can be the same or different;
  • Q represents halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, Ci- C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 9 halogen atoms, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4-alkyl)-silyl-Ci- C4-alkyl, Ci-C4-alkoxyimino-Ci-C4-alkyl, (benzyloxyimino)-Ci-C4-alkyl;
  • A represents phenyl of formula A 1
  • Y 1 represents halogen, nitro, SH, SF 5 , CHO, OCHO, NHCHO, cyano, Ci-C 4 -alkyl, Ci-C 4 -halogenoalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C3-C6-halogenocycloalkyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, -Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-Ci-C4-alkyl, Ci- C4-alkenyloxy-Ci-C4-alkyl, C3-C4-alkynyloxy-Ci-
  • Y 2 , Y 3 , Y 4 and Y 5 independently from each other represent hydrogen or Y 1 ;
  • A represents a heterocycle of formula (A 2 )
  • R 1 to R 3 independently from each other represent hydrogen, halogen, G-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A 3 )
  • R 4 to R 6 independently from each other represent hydrogen, halogen, G-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 4 )
  • R 9 to R 11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, amino, C 1 -C4- alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or O-C4- halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 5 )
  • R and R independently from each other represent hydrogen, halogen, G-C4-alkyl, G-C4-alkoxy, amino, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or G-C4-halogenoalkoxy comprising 1 to 9 halogen atoms
  • R 14 represents hydrogen, halogen, G-C4-alkyl, Ci-C4-alkoxy, amino, G-C4-halogenoalkyl comprising 1 to 9 halogen atoms or G-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 24 )
  • R represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-C4-alkylsulfanyl, G-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms and G-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
  • R 67 , R 68 and R 69 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C 1 -C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, SCi-C4-alkylsulfinyl and G-C4-alkylsulfonyl; or
  • A represents a heterocycle of formula (A 25 )
  • R 70 represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C2-C4-alkenylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
  • R 71 , R 72 and R 73 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, G-C4- halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-C4-alkylsulfanyl, G-C4- halogenoalkoxy having 1 to 5 halogen atoms, G-C4-alkylsulfinyl, G-C4-alkylsulfonyl; or
  • A represents a heterocycle of formula (A 26 ) *
  • R , R , R and R independently from each other represent hydrogen, halogen, hydroxy, cyano, G- C i-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, G-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl and Ci-C4-alkylsulfonyl; or
  • A represents a heterocycle of formula (A 27 )
  • X 1 represents -S-, -SO-, -S0 2 - and -CH 2 -, and
  • R 78 represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and R 79 and R 80 independently from each other represent hydrogen and G-C4-alkyl; or A represents a heterocycle of formula (A 30 )
  • R 83 represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
  • A is a heterocycle of formula (A 31 ) in which
  • T oxygen
  • n 0, 1, 2 or 3;
  • X independently from each other X represents halogen, nitro, cyano, isonitrile, hydroxy, amino, formyl, formyloxy, formylaminocarboxy, carbamoyl, N-hydroxycarbamoyl, carbamate, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, C2-C4-alkenyl, C2-C4-halogenoalkenyl having 1 to 9 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfmyl, C1-C4- halogenoalkylsulfinyl having 1 to 9 halogen atoms, Ci-C4-al
  • Z 1 , Z 2 and Z 3 independently represent hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, or Ci-C4-alkoxycarbonyl; or
  • Z 2 and Z 3 form together with the carbon atom to which they are attached a 3- to 6-membered, saturated carbocycle, which is optionally substituted by 1 to 6 groups Q which can be the same or different;
  • Q represents halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, Ci- C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4- alkyl)-silyl-Ci-C 4 -alkyl;
  • A represents phenyl of formula A 1
  • Y 1 represents halogen, nitro, CHO, OCHO, NHCHO, cyano, Ci-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-halogenocycloalkyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, -Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl, C1-C4
  • Y 2 , Y 3 , Y 4 and Y 5 independently from each other represent hydrogen or Y 1 ;
  • A represents a heterocycle of formula (A 2 )
  • R 1 to R 3 independently from each other represent hydrogen, halogen, Ci-C ralkyl, Ci-C i-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C i-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 3 )
  • R 4 to R 6 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 4 )
  • R 9 to R 11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci- C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 5 )
  • R 12 and R 13 independently from each other represent hydrogen, halogen, Ci-C i-alkyl, Ci-C4-alkoxy, amino, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms, and
  • R 14 represents hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 24 )
  • R 66 represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, and Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
  • R 67 , R 68 and R 69 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
  • A represents a heterocycle of formula (A 25 )
  • R represents hydrogen, halogen, hydroxy, cyano, Ci-G-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
  • R 71 , R 72 and R 73 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
  • A represents a heterocycle of formula (A )
  • R 74 , R 75 , R 76 and R 77 independently from each other represent hydrogen, halogen, hydroxy, cyano, G- C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-G-halogenoalkoxy having 1 to 5 halogen atoms; or
  • A represents a heterocycle of formula (A 27 )
  • X 1 represents -S-, -SO-, -SO2- and -CH 2 -, and
  • R represents G-C4-alkyl and G-C4-halogenoalkyl having 1 to 5 halogen atoms
  • R 7 and R independently from each other represent hydrogen and G-Gi-alkyl
  • A represents a heterocycle of formula (A )
  • R 83 represents hydrogen, halogen, G-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
  • A is a heterocycle of formula (A 31 )
  • T oxygen
  • n 0, 1, 2 or 3;
  • X independently from each other X represents halogen, nitro, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 9 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 9 halogen atoms, C1-C4- alkylsulfinyl, Ci-C4-halogenoalkylsulfinyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfonyl, C1-C4- halogenoalkylsulfonyl having 1 to 9 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms, (C 3
  • Z 1 , Z 2 and Z 3 independently represent hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy; or
  • Z 2 and Z 3 form together with the carbon atom to which they are attached a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
  • Q represents halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, Ci- C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms;
  • A represents phenyl of formula A 1
  • Y 1 represents halogen, nitro, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, G- C4-alkylsulfanyl, -G-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, G-C4-alkoxy, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-G-C4-alkyl, Ci-C4-alkoxycarbonyl, C1-C4- halogenoalkoxycarbonyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl, Ci-C4-halogenoalkylsulfinyl having 1 to 5 halogen atoms, G-C4-alkylsulfonyl, G-C4-halogenoalkylsulfonyl
  • Y 2 , Y 3 , Y 4 and Y 5 independently from each other represent hydrogen or Y 1 ;
  • A represents a heterocycle of formula (A 2 )
  • R 1 to R 3 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C i-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C i-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 3 )
  • R 4 to R 6 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 4 )
  • R 9 to R 11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, G- C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 5 )
  • R and R independently from each other represent hydrogen, halogen, Ci-C i-alkyl, Ci-C4-alkoxy, amino, Ci-C i-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C i-halogenoalkoxy comprising 1 to 9 halogen atoms, and
  • R 14 represents hydrogen, halogen, G-C i-alkyl, G-C4-alkoxy, G-C4-halogenoalkyl comprising 1 to 9 halogen atoms or G-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 24 )
  • R represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, and G-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
  • R 67 , R 68 and R 69 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
  • A represents a heterocycle of formula (A 25 )
  • R 70 represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
  • R 71 , R 72 and R 73 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or A represents a heterocycle of formula (A )
  • R 74 , R 75 , R 76 and R 77 independently from each other represent hydrogen, halogen, hydroxy, cyano, Ci- C
  • A represents a heterocycle of formula (A 27 )
  • X 1 represents -S-, -SO-, -SO2- and -CH2-, and
  • R represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms
  • R and R independently from each other represent hydrogen and Ci-C4-alkyl
  • A represents a heterocycle of formula (A )
  • R represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
  • A is a heterocycle of formula (A 31 ) in which
  • T oxygen
  • n 0, 1 or 2;
  • X independently from each other X represents halogen, nitro, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 9 halogen atoms, Ci-C4-alkoxy, G-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, G-C4-alkylsulfonyl, G-C4-alkylcarbonyl, C1-C4- halogenoalkylcarbonyl having 1 to 9 halogen atoms;
  • Z 1 , Z 2 and Z 3 independently represent hydrogen, halogen, cyano, G-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy;
  • A represents phenyl of formula A 1
  • Y 1 represents halogen, nitro, cyano, Ci-C i-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, G- C4-alkylsulfanyl, G-C4-alkoxy, G-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-G- C4-alkyl, G-C4-alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, C 1-C4- alkylsulfinyl, C i-C4-alkylsulfonyl;
  • Y 2 , Y 3 , Y 4 and Y 5 independently from each other represent hydrogen or Y 1 ;
  • A represents a heterocycle of formula (A 2 )
  • R 1 to R 3 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 3 )
  • R 4 to R 6 independently from each other represent hydrogen, halogen, Ci-Q-alkyl, G-C i-halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 4 )
  • R 9 to R 11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 5 )
  • R 12 and R 13 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, C1-C4- halogenoalkyl comprising 1 to 9 halogen atoms, and
  • R 14 represents hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
  • A represents a heterocycle of formula (A 24 )
  • R represents hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and
  • R 67 , R 68 and R 69 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, C1-C4 halogenoalkyl having 1 to 5 halogen atoms; or
  • A represents a heterocycle of formula (A 25 )
  • R 70 represents hydrogen, halogen, G-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, and
  • R 71 , R 72 and R 73 independently from each other represent hydrogen, halogen, G-C4-alkyl, C1-C4 halogenoalkyl having 1 to 5 halogen atoms; or
  • A represents a heterocycle of formula (A 26 )
  • R 74 , R 75 , R 76 and R 77 independently from each other represent hydrogen, halogen, G-C4-alkyl, C1-C4 halogenoalkyl having 1 to 5 halogen atoms; or
  • A represents a heterocycle of formula (A 27 )
  • X represents -S-
  • R represents Ci-Q-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms
  • R and R independently from each other represent hydrogen and Ci-C4-alkyl
  • A represents a heterocycle of formula (A )
  • R 83 represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
  • A is a heterocycle of formula (A 31 )
  • the compound of formula (I) as defined above is a compound
  • A represents phenyl of formula A 1
  • Y 1 represents the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • Y 2 , Y 3 , Y 4 and Y 5 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • n, X, T, Z 1 and Z 2 , Z 3 and Q have the preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents phenyl of formula A 1
  • Y 1 represents the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • Y 2 , Y 3 , Y 4 and Y 5 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • n, X, T, Z 1 and Z 2 , Z 3 and Q have the more preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents phenyl of formula A 1
  • Y 1 represents the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • Y 2 , Y 3 , Y 4 and Y 5 independently from each other represent the preferred, more preferred, preferred or most preferred meaning as described above;
  • n, X, T, Z 1 and Z 2 , Z 3 and Q have the even more preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents phenyl of formula A 1
  • Y 1 represents the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • Y 2 , Y 3 , Y 4 and Y 5 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • n, X, T, Z 1 and Z 2 , Z 3 and Q have the most preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 4 )
  • R 9 to R 11 mdependently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • A represents a heterocycle of formula (A 5 )
  • R 12 and R 13 independently from each other the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • R 14 represents the preferred, more preferred, even more preferred or most preferred meaning as described above; or n, X, T, Z 1 and Z 2 , Z 3 and Q have the preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 4 )
  • R 9 to R 11 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • A represents a heterocycle of formula (A 5 )
  • R 12 and R 13 independently from each other the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • R 14 represents the preferred, more preferred, even more preferred or most preferred meaning as described above; or n, X, T, Z 1 and Z 2 , Z 3 and Q have the more preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 4 )
  • R 9 to R 11 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • A represents a heterocycle of formula (A 5 )
  • R 14 represents the preferred, more preferred, even more preferred or most preferred meaning as described above; or n, X, T, Z 1 and Z 2 , Z 3 and Q have the even more preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 4 )
  • R 9 to R 11 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • A represents a heterocycle of formula (A 5 )
  • R 12 and R 13 independently from each other the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • R 14 represents the preferred, more preferred, even more preferred or most preferred meaning as described above; or n, X, T, Z 1 and Z 2 , Z 3 and Q have the most preferred meaning described above.
  • the compound of formula (I) as defined above is a compound, A represents a heterocycle of formula (A 2 )
  • R 1 to R 3 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • A represents a heterocycle of formula (A 3 )
  • R 4 to R 6 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z 1 and Z 2 , Z 3 and Q have the preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 2 )
  • A represents a heterocycle of formula (A 3 )
  • R 4 to R 6 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z 1 and Z 2 , Z 3 and Q have the more preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 2 )
  • R 1 to R 3 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • A represents a heterocycle of formula (A 3 )
  • R 4 to R 6 independently from each other represent represent the preferred, more preferred,
  • n, X, T, Z 1 and Z 2 , Z 3 and Q have the even more preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 2 )
  • R 1 to R 3 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
  • A represents a heterocycle of formula (A 3 )
  • R 4 to R 6 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z 1 and Z 2 , Z 3 and Q have the most preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 24 ) in which
  • R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above, and
  • R 67 , R 68 and R 69 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
  • A represents a heterocycle of formula (A 25 )
  • R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above.
  • R 71 , R 72 and R 73 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
  • A represents a heterocycle of formula (A 26 )
  • R , R , R and R independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z 1 and Z 2 , Z 3 and Q have the preferred meaning described above.
  • the compound of formula (I) as defined above is a compound,
  • A represents a heterocycle of formula (A )
  • R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above, and
  • R 67 , R 68 and R 69 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
  • A represents a heterocycle of formula (A 25 )
  • R 7 represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above.
  • R 71 , R 72 and R 73 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
  • A represents a heterocycle of formula (A 26 )
  • R , R , R and R independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z 1 and Z 2 , Z 3 and Q have the more preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 24 )
  • R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above, and
  • R 67 , R 68 and R 69 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
  • A represents a heterocycle of formula (A 25 )
  • R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above.
  • R 71 , R 72 and R 73 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
  • A represents a heterocycle of formula (A ) in which
  • R 74 , R 75 , R 76 and R 77 independently from each other represent the preferred, more preferred,
  • n, X, T, Z 1 and Z 2 , Z 3 and Q have the even more preferred meaning described above.
  • the compound of formula (I) as defined above is a compound
  • A represents a heterocycle of formula (A 24 )
  • R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above, and
  • R 67 , R 68 and R 69 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
  • A represents a heterocycle of formula (A 25 )
  • R 70 represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above; and R 71 , R 72 and R 73 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
  • A represents a heterocycle of formula (A )
  • R , R , R and R independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z 1 and Z 2 , Z 3 and Q have the most preferred meaning described above.
  • Amine derivatives of formula (II) are known or can be prepared by known processes such as reductive amination of aldehydes or ketones (Organic Reactions (Hoboken, NJ, United States) (2002), 59), or reduction of oximes (Journal of Medicinal Chemistry (1984), 27(9), 1108), or nucleophilic substitution of a halogen, mesylate or tosylate (Journal of Medicinal Chemistry (2002), 45, 3887). Furthermore, syntheses of fluorinated amines are described in WO 2007/141009 Al, Chimica Therapeutica (1971), 6(4), 262-267 and Journal of Organic Chemistry (1981), 46(24), 4938-4948.
  • Carboxylic acid derivatives of formula (III) are known or can be prepared by known processes.
  • process PI is conducted in the presence of condensing agents.
  • Suitable condensing agents may be selected in the non- limited list consisting of acid halide former, such as phosgene, phosphorous tribromide, phosphorous trichloride, phosphorous pentachloride, phosphorous trichloride oxide or thionyl chloride; anhydride former, such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; carbodiimides, such as ⁇ , ⁇ '-dicyclohexylcarbodiimide (DCC), l-ethyl-3-(3- dimethylaminopropyl)carbodiimid (EDC) or other customary condensing agents, such as phosphorous pentoxide, polyphosphoric acid, ⁇ , ⁇ '-carbonyl-diimid
  • Process PI is conducted in the presence of a catalyst.
  • Suitable catalyst may be selected from the list consisting of N,N-dimethylpyridin-4-amine, 1-hydroxy-benzotriazole or N,N-dimethylformamide.
  • process PI is conducted in the presence of an acid binder.
  • Suitable acid binders are all inorganic and organic bases that are customary for such reactions.
  • alkaline earth metal alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as caesium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N- dimethylaniline, pyridine, N-methylpiperidine, N,
  • Suitable solvents for carrying out process PI can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlore thane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxy ethane, 1,2-diethoxy ethane or anisole; nitriles, such as acetonitrile, propionitrile, n
  • the amine derivative of formula (II) can be employed as its salt, such as hydrochloride or any other convenient salt.
  • reaction components in other ratios. Work-up is carried out by known methods.
  • Process P2 is performed in the presence of a thionating agent.
  • Suitable thionating agents can be sulfur (S), sulfhydric acid (H2S), sodium sulfide (Na2S), sodium hydrosulfide (NaHS), boron trisulfide (B2S3), bis(diethylaluminium) sulfide ((AlEt ⁇ S), ammonium sulfide ((NH 4 )2S), phosphorous pentasulfide (P2S5), Lawesson's reagent (2,4-bis(4-methoxyphenyl)- 1,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent as described in Journal of the Chemical Society, Perkin 1 (2001), 358, in the optionally presence of a catalytic or stoichiometric or excess amount, quantity of a base such as an inorganic and organic base.
  • a base such as an inorganic and organic base.
  • alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate
  • heterocyclic aromatic bases such as pyridine, picoline, lutidine, collidine
  • tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N- dimethylaniline, N,N-dimethylpyridin-4-amine or N-methyl-piperidine.
  • Suitable solvents for carrying out process P2 can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlore thane, ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane or 1,2-diethoxyethane, nitriles, such as acetonitrile, propionitrile, n- or
  • reaction components in other ratios. Work-up is carried out by known methods.
  • Processes PI and P2 are generally carried out under atmospheric pressure. It is also possible to operate under elevated or reduced pressure.
  • reaction temperatures can be varied within a relatively wide range. In general, these processes are carried out at temperatures from 0 °C to 200 °C, preferably from 10 °C to 160 °C.
  • a way to control the temperature for the processes according to the invention is to use micro-wave technology.
  • reaction mixture is concentrated under reduced pressure.
  • residue that remains can be freed by known methods, such as chromatography or crystallization, from any impurities that can still be present.
  • the invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to the microorganisms and/or in their habitat.
  • the invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to the plant or plant parts.
  • the invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to plant propagation material.
  • the invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to the seed.
  • the invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied the soil on which the plants are grown or intended to be grown.
  • the invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to the microorganisms and/or in their habitat.
  • the invention also relates to a method for controlling phytopathogenic fungi, characterized in that a compound of the formula (I) is applied to the plant or plant parts.
  • the invention also relates to a method for controlling phytopathogenic fungi, characterized in that a compound of the formula (I) is applied to plant propagation material.
  • the invention also relates to a method for controlling phytopathogenic fungi, characterized in that a compound of the formula (I) is applied to the seed.
  • the invention also relates to a method for controlling phytopathogenic fungi, characterized in a compound of the formula (I) is applied the soil on which the plants are grown or intended to be grown.
  • the invention also relates to a method for controlling phytopathogenic bacteria, characterized in that a compound of the formula (I) is applied to the plant or plant parts.
  • the invention also relates to a method for controlling phytopathogenic bacteria, characterized in that a compound of the formula (I) is applied to plant propagation material.
  • the invention also relates to a method for controlling phytopathogenic bacteria, characterized in that a compound of the formula (I) is are applied to the seed.
  • the invention also relates to a method for controlling phytopathogenic bacteria, characterized in that a compound of the formula (I) is applied the soil on which the plants are grown or intended to be grown.
  • the invention further relates to seed which has been treated with at least one compound of the formula (I)-
  • the invention finally provides a method for protecting seed against phytopathogenic microorganisms by using seed treated with at least one compound of the formula (I).
  • the compounds of the formula (I) have potent microbicidal activity and can be used for control of phytopathogenic microorganisms in agriculture.
  • a compound of the formula (I) can be used for control of phytopathogenic microorganisms in crop protection and in the protection of materials.
  • the compounds of the formula (I) have potent microbicidal activity and can be used for control of phytopathogenic fungi in agriculture.
  • a compound of the formula (I) can be used for control of phytopathogenic fungi in crop protection and in the protection of materials.
  • the compounds of the formula (I) have potent microbicidal activity and can be used for control of phytopathogenic bacteria in agriculture.
  • a compound of the formula (I) can be used for control of phytopathogenic bacteria in crop protection and in the protection of materials.
  • the compounds of the formula (I) can be used for curative or protective control of phytopathogenic microorganisms.
  • the invention therefore also relates to curative and protective methods for controlling phytopathogenic microorganisms by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
  • the compounds of the formula (I) can be used for curative or protective control of phytopathogenic bacteria.
  • the invention therefore also relates to curative and protective methods for controlling phytopathogenic bacteria by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
  • the compounds of the formula (I) can be used for curative or protective control of phytopathogenic fungi.
  • the invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow. Plants
  • Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which are protectable and non-protectable by plant breeders' rights.
  • Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples of which include leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes.
  • the plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
  • Plants which can be treated in accordance with the invention include the following plants from the group of the useful plants, ornamentals, turfs, generally used trees which are employed as ornamentals in the public and domestic sectors, and forestry trees.
  • Forestry trees comprise trees for the production of timber, cellulose, paper and products made from parts of the trees.
  • useful plants refers to crop plants which are employed as plants for obtaining foodstuffs, feedstuffs, fuels or for industrial purposes.
  • the useful plants include for example the following types of plants: turf, vines, cereals, for example wheat, barley, rye, oats, rice, maize and millet/sorghum, corn, maize; beet, for example sugar beet and fodder beet; fruits, for example pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries and berries, for example strawberries, raspberries, blackberries; legumes, for example beans, lentils, peas and soybeans; oil crops, for example oilseed rape, canola, mustard, poppies, olives, sunflowers, coconuts, castor oil plants, cacao and peanuts; cucurbits, for example pumpkin/squash, cucumbers and melons; fibre plants, for example cotton, flax, hemp and jute; citrus fruit, for example oranges, lemons, grapefruit and tangerines; vegetables, for example spinach, lettuce, asparagus, cabbage species, carrots, onions, tomatoes, potatoes and bell peppers
  • the following plants are considered to be particularly suitable target crops: cotton, aubergine, turf, pome fruit, stone fruit, soft fruit, maize, wheat, barley, cucumber, tobacco, vines, rice, cereals, pear, beans, soybeans, oilseed rape, tomato, bell pepper, melons, cabbage, potato and apple.
  • trees are: Abies sp., Eucalyptus sp., Picea sp., Pinus sp., Aesculus sp., Platanus sp., Tilia sp., Acer sp., Tsuga sp., Fraxinus sp., Sorbus sp., Betula sp., Crataegus sp., Ulmus sp., Quercus sp., Fagus sp., Salix sp., Populus sp..
  • Examples of turf grasses are including cool-season turf grasses and warm-season turf grasses.
  • Cold-season turf grasses are bluegrasses (Poa spp.), such as Kentucky bluegrass (Poa pratensis L.), rough bluegrass (Poa trivialis L.), Canada bluegrass (Poa compressa L.), annual bluegrass (Poa annua L.), upland bluegrass (Poa glaucantha Gaudin), wood bluegrass (Poa nemoralis L.) and bulbous bluegrass (Poa bulbosa L.); bentgrasses (Agrostis spp.) such as creeping bentgrass (Agrostis palustris Huds.), colonial bentgrass (Agrostis tenuis Sibth.), velvet bentgrass (Agrostis canina L.), South German mixed bentgrass (Agrostis spp.
  • ryegrasses such as annual ryegrass (Lolium multiflorum Lam), perennial ryegrass (Lolium perenne L.) and Italian ryegrass (Lolium multiflorum Lam.); and wheatgrasses (Agropyron spp.), such as fairway wheatgrass (Agropyron cristatum (L.) Gaertn.), crested wheatgrass (Agropyron desertorum (Fisch.) Schult.) and
  • Warm-season turf grasses are Bermuda grass (Cynodon spp. L. C. Rich), zoysia grass (Zoysia spp. Willd.), St. Augustine grass (Stenotaphrum secundatum Walt Kuntze), centipede grass (Eremochloa ophiuroides Munrohack.), carpetgrass (Axonopus affmis Chase), Bahia grass (Paspalum notatum Flugge), Kikuyu grass (Pennisetum clandestinum Hochst ex Chiov.), buffalo grass (Buchloe dactyloids (Nutt.) Engelm.), blue grama (Bouteloua gracilis (H.B.K.) Lag. ex Griffiths), seashore paspalum (Paspalum vaginatum Swartz) and sideoats grama (Bouteloua curtipendula (Michx. Torr.).
  • phytopathogenic microorganisms in particular phytopathogenic fungi which can be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae; Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striiformis; Uromyces species, for example Puccinia
  • brassicae Phytophthora species, for example Phytophthora infestans; Plasmopara species, for example Plasmopara viticola; Pseudoperonospora species, for example Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, for example Pythium ultimum; leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species, for example Alternaria solani; Cercospora species, for example Cercospora beticola; Cladiosporium species, for example Cladiosporium cucumerinum; Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium) or Cochliobolus miyabeanus; Colletotrichum species, for example Colletotrichum lindemuthanium;
  • phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotmia sclerotioium), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).
  • the compounds of the formula (I) can reduce the mycotoxin content in the plant products, in particular harvested material and the foods and feeds prepared therefrom.
  • Mycotoxins include particularly, but not exclusively, the following: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac- DON, T2- and HT2-toxin, fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol (DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins which can be produced, for example, by the following fungi: Fusarium spec, such as F. acuminatum, F. asiaticum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberella
  • Penicillium spec such as P. verrucosum, P. viridicatum, P. citrinum, P. expansum, P. claviforme, P. roqueforti, Claviceps spec, such as C.
  • the compounds of the formula (I) can also be used in the protection of materials, for protection of industrial materials against attack and destruction by phytopathogenic microorganisms, in particular phytopathogenic fungi .
  • the compounds of the formula (I) can be used as antifouling compositions, alone or in combinations with other active ingredients.
  • Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry.
  • industrial materials which are to be protected by inventive compositions from microbial alteration or destruction may be adhesives, glues, paper, wallpaper and board/cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms.
  • Parts of production plants and buildings, for example cooling-water circuits, cooling and heating systems and ventilation and air-conditioning units, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected.
  • Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood.
  • the compounds of the formula (I) may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • the compounds of the formula (I) may also be used against fungal diseases liable to grow on or inside timber.
  • the term "timber" means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood.
  • the method for treating timber according to the invention mainly consists in contacting a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.
  • the compounds of the formula (I) can be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signalling systems, from fouling.
  • Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired.
  • Storage goods of vegetable origin for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, can be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting.
  • Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture.
  • Storage goods of animal origin are, for example, hides, leather, furs and hairs.
  • the inventive compositions may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • Microorganisms capable of degrading or altering the industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms.
  • the compounds of the formula (I) preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi (Ascomycetes, Basidiomycetes, Deuteromycetes and Zygomycetes), and against slime organisms and algae.
  • microorganisms of the following genera Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride; Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Poria
  • the present invention further relates to a composition for controlling phytopathogenic microorganisms, in particular phytopathogenic fungi comprising at least one of the compounds of the formula (I).
  • phytopathogenic fungi comprising at least one of the compounds of the formula (I).
  • These are preferably fungicidal compositions which comprise agriculturally suitable auxiliaries, solvents, carriers, surfactants or extenders.
  • a carrier is a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, in particular for application to plants or plant parts or seed.
  • the carrier which may be solid or liquid, is generally inert and should be suitable for use in agriculture.
  • Useful solid carriers include: for example ammonium salts and natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates; useful solid carriers for granules include: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic flours, and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks; useful emulsifiers and/or foam-formers include: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, aryl
  • oligo- or polymers for example those derived from vinylic monomers, from acrylic acid, from EO and/or PO alone or in combination with, for example, (poly)alcohols or (poly)amines. It is also possible to use lignin and its sulphonic acid derivatives, unmodified and modified celluloses, aromatic and/or aliphatic sulphonic acids and also their adducts with formaldehyde.
  • the active ingredients can be converted to the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
  • customary formulations such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
  • the active ingredients can be applied as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
  • Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading-on and the like. It is also possible to deploy the active ingredients by the ultra-low volume method or to inject the active ingredient preparation/the active ingredient itself into the soil. It is also possible to treat the seed of the plants.
  • the formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, emulsifier, dispersant and/or binder or fixing agent, wetting agent, a water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyes and pigments, antifoams, preservatives, secondary thickeners, stickers, gibberellins and also other processing auxiliaries.
  • the present invention includes not only formulations which are aheady ready for use and can be deployed with a suitable apparatus to the plant or the seed, but also commercial concentrates which have to be diluted with water prior to use.
  • the compounds of the formula (I) may be present as such or in their (commercial) formulations and in the use forms prepared from these formulations as a mixture with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.
  • active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.
  • auxiliaries used may be those substances which are suitable for imparting particular properties to the composition itself or and/or to preparations derived therefrom (for example spray liquors, seed dressings), such as certain technical properties and/or also particular biological properties.
  • Typical auxiliaries include: extenders, solvents and carriers.
  • Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example from the classes of the aromatic and nonaromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which may optionally also be substituted, etherified and/or esterified), the ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulphones and sulphoxides (such as dimethyl sulphoxide).
  • aromatic and nonaromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • the alcohols and polyols which may optionally also
  • Liquefied gaseous extenders or carriers are understood to mean liquids which are gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, or else butane, propane, nitrogen and carbon dioxide.
  • tackifiers such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids.
  • Further additives may be mineral and vegetable oils.
  • Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, or else water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride
  • aliphatic hydrocarbons such as
  • compositions comprising compounds of the formula (I) may additionally comprise further components, for example surfactants.
  • surfactants are emulsifiers and/or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants.
  • Examples thereof are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose.
  • the presence of a surfactant is necessary if one of the active ingredients and/or one of the inert
  • dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Further additives may be perfumes, mineral or vegetable, optionally modified oils, waxes and nutrients (including trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Additional components may be stabilizers, such as cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents which improve chemical and/or physical stability.
  • additional components may also be present, for example protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilizers, sequestering agents, complex formers.
  • the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
  • the formulations contain generally between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, more preferably between 0.5 and 90% of active ingredient, most preferably between 10 and 70 per cent by weight.
  • compositions described above can be used for controlling phytopathogenic microorganisms, in which the compositions comprising compounds of the formula (I) are applied to the phytopathogenic microorganisms and/or in their habitat.
  • the invention furthermore includes a method for treating seed.
  • a further aspect of the present invention relates in particular to seeds (dormant, primed, pregerminated or even with emerged roots and leaves) treated with at least one of the compounds of the formula (I).
  • inventive seeds are used in methods for protection of seeds and emerged plants from the seeds from phytopathogenic microorganisms, in particular phytopathogenic fungi. In these methods, seed treated with at least one inventive active ingredient is used.
  • the compounds of the formula (I) are also suitable for the treatment of seeds and young seedlings.
  • a large part of the damage to crop plants caused by harmful organisms is triggered by the infection of the seeds before sowing or after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even small damage may result in the death of the plant. Accordingly, there is great interest in protecting the seed and the germinating plant by using appropriate compositions.
  • the present invention therefore also relates to a method for protecting seeds, germinating plants and emerged seedlings against attack by animal pests and/or phytopathogenic microorganisms, in particular phytopathogenic fungi by treating the seeds with an inventive composition.
  • the invention also relates to the use of the compositions according to the invention for treating seeds for protecting the seeds, the germinating plants and emerged seedlings against animal pests and/or phytopathogenic microorganisms, in particular phytopathogenic fungimicro.
  • the invention further relates to seeds which has been treated with an inventive composition for protection from animal pests and/or phytopathogenic microorganisms, in particular phytopathogenic fungi.
  • One of the advantages of the present invention is that the treatment of the seeds with these compositions not only protects the seed itself, but also the resulting plants after emergence, from animal pests and/or phytopathogenic harmful microorganisms. In this way, the immediate treatment of the crop at the time of sowing or shortly thereafter protect plants as well as seed treatment in prior to sowing. It is likewise considered to be advantageous that the inventive active ingredients or compositions can be used especially also for transgenic seed, in which case the plant which grows from this seed is capable of expressing a protein which acts against pests, herbicidal damage or abiotic stress. The treatment of such seeds with the inventive active ingredients or compositions, for example an insecticidal protein, can result in control of certain pests.
  • the compounds of the formula (I) are suitable for protection of seed of any plant variety which is used in agriculture, in the greenhouse, in forests or in horticulture. More particularly, the seed is that of cereals (such as wheat, barley, rye, millet and oats), oilseed rape, maize, cotton, soybeen, rice, potatoes, sunflower, beans, coffee, beet (e.g. sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onions and lettuce), lawns and ornamental plants. Of particular significance is the treatment of the seed ofwheat, soybean, oilseed rape, maize and rice.
  • transgenic seed As also described below, the treatment of transgenic seed with the inventive active ingredients or compositions is of particular significance.
  • These heterologous genes in transgenic seeds may originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • These heterologous genes preferably originates from Bacillus sp., in which case the gene product is effective against the European corn borer and/or the Western corn rootworm.
  • the heterologous genes originate from Bacillus thuringiensis.
  • the inventive composition is applied to seeds either alone or in a suitable formulation.
  • the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment.
  • seeds can be treated at any time between harvest and some time after sowing. It is customary to use seed which has been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seed which has been harvested, cleaned and dried down to a moisture content of less than 15% by weight.
  • seed which, after drying, for example, has been treated with water and then dried again or seeds just after priming, or seeds stored in primed conditions or pre- germinated seeds, or seeds sown on nursery trays, tapes or paper.
  • the amount of the inventive composition applied to the seed and/or the amount of further additives is selected such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This must be ensured particularly in the case of active ingredients which can exhibit phytotoxic effects at certain application rates.
  • the compounds of the formula (I) can be applied directly, i.e. without containing any other components and without having been diluted. In general, it is preferable to apply the compositions to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art.
  • the compounds of the formula (I) can be converted to the customary formulations relevant to on-seed applications, such as solutions, emulsions, suspensions, powders, foams, slurries or combined with other coating compositions for seed, such as film forming materials, pelleting materials, fine iron or other metal powders, granules, coating material for inactivated seeds, and also ULV formulations.
  • formulations are prepared in a known manner, by mixing the active ingredients or active ingredient combinations with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • customary additives for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • Useful dyes which may be present in the seed dressing formulations usable in accordance with the invention are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.
  • Useful wetting agents which may be present in the seed dressing formulations usable in accordance with the invention are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients.
  • Usable with preference are alkylnaphthalenesulphonates, such as diisopropyl- or diisobutylnaphthalenesulphonates.
  • Useful dispersants and/or emulsifiers which may be present in the seed dressing formulations usable in accordance with the invention are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Usable with preference are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Useful nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sulphated derivatives thereof.
  • Suitable anionic dispersants are especially lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehyde condensates.
  • Antifoams which may be present in the seed dressing formulations usable in accordance with the invention are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.
  • Preservatives which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.
  • Secondary thickeners which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions.
  • Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
  • Adhesives which may be present in the seed dressing formulations usable in accordance with the invention are all customary binders usable in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
  • the formulations for on-seed applications usable in accordance with the invention can be used to treat a wide variety of different kinds of seed either directly or after prior dilution with water.
  • the concentrates or the preparations obtainable therefrom by dilution with water can be used to dress the seed of cereals, such as wheat, barley, rye, oats, and triticale, and also seeds of maize, soybean, rice, oilseed rape, peas, beans, cotton, sunflowers, and beets, or else a wide variety of different vegetable seeds.
  • the formulations usable in accordance with the invention, or the dilute preparations thereof, can also be used for seeds of transgenic plants. In this case, additional synergistic effects may also occur in interaction with the substances formed by expression.
  • the application rate of the formulations usable in accordance with the invention can be varied within a relatively wide range. It is guided by the particular content of the active ingredients in the formulations and by the seeds.
  • the application rates of each single active ingredient is generally between 0.001 and 15 g per kilogram of seed, preferably between 0.01 and 5 g per kilogram of seed.
  • plants and their parts are treated.
  • wild plant species and plant cultivars or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering methods if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention.
  • Plant cultivars are understood to mean plants which have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
  • the method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds.
  • GMOs genetically modified organisms
  • Genetically modified plants are plants of which a heterologous gene has been stably integrated into genome.
  • the expression "heterologous gene” essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microRNA - miRNA - technology).
  • a heterologous gene that is located in the genome is also called a transgene.
  • a transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
  • Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means).
  • Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
  • Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses.
  • Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
  • Plants and plant cultivars which may also be treated according to the invention are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation.
  • Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance.
  • Further yield traits include seed composition, such as carbohydrate content and composition for example cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
  • Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses).
  • Plants or plant cultivars which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
  • Plants or plant cultivars which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance.
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as Tobacco plants, with altered post-translational protein modification patterns.
  • the application rates can be varied within a relatively wide range, depending on the kind of application.
  • the application rate of the inventive active ingredients is • in the case of treatment of plant parts, for example leaves: from 0.1 to 10 000 g ha, preferably from 10 to 1000 g ha, more preferably from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used);
  • Trimethylsilylcyanide (5.3 mL, 39.7 mmol) was added dropwise to a stirred suspension of Zn (19.036 mg, 0.06 mmol), l-(2,4-dichlorophenyl)ethanone (7.516 g, 39.7 mmol) and dichloromethane (3.8 ml) under nitrogen atmosphere at 0°C.
  • the reaction mixture was stirred at room temperature overnight. It was then diluted with dry dichloromethane (49 mL), cooled again to 0°C, and a solution of DAST (5.78 mL, 43.7 mmol) in dichloromethane (20.4 mL) was added dropwise. The reaction mixture was stirred overnight at room temperature.
  • the reaction mixture is poured in 61 mL of iced water and extracted with dichloromethane.
  • the organic layer was washed sequentially with a 0.5N aqueous HC1 solution, water, a saturated aqueous solution of NaHC(3 ⁇ 4, and water again.
  • the organic layer was dried over sodium sulfate, filtered, and concentrated.
  • the residue obtained was further purified by flash chromatography on silicagel (eluent: cyclohexane/ethylacetate). This afforded 8.576 g (90%) of the title compound.
  • Examples 1-393, 1-399 and 1-400 were obtained in a similar way as the one described above starting with the corresponding aldehyde respectively 2,4-dichlorobenzaldehyde, 2- (trifluoromethyl)benzaldehyde and 2-chlorobenzaldehyde.
  • LogP value is determined by measurement of LC-UV, in an acidic range, with 0.1% formic acid in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
  • LogP value is determined by measurement of LC-UV, in a neutral range, with 0.001 molar ammonium acetate solution in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
  • IH-NMR data of selected examples are written in form of lH-NMR-peak lists. To each signal peak are listed the ⁇ - value in ppm and the signal intensity in round brackets. Between the ⁇ -value - signal intensity pairs are semicolons as delimiters.
  • the peak list of an example has therefore the form: ⁇ (intensityi); 8 2 (intensity 2 ); ; ⁇ ; (intensity); ; ⁇ ⁇ (intensityn)
  • Intensity of sharp signals correlates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectram can be shown.
  • tetramethylsilane For calibrating chemical shift for 1H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilane peak can occur but not necessarily.
  • the IH-NMR peak lists are similar to classical IH-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation.
  • the peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).
  • Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore their peaks can help to recognize the reproduction of our preparation process via "side-products-fingerprints".
  • An expert who calculates the peaks of the target compounds with known methods (MestreC, ACD- simulation, but also with empirically evaluated expectation values) can isolate the peaks of the target compounds as needed optionally using additional intensity filters. This isolation would be similar to relevant peak picking at classical 1H-NMR interpretation.
  • Example 36 H-NMR (400.0 MHz, ds-DMSO):
  • Emulsifier 1 ⁇ of Tween ® 80 per mg of active ingredient
  • the active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of radish are treated by spraying the active ingredient prepared as described above.
  • Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween ® 80.
  • the plants are contaminated by spraying the leaves with an aqueous suspension of Alternaria brassicae spores.
  • the contaminated radish plants are incubated for 6 days at 20°C and at 100% relative humidity.
  • the test is evaluated 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
  • Emulsifier of Tween ® 80 per mg of active ingredient
  • the active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of gherkin are treated by spraying the active ingredient prepared as described above.
  • Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween ® 80.
  • the plants are contaminated by spraying the leaves with an aqueous suspension of Botrytis cinerea spores.
  • the contaminated gherkin plants are incubated for 4 to 5 days at 17°C and at 90% relative humidity.
  • the test is evaluated 4 to 5 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
  • Emulsifier 1 ⁇ of Tween ® 80 per mg of active ingredient
  • the active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of barley are treated by spraying the active ingredient prepared as described above.
  • Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween ® 80.
  • the plants are contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores.
  • the contaminated barley plants are incubated for 48 hours at 20°C and at 100% relative humidity and then for 12 days at 20°C and at 70-80% relative humidity.
  • the test is evaluated 14 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
  • Emulsifier 1 ⁇ of Tween ® 80 per mg of active ingredient
  • the active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of wheat are treated by spraying the active ingredient prepared as described above.
  • Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween ® 80.
  • the plants are contaminated by spraying the leaves with an aqueous suspension of Septoria tritici spores.
  • the contaminated wheat plants are incubated for 72 hours at 18°C and at 100% relative humidity and then for 21 days at 20°C and at 90% relative humidity.
  • the test is evaluated 24 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
  • Emulsifier 1 ⁇ of Tween ® 80 per mg of active ingredient
  • the active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of gherkin are treated by spraying the active ingredient prepared as described above.
  • Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween ® 80.
  • the plants are contaminated by spraying the leaves with an aqueous suspension of Sphaerotheca fuliginea spores.
  • the contaminated gherkin plants are incubated for 72 hours at 18°C and at 100% relative humidity and then for 12 days at 20°C and at 70-80% relative humidity.
  • the test is evaluated 15 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
  • Emulsifier part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the test is evaluated 3 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.
  • Emulsifier part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at approximately 21°C and a relative atmospheric humidity of approximately 90%.
  • the test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

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Abstract

The present invention relates to the use of N-(2-halogen-2-phenethyl) carboxamides for the control of phytopathogenic microorganisms in agriculture, wherein a compound of formula (I) is applied to the phytopathogenic microorganisms, their habitat, the plant, the seed thereof, plant parts, plant propagation material or the soil on which the plants are grown or intended to be grown in an effective amount.

Description

N-(2-Halogen-2-phenethyl)carboxamides as fungicides
The present invention relates to the use of N-(2-halogen-2-phenethyl)carboxamides for the control of phytopathogenic microorganisms in agriculture, wherein a compound of formula (I) is applied to the phytopathogenic microorganisms, their habitat, the plant, the seed thereof, plant parts, plant propagation material or the soil on which the plants are grown or intended to be grown in an effective amount.
The present invention further relates to compositions containing such compounds and methods for the control of phytopathogenic microorganisms on plants, the habitat of such micro organims, the plant, the seed thereof, plant parts, plant propagation material or the soil on which the plants are grown or intended to be grown.
Phytopathogenic microorganisms cause a substantial loss in agricultural production including food and industrial crops and are control with compounds having fungicidal activity. To be useful in agriculture these compounds should have a high activity against phytopathogenic microorganisms, a broad spectrum activity against different species of phytopathogenic microorganisms and should be able to be applied in an environmentally safe way.
In WO-A 2007/141009 certain fungicidal N-(2-phenethyl)-carboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:
Figure imgf000002_0001
wherein A can represent 4-pyrazoles, 5-thiazoles, 4-pyrroles or 4-triazoles; R1, R2, R3 and R4 can represent hydrogen, halogen, nitro, Ci-Ce-aikyl, Cs-Ce-cycloalkyl, C2-Ce-alkenyl, C2-C6-alkynyl; or R1 and R2 represent together a C2-Cs-alkylene group; B can represent substituted phenyl. However, this document does not disclose compounds when A represents another heterocycle than the ones mentioned above.
In WO-A 2012/118139 the endoparasiticidal use of certain N-(2-pyridylethyl) carboxamide and N-(2- phenethyl) carboxamide derivatives are disclosed with following subformula:
Figure imgf000002_0002
wherein X and Y can represent halogen atoms, cyano, nitro, G-Ce-alkyl, Ci-C6-haloalkyl etc.; R1, R2, R3 and R4 are substituents of an alkandiyl chain, exemplified as hydrogen, alkyl and R1 + R2 or R3 + R4 forming together a cyclopropyl ring. However, the document does not exemplify compounds wherein the alkandiyl chain is substituted by halogen, e.g. fluorine.
EP-A 1997800 discloses N-2-(hetero)arylethylcarboxamide derivatives as fungi-controlling agents. The references discloses also certain N-(2-halogen-2-phenethyl)carboxamides where the heterocyclyl attached to the carbonyl group represents pyrazines or 3-pyridyls. However, this document does not disclose evidence of synthesis of such compounds nor corresponding biological efficacy
WO-A 2012/168361 discloses insecticidal thiazolyl carboxamides which embrace certain fluorine- containing phenethyl carboxamides, like following examples 1.106 and 1.107, but are not disclosed as
Figure imgf000003_0001
1 .107
In WO-A 2013/076230 the endoparasiticidal use of certain phenyl-difluoroethyl carboxamides is described with for instance, following concretely mentioned compounds: 3-chloro-N-[2-(4- chlorophenyl)-2,2-difluoroethyl]thiophene-2-carboxamide, 3-bromo-N-[2-(4-chlorophenyl)-2,2- difluoroethyl] thiophene-2-carboxamide, N-[2-(4-chlorophenyl)-2,2-difluoroethyl]-2-
(trifluoromethyl)nicotin-amide, N-[2-(2,4-dichlorophenyl)-2,2-difluoroethyl]-2-(trifluoromethyl)nicotin- amide, 2-chloro-N-[2-(4-chlorophenyl)-2,2-difluoroethyl]-4-(trifluoromethyl)nicotinamide, 2-chloro-N- [2-(2,4-dichlorophenyl)-2,2-difluoroethyl]-4-(trifluoromethyl)nicotinamide, 6-chloro-N-[2-(4-chloro- phenyl)-2,2-difluoroethyl]-4-(trifluoromethyl)nicotinamide and 6-chloro-N-[2-(2,4-dichloro phenyl)- 2,2-difluoroethyl]-4-(trifluoromethyl)nicotinamide. This patent application does not disclose any fungicidal use.
In WO2014/004064 are disclosed certain N-[(pyrazolylsubstituted-phenyl)-2,2 dihalo-ethyl] carboxamides, such as example 150, in above-mentioned document, with a claimed fungicidal efficacy, however such heterocyclophenethyl carboxamides are not part of the present invention and are only remotely connected to the present invention as they explicitly require the specific presence of an additional heterocycle in their general structure.
Therefore there is a need to provide further compounds suitable to control phytopathogenic microorganisms in agriculture with a high activity. The object of the invention, and further objects which are not stated explicitly but can be discerned or derived from the connections discussed herein, are achieved by the use of a compound of formula (I),
Figure imgf000004_0001
(I)
or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen or sulfur;
n represents 0, I, 2, 3, 4 or 5;
X independently from each other X represents halogen, nitro, cyano, isonitrile, hydroxy, amino, sulfanyl, pentafluoro^6-sulfanyl, formyl, formyloxy, formylamino, (hydroxyimino)-Ci-C8-alkyl, (G- G-alkoxyimino)-G-G-alkyl, (G-G-alkenyloxyimino)-G-G-alkyl, (G-G-alkynyloxyimino)-G-G- alkyl, (benzyloxyimino)-Ci-C8-alkyl, carboxy, carbamoyl, N-hydroxycarbamoyl, carbamate, G-G- alkyl, Ci-Cs-halogenoalkyl having 1 to 9 halogen atoms, C2-Cs-alkenyl, C2-C8-halogenoalkenyl having 1 to 9 halogen atoms, C2-Cs-alkynyl, C2-C8-halogenoalkynyl having 1 to 9 halogen atoms, G-G- alkoxy, G-G-halogenoalkoxy having 1 to 9 halogen atoms, G-G-alkylsulfanyl, G-G- halogenoalkylsulfanyl having 1 to 9 halogen atoms, G-Cs-alkylsulfinyl, G-Cs-halogenoalkylsulfinyl having 1 to 9 halogen atoms, G-Cs-alkylsulfonyl, G-G-halogenoalkylsulfonyl having 1 to 9 halogen atoms, G-G-alkylamino, di-(G-C8-alkyl)-amino, C2-C8-alkenyloxy, C2-C8-halogenoalkenyloxy having 1 to 9 halogen atoms, C3-Cs-alkynyloxy, C2-Cs-halogenoalkynyloxy having 1 to 9 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms, C4-C7-cycloalkenyl, C4-C7-halogenocycloalkenyl having 1 to 9 halogen atoms, (C3-C7-cycloalkyl)-G-C8-alkyl, (G-G- cycloalkyl)-C2-C8-alkenyl, (G-G-cycloalkyl)-G-G-alkynyl, tri-(Ci-C8-alkyl)-silyl, tri-(G-G-alkyl)- silyl-G-C8-alkyl, G-G-alkylcarbonyl, G-Cs-halogenoalkylcarbonyl having 1 to 9 halogen atoms, G-C8-alkylcarbonyloxy, G-G-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms, G-G- alkylcarbonylamino, G-Cs-halogenoalkylcarbonylamino having 1 to 9 halogen atoms, G-G- alkoxycarbonyl, G-Cs-halogenoalkoxycarbonyl having 1 to 9 halogen atoms, G-G- alkyloxycarbonyloxy, G-Cs-halogenoalkoxycarbonyloxy having 1 to 9 halogen atoms, G-G- alkylcarbamoyl, di-G-G-alkylcarbamoyl, G-G-alkylaminocarbonyloxy, di-G-Cs- alkylaminocarbonyloxy, N-(G-C8-alkyl)-hydroxycarbamoyl, G-Cs-alkoxycarbamoyl, N-(G-C8- alkyl)-G-C8-alkoxycarbamoyl, aryl-G-G-alkyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-C2-Cs-alkenyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-C2-C8-alkynyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryloxy optionally substituted by 1 to 6 groups Q which can be the same or different, arylsulfanyl optionally substituted by 1 to 6 groups Q which can be the same or different, arylamino optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-G-Cs-alkyloxy optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-Ce-alkylsulfanyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-Cs-alkylamino optionally substituted by 1 to 6 groups Q which can be the same or different, pyridinyloxy which is optionally substituted by 1 to 4 groups Q; or
two substituents X together with the carbon atoms to which they are attached form a 5- or 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 4 groups Q which can be the same or different;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, G-Cs-alkyl, G-Cs-halogenoalkyl having 1 to 5 halogen atoms, G-Cs-alkoxy, G-Cs-alkylsulfanyl, or G-Cs-alkoxycarbonyl; or
Z2 and Z3 form together with the carbon atom to which they are attached a 3- to 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 6 groups Q which can be the same or different;
Q represents halogen, cyano, nitro, G-Cs-alkyl, G-Cs-halogenoalkyl having 1 to 9 halogen atoms, G- Cs-alkoxy, G-Cs-halogenoalkoxy having 1 to 9 halogen atoms, G-C8-alkylsulfanyl, Ci-Cs- halogenoalkylsulfanyl having 1 to 9 halogen atoms, tri-(Ci-C8-alkyl)-silyl, tri-(Ci-C8-alkyl)-silyl-Ci- C8-alkyl, Ci-Cs-alkoxyimino-Ci-Cs-alkyl, (benzyloxyimino)-Ci-C8-alkyl;
A represents phenyl of formula A1
Figure imgf000005_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents halogen, nitro, SH, SF5, CHO, OCHO, NHCHO, cyano, G-Cg-alkyl, G-Cg-halogenoalkyl having 1 to 5 halogen atoms, C2-C8-alkenyl, C2-Cs-alkynyl, C3-C6-cycloalkyl, Cs-Ce-halogenocycloalkyl having 1 to 9 halogen atoms, G-G-alkylsulfanyl, -G-G-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-Cs-alkoxy, G-G-halogenoalkoxy having 1 to 5 halogen atoms, G-G-alkoxy-G-G-alkyl, G- Ce-alkenyloxy-Ci-Cg-alkyl, G-G-alkynyloxy-G-G-alkyl, G-G-alkenyloxy, G-G-alkynyloxy, G-G- alkoxycarbonyl, G-G-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, G-G-alkylcarbonyloxy, G-G-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, G-G-alkylsulfmyl, G-G- halogenoalkylsulfinyl having 1 to 5 halogen atoms, G-G-alkylsulfonyl, G-G-halogenoalkylsulfonyl having 1 to 5 halogen atoms, G-G-alkylsulfonamide, tri-(G-C8)-alkylsilyl, aryl and aryloxy;
Y2, Y3, Y4 and Y5 independently from each other represent hydrogen or Y1; or
A represents a heterocycle of formula (A2)
Figure imgf000006_0001
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, G-G-alkyl, G-G-halogenoalkyl comprising 1 to 9 halogen atoms, G-G-alkoxy or G-G-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A3)
Figure imgf000006_0002
wherein
R4 to R6 independently from each other represent hydrogen, halogen, G-G-alkyl, G-G-halogenoalkyl comprising 1 to 9 halogen atoms, G-G-alkoxy or G-G-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000007_0001
(A4) wherein
R9 to R11 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, amino, C1-C5- alkoxy, G-Cs-alkylsulfanyl, G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or C1-C5- halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A5)
Figure imgf000007_0002
(A5) wherein
R and R independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, amino, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms, and
R14 represents hydrogen, halogen, G-Cs-alkyl, G-Cs-alkoxy, amino, G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or G-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A6)
Figure imgf000007_0003
(A6) wherein
R represents hydrogen or substituted or unsubstitued G-Cs-alkyl, and R20 to R22 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A7)
Figure imgf000008_0001
(A7) wherein
R23 represents hydrogen, halogen, Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, and
R24 represents hydrogen or Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A8)
Figure imgf000008_0002
wherein
R25 represents hydrogen, halogen, Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, and
R26 represents hydrogen, Ci-Cs-alkyl or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A9)
Figure imgf000008_0003
wherein R29 represents hydrogen, halogen, G-G-alkyl, G-G-alkoxy, G-G-halogenoalkoxy comprising 1 to 9 halogen atoms or G-G-halogenoalkyl comprising 1 to 9 halogen atoms, and
R30 represents hydrogen, halogen, G-G-alkyl, G-G-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms, amino, G-G-alkylamino or di-(G- C5-alkyl)-amino; or
A represents a heterocycle of formula (A10)
Figure imgf000009_0001
(A10) wherein
R31 represents hydrogen or G-G-alkyl, and
R32 represents hydrogen, halogen, G-G-alkyl or G-G-halogenoalkyl comprising 1 to 9 halogen atoms, and
R33 represents hydrogen, halogen, nitro, G-G-alkyl, G-G-alkoxy, G-G-halogenoalkoxy comprising 1 to 9 halogen atoms or G-G-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A1 :)
Figure imgf000009_0002
(A11) wherein
R and R independently from each other represent hydrogen, halogen, G-Cs-alkyl, G-G halogenoalkyl comprising 1 to 9 halogen atoms, G-G-alkoxy or a G-G-alkylsulfanyl, and
R represents hydrogen or G-Cs-alkyl; or A represents a heterocycle of formula (A12)
Figure imgf000010_0001
wherein
R40 and R41 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A13)
Figure imgf000010_0002
wherein
R42 and R43 independently from each other represent hydrogen, halogen, G-Cs-alkyl, C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms or amino; or
A represents a heterocycle of formula (A14)
Figure imgf000010_0003
(A14) wherein
R44 and R45 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A15)
Figure imgf000011_0001
(A15) wherein
R47 represents hydrogen, halogen, Ci-Cs-alkyl or G-G-halogenoalkyl comprising 1 to 9 halogen atoms, and
R46 represents hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-Cs-alkylsulfanyl; or
A represents a heterocycle of formula (A16)
Figure imgf000011_0002
(A16) wherein
R49 and R48 independently from each other represent hydrogen, halogen, G-G-alkyl, G-Cs-alkoxy, G- C5-halogenoalkoxy comprising 1 to 9 halogen atoms or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A17)
Figure imgf000011_0003
(A17) wherein
R50 and R51 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, G- G-halogenoalkoxy comprising 1 to 9 halogen atoms or G-G-halogenoalkyl comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A18)
Figure imgf000012_0001
(A18) wherein
R52 represents hydrogen, halogen, G-Cs-alkyl or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A19)
Figure imgf000012_0002
(A19) wherein
R53 represents hydrogen, halogen, G-Cs-alkyl or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A20)
Figure imgf000012_0003
(A20) wherein
R54 and R56 independently from each other represent hydrogen, halogen, G-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms, and
R55 represents hydrogen or G-Cs-alkyl; or A represents a heterocycle of formula (A21)
Figure imgf000013_0001
(A21) wherein
R57 and R59 independently from each other represent hydrogen, halogen, G-Cj-alkyl or C1-C5 halogenoalkyl comprising 1 to 9 halogen atoms, and
R58 represents hydrogen or Ci-Cs-alkyl; or
A represents a heterocycle of formula (A22)
Figure imgf000013_0002
*
(A22) wherein
R60 and R61 independently from each other represent hydrogen, halogen, C i-C -alkyl or G-C5 halogenoalkyl comprising 1 to 9 halogen atoms, and
R62 represents a hydrogen atom or G-Cs-alkyl; or
A represents a heterocycle of formula (A23)
Figure imgf000013_0003
(A23) wherein
R represents hydrogen, halogen, Ci-Cs-alkyl, cyano, Ci-Cs-alkoxy, Ci-Cs-alkylsulfanyl, C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms, Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms, amino, Ci-Cs-alkylamino or di(Ci-C5-alkyl)amino, and
R64 represents hydrogen or Ci-Cs-alkyl, and
R65 represents hydrogen, halogen, Ci-Cs-alkyl, Cs-Cs-cycloalkyl, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-Cs-alkoxy, C3-Cs-alkynyloxy or Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000014_0001
in which
R66 represents hydrogen, halogen, hydroxy, cyano, Ci-C t-alkyl, Ci-C/i-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms and Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, SCi-C4-alkylsulfinyl and Ci-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A25)
Figure imgf000014_0002
in which
R70 represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, G-Cs-alkylsulfanyl, C2-C5-alkenylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
R71, R72 and R73 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A )
Figure imgf000015_0001
in which
R7 , R75, R7 and R77 independently from each other represent hydrogen, halogen, hydroxy, cyano, Ci- C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl and Ci-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A27)
Figure imgf000015_0002
in which
X1 represents -S-, -SO-, -SO2- and -CH2-, and
R represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R7 and R independently from each other represent hydrogen and Ci-C4-alkyl; or
A represents a heterocycle of formula (A )
Figure imgf000015_0003
in which
R81 represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
A represents a heterocycle of formula (A )
Figure imgf000016_0001
in which
R represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (AJU)
Figure imgf000016_0002
in which
R represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
A is a heterocycle of formula (A31)
Figure imgf000016_0003
in which
R represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
In the above definitions, unless stated otherwise, carboxy means -C(=0)OH,
carbonyl means -C(=0)-,
carbamoyl means -C(=0)NH2, alkylcarbamoyl means -C(=0)NHalkyl dialkylcarbamoyl means -C(=0)N(alkyl)2
N-hydroxycarbamoyl means -C(=0)NHOH,
SO represents a sulfoxyde group,
SO2 represents a sulfone group, an alkyl group, an alkenyl group and an alkynyl group as well as moieties containing these terms, can be linear or branched.
The term "aryl", also in terms like arylalkyl, arylalkenyl, arylalkynyl, aryloxy means phenyl or naphthyl, wherein phenyl is optionally substituted by 1 to 5 groups Q, and naphtyl is optionally substituted by 1 to 6 groups Q.
The term "heterocyclyl" means a saturated, partially saturated or unsaturated 4-, 5-, 6-, 7-, 8-, 9-, or 10- membered ring comprising 1 to 4 heteroatoms selected from the list consisting of oxygen (0), nitrogen (N), and sulfur (S).
Heteroatom means an atom selected from the group consisting of O, N, and S.
Unless indicated otherwise, if more than one halogen atom is present in a halogenated radical, like e.g. halogenoalkyl, halogenoalkoxy, those halogen atoms can be the same or different.
In the definitions of the symbols given in the above formulae, collective terms were used which are generally representative of the following substituents:
The definition Ci-Ce-alkyl comprises the largest range defined here for an alkyl radical. Specifically, this definition comprises the meanings methyl, ethyl, n , isopropyl, n , iso , sec , tert-butyl, and also in each case all isomeric pentyls, hexyls, heptyls and octyls, such as methyl, ethyl, propyl, 1 -me-thylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-diTne^thylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 -ethylbutyl, 2-ethylbutyl, l-ethyl-3-methylpropyl, n-heptyl, 1 -methylhexyl, 1- ethylpentyl, 2-ethylpentyl, 1 -propylbutyl, octyl, 1 -me-thylheptyl, 2-methylheptyl, 1-ethylhexyl, 2- ethylhexyl, 1-propylpentyl and 2-propylpentyl, in particular propyl, 1-methylethyl, butyl, 1- me^thyl-'bu-'tyl, 2-methylbutyl, 3 -methylbutyl, 1,1-dimethylethyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, pentyl,
Figure imgf000017_0001
1 -ethylpropyl, hexyl, 3-methylpentyl, heptyl, 1 -methylhexyl, l-ethyl-3- methylbutyl, 1-methylheptyl, 1
Figure imgf000017_0002
1,3-dimethyloctyl, 4-mefhyloctyl, 1,2,2,3- tetramethylbutyl, 1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl, 1,3-dimethylpentyl, 1,3-dimethylhexyl, 5- methyl-3-hexyl, 2-methyl-4-heptyl and l-methyl-2-cyclopropylethyl. A preferred range is Cl-C4-alkyl, such as methyl, ethyl, n , isopropyl, n , iso , sec , tert-butyl. The definition Cl-C3-alkyl comprises methyl, ethyl, n , isopropyl.
The definition halogen comprises fluorine, chlorine, bromine and iodine.
Halogen-substituted alkyl - referred to as G-C8-halogenoalkyl - represents, for example, G-Cs-alkyl as defined above substituted by one or more halogen substituents which can be the same or different. Preferably G-Cs-haloalkyl represents chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1- fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 1-fluoro-l-methylethyl, 2-fluoro-l,l-dimethylethyl, 2-chloro-l,l-dimethylethyl, 2-fluoro-l -fluoromethyl- 1 -methylethyl, 2- fluoro-l,l-di(fluoromethyl)-ethyl, 3-chloro-l-methylbutyl, 2-chloro-l-methylbutyl, 1 -chlorobutyl, 3,3- dichloro-l-methylbutyl, 3-chloro-l-methylbutyl, l-methyl-3-trifluoromethylbutyl, 3 -methyl- 1 - trifluoromethylbutyl .
The definition C2-Cs-alkenyl comprises the largest range defined here for an alkenyl radical. Specifically, this definition comprises the meanings ethenyl, n , isopropenyl, n , iso , sec , tert-butenyl, and also in each case all isomeric pentenyls, hexenyls, heptenyls, octenyls, 1 -methyl- 1-propenyl, 1- ethyl- 1-butenyl, 2,4-dimethyl-l-pentenyl, 2,4-dimethyl-2-pentenyl. Halogen-substituted alkenyl - referred to as C2-C8- halogenoalkenyl - represents, for example, C2-C8-alkenyl as defined above substituted by one or more halogen substituents which can be the same or different.
The definition C2-Cs-alkynyl comprises the largest range defined here for an alkynyl radical. Specifically, this definition comprises the meanings ethynyl, n , isopropynyl, n , iso , sec , tert-butynyl, and also in each case all isomeric pentynyls, hexynyls, heptynyls, octynyls. Halogen-substituted alkynyl - referred to as C2-Cs-halogenoalkynyl - represents, for example, C2-C8-alkynyl as defined above substituted by one or more halogen substituents which can be the same or different.
The definition C3-C7-cycloalkyl comprises monocyclic saturated hydrocarbyl groups having 3 to 7 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
The definition halogen-substituted cycloalkyl and halocycloalkyl comprises monocyclic saturated hydrocarbyl groups having 3 to 7 carbon ring members, such as 1 -fluoro-cyclopropyl, 1-chloro- cyclopropyl, 1-bromo-cyclopropyl, 2,2-dichloro-l-methyl-cyclopropyl, 2,2-dibromo-i-methyl- cyclopropyl, 1 -fluoro-cyclobutyl, 1 -chloro-cyclobutyl, 1 -fluoro-cyclopentyl, 1 -chloro-cyclopentyl, 1- fluoro-cyclohexyl or 1-chloro-cyclohexyl.
Compounds of the present invention can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound. The invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term "scalemic" denotes a mixture of enantiomers in different proportions) and to the mixtures of all the possible stereoisomers, in all proportions. The diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se by the man ordinary skilled in the art.
Compounds of the present invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound. The invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions. The geometric isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.
Any of the compounds of formula (I) wherein X represents a hydroxy, a sulfanyl or an amino may be found in its tautomeric form resulting from the shift of the proton of said hydroxy, sulfanyl or amino group. Such tautomeric forms of such compounds are also part of the present invention. More generally speaking, all tautomeric forms of compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group, as well as the tautomeric forms of the compounds which can optionally be used as intermediates in the preparation processes and which will be defined in the description of these processes, are also part of the present invention.
Definitions
"Agriculture" shall encompass the production of food and feed crops, forestry, the protection of stored products including food, feed but also other materials of plant origin. Preferably agriculture shall encompass the production of food and feed crops, forestry, the protection of stored products being food, feed, and materials of plant origin.
"Plant product" mean any product derived from a plant.
In the context of the present invention, "control of phytopathogenic microorganisms" means a reduction in infestation by phytopathogenic microorganisms, compared with the untreated plant, the seed of a plant, the plant propagation material or the plant product, measured as efficacy, preferably a reduction by 25-50 %, compared with the untreated plant, the seed of a plant, the plant propagation material or the plant product (100 %), more preferably a reduction by 40-79 %, compared with the the untreated plant, the seed of a plant, the plant propagation material or the plant product (100 %); even more preferably, the infection by phytopathogenic microorganisms is entirely suppressed (by 70-100 %). The control may be curative, i.e. for treatment of the plant, the seed of a plant, the plant propagation material or the plant product or protective, for protection of the untreated plant, the seed of a plant, the plant propagation material or the plant product, which have not yet been infected.
An "effective amount" means an amount of the inventive compound which is sufficient to control the phytopathogenic microorganism in a satisfactory manner or to eradicate the phytopathogenic microorganism completely, and which, at the same time, does not cause any significant symptoms of phytotoxicity. In general, this application rate may vary within a relatively wide range. It depends on several factors, for example on the phytopathogenic microorganism to be controlled, the plant, the climatic conditions and the ingredients of the inventive compositions.
Phytopathogenic microorganisms mean fungi and bacteria capable of infecting a plant, a seed of a plant, a plant propagation material or a plant product.
Preferably phytopathogenic microorganism means phytopathogenic fungi.
Fungi means Plasmodiophoromycetes, Peronosporomycetes (Syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (Syn. Fungi imperfecti).
Bacteria means species including Pseudomonadaceae, Rhizobiaceae, Enter obacteriaceae, Corynebacteriaceae and Streptomycetaceae capable of infecting a plant, a seed of a plant, a plant propagation material or a plant product.
Preferably the present invention provides the use of a compound of formula (I) as defined above
Figure imgf000020_0001
(I)
or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen or sulfur;
n represents 0, 1, 2, 3 or 4;
X independently from each other X represents halogen, nitro, cyano, isonitrile, hydroxy, amino, sulfanyl, pentafluoro^6-sulfanyl, formyl, formyloxy, formylamino, (hydroxyimino)-Ci-C4-alkyl, (Ci- C4-alkoxyimino)-Ci-C4-alkyl, (C3-C4-alkenyloxyimino)-Ci-C4-alkyl, (C3-C4-alkynyloxyimino)-Ci-C4- alkyl, (benzyloxyimino)-Ci-C4-alkyl, carboxy, carbamoyl, N-hydroxycarbamoyl, carbamate, C1-C4- alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, C2-C4-alkenyl, C2-C4-halogenoalkenyl having 1 to 9 halogen atoms, C2-C4-alkynyl, C2-C4-halogenoalkynyl having 1 to 9 halogen atoms, C1-C4- alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfinyl, Ci-C4-halogenoalkylsulfinyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfonyl, Ci-C4-halogenoalkylsulfonyl having 1 to 9 halogen atoms, Ci-C4-alkylamino, di-(Ci-C4-alkyl)-amino, C2-C4-alkenyloxy, C2-C4-halogenoalkenyloxy having 1 to 9 halogen atoms, C3-C4-alkynyloxy, C2-C4-halogenoalkynyloxy having 1 to 9 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms, C4-C7-cycloalkenyl, C4-C7-halogenocycloalkenyl having 1 to 9 halogen atoms, (C3-C7-cycloalkyl)-Ci-C4-alkyl, (C3-C7- cycloalkyl)-C2-C4-alkenyl, (C3-C7-cycloalkyl)-C2-C4-alkynyl, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4-alkyl)- silyl-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-halogenoalkylcarbonyl having 1 to 9 halogen atoms, Ci-C4-alkylcarbonyloxy, Ci-C4-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms, C1-C4- alkylcarbonylamino, Ci-C4-halogenoalkylcarbonylamino having 1 to 9 halogen atoms, C1-C4- alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 9 halogen atoms, C1-C4- alkyloxycarbonyloxy, Ci-C4-halogenoalkoxycarbonyloxy having 1 to 9 halogen atoms, C1-C4- alkylcarbamoyl, di-Ci-C4-alkylcarbamoyl, Ci-C4-alkylaminocarbonyloxy, di-Ci-C4- alkylaminocarbonyloxy, N-(Ci-C4-alkyl)-hydroxycarbamoyl, Ci-C4-alkoxycarbamoyl, N-(Ci-C4- alkyl)-Ci-C4-alkoxycarbamoyl, aryl-Ci-C4-alkyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-C2-C4-alkenyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-C2-C4-alkynyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryloxy optionally substituted by 1 to 6 groups Q which can be the same or different, arylsulfanyl optionally substituted by 1 to 6 groups Q which can be the same or different, arylamino optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-C4-alkyloxy optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-C4-alkylsulfanyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-C4-alkylamino optionally substituted by 1 to 6 groups Q which can be the same or different, pyridinyloxy which is optionally substituted by 1 to 4 groups Q; or
two substituents X together with the carbon atoms to which they are attached form a 5- or 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 4 groups Q which can be the same or different;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, G-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, or Ci-C4-alkoxycarbonyl; or
Z2 and Z3 form together with the carbon atom to which they are attached a 3- to 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 6 groups Q which can be the same or different;
Q represents halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, Ci- C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 9 halogen atoms, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4-alkyl)-silyl-Ci- C4-alkyl, Ci-C4-alkoxyimino-Ci-C4-alkyl, (benzyloxyimino)-Ci-C4-alkyl;
A represents phenyl of formula A1
Figure imgf000022_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents halogen, nitro, SH, SF5, CHO, OCHO, NHCHO, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C3-C6-halogenocycloalkyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, -Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-Ci-C4-alkyl, Ci- C4-alkenyloxy-Ci-C4-alkyl, C3-C4-alkynyloxy-Ci-C4-alkyl, C2-C4-alkenyloxy, C3-C4-alkynyloxy, C1-C4- alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, Ci-C4-alkylcarbonyloxy, Ci-C4-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl, C1-C4- halogenoalkylsulfinyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfonyl, Ci-C4-halogenoalkylsulfonyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfonamide, tri-(Ci-C4)-alkylsilyl, aryl and aryloxy;
Y2, Y3, Y4 and Y5 independently from each other represent hydrogen or Y1; or
A represents a heterocycle of formula (A2)
Figure imgf000022_0002
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, G-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A3)
Figure imgf000023_0001
(A3) wherein
R4 to R6 independently from each other represent hydrogen, halogen, G-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000023_0002
(A4) wherein
R9 to R11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, amino, C1-C4- alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or O-C4- halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A5)
Figure imgf000023_0003
(A5) wherein
R and R independently from each other represent hydrogen, halogen, G-C4-alkyl, G-C4-alkoxy, amino, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or G-C4-halogenoalkoxy comprising 1 to 9 halogen atoms, and R14 represents hydrogen, halogen, G-C4-alkyl, Ci-C4-alkoxy, amino, G-C4-halogenoalkyl comprising 1 to 9 halogen atoms or G-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000024_0001
in which
R represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-C4-alkylsulfanyl, G-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms and G-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, SCi-C4-alkylsulfinyl and G-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A25)
Figure imgf000024_0002
in which
R70 represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C2-C4-alkenylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
R71, R72 and R73 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, G-C4- halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-C4-alkylsulfanyl, G-C4- halogenoalkoxy having 1 to 5 halogen atoms, G-C4-alkylsulfinyl, G-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A26) *
Figure imgf000025_0001
in which
R , R , R and R independently from each other represent hydrogen, halogen, hydroxy, cyano, G- C i-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, G-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl and Ci-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A27)
Figure imgf000025_0002
in which
X1 represents -S-, -SO-, -S02- and -CH2-, and
R78 represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and R79 and R80 independently from each other represent hydrogen and G-C4-alkyl; or A represents a heterocycle of formula (A30)
Figure imgf000025_0003
in which
R83 represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; A is a heterocycle of formula (A31)
Figure imgf000026_0001
in which
R represents hydrogen, halogen, Ci-C i-alkyl and Ci-C rhalogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
More preferably the present invention provides the use of a compound of formula (I) as defined above
Figure imgf000026_0002
or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen;
n represents 0, 1, 2 or 3;
X independently from each other X represents halogen, nitro, cyano, isonitrile, hydroxy, amino, formyl, formyloxy, formylaminocarboxy, carbamoyl, N-hydroxycarbamoyl, carbamate, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, C2-C4-alkenyl, C2-C4-halogenoalkenyl having 1 to 9 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfmyl, C1-C4- halogenoalkylsulfinyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfonyl, Ci-C4-halogenoalkylsulfonyl having 1 to 9 halogen atoms, Ci-C4-alkylamino, di-(Ci-C4-alkyl)-amino, C2-C4-alkenyloxy, C2-C4- halogenoalkenyloxy having 1 to 9 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms, (C3-C7-cycloalkyl)-Ci-C4-alkyl, (C3-C7-cycloalkyl)-C2-C4-alkenyl, (C3-C7- cycloalkyl)-C2-C4-alkynyl, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4-alkyl)-silyl-Ci-C4-alkyl, G-C4- alkylcarbonyl, Ci-C4-halogenoalkylcarbonyl having 1 to 9 halogen atoms, Ci-C4-alkylcarbonyloxy, Ci-C4-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms, Ci-C4-alkoxycarbonyl, C1-C4- halogenoalkoxycarbonyl having 1 to 9 halogen atoms, aryl-Ci-C4-alkyl optionally substituted by 1 to 6 groups Q which can be the same or different, pyridinyloxy which is optionally substituted by 1 to 4 groups Q; or
two substituents X together with the carbon atoms to which they are attached form a 5- or 6-membered, saturated carbocycle, which is optionally substituted by 1 to 4 groups Q which can be the same or different;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, or Ci-C4-alkoxycarbonyl; or
Z2 and Z3 form together with the carbon atom to which they are attached a 3- to 6-membered, saturated carbocycle, which is optionally substituted by 1 to 6 groups Q which can be the same or different;
Q represents halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, Ci- C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4- alkyl)-silyl-Ci-C4-alkyl;
A represents phenyl of formula A1
Figure imgf000027_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents halogen, nitro, CHO, OCHO, NHCHO, cyano, Ci-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-halogenocycloalkyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, -Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl, C1-C4- halogenoalkylsulfinyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfonyl, Ci-C4-halogenoalkylsulfonyl having 1 to 5 halogen atoms, tri-(Ci-C4)-alkylsilyl;
Y2, Y3, Y4 and Y5 independently from each other represent hydrogen or Y1; or
A represents a heterocycle of formula (A2)
Figure imgf000028_0001
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, Ci-C ralkyl, Ci-C i-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C i-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A3)
Figure imgf000028_0002
(A3) wherein
R4 to R6 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000028_0003
(A4) wherein
R9 to R11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci- C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A5)
Figure imgf000029_0001
(A5) wherein
R12 and R13 independently from each other represent hydrogen, halogen, Ci-C i-alkyl, Ci-C4-alkoxy, amino, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms, and
R14 represents hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000029_0002
in which
R66 represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, and Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A25)
Figure imgf000029_0003
in which R represents hydrogen, halogen, hydroxy, cyano, Ci-G-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
R71, R72 and R73 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A )
Figure imgf000030_0001
in which
R74, R75, R76 and R77 independently from each other represent hydrogen, halogen, hydroxy, cyano, G- C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-G-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A27)
Figure imgf000030_0002
in which
X1 represents -S-, -SO-, -SO2- and -CH2-, and
R represents G-C4-alkyl and G-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R7 and R independently from each other represent hydrogen and G-Gi-alkyl; or
A represents a heterocycle of formula (A )
Figure imgf000030_0003
in which R83 represents hydrogen, halogen, G-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; A is a heterocycle of formula (A31)
Figure imgf000031_0001
in which
R represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
Even more preferably the present invention provides the use of a compound of formula (I) as defined above
Figure imgf000031_0002
(I)
or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen;
n represents 0, 1, 2 or 3;
X independently from each other X represents halogen, nitro, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 9 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 9 halogen atoms, C1-C4- alkylsulfinyl, Ci-C4-halogenoalkylsulfinyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfonyl, C1-C4- halogenoalkylsulfonyl having 1 to 9 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms, (C3-C7-cycloalkyl)-Ci-C4-alkyl, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4-alkyl)-silyl-Ci- C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-halogenoalkylcarbonyl having 1 to 9 halogen atoms; or two substituents X together with the carbon atoms to which they are attached form a cyclopentyl or cyclohexyl;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy; or
Z2 and Z3 form together with the carbon atom to which they are attached a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
Q represents halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, Ci- C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms;
A represents phenyl of formula A1
Figure imgf000032_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents halogen, nitro, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, G- C4-alkylsulfanyl, -G-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, G-C4-alkoxy, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-G-C4-alkyl, Ci-C4-alkoxycarbonyl, C1-C4- halogenoalkoxycarbonyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl, Ci-C4-halogenoalkylsulfinyl having 1 to 5 halogen atoms, G-C4-alkylsulfonyl, G-C4-halogenoalkylsulfonyl having 1 to 5 halogen atoms;
Y2, Y3, Y4 and Y5 independently from each other represent hydrogen or Y1; or
A represents a heterocycle of formula (A2)
Figure imgf000032_0002
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C i-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C i-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A3)
Figure imgf000033_0001
(A3) wherein
R4 to R6 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000033_0002
(A4) wherein
R9 to R11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, G- C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A5)
Figure imgf000033_0003
(A5) wherein
R and R independently from each other represent hydrogen, halogen, Ci-C i-alkyl, Ci-C4-alkoxy, amino, Ci-C i-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C i-halogenoalkoxy comprising 1 to 9 halogen atoms, and
R14 represents hydrogen, halogen, G-C i-alkyl, G-C4-alkoxy, G-C4-halogenoalkyl comprising 1 to 9 halogen atoms or G-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000034_0001
in which
R represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, and G-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A25)
Figure imgf000034_0002
in which
R70 represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
R71, R72 and R73 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or A represents a heterocycle of formula (A )
Figure imgf000035_0001
in which
R74, R75, R76 and R77 independently from each other represent hydrogen, halogen, hydroxy, cyano, Ci- C |-alkyl, Ci-C i-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A27)
Figure imgf000035_0002
in which
X1 represents -S-, -SO-, -SO2- and -CH2-, and
R represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R and R independently from each other represent hydrogen and Ci-C4-alkyl; or
A represents a heterocycle of formula (A )
Figure imgf000035_0003
in which
R represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
A is a heterocycle of formula (A31)
Figure imgf000036_0001
in which
R84 represents hydrogen, halogen, Ci-C4-alkyl and G-C4-halogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
Most preferably the present invention provides the use of a compound of formula (I) as defined above
Figure imgf000036_0002
(I)
or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen;
n represents 0, 1 or 2;
X independently from each other X represents halogen, nitro, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 9 halogen atoms, Ci-C4-alkoxy, G-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, G-C4-alkylsulfonyl, G-C4-alkylcarbonyl, C1-C4- halogenoalkylcarbonyl having 1 to 9 halogen atoms;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, G-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy;
A represents phenyl of formula A1
Figure imgf000037_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents halogen, nitro, cyano, Ci-C i-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, G- C4-alkylsulfanyl, G-C4-alkoxy, G-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-G- C4-alkyl, G-C4-alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, C 1-C4- alkylsulfinyl, C i-C4-alkylsulfonyl;
Y2, Y3, Y4 and Y5 independently from each other represent hydrogen or Y1; or
A represents a heterocycle of formula (A2)
Figure imgf000037_0002
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A3)
Figure imgf000037_0003
(A3) wherein R4 to R6 independently from each other represent hydrogen, halogen, Ci-Q-alkyl, G-C i-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000038_0001
(A4) wherein
R9 to R11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A5)
Figure imgf000038_0002
(A5) wherein
R12 and R13 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, C1-C4- halogenoalkyl comprising 1 to 9 halogen atoms, and
R14 represents hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000038_0003
in which R represents hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, C1-C4 halogenoalkyl having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A25)
Figure imgf000039_0001
in which
R70 represents hydrogen, halogen, G-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R71, R72 and R73 independently from each other represent hydrogen, halogen, G-C4-alkyl, C1-C4 halogenoalkyl having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A26)
Figure imgf000039_0002
in which
R74, R75, R76 and R77 independently from each other represent hydrogen, halogen, G-C4-alkyl, C1-C4 halogenoalkyl having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A27)
Figure imgf000039_0003
in which
X represents -S-, and R represents Ci-Q-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R and R independently from each other represent hydrogen and Ci-C4-alkyl; or
A represents a heterocycle of formula (A )
Figure imgf000040_0001
in which
R83 represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; A is a heterocycle of formula (A31)
Figure imgf000040_0002
in which
R84 represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
In one embodiment the compound of formula (I) as defined above is a compound,
A represents phenyl of formula A1
Figure imgf000040_0003
(A1) wherein * indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents the preferred, more preferred, even more preferred or most preferred meaning as described above;
Y2, Y3, Y4 and Y5 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
n, X, T, Z1 and Z2, Z3 and Q have the preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents phenyl of formula A1
Figure imgf000041_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents the preferred, more preferred, even more preferred or most preferred meaning as described above;
Y2, Y3, Y4 and Y5 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
n, X, T, Z1 and Z2, Z3 and Q have the more preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents phenyl of formula A1
Figure imgf000041_0002
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents the preferred, more preferred, even more preferred or most preferred meaning as described above;
Y2, Y3, Y4 and Y5 independently from each other represent the preferred, more preferred, preferred or most preferred meaning as described above;
n, X, T, Z1 and Z2, Z3 and Q have the even more preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents phenyl of formula A1
Figure imgf000042_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents the preferred, more preferred, even more preferred or most preferred meaning as described above;
Y2, Y3, Y4 and Y5 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;
n, X, T, Z1 and Z2, Z3 and Q have the most preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A4)
Figure imgf000042_0002
(A4) wherein
R9 to R11 mdependently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;; or
A represents a heterocycle of formula (A5)
Figure imgf000043_0001
(A5) wherein
R12 and R13 independently from each other the preferred, more preferred, even more preferred or most preferred meaning as described above;, and
R14 represents the preferred, more preferred, even more preferred or most preferred meaning as described above; or n, X, T, Z1 and Z2, Z3 and Q have the preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A4)
Figure imgf000043_0002
(A4) wherein
R9 to R11 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;; or
A represents a heterocycle of formula (A5)
Figure imgf000044_0001
(A5) wherein
R12 and R13 independently from each other the preferred, more preferred, even more preferred or most preferred meaning as described above;, and
R14 represents the preferred, more preferred, even more preferred or most preferred meaning as described above; or n, X, T, Z1 and Z2, Z3 and Q have the more preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A4)
Figure imgf000044_0002
(A4) wherein
R9 to R11 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;; or
A represents a heterocycle of formula (A5)
Figure imgf000044_0003
(A5) wherein R and R independently from each other the preferred, more preferred, even more preferred or most preferred meaning as described above;, and
R14 represents the preferred, more preferred, even more preferred or most preferred meaning as described above; or n, X, T, Z1 and Z2, Z3 and Q have the even more preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A4)
Figure imgf000045_0001
(A4) wherein
R9 to R11 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above;; or
A represents a heterocycle of formula (A5)
Figure imgf000045_0002
(A5) wherein
R12 and R13 independently from each other the preferred, more preferred, even more preferred or most preferred meaning as described above;, and
R14 represents the preferred, more preferred, even more preferred or most preferred meaning as described above; or n, X, T, Z1 and Z2, Z3 and Q have the most preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound, A represents a heterocycle of formula (A2)
Figure imgf000046_0001
(A2) wherein
R1 to R3 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A3)
Figure imgf000046_0002
(A3) wherein
R4 to R6 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z1 and Z2, Z3 and Q have the preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A2)
Figure imgf000046_0003
(A2) wherein R1 to R3 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A3)
Figure imgf000047_0001
(A3) wherein
R4 to R6 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z1 and Z2, Z3 and Q have the more preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A2)
Figure imgf000047_0002
(A2) wherein
R1 to R3 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A3)
Figure imgf000047_0003
(A3) wherein
R4 to R6 independently from each other represent represent the preferred, more preferred,
preferred or most preferred meaning as described above; n, X, T, Z1 and Z2, Z3 and Q have the even more preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A2)
Figure imgf000048_0001
(A2) wherein
R1 to R3 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A3)
Figure imgf000048_0002
(A3) wherein
R4 to R6 independently from each other represent represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z1 and Z2, Z3 and Q have the most preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A24)
Figure imgf000049_0001
in which
R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above, and
R67, R68 and R69 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A25)
Figure imgf000049_0002
in which
R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above; and
R71, R72 and R73 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A26)
Figure imgf000049_0003
in which
R , R , R and R independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z1 and Z2, Z3 and Q have the preferred meaning described above. embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A )
Figure imgf000050_0001
in which
R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above, and
R67, R68 and R69 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A25)
Figure imgf000050_0002
in which
R7 represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above; and
R71, R72 and R73 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A26)
*
Figure imgf000050_0003
in which
R , R , R and R independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z1 and Z2, Z3 and Q have the more preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A24)
Figure imgf000051_0001
in which
R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above, and
R67, R68 and R69 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A25)
Figure imgf000051_0002
in which
R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above; and
R71, R72 and R73 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A )
Figure imgf000052_0001
in which
R74, R75, R76 and R77 independently from each other represent the preferred, more preferred,
preferred or most preferred meaning as described above; n, X, T, Z1 and Z2, Z3 and Q have the even more preferred meaning described above.
In one embodiment the compound of formula (I) as defined above is a compound,
A represents a heterocycle of formula (A24)
Figure imgf000052_0002
in which
R represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above, and
R67, R68 and R69 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A25)
Figure imgf000052_0003
in which
R70 represents represent the preferred, more preferred, even more preferred or most preferred meaning as described above; and R71, R72 and R73 independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; or
A represents a heterocycle of formula (A )
Figure imgf000053_0001
in which
R , R , R and R independently from each other represent the preferred, more preferred, even more preferred or most preferred meaning as described above; n, X, T, Z1 and Z2, Z3 and Q have the most preferred meaning described above.
The above mentioned preferences with regard to the substituents of the compounds according to the invention can be combined in various manners. These combinations of preferred features thus provide preferred sub-classes of compounds according to the invention.
Preparation
When T represents an oxygen atom, the compounds of formula (Γ). mentioned in the present invention can be prepared according to a process PI
Figure imgf000054_0001
Process PI
Thus, there is provided a process PI for the preparation of a compound of formula (I) as herein- defined and wherein T represents O and that comprises reaction of an amine of formula (II) or one of its salts:
Figure imgf000054_0002
(ll)
in which Z1, Z2, Z3, X and n have the meanings mentioned above for the compounds of formula (I), with a carboxylic acid derivative of formula (III):
Figure imgf000054_0003
wherein A represents A1 to A31 as defined above, L1 represents a leaving group selected from the group consisting of halogen, OH, -OR3, -OC(=0)Ra, Ra being Ci-Ce-alkyl, a Ci-Ce-haloalkyl, benzyl, 4- methoxybenzyl or pentafluorophenyl, or a group of formula 0-C(=0)Ab ; in the presence of a catalyst and in the presence of a condensing agent in case L1 represents OH, and in the presence of an acid binder in case L1 represents a halogen atom.
Amine derivatives of formula (II) are known or can be prepared by known processes such as reductive amination of aldehydes or ketones (Organic Reactions (Hoboken, NJ, United States) (2002), 59), or reduction of oximes (Journal of Medicinal Chemistry (1984), 27(9), 1108), or nucleophilic substitution of a halogen, mesylate or tosylate (Journal of Medicinal Chemistry (2002), 45, 3887). Furthermore, syntheses of fluorinated amines are described in WO 2007/141009 Al, Chimica Therapeutica (1971), 6(4), 262-267 and Journal of Organic Chemistry (1981), 46(24), 4938-4948.
Carboxylic acid derivatives of formula (III) are known or can be prepared by known processes.
In case L1 represents OH, process PI is conducted in the presence of condensing agents. Suitable condensing agents may be selected in the non- limited list consisting of acid halide former, such as phosgene, phosphorous tribromide, phosphorous trichloride, phosphorous pentachloride, phosphorous trichloride oxide or thionyl chloride; anhydride former, such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; carbodiimides, such as Ν,Ν'-dicyclohexylcarbodiimide (DCC), l-ethyl-3-(3- dimethylaminopropyl)carbodiimid (EDC) or other customary condensing agents, such as phosphorous pentoxide, polyphosphoric acid, Ν,Ν'-carbonyl-diimidazole, 2-ethoxy-N-ethoxycarbonyl-l,2- dihydroquinoline (EEDQ), triphenylphosphine/tetrachloro-methane, 4-(4,6-dimethoxy[l .3.5]-triazin-2- yl)-4-methylmorpholinium chloride hydrate, bromo-tripyrrolidinophosphoniumhexafluorophosphate or propanephosphonic anhydride (T3P).
Process PI is conducted in the presence of a catalyst. Suitable catalyst may be selected from the list consisting of N,N-dimethylpyridin-4-amine, 1-hydroxy-benzotriazole or N,N-dimethylformamide.
In case L1 represents a halogen atom, process PI is conducted in the presence of an acid binder. Suitable acid binders are all inorganic and organic bases that are customary for such reactions. Preference is given to using alkaline earth metal, alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as caesium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N- dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylpyridin-4-amine, diazabicyclooctane (DABCO), diazabicyclo-nonene (DBN) or diazabicycloundecene (DBU).
It is also possible to work in the absence of an additional condensing agent or to employ an excess of the amine component, so that it simultaneously acts as acid binder agent.
Suitable solvents for carrying out process PI can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlore thane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxy ethane, 1,2-diethoxy ethane or anisole; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, Ν,Ν-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone, or hexamethylphosphoric triamide; alcohols such as methanol, ethanol, propanol, iso-propanol; esters, such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, or sulfones, such as sulfolane.
When carrying out process PI, the amine derivative of formula (II) can be employed as its salt, such as hydrochloride or any other convenient salt.
When carrying out process PI , 1 mole or an excess of the amine derivative of formula (II) and from 1 to 3 moles of the acid binder can be employed per mole of the reagent of formula (III).
It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
There is provided a second process P2 for the preparation of a compound of formula (I") wherein T represents S, starting from a compound of formula (Γ) wherein T represents O and illustrated according to the following reaction scheme :
Figure imgf000056_0001
(Ϊ) (I")
Process P2 in which Z1, Z2, Z3, X and n have the meanings mentioned above for the compounds of formula (I), A represents A1 to A31 as defined above.
Process P2 is performed in the presence of a thionating agent.
Starting amide derivatives of formula (Γ) wherein T represents O can be prepared according to process
Suitable thionating agents can be sulfur (S), sulfhydric acid (H2S), sodium sulfide (Na2S), sodium hydrosulfide (NaHS), boron trisulfide (B2S3), bis(diethylaluminium) sulfide ((AlEt^S), ammonium sulfide ((NH4)2S), phosphorous pentasulfide (P2S5), Lawesson's reagent (2,4-bis(4-methoxyphenyl)- 1,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent as described in Journal of the Chemical Society, Perkin 1 (2001), 358, in the optionally presence of a catalytic or stoichiometric or excess amount, quantity of a base such as an inorganic and organic base. Preference is given to using alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate ; heterocyclic aromatic bases, such as pyridine, picoline, lutidine, collidine ; and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N- dimethylaniline, N,N-dimethylpyridin-4-amine or N-methyl-piperidine.
Suitable solvents for carrying out process P2 can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlore thane, ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane or 1,2-diethoxyethane, nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile, sulfurous solvents, such as sulfolane or carbon disulfide.
When carrying out process P2, 1 mole or an excess of the sulfur equivalent of the thionating agent and from 1 to 3 moles of the base can be employed per mole of the amide reactant (I).
It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
Processes PI and P2 are generally carried out under atmospheric pressure. It is also possible to operate under elevated or reduced pressure.
When carrying out processes PI and P2, the reaction temperatures can be varied within a relatively wide range. In general, these processes are carried out at temperatures from 0 °C to 200 °C, preferably from 10 °C to 160 °C. A way to control the temperature for the processes according to the invention is to use micro-wave technology.
In general, the reaction mixture is concentrated under reduced pressure. The residue that remains can be freed by known methods, such as chromatography or crystallization, from any impurities that can still be present.
Methods and uses The invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to the microorganisms and/or in their habitat.
The invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to the plant or plant parts.
The invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to plant propagation material.
The invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to the seed.
The invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied the soil on which the plants are grown or intended to be grown.
The invention also relates to a method for controlling phytopathogenic microorganisms, characterized in that a compound of the formula (I) is applied to the microorganisms and/or in their habitat.
The invention also relates to a method for controlling phytopathogenic fungi, characterized in that a compound of the formula (I) is applied to the plant or plant parts.
The invention also relates to a method for controlling phytopathogenic fungi, characterized in that a compound of the formula (I) is applied to plant propagation material.
The invention also relates to a method for controlling phytopathogenic fungi, characterized in that a compound of the formula (I) is applied to the seed.
The invention also relates to a method for controlling phytopathogenic fungi, characterized in a compound of the formula (I) is applied the soil on which the plants are grown or intended to be grown.
The invention also relates to a method for controlling phytopathogenic bacteria, characterized in that a compound of the formula (I) is applied to the plant or plant parts.
The invention also relates to a method for controlling phytopathogenic bacteria, characterized in that a compound of the formula (I) is applied to plant propagation material.
The invention also relates to a method for controlling phytopathogenic bacteria, characterized in that a compound of the formula (I) is are applied to the seed.
The invention also relates to a method for controlling phytopathogenic bacteria, characterized in that a compound of the formula (I) is applied the soil on which the plants are grown or intended to be grown. The invention further relates to seed which has been treated with at least one compound of the formula (I)-
The invention finally provides a method for protecting seed against phytopathogenic microorganisms by using seed treated with at least one compound of the formula (I).
The compounds of the formula (I) have potent microbicidal activity and can be used for control of phytopathogenic microorganisms in agriculture.
In one embodiment a compound of the formula (I) can be used for control of phytopathogenic microorganisms in crop protection and in the protection of materials.
The compounds of the formula (I) have potent microbicidal activity and can be used for control of phytopathogenic fungi in agriculture.
In one embodiment a compound of the formula (I) can be used for control of phytopathogenic fungi in crop protection and in the protection of materials.
The compounds of the formula (I) have potent microbicidal activity and can be used for control of phytopathogenic bacteria in agriculture.
In one embodiment a compound of the formula (I) can be used for control of phytopathogenic bacteria in crop protection and in the protection of materials.
The compounds of the formula (I) can be used for curative or protective control of phytopathogenic microorganisms. The invention therefore also relates to curative and protective methods for controlling phytopathogenic microorganisms by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
The compounds of the formula (I) can be used for curative or protective control of phytopathogenic bacteria. The invention therefore also relates to curative and protective methods for controlling phytopathogenic bacteria by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
The compounds of the formula (I) can be used for curative or protective control of phytopathogenic fungi. The invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow. Plants
All plants and plant parts can be treated in accordance with the invention. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which are protectable and non-protectable by plant breeders' rights. Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples of which include leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes. The plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
Plants which can be treated in accordance with the invention include the following plants from the group of the useful plants, ornamentals, turfs, generally used trees which are employed as ornamentals in the public and domestic sectors, and forestry trees. Forestry trees comprise trees for the production of timber, cellulose, paper and products made from parts of the trees.
The term useful plants as used in the present context refers to crop plants which are employed as plants for obtaining foodstuffs, feedstuffs, fuels or for industrial purposes.
The useful plants include for example the following types of plants: turf, vines, cereals, for example wheat, barley, rye, oats, rice, maize and millet/sorghum, corn, maize; beet, for example sugar beet and fodder beet; fruits, for example pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries and berries, for example strawberries, raspberries, blackberries; legumes, for example beans, lentils, peas and soybeans; oil crops, for example oilseed rape, canola, mustard, poppies, olives, sunflowers, coconuts, castor oil plants, cacao and peanuts; cucurbits, for example pumpkin/squash, cucumbers and melons; fibre plants, for example cotton, flax, hemp and jute; citrus fruit, for example oranges, lemons, grapefruit and tangerines; vegetables, for example spinach, lettuce, asparagus, cabbage species, carrots, onions, tomatoes, potatoes and bell peppers; Lauraceae, for example avocado, Cinnamomum, camphor, or else plants such as tobacco, nuts, coffee, aubergine, sugar cane, tea, pepper, grapevines, hops, bananas, latex plants and ornamentals, for example flowers, shrubs, deciduous trees and coniferous frees. This enumeration is no limitation.
The following plants are considered to be particularly suitable target crops: cotton, aubergine, turf, pome fruit, stone fruit, soft fruit, maize, wheat, barley, cucumber, tobacco, vines, rice, cereals, pear, beans, soybeans, oilseed rape, tomato, bell pepper, melons, cabbage, potato and apple. Examples of trees are: Abies sp., Eucalyptus sp., Picea sp., Pinus sp., Aesculus sp., Platanus sp., Tilia sp., Acer sp., Tsuga sp., Fraxinus sp., Sorbus sp., Betula sp., Crataegus sp., Ulmus sp., Quercus sp., Fagus sp., Salix sp., Populus sp..
Examples of turf grasses are including cool-season turf grasses and warm-season turf grasses.
Cold-season turf grasses are bluegrasses (Poa spp.), such as Kentucky bluegrass (Poa pratensis L.), rough bluegrass (Poa trivialis L.), Canada bluegrass (Poa compressa L.), annual bluegrass (Poa annua L.), upland bluegrass (Poa glaucantha Gaudin), wood bluegrass (Poa nemoralis L.) and bulbous bluegrass (Poa bulbosa L.); bentgrasses (Agrostis spp.) such as creeping bentgrass (Agrostis palustris Huds.), colonial bentgrass (Agrostis tenuis Sibth.), velvet bentgrass (Agrostis canina L.), South German mixed bentgrass (Agrostis spp. including Agrostis tenuis Sibth., Agrostis canina L., and Agrostis palustris Huds.), and redtop (Agrostis alba L.); fescues (Festuca spp.), such as red fescue (Festuca rubra L. spp. rubra), creeping fescue (Festuca rubra L.), chewings fescue (Festuca rubra commutata Gaud.), sheep fescue (Festuca ovina L.), hard fescue (Festuca longifolia Thuill.), hair fescue (Festucu capillata Lam), tall fescue (Festuca arundinacea Schreb.) and meadow fescue (Festuca elanor L.); ryegrasses (Lolium spp.), such as annual ryegrass (Lolium multiflorum Lam), perennial ryegrass (Lolium perenne L.) and Italian ryegrass (Lolium multiflorum Lam.); and wheatgrasses (Agropyron spp.), such as fairway wheatgrass (Agropyron cristatum (L.) Gaertn.), crested wheatgrass (Agropyron desertorum (Fisch.) Schult.) and western wheatgrass (Agropyron smithii Rydb.); and further cool-season turf grasses like beachgrass (Ammophila breviligulata Fern.), smooth bromegrass (Bromus inermis Leyss.), cattails such as timothy (Phleum pratense L.), sand cattail (Phleum subulatum L.), orchardgrass (Dactylis glomerata L.), weeping alkaligrass (Puccinellia distans (L.) Pari.) and crested dog's- tail (Cynosurus cristatus L.).
Warm-season turf grasses are Bermuda grass (Cynodon spp. L. C. Rich), zoysia grass (Zoysia spp. Willd.), St. Augustine grass (Stenotaphrum secundatum Walt Kuntze), centipede grass (Eremochloa ophiuroides Munro Hack.), carpetgrass (Axonopus affmis Chase), Bahia grass (Paspalum notatum Flugge), Kikuyu grass (Pennisetum clandestinum Hochst ex Chiov.), buffalo grass (Buchloe dactyloids (Nutt.) Engelm.), blue grama (Bouteloua gracilis (H.B.K.) Lag. ex Griffiths), seashore paspalum (Paspalum vaginatum Swartz) and sideoats grama (Bouteloua curtipendula (Michx. Torr.).
Pathogens
Non-limiting examples of phytopathogenic microorganisms, in particular phytopathogenic fungi which can be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae; Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striiformis; Uromyces species, for example Uromyces appendicular^; diseases caused by pathogens from the group of the Oomycetes, for example Albugo species, for example Albugo Candida; Bremia species, for example Bremia lactucae; Peronospora species, for example Peronospora pisi or P. brassicae; Phytophthora species, for example Phytophthora infestans; Plasmopara species, for example Plasmopara viticola; Pseudoperonospora species, for example Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, for example Pythium ultimum; leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species, for example Alternaria solani; Cercospora species, for example Cercospora beticola; Cladiosporium species, for example Cladiosporium cucumerinum; Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium) or Cochliobolus miyabeanus; Colletotrichum species, for example Colletotrichum lindemuthanium; Cycloconium species, for example Cycloconium oleaginum; Diaporthe species, for example Diaporthe cirri; Elsinoe species, for example Elsinoe fawcettii; Gloeosporium species, for example Gloeosporium laeticolor; Glomerella species, for example Glomerella cingulata; Guignardia species, for example Guignardia bidwelli; Leptosphaeria species, for example Leptosphaeria maculans; Magnaporthe species, for example Magnaporthe grisea; Microdochium species, for example Microdochium nivale; Mycosphaerella species, for example Mycosphaerella graminicola, Mycosphaerella arachidicola or Mycosphaerella fijiensis; Phaeosphaeria species, for example Phaeosphaeria nodorum; Pyrenophora species, for example Pyrenophora teres or Pyrenophora tritici repentis; Ramularia species, for example Ramularia collo-cygni or Ramularia areola; Rhynchosporium species, for example Rhynchosporium secalis; Septoria species, for example Septoria apii or Septoria lycopersici; Stagonospora species, for example Stagonospora nodorum; Typhula species, for example Typhula incarnata; Venturia species, for example Venturia inaequalis; root and stem diseases caused, for example, by Corticium species, for example Corticium graminearum; Fusarium species, for example Fusarium oxysporum; Gaeumannomyces species, for example Gaeumannomyces graminis; Plasmodiophora species, for example Plasmodiophora brassicae; Rhizoctonia species, for example Rhizoctonia solani; Sarocladium species, for example Sarocladium oryzae; Sclerotium species, for example Sclerotium oryzae; Tapesia species, for example Tapesia acuformis; Thielaviopsis species, for example Thielaviopsis basicola; ear and panicle diseases (including corn cobs) caused, for example, by Alternaria species, for example Alternaria spp.; Aspergillus species, for example Aspergillus flavus; Cladosporium species, for example Cladosporium cladosporioides; Claviceps species, for example Claviceps purpurea; Fusarium species, for example Fusarium culmorum; Gibberella species, for example Gibberella zeae; Monographella species, for example Monographella nivalis; Stagnospora species, for example Stagnospora nodorum; diseases caused by smut fungi, for example Sphacelotheca species, for example Sphacelotheca reiliana; Tilletia species, for example Tilletia caries or Tilletia controversa; Urocystis species, for example Urocystis occulta; Ustilago species, for example Ustilago nuda; fruit rot caused, for example, by Aspergillus species, for example Aspergillus flavus; Botrytis species, for example Botrytis cinerea; Penicillium species, for example Penicillium expansum or Penicillium purpurogenum; Rhizopus species, for example Rhizopus stolonifer; Sclerotinia species, for example Sclerotinia sclerotiorum; Verticilium species, for example Verticilium alboatrum; seed- and soil-borne rot and wilt diseases, and also diseases of seedlings, caused, for example, by Alternaria species, for example Alternaria brassicicola; Aphanomyces species, for example Aphanomyces euteiches; Ascochyta species, for example Ascochyta lentis; Aspergillus species, for example Aspergillus flavus; Cladosporium species, for example Cladosporium herbarum; Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, Bipolaris Syn: Helminthosporium); Colletotrichum species, for example Colletotrichum coccodes; Fusarium species, for example Fusarium culmorum; Gibberella species, for example Gibberella zeae; Macrophomina species, for example Macrophomina phaseolina; Microdochium species, for example Microdochium nivale; Monographella species, for example Monographella nivalis; Penicillium species, for example Penicillium expansum; Phoma species, for example Phoma lingam; Phomopsis species, for example Phomopsis sojae; Phytophthora species, for example Phytophthora cactoram; Pyrenophora species, for example Pyrenophora graminea; Pyricularia species, for example Pyricularia oryzae; Pythium species, for example Pythium ultimum; Rhizoctonia species, for example Rhizoctonia solani; Rhizopus species, for example Rhizopus oryzae; Sclerotium species, for example Sclerotium rolfsii; Septoria species, for example Septoria nodorum; Typhula species, for example Typhula incarnata; Verticillium species, for example Verticillium dahliae; cancers, galls and witches' broom caused, for example, by Nectria species, for example Nectria galligena; wilt diseases caused, for example, by Monilinia species, for example Monilinia laxa; deformations of leaves, flowers and fruits caused, for example, by Exobasidium species, for example Exobasidium vexans; Taphrina species, for example Taphrina deformans; degenerative diseases in woody plants, caused, for example, by Esca species, for example Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranea; Ganoderma species, for example Ganoderma boninense; diseases of flowers and seeds caused, for example, by Botrytis species, for example Botrytis cinerea; diseases of plant tubers caused, for example, by Rhizoctonia species, for example Rhizoctonia solani; Helminthosporium species, for example Helminthosporium solani; diseases caused by bacterial pathogens, for example Xanthomonas species, for example Xanthomonas campestris pv. oryzae; Pseudomonas species, for example Pseudomonas syringae pv. lachrymans; Erwinia species, for example Erwinia amylovora.
Preference is given to controlling the following diseases of soya beans:
Fungal diseases on leaves, stems, pods and seeds caused, for example, by Alternaria leaf spot (Alternaria spec, atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cercospora leaf spot and blight (Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospora manshurica), drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), pod and stem blight (Phomopsis sojae), powdery mildew (Micro sphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphaceloma glycines), stemphylium leaf blight (Stemphyliurn botryosum), target spot (Corynespora cassiicola).
Fungal diseases on roots and the stem base caused, for example, by black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotmia sclerotioium), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola). Mycotoxins
In addition, the compounds of the formula (I) can reduce the mycotoxin content in the plant products, in particular harvested material and the foods and feeds prepared therefrom. Mycotoxins include particularly, but not exclusively, the following: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac- DON, T2- and HT2-toxin, fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol (DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins which can be produced, for example, by the following fungi: Fusarium spec, such as F. acuminatum, F. asiaticum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberella zeae),
F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F. proliferatum, F. poae, F. pseudogmminearum, F. sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides etc., and also by Aspergillus spec, such as A. flavus, A. parasiticus, A. nomius, A. ochraceus, A. clavatus, A. terreus, A. versicolor, Penicillium spec, such as P. verrucosum, P. viridicatum, P. citrinum, P. expansum, P. claviforme, P. roqueforti, Claviceps spec, such as C.
purpurea, C. fusiformis, C. paspali, C. africana, Stachybotrys spec, and others.
Material Protection
The compounds of the formula (I) can also be used in the protection of materials, for protection of industrial materials against attack and destruction by phytopathogenic microorganisms, in particular phytopathogenic fungi .
In addition, the compounds of the formula (I) can be used as antifouling compositions, alone or in combinations with other active ingredients.
Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry. For example, industrial materials which are to be protected by inventive compositions from microbial alteration or destruction may be adhesives, glues, paper, wallpaper and board/cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms. Parts of production plants and buildings, for example cooling-water circuits, cooling and heating systems and ventilation and air-conditioning units, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood.
The compounds of the formula (I) may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
In the case of treatment of wood the compounds of the formula (I) may also be used against fungal diseases liable to grow on or inside timber. The term "timber" means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood. The method for treating timber according to the invention mainly consists in contacting a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.
In addition, the compounds of the formula (I) can be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signalling systems, from fouling.
The compounds of the formula (I) can also be employed for protecting storage goods. Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired. Storage goods of vegetable origin, for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, can be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting. Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture. Storage goods of animal origin are, for example, hides, leather, furs and hairs. The inventive compositions may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
Microorganisms capable of degrading or altering the industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms. The compounds of the formula (I) preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi (Ascomycetes, Basidiomycetes, Deuteromycetes and Zygomycetes), and against slime organisms and algae. Examples include microorganisms of the following genera: Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride; Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Cladosporium spp., Paecilomyces spp. Mucor spp., Escherichia, such as Escherichia coli; Pseudomonas, such as Pseudomonas aeruginosa; Staphylococcus, such as Staphylococcus aureus, Candida spp. and Saccharomyces spp., such as Saccharomyces cerevisae.
Formulations
The present invention further relates to a composition for controlling phytopathogenic microorganisms, in particular phytopathogenic fungi comprising at least one of the compounds of the formula (I). These are preferably fungicidal compositions which comprise agriculturally suitable auxiliaries, solvents, carriers, surfactants or extenders.
According to the invention, a carrier is a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, in particular for application to plants or plant parts or seed. The carrier, which may be solid or liquid, is generally inert and should be suitable for use in agriculture. Useful solid carriers include: for example ammonium salts and natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates; useful solid carriers for granules include: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic flours, and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks; useful emulsifiers and/or foam-formers include: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; suitable dispersants are nonionic and/or ionic substances, for example from the classes of the alcohol-POE and/or -POP ethers, acid and/or POP POE esters, alkylaryl and/or POP POE ethers, fat and/or POP POE adducts, POE- and/or POP-polyol derivatives, POE- and/or POP-sorbitan or -sugar adducts, alkyl or aryl sulphates, alkyl- or arylsulphonates and alkyl or aryl phosphates or the corresponding PO-ether adducts. Additionally suitable are oligo- or polymers, for example those derived from vinylic monomers, from acrylic acid, from EO and/or PO alone or in combination with, for example, (poly)alcohols or (poly)amines. It is also possible to use lignin and its sulphonic acid derivatives, unmodified and modified celluloses, aromatic and/or aliphatic sulphonic acids and also their adducts with formaldehyde.
The active ingredients can be converted to the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
The active ingredients can be applied as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances. Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading-on and the like. It is also possible to deploy the active ingredients by the ultra-low volume method or to inject the active ingredient preparation/the active ingredient itself into the soil. It is also possible to treat the seed of the plants.
The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, emulsifier, dispersant and/or binder or fixing agent, wetting agent, a water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyes and pigments, antifoams, preservatives, secondary thickeners, stickers, gibberellins and also other processing auxiliaries. The present invention includes not only formulations which are aheady ready for use and can be deployed with a suitable apparatus to the plant or the seed, but also commercial concentrates which have to be diluted with water prior to use.
The compounds of the formula (I) may be present as such or in their (commercial) formulations and in the use forms prepared from these formulations as a mixture with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.
The auxiliaries used may be those substances which are suitable for imparting particular properties to the composition itself or and/or to preparations derived therefrom (for example spray liquors, seed dressings), such as certain technical properties and/or also particular biological properties. Typical auxiliaries include: extenders, solvents and carriers.
Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example from the classes of the aromatic and nonaromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which may optionally also be substituted, etherified and/or esterified), the ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulphones and sulphoxides (such as dimethyl sulphoxide).
Liquefied gaseous extenders or carriers are understood to mean liquids which are gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, or else butane, propane, nitrogen and carbon dioxide.
In the formulations it is possible to use tackifiers such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Further additives may be mineral and vegetable oils.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, or else water.
Compositions comprising compounds of the formula (I) may additionally comprise further components, for example surfactants. Suitable surfactants are emulsifiers and/or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants. Examples thereof are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose. The presence of a surfactant is necessary if one of the active ingredients and/or one of the inert carriers is insoluble in water and when application is effected in water. The proportion of surfactants is between 5 and 40 per cent by weight of the inventive composition.
It is possible to use dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Further additives may be perfumes, mineral or vegetable, optionally modified oils, waxes and nutrients (including trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Additional components may be stabilizers, such as cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents which improve chemical and/or physical stability.
If appropriate, other additional components may also be present, for example protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilizers, sequestering agents, complex formers. In general, the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
The formulations contain generally between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, more preferably between 0.5 and 90% of active ingredient, most preferably between 10 and 70 per cent by weight.
The formulations described above can be used for controlling phytopathogenic microorganisms, in which the compositions comprising compounds of the formula (I) are applied to the phytopathogenic microorganisms and/or in their habitat.
Seed Treatment
The invention furthermore includes a method for treating seed.
A further aspect of the present invention relates in particular to seeds (dormant, primed, pregerminated or even with emerged roots and leaves) treated with at least one of the compounds of the formula (I). The inventive seeds are used in methods for protection of seeds and emerged plants from the seeds from phytopathogenic microorganisms, in particular phytopathogenic fungi. In these methods, seed treated with at least one inventive active ingredient is used.
The compounds of the formula (I) are also suitable for the treatment of seeds and young seedlings. A large part of the damage to crop plants caused by harmful organisms is triggered by the infection of the seeds before sowing or after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even small damage may result in the death of the plant. Accordingly, there is great interest in protecting the seed and the germinating plant by using appropriate compositions.
It is also desirable to optimize the amount of the active ingredient used so as to provide the best possible protection for the seeds, the germinating plants and emerged seedlings from attack by phytopathogenic fungi, but without damaging the plants themselves by the active ingredient used. In particular, methods for the treatment of seed should also take into consideration the intrinsic phenotypes of transgenic plants in order to achieve optimum protection of the seed and the germinating plant with a minimum of crop protection compositions being employed.
The present invention therefore also relates to a method for protecting seeds, germinating plants and emerged seedlings against attack by animal pests and/or phytopathogenic microorganisms, in particular phytopathogenic fungi by treating the seeds with an inventive composition. The invention also relates to the use of the compositions according to the invention for treating seeds for protecting the seeds, the germinating plants and emerged seedlings against animal pests and/or phytopathogenic microorganisms, in particular phytopathogenic fungimicro. The invention further relates to seeds which has been treated with an inventive composition for protection from animal pests and/or phytopathogenic microorganisms, in particular phytopathogenic fungi.
One of the advantages of the present invention is thatthe treatment of the seeds with these compositions not only protects the seed itself, but also the resulting plants after emergence, from animal pests and/or phytopathogenic harmful microorganisms. In this way, the immediate treatment of the crop at the time of sowing or shortly thereafter protect plants as well as seed treatment in prior to sowing. It is likewise considered to be advantageous that the inventive active ingredients or compositions can be used especially also for transgenic seed, in which case the plant which grows from this seed is capable of expressing a protein which acts against pests, herbicidal damage or abiotic stress. The treatment of such seeds with the inventive active ingredients or compositions, for example an insecticidal protein, can result in control of certain pests. Surprisingly, a further synergistic effect can be observed in this case, which additionally increases the effectiveness for protection against attack by pests., microorganisms, weeds or abiotic stress. The compounds of the formula (I) are suitable for protection of seed of any plant variety which is used in agriculture, in the greenhouse, in forests or in horticulture. More particularly, the seed is that of cereals (such as wheat, barley, rye, millet and oats), oilseed rape, maize, cotton, soybeen, rice, potatoes, sunflower, beans, coffee, beet (e.g. sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onions and lettuce), lawns and ornamental plants. Of particular significance is the treatment of the seed ofwheat, soybean, oilseed rape, maize and rice.
As also described below, the treatment of transgenic seed with the inventive active ingredients or compositions is of particular significance. This refers to the seed of plants containing at least one heterologous gene which allows the expression of a polypeptide or protein, e.g. having insecticidal properties. These heterologous genes in transgenic seeds may originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. These heterologous genes preferably originates from Bacillus sp., in which case the gene product is effective against the European corn borer and/or the Western corn rootworm. Particularly preferably, the heterologous genes originate from Bacillus thuringiensis.
In the context of the present invention, the inventive composition is applied to seeds either alone or in a suitable formulation. Preferably, the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment. In general, seeds can be treated at any time between harvest and some time after sowing. It is customary to use seed which has been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seed which has been harvested, cleaned and dried down to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seed which, after drying, for example, has been treated with water and then dried again, or seeds just after priming, or seeds stored in primed conditions or pre- germinated seeds, or seeds sown on nursery trays, tapes or paper.
When treating the seeds, it generally has to be ensured that the amount of the inventive composition applied to the seed and/or the amount of further additives is selected such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This must be ensured particularly in the case of active ingredients which can exhibit phytotoxic effects at certain application rates.
The compounds of the formula (I) can be applied directly, i.e. without containing any other components and without having been diluted. In general, it is preferable to apply the compositions to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art. The compounds of the formula (I) can be converted to the customary formulations relevant to on-seed applications, such as solutions, emulsions, suspensions, powders, foams, slurries or combined with other coating compositions for seed, such as film forming materials, pelleting materials, fine iron or other metal powders, granules, coating material for inactivated seeds, and also ULV formulations. These formulations are prepared in a known manner, by mixing the active ingredients or active ingredient combinations with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
Useful dyes which may be present in the seed dressing formulations usable in accordance with the invention are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.
Useful wetting agents which may be present in the seed dressing formulations usable in accordance with the invention are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients. Usable with preference are alkylnaphthalenesulphonates, such as diisopropyl- or diisobutylnaphthalenesulphonates.
Useful dispersants and/or emulsifiers which may be present in the seed dressing formulations usable in accordance with the invention are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Usable with preference are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Useful nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sulphated derivatives thereof. Suitable anionic dispersants are especially lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehyde condensates.
Antifoams which may be present in the seed dressing formulations usable in accordance with the invention are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.
Preservatives which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.
Secondary thickeners which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
Adhesives which may be present in the seed dressing formulations usable in accordance with the invention are all customary binders usable in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose. The formulations for on-seed applications usable in accordance with the invention can be used to treat a wide variety of different kinds of seed either directly or after prior dilution with water. For instance, the concentrates or the preparations obtainable therefrom by dilution with water can be used to dress the seed of cereals, such as wheat, barley, rye, oats, and triticale, and also seeds of maize, soybean, rice, oilseed rape, peas, beans, cotton, sunflowers, and beets, or else a wide variety of different vegetable seeds. The formulations usable in accordance with the invention, or the dilute preparations thereof, can also be used for seeds of transgenic plants. In this case, additional synergistic effects may also occur in interaction with the substances formed by expression.
For treatment of seeds with the formulations usable in accordance with the invention, or the preparations prepared therefrom by adding water, all mixing units usable customarily for on-seed applications are useful. Specifically, the procedure in on-seed applications is to place the seeds into a mixer, to add the particular desired amount of the formulations, either as such or after prior dilution with water, and to mix everything until all applied formulations are distributed homogeneously on the seeds. If appropriate, this is followed by a drying operation.
The application rate of the formulations usable in accordance with the invention can be varied within a relatively wide range. It is guided by the particular content of the active ingredients in the formulations and by the seeds. The application rates of each single active ingredient is generally between 0.001 and 15 g per kilogram of seed, preferably between 0.01 and 5 g per kilogram of seed.
GMO
As already mentioned above, it is possible to treat all plants and their parts in accordance with the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms "parts" or "parts of plants" or "plant parts" have been explained above. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention. Plant cultivars are understood to mean plants which have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
The method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds. Genetically modified plants (or transgenic plants) are plants of which a heterologous gene has been stably integrated into genome. The expression "heterologous gene" essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microRNA - miRNA - technology). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means).
Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
Plants and plant cultivars which may also be treated according to the invention, are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further yield traits include seed composition, such as carbohydrate content and composition for example cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses).
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance. Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as Tobacco plants, with altered post-translational protein modification patterns.
Application Rates
When using the compounds of the formula (I) as fungicides, the application rates can be varied within a relatively wide range, depending on the kind of application. The application rate of the inventive active ingredients is • in the case of treatment of plant parts, for example leaves: from 0.1 to 10 000 g ha, preferably from 10 to 1000 g ha, more preferably from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used);
• in the case of seed treatment: from 0.1 to 200 g per 100 kg of seed, preferably from 1 to 150 g per 100 kg of seed, more preferably from 2.5 to 25 g per 100 kg of seed, even more preferably from 2.5 to 12.5 g per 100 kg of seed;
• in the case of soil treatment: from 0.1 to 10 000 g/ha, preferably from 1 to 5000 g/ha.
These application rates are merely by way of example and are not limiting for the purposes of the invention.
The following examples illustrate in a non-limiting manner the preparation and efficacy of the compounds of formula (I) according to the invention.
Synthesis examples
-[2-(2,4-dichlorophenyl)-2,2-difluoroethyl]-2-(trifluoromethyl)benzamide (example 1-1)
Figure imgf000076_0001
190 mg (1 mmol) of 2-(trifluoromethyl)benzoic acid and 248.6 mg (1.1 mmol) of 2-(2,4- dichlorophenyl)-2,2-difluoroethanamine, 76.5 mg (0.5 mmol) of hydroxybenzotriazole, 61 mg (0.5 mmol) of DMAP, 191.7 mg (1 mmol) of EDC hydrochloride and 129.2 mg (1 mmol) of diisopropyl ethylamine were well stirred in 10 mL dichloromethane at room temperature for 16 hours. The reaction mixture was quenched with 10 mL water, the organic layer was separated and the aqueous layer again extracted with dichloromethane. The combined organic extracts were dried over a silica gel / sodium sulfate cartridge. The solvent was evaporated and the crude mixture chromatographed over silica gel and a n-hexane / ethyl acetate gradient to afford 242 mg (59,8 %) of the title compound as colourless solid. ¾-NMR: 400 MHz, d6-DMSO, δ, 8.98 (t, 1H, NH), 7.80 - 7.54 (m, 6H), 7.37 (d, 1H), 4.21 - 4.13 (m, 2H).
N- [2-(2,4-dichlorophenyl)-2-fluoropropyl] -2-(trifluoromethyl)benzamide (example 1-406)
Figure imgf000077_0001
Step 1: Synthesis of 2-(2,4-dichlorophenyl)-2-fluoropropanenitrile
Trimethylsilylcyanide (5.3 mL, 39.7 mmol) was added dropwise to a stirred suspension of Zn (19.036 mg, 0.06 mmol), l-(2,4-dichlorophenyl)ethanone (7.516 g, 39.7 mmol) and dichloromethane (3.8 ml) under nitrogen atmosphere at 0°C. The reaction mixture was stirred at room temperature overnight. It was then diluted with dry dichloromethane (49 mL), cooled again to 0°C, and a solution of DAST (5.78 mL, 43.7 mmol) in dichloromethane (20.4 mL) was added dropwise. The reaction mixture was stirred overnight at room temperature. The reaction mixture is poured in 61 mL of iced water and extracted with dichloromethane. The organic layer was washed sequentially with a 0.5N aqueous HC1 solution, water, a saturated aqueous solution of NaHC(¾, and water again. The organic layer was dried over sodium sulfate, filtered, and concentrated. The residue obtained was further purified by flash chromatography on silicagel (eluent: cyclohexane/ethylacetate). This afforded 8.576 g (90%) of the title compound.
¾ NMR: 400 MHz, CD3CN, δ, 7.63 (m, 2H), 7.50 (dd, 1H), 2.20 (d, 3H).
Step 2: Synthesis of 2-(2,4-dichlorophenyl)-2-fluoropropan-l-amine hydrochloride
9.79g of 2-(2,4-dichlorophenyl)-2-fluoropropanenitrile (44.8mmol) in anhydrous tetrahydrofurane (614 mL) was cooled to 0°C. 1 M borane-THF (134.6 mL, 134 mmol) was added dropwise. The reaction mixture returned to room temperature and was stirred at room temperature for 4 hours. It was then was quenched with ethanol and was acidified with 1M HCI in diethyl ether and concentrated in vacuo. The residue was triturated with acetone and filtrated. This led to the 5.176 g (41.9%) of the title compound. ¾ NMR: 400 MHz, DMSO-d6, δ, 8.10 (s, 3H), 7.73 (s, 1H), 7.59 (m, 2H), 3.67 -3.50 (m, 2H), 1.87 (d, 3H); HPLC-MS: logP = 0.89; Mass (m z): 222.0 (M+H-HC1)+.
Step 3: Synthesis N-[2-(2,4-dichlorophenyl)-2-fluoropropyl]-2-(trifluoromethyl)benzamide
155 mg of 2-(2,4-dichlorophenyl)-2-fluoropropan-l-amine hydrochloride (0.56 mmol) were placed in dichloromethane (5 mL). Triethylamine (0.236 mL, 1.69 mmol) and 2-(trifluoromethyl)benzoyl chloride (141 mg, 0.67 mmol) were added. The reaction mixture was left under stirring at room temperature overnight. Some ethyl acetate was added. The organic phase was washed with brine, dried over sodium sulfate and concentrated in vacuo. The residue obtained was purified by flash chromatography on silicagel (eluent: cyclohexane/ethylacetate). This afforded 174 mg (78%) of the title compound (example 1-406). ¾ NMR: see peak list; HPLC-MS: logP = 3.70; Mass (m z): 395.0 (M+H)+.
N- [2-(2,4-dichlorophenyl)-2-fluoropropyl] -2-(trifluoromethyl)benzamide (example 1-393) N-{2-fluoro-2-[2-(trifluoromethyl)phenyl]ethyl}-2-(trifluoromethyl)benzamide (example 1-399) N- 2-(2-chlorophenyl)-2-fluoroethyl]-2-(trilluoromethyl)benzamide (example 1-400)
Figure imgf000078_0001
Examples 1-393, 1-399 and 1-400 were obtained in a similar way as the one described above starting with the corresponding aldehyde respectively 2,4-dichlorobenzaldehyde, 2- (trifluoromethyl)benzaldehyde and 2-chlorobenzaldehyde.
The preferred and exemplary compounds according to the invention listed in Table 1 can be synthesized analogous to the above mentioned processes.
The examples shown below further illustrate the invention without limiting it.
Preferred compounds of formula (I) according to the present invention are listed in the following table 1.
Figure imgf000078_0002
(I)
Figure imgf000079_0001
BCS143101 Foreign Country -79 flhl 2uoropeny-
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000081_0002
Figure imgf000082_0001
dihlhil 235tcoroeny---,
Figure imgf000082_0002
BCS143101 Foreign Country ihltnropeny -
Figure imgf000083_0001
BCS143101 Foreign Country
Figure imgf000084_0001
BCS143101 Foreign Country
Figure imgf000085_0001
BCS143101 Foreign Country
Figure imgf000086_0001
BCS143101 Foreign Country hlcyanopeny -
Figure imgf000087_0001
BCS143101 Foreign Country idhloopeny -
Figure imgf000088_0001
BCS143101 Foreign Country
Figure imgf000089_0001
BCS143101 Foreign Country
Figure imgf000090_0001
BCS143101 Foreign Country -90- li2oropyrazn--
Figure imgf000091_0001
BCS143101 Foreign Country
Figure imgf000092_0001
flhluoropeny -
Figure imgf000092_0002
BCS143101 Foreign Country hlidil 32 C3Hcoropyrny ---
Figure imgf000093_0001
BCS143101 Foreign Country bhl 2 C3Hromopeny-
Figure imgf000094_0001
BCS143101 Foreign Country 94-
Figure imgf000095_0001
BCS143101 Foreign Country
Figure imgf000096_0001
Measurement of LogP values was performed according to EEC directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversed phase columns with the following methods: w LogP value is determined by measurement of LC-UV, in an acidic range, with 0.1% formic acid in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
[b] LogP value is determined by measurement of LC-UV, in a neutral range, with 0.001 molar ammonium acetate solution in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
Calibration was done with straight-chain alkan2-ones (with 3 to 16 carbon atoms) with known LogP values (measurement of LogP values using retention times with linear interpolation between successive alkanones). Lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.
NMR-Peak lists
IH-NMR data of selected examples are written in form of lH-NMR-peak lists. To each signal peak are listed the δ- value in ppm and the signal intensity in round brackets. Between the δ-value - signal intensity pairs are semicolons as delimiters.
The peak list of an example has therefore the form: δι (intensityi); 82 (intensity2); ; δ; (intensity); ; δη (intensityn)
Intensity of sharp signals correlates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectram can be shown.
For calibrating chemical shift for 1H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilane peak can occur but not necessarily.
The IH-NMR peak lists are similar to classical IH-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation.
Additionally they can show like classical IH-NMR prints signals of solvents, stereoisomers of the target compounds, which are also object of the invention, and/or peaks of impurities. To show compound signals in the delta-range of solvents and/or water the usual peaks of solvents, for example peaks of DMSO in DMSO-D6 and the peak of water are shown in our 1H-NM peak lists and have usually on average a high intensity .
The peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).
Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore their peaks can help to recognize the reproduction of our preparation process via "side-products-fingerprints".
An expert, who calculates the peaks of the target compounds with known methods (MestreC, ACD- simulation, but also with empirically evaluated expectation values) can isolate the peaks of the target compounds as needed optionally using additional intensity filters. This isolation would be similar to relevant peak picking at classical 1H-NMR interpretation.
Further details of NMR-data description with peak lists you find in the publication "Citation of NMR Peaklist Data within Patent Applications" of the Research Disclosure Database Number 564025.
Example 1 : ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.485 (0.4); 8.469 (0.8); 8.454 (0.4); 8.315 (0.7); 7.853 (2.0); 7.840 (2.1); 7.577 (16.0); 7.149 (2.1); 7.135 (2.1); 4.065 (0.5); 4.050 (0.6); 4.030 (1.2); 4.014 (1.2); 3.994 (0.6); 3.978 (0.6); 3.321 (14.4); 3.297 (0.4); 2.506 (18.4); 2.502 (24.4); 2.497 (18.9); 1.397 (1.4); 0.007 (0.4); 0.000 (8.3); -0.008 (0.5) Example 2: LH-NMR (400.0 MHz, de-DMSO):
□□ 8.564 (0.7); 8.549 (1.3); 8.533 (0.7); 8.315 (0.4); 7.819 (3.5); 7.806 (3.6); 7.607 (0.7); 7.583 (16.0);
7.567 (0.7); 7.559 (0.7); 7.178 (3.8); 7.164 (3.7); 4.064 (0.9); 4.049 (0.9); 4.029 (2.0); 4.013 (2.0); 3.993 (1.0); 3.977 (1.0); 3.322 (14.0); 2.511 (11.8); 2.507 (22.6); 2.502 (29.6); 2.498 (22.2); 1.398 (7.8); 0.008 (0.5); 0.000 (11.3); -0.008 (0.5)
Example 3: LH-NMR (400.0 MHz, de-DMSO):
□□ 8.769 (1.4); 8.753 (2.8); 8.737 (1.3); 7.914 (8.4); 7.909 (8.3); 7.798 (4.4); 7.793 (4.4); 7.590 (3.2);
7.568 (8.3); 7.546 (4.5); 7.541 (4.1); 7.525 (1.7); 7.520 (1.7); 6.852 (8.8); 6.847 (8.6); 4.145 (1.5); 4.129 (1.5); 4.110 (3.4); 4.094 (3.3); 4.074 (1.7); 4.056 (2.3); 4.038 (3.7); 4.020 (3.7); 4.002 (1.2); 3.324 (89.3); 2.676 (0.5); 2.671 (0.7); 2.667 (0.5); 2.524 (2.2); 2.511 (39.4); 2.507 (77.0); 2.502 (100.9); 2.498 (73.7); 2.493 (35.8); 2.334 (0.5); 2.329 (0.7); 2.324 (0.5); 1.989 (16.0); 1.336 (0.4); 1.249 (0.5); 1.193 (4.3); 1.175 (8.4); 1.157 (4.1); 0.008 (1.2); 0.000 (32.6); -0.009 (1.2)
Example 4: [H-NMR (400.0 MHz, de-DMSO):
□□ 8.536 (2.8); 8.520 (5.2); 8.504 (2.6); 8.316 (0.5); 7.836 (15.3); 7.823 (15.9); 7.794 (8.3); 7.789 (8.3); 7.767 (0.4); 7.754 (0.4); 7.710 (0.5); 7.704 (0.5); 7.693 (0.6); 7.672 (0.6); 7.621 (7.8); 7.600 (14.5); 7.577 (1.3); 7.560 (8.1); 7.555 (7.6); 7.539 (4.4); 7.533 (4.2); 7.510 (0.7); 7.484 (0.6); 7.460 (0.5); 7.454 (0.5); 7.432 (0.6); 7.423 (0.6); 7.407 (0.6); 7.382 (0.5); 7.369 (0.5); 7.337 (0.6); 7.284 (0.4); 7.132 (16.0); 7.119 (15.2); 6.574 (0.6); 4.213 (3.4); 4.198 (3.5); 4.179 (7.2); 4.163 (6.9); 4.144 (3.8); 4.128 (3.5); 4.056 (0.8); 4.038 (1.5); 4.020 (1.5); 4.002 (0.9); 3.949 (0.5); 3.942 (0.5); 3.889 (0.4); 3.324 (177.6); 3.281 (0.8); 3.197 (1.9); 3.152 (1.5); 3.133 (1.5); 3.102 (1.4); 3.084 (1.4); 2.676 (1.5); 2.671 (1.8); 2.666 (1.5); 2.511 (82.8); 2.506 (147.7); 2.502 (187.0); 2.497 (135.4); 2.493 (66.0); 2.374 (5.4); 2.333 (5.5); 2.329 (5.8); 2.324 (5.5); 1.989 (4.4); 1.336 (1.2); 1.249 (1.2); 1.235 (0.3); 1.193 (1.3); 1.187 (0.4); 1.175 (2.5); 1.157 (1.3); 1.148 (0.3); 0.008 (4.7); 0.000 (58.9); -0.009 (2.5); - 0.127 (0.5); -0.150 (0.6); -0.181 (0.4); -0.194 (0.4)
Example 5: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.640 (2.3); 8.624 (4.8); 8.609 (2.3); 7.790 (7.4); 7.785 (7.4); 7.709 (15.2); 7.696 (15.8); 7.651
(7.8) ; 7.629 (12.3); 7.563 (6.3); 7.558 (6.0); 7.542 (4.0); 7.537 (3.9); 7.202 (16.0); 7.190 (15.2); 6.574 (0.5); 4.197 (2.6); 4.181 (2.7); 4.162 (5.8); 4.146 (5.6); 4.127 (2.9); 4.111 (2.7); 4.038 (0.7); 4.020 (0.7); 3.324 (95.6); 2.676 (0.6); 2.671 (0.8); 2.667 (0.6); 2.525 (2.6); 2.511 (45.5); 2.507 (89.9); 2.502 (118.1); 2.498 (85.2); 2.493 (40.4); 2.333 (0.6); 2.329 (0.8); 2.324 (0.5); 1.989 (2.8); 1.336 (0.7); 1.249 (0.7); 1.193 (0.8); 1.175 (1.6); 1.157 (0.8); 0.008 (1.7); 0.000 (43.9); -0.009 (1.3)
Example 6: LH-NMR (400.0 MHz, de-DMSO):
□□ 8.791 (2.2); 8.776 (4.4); 8.760 (2.2); 7.791 (8.9); 7.787 (9.1); 7.623 (7.9); 7.601 (16.0); 7.588 (0.4); 7.581 (0.6); 7.566 (8.7); 7.561 (8.1); 7.545 (4.6); 7.539 (5.0); 7.530 (2.1); 7.525 (4.2); 7.522 (3.0); 7.520 (3.3); 7.517 (2.8); 7.511 (3.0); 7.509 (3.0); 7.507 (3.3); 7.504 (4.4); 7.499 (2.7); 7.490 (2.3); 7.486 (2.5); 7.454 (3.4); 7.449 (3.3); 7.435 (6.5); 7.430 (6.2); 7.416 (4.6); 7.412 (3.8); 7.281 (5.1); 7.265 (6.2); 7.263 (10.0); 7.257 (6.0); 7.254 (5.3); 7.246 (9.8); 7.244 (8.7); 7.236 (4.3); 7.233 (4.3); 7.228 (5.1); 7.225 (3.9); 6.575 (0.8); 4.215 (3.3); 4.199 (3.4); 4.180 (7.5); 4.164 (7.3); 4.145 (3.8); 4.129 (3.6); 4.056 (0.9); 4.038 (2.8); 4.020 (2.8); 4.003 (1.0); 3.325 (86.4); 2.676 (0.5); 2.671 (0.7); 2.667 (0.5); 2.525 (2.2); 2.520 (3.4); 2.511 (38.9); 2.507 (77.5); 2.502 (102.5); 2.498 (74.0); 2.493 (34.9); 2.334 (0.5); 2.329 (0.7); 2.324 (0.5); 1.989 (12.5); 1.336 (0.9); 1.249 (1.0); 1.193 (3.4); 1.188 (0.4); 1.175 (6.8); 1.157 (3.3); 0.008 (1.4); 0.000 (39.4); -0.009 (1.1)
Example 7: LH-NMR (400.0 MHz, de-DMSO):
□□ 9.212 (2.2); 9.196 (4.4); 9.181 (2.2); 7.796 (7.7); 7.793 (7.5); 7.609 (3.2); 7.587 (16.0); 7.580 (10.7); 7.575 (9.2); 7.559 (1.9); 7.554 (2.0); 7.537 (1.4); 7.520 (3.0); 7.516 (2.6); 7.504 (2.1); 7.499 (5.5); 7.495 (2.0); 7.482 (2.7); 7.478 (3.2); 7.461 (1.5); 7.165 (1.3); 7.162 (1.7); 7.155 (9.5); 7.136 (12.3); 7.115 (7.9); 7.108 (1.3); 4.242 (2.7); 4.226 (2.8); 4.206 (6.2); 4.191 (6.0); 4.171 (3.1); 4.155
(2.9) ; 3.326 (127.7); 2.676 (0.6); 2.671 (0.8); 2.667 (0.6); 2.524 (2.5); 2.511 (44.3); 2.507 (86.8); 2.502 (113.3); 2.497 (81.5); 2.493 (38.5); 2.333 (0.5); 2.329 (0.7); 2.324 (0.5); 1.989 (1.2); 1.336 (0.8); 1.250 (0.9); 1.193 (0.4); 1.188 (0.3); 1.175 (0.7); 1.157 (0.3); 0.008 (1.5); 0.000 (40.1); -0.009 (1.3)
Example 8: LH-NMR (400.0 MHz, ds-DMSO):
□□ 8.913 (2.8); 8.897 (5.8); 8.882 (2.8); 7.791 (9.4); 7.787 (9.8); 7.678 (10.4); 7.656 (16.0); 7.644 (0.4); 7.628 (8.4); 7.625 (8.2); 7.608 (10.3); 7.605 (9.7); 7.586 (8.3); 7.581 (7.9); 7.565 (5.4); 7.559 (5.2); 7.428 (3.5); 7.425 (3.8); 7.419 (0.6); 7.409 (9.9); 7.406 (9.8); 7.391 (7.8); 7.388 (7.1); 7.363 (6.6); 7.358 (7.7); 7.343 (7.4); 7.339 (8.4); 7.324 (3.8); 7.320 (3.5); 7.227 (9.4); 7.223 (9.3); 7.209 (7.9); 7.204 (7.3); 4.208 (3.5); 4.193 (3.5); 4.174 (7.8); 4.158 (7.6); 4.139 (3.9); 4.123 (3.7); 4.056 (0.3); 4.038 (0.9); 4.020 (1.0); 4.002 (0.3); 3.324 (94.7); 2.675 (0.6); 2.671 (0.9); 2.666 (0.6); 2.524 (2.5); 2.519 (3.9); 2.511 (47.2); 2.506 (95.2); 2.502 (126.5); 2.497 (91.5); 2.492 (43.4); 2.333 (0.6); 2.328 (0.9); 2.324 (0.6); 2.038 (0.4); 2.035 (0.4); 1.989 (4.1); 1.336 (0.7); 1.249 (0.8); 1.193 (1.2); 1.175 (2.3); 1.157 (1.1); 0.008 (1.7); 0.000 (51.8); -0.009 (1.5)
Example 9: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.735 (1.1); 8.720 (2.3); 8.704 (1.1); 7.926 (8.8); 7.921 (8.7); 7.592 (1.5); 7.585 (0.9); 7.577 (1.6); 7.569 (15.5); 7.564 (16.0); 7.556 (1.5); 7.548 (0.8); 7.541 (1.6); 6.867 (9.1); 6.862 (8.9); 3.994 (1.4); 3.978 (1.4); 3.958 (3.2); 3.942 (3.1); 3.921 (1.6); 3.905 (1.5); 3.325 (42.4); 2.672 (0.4); 2.525 (1.0); 2.520 (1.6); 2.512 (19.2); 2.507 (38.5); 2.503 (50.9); 2.498 (36.8); 2.493 (17.3); 2.329 (0.3); 0.008 (0.8); 0.000 (24.8); -0.009 (0.7)
Example 10: ^-NMR (400.0 MHz, -DMSO):
□□ 8.617 (1.2); 8.602 (2.4); 8.586 (1.2); 7.722 (7.4); 7.710 (7.7); 7.611 (1.7); 7.604 (1.0); 7.588 (16.0); 7.582 (15.5); 7.566 (0.9); 7.559 (1.6); 7.218 (7.8); 7.205 (7.5); 4.048 (1.4); 4.033 (1.5); 4.013 (3.2); 3.997 (3.1); 3.977 (1.6); 3.961 (1.5); 3.324 (60.2); 2.675 (0.4); 2.671 (0.5); 2.666 (0.4); 2.524 (1.9); 2.511 (30.3); 2.506 (58.7); 2.502 (76.8); 2.497 (56.0); 2.493 (27.1); 2.333 (0.4); 2.329 (0.5); 2.324 (0.4); 1.336 (0.3); 1.249 (0.3); 0.008 (1.2); 0.000 (30.1); -0.009 (1.0)
Example 11 : :H-NMR (400.0 MHz, ds-DMSO):
□□ 8.767 (0.6); 7.581 (16.0); 7.535 (0.6); 7.532 (0.4); 7.530 (0.5); 7.528 (0.4); 7.521 (0.5); 7.520 (0.5); 7.517 (0.5); 7.514 (0.7); 7.509 (0.4); 7.501 (0.4); 7.497 (0.7); 7.493 (0.5); 7.479 (1.0); 7.475 (0.9); 7.460 (0.7); 7.456 (0.5); 7.294 (0.7); 7.279 (0.9); 7.276 (1.1); 7.273 (0.7); 7.269 (0.8); 7.267 (0.8); 7.260 (1.4); 7.258 (1.2); 7.248 (0.6); 7.246 (0.6); 7.242 (0.8); 7.239 (0.6); 4.064 (0.5); 4.048 (0.5); 4.028 (1.1); 4.012 (1.1); 3.992 (0.6); 3.976 (0.5); 3.325 (17.9); 2.525 (0.4); 2.520 (0.6); 2.511 (6.9); 2.507 (13.8); 2.502 (18.2); 2.497 (13.2); 2.493 (6.2); 0.000 (8.3)
Example 12: 'H-NMR (400.0 MHz, ck-DMSO):
□□ 9.209 (0.4); 9.194 (0.7); 9.178 (0.3); 7.581 (16.0); 7.528 (0.5); 7.523 (0.5); 7.511 (0.4); 7.507 (1.0); 7.502 (0.4); 7.490 (0.5); 7.486 (0.6); 7.165 (1.6); 7.146 (2.1); 7.125 (1.3); 4.090 (0.5); 4.074 (0.5); 4.054 (1.1); 4.038 (1.1); 4.018 (0.6); 4.003 (0.5); 3.324 (15.8); 2.524 (0.4); 2.511 (7.5); 2.506 (14.6); 2.502 (19.1); 2.497 (13.8); 2.493 (6.5); 0.000 (8.2)
Example 13: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.865 (2.6); 8.849 (5.3); 8.833 (2.5); 7.862 (6.8); 7.859 (8.2); 7.846 (1.9); 7.841 (8.2); 7.838 (8.2); 7.790 (8.3); 7.785 (8.5); 7.695 (9.2); 7.674 (13.2); 7.586 (7.0); 7.581 (6.7); 7.565 (4.9); 7.560 (4.6); 7.448 (0.3); 7.438 (3.9); 7.436 (4.0); 7.420 (9.0); 7.417 (7.3); 7.401 (5.3); 7.398 (5.0); 7.176 (3.6); 7.172 (6.1); 7.160 (7.7); 7.156 (16.0); 7.141 (6.6); 7.137 (15.4); 4.198 (3.0); 4.182 (3.0); 4.163 (6.7); 4.147 (6.4); 4.128 (3.3); 4.112 (3.1); 3.323 (104.8); 2.675 (0.8); 2.671 (1.1); 2.666 (0.8); 2.662 (0.4); 2.524 (3.5); 2.519 (5.6); 2.511 (60.5); 2.506 (119.8); 2.501 (157.2); 2.497 (113.5); 2.492 (53.8); 2.337
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
2.511 (30.7); 2.507 (62.1); 2.502 (81.6); 2.497 (57.8); 2.493 (26.9); 2.333 (0.4); 2.329 (0.5); 2.324 (0.4); 1.398 (0.5); 0.146 (0.4); 0.008 (3.7); 0.000 (98.4); -0.009 (3.1); -0.150 (0.4)
Example 34: ^-NMR (400.0 MHz, -DMSO):
□□ 8.805 (0.5); 8.790 (1.0); 8.774 (0.5); 7.575 (16.0); 7.284 (5.0); 5.756 (1.8); 4.021 (0.6); 4.005 (0.6); 3.985 (1.4); 3.969 (1.3); 3.949 (0.7); 3.933 (0.6); 3.325 (6.6); 2.508 (9.8); 2.503 (11.9); 2.499 (8.2); 0.008 (1.0); 0.000 (13.5); -0.008 (0.4)
Example 35: ^-NMR (400.0 MHz, de-DMSO):
□□ 20.009 (0.6); 13.899 (0.6); 9.077 (3.2); 9.061 (6.1); 9.046 (3.0); 8.315 (4.4); 8.136 (0.7); 8.115 (0.5); 7.870 (4.8); 7.857 (5.2); 7.848 (5.9); 7.835 (5.5); 7.807 (10.5); 7.802 (10.6); 7.673 (10.1); 7.652 (16.0); 7.595 (8.9); 7.590 (8.1); 7.574 (5.2); 7.568 (5.0); 7.540 (0.6); 7.527 (3.0); 7.522 (3.2); 7.506
(5.0) ; 7.499 (4.8); 7.484 (2.3); 7.479 (2.4); 7.248 (5.4); 7.241 (4.9); 7.226 (5.5); 7.220 (4.7); 6.573 (3.5); 4.215 (3.7); 4.199 (3.6); 4.180 (8.0); 4.164 (7.6); 4.144 (4.0); 4.128 (3.7); 3.380 (0.6); 3.368 (0.7); 3.342 (1.5); 3.320 (630.8); 3.278 (0.7); 3.256 (0.6); 2.675 (6.7); 2.670 (9.4); 2.666 (6.6); 2.633 (0.7); 2.627 (0.9); 2.622 (1.0); 2.617 (0.9); 2.566 (0.8); 2.541 (5.6); 2.524 (23.7); 2.519 (38.2); 2.510 (545.9); 2.506 (1105.3); 2.501 (1449.4); 2.497 (1025.0); 2.492 (478.0); 2.448 (1.5); 2.429 (1.3); 2.337
(3.1) ; 2.333 (6.8); 2.328 (9.1); 2.324 (6.5); 1.989 (0.7); 1.398 (1.3); 0.146 (7.0); 0.046 (0.8); 0.038 (0.9); 0.027 (1.2); 0.023 (2.1); 0.008 (58.6); 0.000 (1634.6); -0.009 (52.2); -0.020 (3.2); -0.025 (1.5); - 0.029 (1.2); -0.042 (0.9); -0.057 (0.6); -0.063 (1.3); -0.072 (0.5); -0.095 (0.6); -0.150 (6.9)
Example 36: :H-NMR (400.0 MHz, ds-DMSO):
□□ 9.223 (2.1); 9.207 (4.2); 9.192 (2.2); 8.318 (0.5); 7.809 (7.6); 7.806 (7.9); 7.707 (0.8); 7.687 (2.6); 7.667 (3.6); 7.654 (2.9); 7.639 (4.3); 7.622 (11.9); 7.604 (16.0); 7.592 (9.0); 7.587 (8.0); 7.570 (2.2); 7.566 (2.3); 4.260 (2.4); 4.244 (2.5); 4.224 (5.2); 4.208 (5.1); 4.188 (2.7); 4.172 (2.5); 3.328 (138.5); 2.676 (1.1); 2.671 (1.4); 2.667 (1.1); 2.506 (175.9); 2.502 (227.2); 2.498 (170.6); 2.333 (1.1); 2.329 (1.4); 2.324 (1.1); 1.989 (0.6); 1.398 (1.1); 0.008 (1.9); 0.000 (43.9)
Example 37: :H-NMR (400.0 MHz, ds-DMSO):
□□ 9.041 (3.9); 9.026 (7.6); 9.010 (3.9); 7.804 (13.2); 7.800 (13.3); 7.714 (6.6); 7.709 (7.1); 7.691 (6.8); 7.685 (6.9); 7.663 (9.5); 7.641 (16.0); 7.623 (3.4); 7.617 (3.0); 7.601 (7.4); 7.595 (7.4); 7.587 (11.6); 7.582 (12.9); 7.566 (6.3); 7.561 (5.7); 7.468 (6.1); 7.454 (6.9); 7.447 (5.5); 7.433 (4.6); 5.759 (0.6); 4.214 (4.1); 4.199 (4.3); 4.179 (9.0); 4.163 (8.7); 4.143 (4.7); 4.128 (4.3); 3.337 (175.9); 2.673 (0.7); 2.508 (92.7); 2.504 (111.1); 2.331 (0.7); 0.000 (24.3)
Example 38: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.939 (3.3); 8.923 (6.8); 8.908 (3.2); 8.315 (1.0); 7.886 (7.9); 7.872 (8.3); 7.864 (8.2); 7.850 (7.8); 7.795 (11.0); 7.790 (11.1); 7.711 (11.5); 7.690 (16.0); 7.590 (8.4); 7.585 (7.9); 7.569 (6.1); 7.564 (5.7); 7.112 (4.2); 7.104 (4.8); 7.090 (8.0); 7.082 (9.2); 7.068 (4.0); 7.061 (4.6); 7.039 (8.9); 7.031 (6.9); 7.016 (9.3); 7.009 (6.6); 6.573 (0.5); 4.198 (3.7); 4.182 (3.8); 4.163 (8.2); 4.147 (8.0); 4.128 (4.1); 4.112 (3.9); 3.320 (160.9); 2.675 (1.8); 2.670 (2.5); 2.666 (1.8); 2.662 (0.8); 2.541 (1.2); 2.524 (7.0); 2.510 (153.2); 2.506 (299.1); 2.501 (384.7); 2.497 (271.8); 2.492 (127.3); 2.462 (1.0); 2.442 (0.6);
Figure imgf000106_0001
Figure imgf000107_0001
(1.6); 1.651 (2.8); 1.072 (8.7); 1.055 (9.5); 1.037 (1.2); 0.000 (26.1); -0.008 (1.0) Example 47: ^-NMR (400.0 MHz, -DMSO):
□□ 9.158 (3.0); 9.142 (6.3); 9.127 (3.0); 8.561 (0.4); 8.555 (0.5); 8.316 (2.1); 8.203 (0.5); 8.198 (0.5); 8.030 (8.3); 8.027 (8.4); 8.010 (9.7); 8.007 (9.4); 7.795 (12.0); 7.793 (14.0); 7.776 (9.8); 7.773 (9.5); 7.758 (6.7); 7.755 (6.1); 7.707 (6.3); 7.704 (6.7); 7.687 (7.9); 7.684 (8.5); 7.678 (10.7); 7.668 (4.3); 7.665 (4.3); 7.656 (16.0); 7.618 (0.4); 7.609 (0.4); 7.586 (8.4); 7.581 (8.1); 7.565 (5.3); 7.560 (5.2); 7.432 (8.8); 7.428 (9.0); 7.413 (8.3); 7.409 (7.8); 7.221 (0.4); 4.215 (3.5); 4.199 (3.5); 4.179 (7.9); 4.164 (7.8); 4.144 (4.0); 4.128 (3.8); 3.650 (0.4); 3.635 (0.4); 3.324 (876.5); 3.154 (0.4); 3.137 (0.6); 2.709 (0.6); 2.680 (1.8); 2.675 (3.9); 2.671 (5.3); 2.666 (3.8); 2.662 (1.7); 2.541 (2.9); 2.524 (13.4); 2.51 1 (300.6); 2.506 (604.9); 2.502 (792.3); 2.497 (561.8); 2.493 (262.8); 2.333 (3.9); 2.328 (5.2); 2.324 (3.8); 2.320 (1.7); 2.074 (1.1); 0.146 (4.9); 0.041 (0.3); 0.031 (0.6); 0.008 (43.3); 0.000 (1111.2); -0.009 (36.7); -0.021 (2.1); -0.150 (4.9)
Example 48: ^-NMR (400.0 MHz, -DMSO):
□□ 9.309 (3.4); 9.294 (6.2); 9.278 (3.0); 9.015 (10.5); 9.009 (12.0); 8.996 (0.4); 8.963 (12.8); 8.957
(10.0) ; 7.816 (10.3); 7.812 (10.0); 7.635 (7.2); 7.614 (16.0); 7.586 (9.6); 7.581 (8.9); 7.565 (4.0); 7.560 (3.9); 4.285 (3.8); 4.269 (3.9); 4.249 (8.3); 4.233 (7.8); 4.212 (4.2); 4.196 (3.8); 3.888 (0.9); 3.326 (1 12.1); 2.676 (0.6); 2.672 (0.8); 2.668 (0.6); 2.507 (96.8); 2.503 (1 17.5); 2.498 (82.8); 2.334 (0.6); 2.329 (0.8); 2.325 (0.6); 2.075 (2.5); 0.146 (0.7); 0.008 (10.8); 0.000 (143.6); -0.008 (5.4); -0.150 (0.7) Example 49: :H-NMR (400.0 MHz, ds-DMSO):
□□ 9.261 (2.0); 9.245 (4.0); 9.229 (2.0); 8.696 (13.4); 8.690 (16.0); 8.635 (15.8); 8.628 (12.9); 8.316 (1.5); 7.811 (6.8); 7.806 (6.9); 7.641 (6.1); 7.620 (12.4); 7.584 (6.5); 7.579 (6.1); 7.563 (3.1); 7.558 (3.1); 4.274 (2.6); 4.258 (2.6); 4.238 (5.9); 4.223 (5.7); 4.203 (2.9); 4.187 (2.8); 3.323 (291.1); 2.680 (0.8); 2.675 (1.7); 2.671 (2.3); 2.666 (1.7); 2.662 (0.8); 2.541 (1.2); 2.524 (5.5); 2.519 (9.0); 2.51 1 (128.4); 2.506 (261.5); 2.502 (345.0); 2.497 (245.3); 2.493 (114.5); 2.338 (0.8); 2.333 (1.7); 2.328 (2.3); 2.324 (1.6); 2.319 (0.8); 1.989 (1.3); 1.193 (0.3); 1.175 (0.7); 1.157 (0.3); 0.146 (2.1); 0.008
(18.1) ; 0.000 (499.2); -0.009 (16.7); -0.034 (0.4); -0.150 (2.2)
Example 50: LH-NMR (400.0 MHz, de-DMSO):
□□ 8.759 (0.6); 8.744 (1.2); 8.728 (0.6); 7.777 (2.0); 7.773 (2.1); 7.646 (1.9); 7.625 (3.1); 7.561 (1.6); 7.556 (1.6); 7.540 (1.0); 7.535 (1.0); 7.428 (0.6); 7.424 (0.7); 7.408 (1.4); 7.406 (1.4); 7.390 (1.1); 7.386 (1.1); 7.315 (2.1); 7.296 (1.5); 7.253 (1.2); 7.250 (1.3); 7.234 (2.0); 7.231 (1.8); 7.178 (1.3); 7.176 (1.2); 7.160 (1.8); 7.157 (1.7); 7.141 (0.7); 7.139 (0.7); 4.184 (0.7); 4.169 (0.7); 4.150 (1.5); 4.134 (1.5); 4.115 (0.8); 4.099 (0.7); 3.325 (13.3); 2.524 (0.3); 2.51 1 (8.7); 2.506 (17.4); 2.502 (22.6); 2.497 (16.3); 2.493 (7.8); 2.346 (16.0); 1.989 (0.5); 1.398 (0.3); 0.008 (1.2); 0.000 (30.7); -0.009 (1.1) Example 51 : ¾-NMR (400.0 MHz, d^-DMSO):
□□ 8.800 (2.0); 8.785 (3.8); 8.770 (2.0); 7.717 (12.9); 7.695 (16.0); 7.552 (1.6); 7.547 (1.9); 7.539 (1.9); 7.534 (3.9); 7.529 (3.8); 7.526 (4.3); 7.518 (13.0); 7.508 (4.2); 7.495 (9.8); 7.486 (3.7); 7.481 (3.1); 7.467 (5.9); 7.462 (5.6); 7.455 (0.8); 7.448 (4.3); 7.444 (3.4); 7.292 (4.5); 7.272 (9.5); 7.268
Figure imgf000109_0001
(12.0); 0.000 (179.8); -0.008 (6.8); -0.027 (0.3); -0.150 (0.8)
Example 56: ^-NMR (400.0 MHz, -DMSO):
□□ 9.173 (2.5); 9.157 (5.1); 9.142 (2.5); 8.798 (5.3); 8.795 (5.7); 8.786 (5.6); 8.783 (5.6); 7.879 (4.4); 7.876 (4.7); 7.859 (6.8); 7.857 (6.6); 7.784 (6.4); 7.772 (6.2); 7.764 (4.6); 7.752 (6.2); 7.747 (13.3); 7.725 (16.0); 7.718 (2.0); 7.681 (0.3); 7.658 (0.4); 7.531 (10.6); 7.510 (8.7); 7.215 (0.3); 4.130 (2.9); 4.114 (2.9); 4.094 (6.7); 4.078 (6.5); 4.057 (3.4); 4.042 (3.2); 3.327 (32.3); 2.892 (0.9); 2.732 (0.7); 2.677 (0.4); 2.672 (0.5); 2.667 (0.3); 2.525 (1.3); 2.512 (27.6); 2.508 (55.4); 2.503 (73.0); 2.498 (51.7); 2.494 (24.2); 2.334 (0.3); 2.330 (0.5); 2.325 (0.3); 0.146 (0.5); 0.008 (4.6); 0.000 (115.8); -0.009 (3.8); -0.018 (0.4); -0.150 (0.5)
Example 57: ^-NMR (400.0 MHz, de-DMSO):
□□ 9.229 (2.4); 9.213 (4.9); 9.198 (2.4); 7.719 (13.0); 7.697 (16.0); 7.543 (1.6); 7.526 (4.8); 7.518
(11.4) ; 7.505 (8.0); 7.497 (9.4); 7.489 (4.7); 7.484 (4.0); 7.468 (1.7); 7.172 (1.2); 7.169 (1.7); 7.162
(10.3) ; 7.143 (13.3); 7.122 (8.6); 7.115 (1.5); 4.116 (3.0); 4.100 (3.0); 4.080 (7.0); 4.065 (6.8); 4.044 (3.5); 4.028 (3.3); 3.326 (37.6); 2.676 (0.4); 2.671 (0.6); 2.667 (0.4); 2.525 (1.5); 2.511 (32.9); 2.507
(66.5) ; 2.502 (87.3); 2.498 (62.4); 2.493 (29.5); 2.333 (0.4); 2.329 (0.6); 2.324 (0.4); 0.146 (0.5); 0.008 (4.1); 0.000 (114.8); -0.009 (4.0); -0.150 (0.5)
Example 58: LH-NMR (400.0 MHz, de-DMSO):
□□ 9.098 (1.6); 9.083 (3.2); 9.067 (1.6); 7.940 (3.8); 7.921 (4.7); 7.868 (1.2); 7.849 (3.5); 7.831 (3.5); 7.798 (5.7); 7.779 (8.8); 7.760 (8.6); 7.743 (2.7); 7.727 (4.4); 7.708 (3.2); 7.670 (3.2); 7.651 (3.9); 7.632 (1.5); 7.428 (4.5); 7.410 (4.0); 4.102 (2.1); 4.086 (2.0); 4.065 (4.6); 4.056 (2.5); 4.049 (4.4); 4.038 (4.2); 4.029 (2.4); 4.020 (4.4); 4.013 (2.2); 4.002 (1.4); 3.324 (34.9); 2.676 (0.5); 2.671 (0.6);
2.666 (0.5); 2.524 (1.5); 2.511 (37.2); 2.506 (73.8); 2.502 (95.2); 2.497 (67.2); 2.493 (31.1); 2.333 (0.5); 2.329 (0.6); 2.324 (0.4); 1.989 (16.0); 1.398 (0.8); 1.193 (4.3); 1.175 (8.6); 1.157 (4.2); 0.146 (0.6); 0.008 (4.4); 0.000 (126.6); -0.009 (4.1); -0.150 (0.6)
Example 59: :H-NMR (400.0 MHz, ds-DMSO):
□□ 8.860 (2.6); 8.845 (4.8); 8.830 (2.5); 7.928 (6.3); 7.909 (8.2); 7.822 (2.1); 7.805 (6.1); 7.785 (6.2); 7.756 (5.6); 7.740 (16.0); 7.721 (7.2); 7.554 (1.6); 7.550 (1.9); 7.541 (2.1); 7.536 (4.1); 7.532 (3.6); 7.521 (3.6); 7.516 (4.5); 7.511 (2.8); 7.502 (2.3); 7.497 (2.5); 7.486 (3.5); 7.482 (3.3); 7.467 (6.9); 7.463 (6.8); 7.448 (4.4); 7.444 (3.6); 7.297 (5.3); 7.274 (11.4); 7.256 (10.5); 7.238 (4.6); 4.116 (3.8); 4.100 (3.8); 4.080 (8.3); 4.064 (8.0); 4.045 (4.2); 4.029 (3.9); 3.326 (51.4); 2.676 (0.5); 2.671 (0.7);
2.667 (0.5); 2.542 (0.4); 2.507 (79.7); 2.502 (101.5); 2.498 (73.0); 2.334 (0.5); 2.329 (0.7); 2.325 (0.5); 0.146 (0.5); 0.008 (5.7); 0.000 (109.5); -0.008 (4.4); -0.150 (0.5)
Example 60: ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.007 (4.5); 8.992 (9.0); 8.976 (4.5); 8.317 (0.7); 7.933 (10.7); 7.914 (13.2); 7.863 (3.3); 7.844 (9.8); 7.826 (9.7); 7.796 (16.0); 7.774 (9.6); 7.751 (9.8); 7.733 (3.9); 7.645 (12.8); 7.642 (13.1); 7.625
(15.4) ; 7.623 (15.1); 7.446 (5.1); 7.443 (5.6); 7.427 (14.0); 7.424 (14.4); 7.409 (11.1); 7.406 (10.4); 7.376 (8.8); 7.372 (10.6); 7.357 (11.4); 7.352 (12.6); 7.338 (5.4); 7.333 (5.1); 7.270 (14.5); 7.266 (13.9); 7.251 (12.0); 7.247 (10.9); 4.094 (5.9); 4.079 (5.9); 4.059 (12.9); 4.043 (12.5); 4.022 (6.6); 4.007 (6.1); 3.324 (144.6); 2.675 (1.2); 2.671 (1.7); 2.666 (1.2); 2.541 (0.9); 2.524 (4.9); 2.510 (97.2);
2.506 (192.9); 2.502 (252.3); 2.497 (181.8); 2.493 (87.2); 2.333 (1.2); 2.328 (1.6); 2.324 (1.2); 1.989 (2.3); 1.398 (0.7); 1.193 (0.6); 1.175 (1.2); 1.157 (0.6); 0.146 (1.4); 0.008 (12.9); 0.000 (304.2); -0.009 (11.0); -0.022 (0.4); -0.150 (1.4)
Example 61 : :H-NMR (400.0 MHz, de-DMSO):
□□ 8.959 (3.6); 8.943 (7.3); 8.927 (3.6); 8.317 (0.4); 7.933 (8.2); 7.913 (10.2); 7.875 (11.4); 7.868
(3.1) ; 7.856 (12.4); 7.855 (12.9); 7.849 (8.0); 7.830 (7.8); 7.807 (12.1); 7.790 (5.1); 7.769 (5.3); 7.750 (7.3); 7.731 (2.9); 7.456 (5.0); 7.453 (5.0); 7.437 (11.2); 7.435 (11.1); 7.418 (6.9); 7.416 (6.6); 7.210 (8.8); 7.206 (11.8); 7.190 (9.3); 7.187 (16.0); 7.168 (10.5); 7.164 (8.4); 7.149 (5.4); 7.145 (4.5); 4.087 (4.3); 4.071 (4.3); 4.051 (9.4); 4.035 (9.1); 4.015 (4.8); 3.999 (4.4); 3.324 (114.3); 2.675 (0.9); 2.671
(1.2) ; 2.666 (0.9); 2.541 (0.7); 2.524 (3.2); 2.511 (70.6); 2.506 (140.3); 2.502 (182.7); 2.497 (131.2); 2.493 (62.8); 2.333 (0.9); 2.329 (1.2); 2.324 (0.9); 1.989 (0.8); 1.398 (1.7); 1.175 (0.4); 0.146 (1.0); 0.008 (9.0); 0.000 (210.9); -0.008 (7.6); -0.150 (1.0)
Example 62: :H-NMR (400.0 MHz, de-DMSO):
□□ 9.259 (2.6); 9.244 (5.2); 9.228 (2.6); 8.042 (7.1); 8.040 (7.3); 8.022 (8.3); 8.020 (8.1); 7.938 (5.9); 7.919 (7.2); 7.861 (1.8); 7.842 (5.2); 7.824 (5.7); 7.814 (3.7); 7.811 (3.9); 7.795 (14.3); 7.792 (9.8); 7.776 (12.3); 7.774 (9.4); 7.757 (5.4); 7.738 (2.2); 7.720 (5.1); 7.716 (5.6); 7.700 (6.6); 7.697 (6.8); 7.681 (3.3); 7.677 (3.2); 7.491 (7.7); 7.488 (7.9); 7.472 (7.1); 7.469 (6.7); 4.106 (3.1); 4.090 (3.2); 4.070 (6.9); 4.055 (7.1); 4.038 (5.0); 4.034 (3.8); 4.020 (5.9); 4.003 (1.4); 3.326 (37.0); 2.676 (0.4); 2.671 (0.5); 2.667 (0.4); 2.511 (32.8); 2.507 (64.4); 2.502 (83.7); 2.498 (60.4); 2.494 (29.2); 2.334 (0.4); 2.329 (0.5); 2.325 (0.4); 1.989 (16.0); 1.398 (0.4); 1.193 (4.3); 1.175 (8.4); 1.157 (4.1); 0.146 (0.5); 0.008 (5.1); 0.000 (108.6); -0.009 (4.2); -0.150 (0.5)
Example 63: :H-NMR (400.0 MHz, -DMSO):
□□ 9.270 (3.0); 9.254 (6.0); 9.239 (3.0); 8.811 (6.9); 8.809 (7.2); 8.799 (7.2); 8.797 (7.1); 7.950 (7.0); 7.930 (8.5); 7.905 (5.8); 7.903 (6.1); 7.886 (8.7); 7.883 (8.6); 7.857 (6.3); 7.838 (6.4); 7.804 (13.0); 7.790 (16.0); 7.771 (11.6); 7.751 (2.6); 4.129 (3.7); 4.113 (3.7); 4.092 (8.3); 4.076 (8.0); 4.055 (4.2); 4.039 (4.3); 4.021 (0.5); 3.327 (39.2); 2.677 (0.4); 2.672 (0.6); 2.668 (0.4); 2.525 (1.6); 2.512 (34.6);
2.507 (69.0); 2.503 (89.9); 2.498 (64.2); 2.494 (30.3); 2.334 (0.4); 2.330 (0.6); 2.325 (0.4); 1.990 (1.7); 1.193 (0.5); 1.175 (1.0); 1.158 (0.5); 0.146 (0.6); 0.008 (5.0); 0.000 (124.6); -0.009 (4.4); -0.150 (0.5) Example 64: :H-NMR (400.0 MHz, de-DMSO):
□□ 9.303 (2.7); 9.287 (5.4); 9.272 (2.7); 7.936 (6.4); 7.916 (7.4); 7.835 (2.0); 7.817 (5.8); 7.798 (5.7); 7.772 (5.1); 7.747 (9.8); 7.727 (5.3); 7.551 (1.6); 7.535 (3.5); 7.530 (3.3); 7.518 (2.5); 7.513 (6.7); 7.509 (2.7); 7.497 (3.4); 7.492 (4.0); 7.476 (1.8); 7.178 (2.0); 7.171 (11.3); 7.150 (16.0); 7.130 (9.7); 7.123 (1.8); 4.127 (3.6); 4.112 (3.6); 4.091 (8.0); 4.075 (7.7); 4.055 (4.9); 4.038 (6.3); 4.020 (3.0); 4.003 (1.0); 3.326 (73.0); 2.676 (0.5); 2.671 (0.7); 2.667 (0.5); 2.541 (0.3); 2.524 (1.8); 2.511 (41.0); 2.507 (83.1); 2.502 (109.8); 2.498 (79.9); 2.493 (38.9); 2.333 (0.5); 2.329 (0.7); 2.324 (0.5); 1.989
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
(1.7); 3.771 (6.1); 3.755 (6.1); 3.738 (3.8); 3.735 (3.0); 3.719 (2.7); 3.716 (2.7); 3.701 (2.2); 2.473 (0.5); 2.468 (1.0); 2.463 (1.3); 2.459 (0.9); 2.454 (0.5); 2.160 (454.1); 2.120 (1.8); 2.114 (2.4); 2.107 (2.9); 2.101 (2.0); 2.095 (1.1); 1.964 (19.3); 1.958 (39.4); 1.952 (183.7); 1.946 (324.8); 1.940 (428.5); 1.934 (292.1); 1.928 (148.2); 1.915 (2.4); 1.781 (1.0); 1.775 (1.8); 1.769 (2.4); 1.762 (1.7); 1.756 (0.8); 1.340 (0.4); 1.285 (0.6); 1.270 (1.8); 1.184 (0.4); 1.010 (0.3); 0.881 (0.4); 0.858 (0.5); 0.146 (2.1); 0.008 (22.6); 0.000 (492.7); -0.009 (16.9); -0.150 (2.0)
Example 93: ^-NM (400.0 MHz, CD3CN):
□□ 8.567 (10.8); 8.561 (16.0); 8.540 (15.9); 8.534 (10.1); 7.940 (1.7); 7.574 (4.9); 7.567 (4.9); 7.556
(4.1) ; 7.554 (4.1); 7.550 (6.2); 7.541 (0.4); 7.471 (2.8); 7.468 (3.6); 7.464 (3.2); 7.461 (1.9); 7.453 (4.5); 7.451 (4.3); 7.448 (5.2); 7.446 (5.1); 7.434 (0.6); 7.424 (1.3); 7.419 (2.3); 7.405 (7.3); 7.400 (6.5); 7.397 (8.1); 7.389 (14.4); 7.382 (5.1); 7.378 (5.5); 7.373 (4.2); 7.360 (1.3); 7.354 (0.9); 6.113
(2.5) ; 6.105 (2.6); 6.095 (2.7); 6.087 (2.5); 5.996 (2.5); 5.988 (2.6); 5.978 (2.7); 5.969 (2.5); 5.448
(1.3) ; 4.006 (1.4); 3.997 (1.4); 3.990 (1.4); 3.982 (1.4); 3.969 (2.3); 3.961 (2.3); 3.954 (2.3); 3.945
(2.2) ; 3.937 (1.3); 3.928 (1.3); 3.921 (1.3); 3.912 (1.3); 3.900 (2.4); 3.892 (2.4); 3.885 (2.4); 3.876
(2.4) ; 3.871 (2.4); 3.855 (2.7); 3.852 (2.9); 3.836 (2.6); 3.819 (3.4); 3.803 (3.1); 3.801 (3.6); 3.785
(2.6) ; 3.767 (1.5); 3.765 (1.6); 3.749 (1.2); 2.469 (0.8); 2.464 (1.1); 2.460 (0.8); 2.174 (213.0); 2.127 (0.4); 2.120 (0.7); 2.114 (1.0); 2.108 (1.2); 2.102 (0.9); 2.096 (0.5); 1.965 (8.1); 1.959 (17.2); 1.953 (78.9); 1.947 (139.7); 1.941 (182.0); 1.934 (123.1); 1.928 (62.3); 1.781 (0.5); 1.775 (0.8); 1.769 (1.1); 1.763 (0.7); 1.757 (0.4); 1.270 (1.1); 0.146 (1.0); 0.008 (11.1); 0.000 (238.5); -0.009 (8.2); -0.150 (1.0) Example 94: ^-NMR (400.0 MHz, CD3CN):
□□ 7.598 (4.9); 7.592 (5.4); 7.580 (5.0); 7.574 (6.3); 7.530 (13.3); 7.517 (14.3); 7.460 (4.0); 7.457
(3.5) ; 7.445 (4.5); 7.441 (6.3); 7.438 (5.6); 7.422 (2.0); 7.418 (2.5); 7.404 (6.6); 7.400 (6.0); 7.387
(9.3) ; 7.384 (9.5); 7.371 (5.3); 7.366 (4.6); 7.352 (1.9); 7.348 (1.5); 7.288 (0.4); 7.278 (0.4); 7.204 (16.0); 7.191 (14.4); 7.164 (0.4); 6.119 (2.4); 6.110 (2.6); 6.103 (2.6); 6.093 (2.4); 6.002 (2.4); 5.993
(2.6) ; 5.986 (2.7); 5.976 (2.4); 5.447 (6.0); 3.986 (0.8); 3.976 (1.0); 3.971 (0.9); 3.961 (0.9); 3.949
(2.4) ; 3.940 (2.5); 3.934 (2.5); 3.925 (2.5); 3.912 (3.0); 3.895 (4.3); 3.886 (2.8); 3.876 (3.8); 3.871 (3.0); 3.858 (4.3); 3.842 (4.8); 3.826 (2.7); 3.805 (1.3); 3.789 (0.8); 2.149 (171.2); 2.120 (1.0); 2.114 (1.2); 2.108 (1.4); 2.101 (1.0); 2.095 (1.0); 1.972 (1.4); 1.964 (8.4); 1.958 (17.9); 1.952 (84.3); 1.946 (151.2); 1.940 (199.1); 1.934 (137.0); 1.928 (70.4); 1.781 (0.5); 1.775 (0.9); 1.769 (1.2); 1.763 (0.8); 1.756 (0.4); 1.437 (0.4); 1.270 (0.4); 1.204 (0.4); 1.200 (0.5); 0.146 (1.2); 0.008 (11.7); 0.000 (273.2); - 0.008 (11.1); -0.150 (1.2)
Example 95: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.695 (3.5); 8.673 (3.6); 7.753 (6.7); 7.749 (7.1); 7.602 (4.3); 7.580 (8.8); 7.544 (5.6); 7.539 (5.3); 7.522 (2.8); 7.518 (2.8); 7.510 (1.5); 7.501 (1.5); 7.496 (3.0); 7.493 (2.2); 7.491 (2.3); 7.489 (2.0); 7.482 (2.1); 7.480 (2.1); 7.478 (2.4); 7.475 (3.2); 7.470 (1.8); 7.462 (1.6); 7.457 (1.6); 7.322 (2.0); 7.317 (2.2); 7.303 (4.2); 7.299 (4.3); 7.285 (3.6); 7.280 (3.1); 7.249 (3.7); 7.235 (4.7); 7.233 (5.5); 7.230 (3.7); 7.227 (4.0); 7.225 (4.5); 7.222 (4.0); 7.217 (6.9); 7.215 (6.5); 7.204 (3.0); 7.202 (3.2); 7.198 (3.5); 7.196 (2.5); 6.574 (0.7); 5.757 (1.2); 5.196 (0.7); 5.180 (1.0); 5.158 (1.2); 5.141 (1.3); 5.125 (1.2); 5.109 (0.9); 5.104 (1.1); 5.087 (0.7); 3.326 (56.8); 2.676 (0.3); 2.671 (0.5); 2.667 (0.3); 2.525 (1.1); 2.520 (1.7); 2.511 (26.2); 2.507 (54.7); 2.502 (72.5); 2.498 (51.7); 2.493 (24.4); 2.329 (0.4); 2.325 (0.3); 1.314 (16.0); 1.297 (15.8); 0.146 (0.7); 0.016 (0.4); 0.008 (6.2); 0.000 (166.3); -0.009 (5.9); -0.018 (0.4); -0.150 (0.7)
Example 96: :H-NMR (400.0 MHz, de-DMSO):
□□ 9.117 (3.8); 9.094 (3.9); 7.762 (7.3); 7.579 (2.1); 7.558 (13.0); 7.553 (10.2); 7.548 (8.1); 7.531 (1.3); 7.527 (1.5); 7.517 (1.2); 7.501 (2.5); 7.496 (2.2); 7.484 (1.7); 7.480 (4.6); 7.475 (1.7); 7.463
(2.3) ; 7.459 (2.7); 7.442 (1.2); 7.137 (1.3); 7.129 (7.8); 7.110 (10.1); 7.089 (6.6); 7.082 (1.2); 6.575 (0.8); 5.757 (1.3); 5.205 (0.7); 5.188 (1.1); 5.183 (0.9); 5.166 (1.2); 5.151 (1.2); 5.135 (1.3); 5.118 (1.0); 5.113 (1.2); 5.095 (0.7); 3.325 (38.4); 2.671 (0.5); 2.525 (1.2); 2.511 (27.5); 2.507 (55.8); 2.502 (73.0); 2.498 (51.6); 2.493 (24.1); 2.333 (0.3); 2.329 (0.5); 2.324 (0.3); 1.989 (0.3); 1.296 (16.0); 1.279 (15.7); 1.103 (0.4); 0.146 (0.7); 0.008 (5.5); 0.000 (151.8); -0.009 (5.4); -0.150 (0.7)
Example 97: ^-NMR (400.0 MHz, -DMSO):
□□ 8.822 (3.9); 8.800 (4.0); 7.771 (6.6); 7.766 (6.9); 7.631 (4.0); 7.610 (9.8); 7.605 (6.7); 7.602 (5.8); 7.582 (12.1); 7.579 (6.4); 7.562 (2.5); 7.557 (2.4); 7.411 (2.2); 7.408 (2.4); 7.393 (6.1); 7.390 (5.9); 7.374 (4.7); 7.371 (4.2); 7.347 (4.0); 7.342 (4.5); 7.328 (4.8); 7.323 (5.0); 7.309 (2.2); 7.304 (2.0); 7.089 (5.6); 7.085 (5.6); 7.071 (5.0); 7.066 (4.8); 6.574 (0.6); 5.177 (0.7); 5.161 (1.0); 5.139 (1.2); 5.122 (1.4); 5.106 (1.2); 5.089 (0.9); 5.084 (1.1); 5.067 (0.7); 3.324 (74.0); 2.675 (0.5); 2.671 (0.7);
2.666 (0.5); 2.541 (0.4); 2.524 (1.7); 2.511 (39.1); 2.506 (78.6); 2.502 (102.0); 2.497 (72.1); 2.493 (33.7); 2.333 (0.5); 2.328 (0.6); 2.324 (0.5); 1.398 (1.1); 1.317 (16.0); 1.300 (15.7); 0.146 (1.0); 0.021 (0.4); 0.008 (8.3); 0.000 (219.3); -0.009 (7.9); -0.150 (1.0)
Example 98: :H-NMR (400.0 MHz, -DMSO):
□□ 8.783 (4.1); 8.760 (4.2); 8.316 (1.8); 7.836 (6.0); 7.817 (6.4); 7.768 (6.8); 7.764 (7.2); 7.637 (3.9); 7.615 (9.4); 7.589 (6.1); 7.585 (5.8); 7.568 (2.4); 7.564 (2.5); 7.419 (3.0); 7.402 (6.1); 7.400 (6.0); 7.383 (3.5); 7.381 (3.4); 7.161 (2.9); 7.157 (3.1); 7.141 (4.9); 7.138 (5.1); 7.122 (2.5); 7.118 (2.5); 6.986 (5.2); 6.982 (5.1); 6.967 (4.9); 6.963 (4.6); 6.573 (0.7); 5.155 (0.7); 5.138 (1.1); 5.117 (1.3); 5.101 (1.3); 5.084 (1.3); 5.062 (1.1); 5.045 (0.7); 3.323 (210.7); 3.300 (1.1); 2.675 (1.4); 2.670 (1.9);
2.667 (1.4); 2.541 (1.0); 2.506 (227.9); 2.501 (292.1); 2.497 (211.9); 2.333 (1.4); 2.328 (1.9); 2.324
(1.4) ; 1.989 (0.4); 1.398 (4.1); 1.322 (16.0); 1.305 (15.8); 0.146 (2.4); 0.007 (27.3); 0.000 (481.5); - 0.009 (21.2); -0.150 (2.4)
Example 99: :H-NMR (400.0 MHz, de-DMSO):
□□ 9.041 (4.1); 9.018 (4.1); 8.036 (5.4); 8.034 (5.6); 8.016 (6.3); 8.013 (6.1); 7.780 (7.7); 7.775 (7.3); 7.765 (6.3); 7.763 (6.3); 7.747 (4.1); 7.744 (4.0); 7.694 (3.8); 7.690 (4.1); 7.674 (5.0); 7.670 (5.1); 7.655 (2.6); 7.651 (2.5); 7.640 (4.6); 7.619 (9.5); 7.584 (5.7); 7.579 (5.3); 7.563 (2.7); 7.558 (2.7); 7.261 (5.6); 7.258 (5.7); 7.243 (5.4); 7.239 (5.1); 5.757 (2.4); 5.152 (0.7); 5.134 (1.2); 5.112 (1.3); 5.099 (1.1); 5.095 (1.1); 5.082 (1.3); 5.060 (1.2); 5.042 (0.7); 4.186 (0.7); 4.168 (2.1); 4.150 (2.1); 4.133 (0.7); 4.056 (0.4); 4.038 (1.3); 4.020 (1.4); 4.003 (6.0); 3.326 (56.9); 2.675 (0.4); 2.671 (0.5); 2.667 (0.4); 2.541 (0.5); 2.524 (1.2); 2.511 (29.6); 2.507 (60.5); 2.502 (80.0); 2.498 (57.3); 2.493 (27.3); 2.333 (0.4); 2.329 (0.5); 2.324 (0.4); 1.989 (5.8); 1.303 (16.0); 1.286 (15.8); 1.233 (2.6); 1.216 (4.9); 1.198 (2.5); 1.193 (1.7); 1.175 (3.2); 1.157 (1.6); 0.146 (0.8); 0.016 (0.4); 0.008 (6.2); 0.000 (173.8); -0.009 (6.3); -0.150 (0.8)
Example 100: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.923 (4.0); 8.900 (4.0); 7.783 (6.7); 7.778 (7.1); 7.745 (4.1); 7.725 (5.8); 7.707 (1.9); 7.690 (4.9); 7.672 (3.7); 7.656 (4.6); 7.640 (4.3); 7.634 (10.0); 7.622 (4.5); 7.600 (6.8); 7.596 (5.5); 7.579 (2.7); 7.574 (2.7); 7.194 (5.0); 7.176 (4.6); 6.574 (1.1); 5.757 (0.9); 5.189 (0.7); 5.171 (1.2); 5.154 (1.1); 5.149 (1.2); 5.136 (1.1); 5.132 (1.1); 5.118 (1.3); 5.114 (1.1); 5.101 (1.0); 5.096 (1.2); 5.078 (0.7); 3.328 (111.7); 2.676 (0.4); 2.671 (0.5); 2.667 (0.4); 2.525 (1.2); 2.520 (2.0); 2.511 (29.7); 2.507 (61.9); 2.502 (82.0); 2.498 (58.3); 2.493 (27.2); 2.333 (0.4); 2.329 (0.5); 2.324 (0.4); 1.989 (0.6); 1.282 (16.0); 1.265 (15.9); 1.175 (0.4); 0.146 (0.8); 0.008 (6.8); 0.000 (195.2); -0.009 (6.9); -0.150 (0.8)
Example 101 : ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.085 (4.1); 9.063 (4.1); 8.783 (4.5); 8.774 (4.5); 8.772 (4.5); 8.105 (0.6); 8.090 (0.6); 7.798 (6.9); 7.794 (7.2); 7.775 (3.1); 7.763 (3.1); 7.756 (5.0); 7.744 (5.1); 7.690 (5.6); 7.673 (3.4); 7.671 (3.3); 7.650 (4.5); 7.629 (10.1); 7.600 (6.1); 7.595 (5.6); 7.579 (2.7); 7.574 (2.6); 6.596 (0.8); 6.579 (0.8); 5.757 (1.5); 5.191 (0.7); 5.173 (1.1); 5.151 (1.2); 5.141 (1.0); 5.133 (0.9); 5.122 (1.3); 5.101 (1.1); 5.082 (0.7); 4.056 (0.4); 4.039 (1.1); 4.021 (1.1); 4.003 (0.4); 3.326 (47.0); 2.949 (12.2); 2.676 (0.3); 2.672 (0.5); 2.668 (0.3); 2.525 (1.1); 2.512 (28.0); 2.507 (55.8); 2.503 (72.6); 2.498 (51.9); 2.494 (24.8); 2.334 (0.3); 2.330 (0.4); 1.990 (4.9); 1.286 (16.0); 1.269 (15.8); 1.193 (1.3); 1.176 (2.5); 1.158 (1.3); 1.064 (0.4); 1.047 (0.4); 0.146 (0.6); 0.008 (5.5); 0.000 (117.2); -0.009 (4.2); -0.150 (0.6) Example 102: ¾-NMR (400.0 MHz, CD3CN):
□□ 7.899 (7.3); 7.897 (7.3); 7.879 (7.9); 7.877 (7.8); 7.868 (0.8); 7.646 (0.4); 7.627 (0.5); 7.596 (5.0); 7.592 (5.5); 7.578 (5.9); 7.573 (6.5); 7.564 (0.8); 7.546 (0.8); 7.534 (1.1); 7.529 (1.1); 7.515 (1.3); 7.510 (1.4); 7.496 (0.3); 7.471 (4.9); 7.452 (8.5); 7.448 (7.1); 7.445 (7.9); 7.442 (7.2); 7.437 (2.1); 7.426 (16.0); 7.424 (13.2); 7.408 (12.7); 7.405 (9.3); 7.401 (7.9); 7.395 (7.7); 7.388 (2.8); 7.381 (6.6); 7.377 (5.9); 7.370 (1.8); 7.362 (3.6); 7.358 (3.5); 7.343 (1.6); 7.339 (1.8); 7.320 (1.2); 7.316 (0.9); 7.308 (0.8); 7.297 (8.0); 7.293 (8.4); 7.278 (6.4); 7.274 (6.4); 7.259 (0.9); 7.255 (0.9); 7.240 (0.6); 7.236 (0.6); 7.203 (0.4); 7.169 (4.5); 7.165 (4.5); 7.149 (6.7); 7.146 (6.4); 7.130 (4.0); 7.126 (3.8); 7.050 (2.8); 7.030 (3.5); 7.009 (1.8); 6.119 (2.4); 6.110 (2.5); 6.101 (2.6); 6.093 (2.4); 6.072 (0.3); 6.054 (0.3); 6.046 (0.3); 6.002 (2.4); 5.993 (2.5); 5.984 (2.6); 5.976 (2.5); 5.956 (0.3); 5.946 (0.8); 5.937 (0.7); 5.929 (0.8); 5.918 (0.5); 5.826 (0.5); 5.812 (0.8); 5.798 (0.5); 5.447 (0.4); 4.550 (1.9); 3.970 (1.4); 3.962 (1.4); 3.955 (1.5); 3.946 (1.5); 3.934 (2.3); 3.925 (2.3); 3.918 (2.3); 3.910 (2.2); 3.902 (1.4); 3.894 (1.4); 3.887 (1.5); 3.878 (1.5); 3.866 (2.4); 3.857 (2.3); 3.850 (2.5); 3.842 (2.2); 3.829 (2.3); 3.813 (3.0); 3.796 (2.6); 3.793 (1.8); 3.775 (4.0); 3.760 (4.4); 3.742 (2.5); 3.739 (1.6); 3.723 (1.7); 3.706 (1.3); 3.019 (1.2); 3.014 (1.4); 3.010 (1.1); 2.996 (1.1); 2.952 (1.6); 2.937 (2.4); 2.867 (0.4); 2.851 (0.9); 2.836 (1.2); 2.820 (0.9); 2.804 (0.4); 2.140 (182.7); 2.120 (2.6); 2.113 (2.5); 2.107 (2.7); 2.101 (1.8); 2.095 (1.1); 1.964 (13.7); 1.958 (27.8); 1.952 (143.6); 1.946 (257.8); 1.940 (341.6); 1.933 (232.9); 1.927 (119.2); 1.780 (0.9); 1.774 (1.5); 1.768 (2.1); 1.762 (1.4); 1.756 (0.8); 1.268 (0.4); 1.022 (8.3); 1.017 (8.4); 1.007 (8.2); 1.002 (8.2); 0.146 (1.1); 0.008 (8.8); 0.000 (268.3); - 0.009 (8.9); -0.150 (1.2)
Example 103: ¾-NMR (400.0 MHz, CD3CN):
□□ 8.832 (16.0); 7.861 (0.9); 7.577 (2.2); 7.571 (2.2); 7.558 (2.0); 7.554 (2.9); 7.471 (1.7); 7.467 (1.5); 7.451 (2.6); 7.425 (0.6); 7.421 (1.0); 7.407 (3.2); 7.402 (3.2); 7.399 (3.8); 7.391 (6.3); 7.383 (2.6) 7.381 (2.7); 7.375 (2.0); 7.362 (0.6); 7.357 (0.5); 6.109 (1.1); 6.101 (1.2); 6.090 (1.2); 6.082 (1.2) 5.991 (1.1); 5.983 (1.2); 5.972 (1.2); 5.964 (1.2); 5.447 (1.0); 4.036 (0.6); 4.027 (0.7); 4.020 (0.6) 4.012 (0.6); 3.999 (1.0); 3.991 (1.0); 3.983 (1.0); 3.975 (0.9); 3.964 (0.7); 3.956 (0.6); 3.948 (0.7) 3.940 (0.6); 3.928 (1.0); 3.920 (1.0); 3.912 (1.0); 3.904 (1.0); 3.860 (0.9); 3.844 (1.1); 3.841 (1.1) 3.825 (1.2); 3.809 (1.4); 3.805 (0.9); 3.794 (1.3); 3.790 (1.4); 3.775 (1.2); 3.757 (0.7); 3.754 (0.7) 3.738 (0.6); 2.142 (96.9); 2.120 (0.7); 2.114 (0.8); 2.107 (0.9); 2.101 (0.6); 1.964 (4.9); 1.958 (10. 5); 1.952 (49.1); 1.946 (87.7); 1.940 (115.6); 1.934 (79.1); 1.928 (40.5); 1.774 (0.5); 1.768 (0.7); 1.7C »2 (0.5); 0.963 (0.4); 0.946 (0.4); 0.146 (0.5); 0.008 (3.9); 0.000 (103.2); -0.008 (3.9); -0.150 (0.5)
Example 104: ¾-NMR (400.0 MHz, CD3CN):
□□ 7.628 (7.7); 7.610 (6.7); 7.608 (7.4); 7.592 (5.4); 7.587 (5.3); 7.573 (6.1); 7.569 (6.2); 7.532 ( 0.5); 7.517 (0.6); 7.470 (4.4); 7.454 (5.1); 7.451 (7.5); 7.448 (5.6); 7.443 (3.1); 7.439 (3.2); 7.424 (8.2) 7.420 (7.8); 7.405 (9.8); 7.401 (16.0); 7.396 (7.5); 7.385 (9.3); 7.382 (11.8); 7.377 (5.5); 7.363 (2. 5); 7.358 (2.4); 7.348 (12.5); 7.346 (11.6); 7.344 (10.8); 7.339 (2.8); 7.332 (5.4); 7.327 (9.9); 7.322 1.7); 7.321 (4.8); 7.308 (3.4); 7.303 (3.0); 7.297 (0.8); 7.114 (1.9); 6.106 (2.3); 6.098 (2.5); 6.089 (2.6) 6.080 (2.4); 5.989 (2.3); 5.980 (2.4); 5.972 (2.6); 5.963 (2.4); 5.448 (0.5); 4.543 (1.5); 3.965 (1.2) 3.956 (1.3); 3.949 (1.2); 3.940 (1.3); 3.928 (2.3); 3.919 (2.3); 3.913 (2.3); 3.904 (2.3); 3.898 (1.2) 3.889 (1.2); 3.882 (1.2); 3.874 (1.2); 3.861 (2.5); 3.852 (4.3); 3.846 (2.7); 3.836 (4.7); 3.819 (2.4) 3.815 (1.5); 3.798 (4.1); 3.782 (4.6); 3.765 (2.5); 3.745 (1.8); 3.728 (1.2); 3.038 (0.4); 2.969 (0.4) 2.956 (0.5); 2.474 (0.8); 2.469 (1.5); 2.464 (2.1); 2.460 (1.4); 2.455 (0.7); 2.172 (557.9); 2.120 (1. 8); 2.114 (2.4); 2.108 (2.9); 2.102 (2.0); 2.095 (1.2); 1.965 (18.2); 1.959 (39.1); 1.953 (177.8); 1.947 (315.9); 1.940 (413.7); 1.934 (281.0); 1.928 (141.9); 1.876 (0.4); 1.781 (1.1); 1.775 (1.8); 1.769 (. 1.763 (1.7); 1.756 (0.9); 1.436 (0.4); 1.269 (1.7); 1.039 (2.0); 1.033 (2.1); 1.023 (2.0); 1.018 (2.0) 0.146 (1.3); 0.096 (0.6); 0.008 (13.7); 0.000 (319.9); -0.009 (10.9); -0.150 (1.4)
Example 105: ¾-NMR (400.0 MHz, CD3CN):
□□ 7.757 (7.1); 7.738 (9.3); 7.687 (2.9); 7.668 (8.0); 7.650 (6.2); 7.627 (6.1); 7.608 (7.2); 7.589 (2.6); 7.555 (11.7); 7.552 (10.0); 7.547 (12.5); 7.535 (16.0); 7.464 (9.1); 7.456 (10.0); 7.451 (10.6); 7.435 (6.1); 7.430 (5.7); 7.408 (0.3); 7.139 (2.8); 6.050 (3.1); 6.042 (3.3); 6.033 (3.3); 6.025 (3.2); 5.934 (3.1); 5.925 (3.2); 5.917 (3.3); 5.908 (3.1); 5.448 (0.8); 3.960 (1.5); 3.952 (1.6); 3.945 (1.5); 3.936 (1.5); 3.924 (2.5); 3.915 (2.6); 3.908 (2.6); 3.900 (2.5); 3.894 (1.7); 3.885 (1.5); 3.879 (1.6); 3.870 (1.5); 3.857 (2.6); 3.849 (2.6); 3.842 (2.7); 3.833 (2.5); 3.822 (2.5); 3.805 (4.2); 3.789 (2.6); 3.767 (3.8); 3.750 (4.7); 3.733 (2.6); 3.713 (2.5); 3.697 (1.4); 2.463 (0.7); 2.149 (238.8); 2.120 (1.3); 2.114 (1.7); 2.108 (1.9); 2.102 (1.3); 2.096 (0.8); 1.965 (10.5); 1.958 (24.2); 1.953 (120.9); 1.947 (218.4); 1.940 (292.7); 1.934 (203.3); 1.928 (106.0); 1.781 (0.7); 1.775 (1.3); 1.769 (1.7); 1.763 (1.2); 1.757 (0.6); 1.285 (0.4); 1.269 (0.7); 0.146 (0.7); 0.008 (5.7); 0.000 (153.1); -0.150 (0.8)
Example 106: ¾-NMR (400.0 MHz, CD3CN):
□□ 7.896 (6.1); 7.876 (7.0); 7.859 (0.4); 7.584 (0.4); 7.565 (7.3); 7.544 (16.0); 7.453 (6.3); 7.447 (7.1); 7.432 (4.8); 7.427 (10.2); 7.408 (4.4); 7.406 (4.4); 7.294 (5.9); 7.290 (6.5); 7.275 (4.7); 7.272 (4.8); 7.169 (3.4); 7.165 (3.4); 7.149 (5.3); 7.146 (5.2); 7.131 (2.9); 7.126 (2.8); 7.022 (1.8); 6.083 (2.1); 6.075 (2.2); 6.067 (2.3); 6.058 (2.1); 5.967 (2.0); 5.958 (2.2); 5.951 (2.3); 5.942 (2.1); 5.447 (1.0); 3.946 (0.9); 3.937 (0.9); 3.931 (1.0); 3.922 (0.9); 3.910 (2.0); 3.901 (2.0); 3.894 (2.0); 3.885 (2.0); 3.874 (1.0); 3.867 (1.0); 3.858 (1.1); 3.853 (2.0); 3.846 (2.2); 3.837 (5.5); 3.831 (2.4); 3.821 (3.6); 3.800 (1.9); 3.796 (2.2); 3.780 (3.7); 3.764 (1.9); 3.743 (1.6); 3.727 (0.8); 2.135 (175.1); 2.114 (2.7); 2.107 (2.8); 2.101 (2.0); 2.095 (1.1); 1.964 (15.4); 1.958 (34.8); 1.952 (162.5); 1.946 (291.3); 1.940 (387.4); 1.934 (268.0); 1.928 (138.9); 1.781 (0.9); 1.775 (1.7); 1.768 (2.2); 1.762 (1.6); 1.756 (0.8); 1.269 (0.6); 0.146 (0.9); 0.008 (8.8); 0.000 (198.0); -0.008 (9.3); -0.149 (0.9)
Example 107: ¾-NMR (400.0 MHz, CD3CN):
□□ 7.629 (4.8); 7.626 (5.7); 7.608 (5.0); 7.606 (4.6); 7.589 (0.4); 7.561 (5.1); 7.545 (5.6); 7.540 (13.0); 7.522 (4.0); 7.451 (4.6); 7.447 (3.6); 7.430 (3.1); 7.425 (3.3); 7.419 (1.9); 7.406 (2.4); 7.401 (5.3); 7.385 (4.6); 7.382 (4.0); 7.345 (9.8); 7.343 (9.1); 7.327 (7.4); 7.326 (6.3); 7.324 (5.6); 7.308 (2.0); 7.303 (1.5); 7.262 (1.4); 7.235 (1.4); 7.094 (1.3); 6.072 (1.5); 6.062 (1.6); 6.056 (1.6); 6.047 (1.5); 5.956 (1.5); 5.946 (1.6); 5.940 (1.6); 5.931 (1.5); 5.448 (0.9); 3.943 (0.6); 3.933 (0.6); 3.927 (0.6); 3.918 (0.7); 3.906 (1.6); 3.897 (1.6); 3.891 (1.6); 3.881 (1.7); 3.871 (2.0); 3.865 (0.7); 3.855 (3.5); 3.843 (2.0); 3.839 (2.0); 3.834 (2.2); 3.828 (1.8); 3.819 (2.8); 3.814 (1.8); 3.798 (3.1); 3.782 (1.5); 3.761 (1.0); 3.746 (0.5); 3.697 (1.8); 3.679 (2.9); 3.605 (1.3); 3.580 (3.7); 3.555 (3.7); 3.530 (1.3); 3.484 (1.7); 3.257 (16.0); 2.901 (0.5); 2.890 (0.5); 2.773 (0.4); 2.510 (10.7); 2.475 (0.7); 2.470 (1.3); 2.465 (1.7); 2.460 (1.2); 2.170 (845.5); 2.127 (1.2); 2.120 (1.9); 2.1 14 (2.5); 2.108 (3.1); 2.102 (2.2); 2.096 (1.3); 2.073 (0.4); 1.965 (17.2); 1.959 (43.3); 1.953 (195.3); 1.947 (347.1); 1.941 (452.4); 1.935 (312.6); 1.928 (160.9); 1.781 (1.2); 1.775 (2.0); 1.769 (2.8); 1.763 (1.9); 1.757 (1.0); 1.271 (0.6); 0.146 (0.9); 0.008 (10.6); 0.000 (239.8); -0.009 (11.2); -0.042 (0.3); -0.150 (1.0)
Example 108: ¾-NMR (400.0 MHz, CD3CN):
□□ 7.553 (9.2); 7.543 (7.9); 7.538 (10.8); 7.533 (16.0); 7.454 (2.9); 7.446 (8.5); 7.441 (8.1); 7.436 (10.1); 7.432 (11.4); 7.430 (12.4); 7.424 (9.7); 7.420 (6.2); 7.414 (6.4); 7.408 (8.3); 7.397 (2.7); 7.392 (5.7); 7.388 (5.7); 7.380 (12.8); 7.374 (8.0); 7.371 (11.0); 7.368 (6.1); 7.366 (5.9); 7.355 (4.8); 7.351
(5.5) ; 7.347 (2.1); 7.335 (1.4); 7.332 (1.6); 7.097 (2.1); 6.069 (2.6); 6.059 (2.9); 6.054 (3.0); 6.044
(2.6) ; 5.953 (2.5); 5.943 (2.9); 5.938 (3.0); 5.928 (2.6); 5.447 (1.0); 3.941 (0.5); 3.931 (0.7); 3.925 (0.6); 3.915 (0.7); 3.904 (3.2); 3.894 (3.8); 3.890 (5.3); 3.879 (4.1); 3.875 (6.0); 3.864 (0.9); 3.859
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
7.569 (2.7); 7.506 (1.5); 7.489 (3.1); 7.485 (3.4); 7.468 (6.1); 7.452 (3.4); 7.447 (3.8); 7.431 (1.7); 7.324 (2.4); 7.061 (9.7); 7.041 (16.0); 7.021 (8.5); 6.042 (2.2); 6.029 (2.2); 5.923 (2.2); 5.912 (2.2); 3.936 (0.9); 3.927 (1.1); 3.920 (1.0); 3.912 (1.0); 3.899 (2.1); 3.890 (2.2); 3.884 (2.3); 3.875 (2.1); 3.865 (0.9); 3.856 (1.0); 3.847 (2.6); 3.828 (4.9); 3.819 (2.9); 3.812 (4.9); 3.804 (2.8); 3.797 (3.1); 3.780 (3.4); 3.763 (2.4); 3.743 (1.1); 3.727 (0.8); 2.140 (141.7); 2.114 (1.5); 2.108 (1.5); 2.102 (1.1); 1.952 (86.9); 1.946 (150.8); 1.940 (195.7); 1.934 (140.8); 1.928 (75.6); 1.781 (0.5); 1.775 (0.9); 1.769 (1.1); 1.763 (0.8); 1.269 (0.5); 0.146 (0.9); 0.000 (174.7); -0.150 (0.9)
Example 132: ¾-NMR (400.0 MHz, CD3CN):
□□ 8.018 (6.9); 7.997 (7.5); 7.809 (5.3); 7.791 (16.0); 7.770 (14.4); 7.750 (14.5); 7.731 (8.0); 7.674
(5.1) ; 7.654 (7.1); 7.635 (3.3); 7.613 (4.5); 7.594 (6.5); 7.574 (3.3); 7.555 (8.1); 7.537 (6.5); 7.347 (3.4); 6.081 (2.8); 6.063 (2.6); 5.962 (2.7); 5.944 (2.6); 5.448 (3.1); 3.957 (1.2); 3.950 (1.4); 3.941 (1.4); 3.934 (1.4); 3.921 (1.8); 3.914 (2.0); 3.905 (2.0); 3.898 (1.9); 3.881 (1.3); 3.875 (1.4); 3.865 (1.4); 3.858 (1.4); 3.844 (1.9); 3.838 (2.1); 3.828 (2.1); 3.821 (1.8); 3.771 (1.5); 3.752 (2.1); 3.736 (2.4); 3.723 (2.5); 3.709 (2.7); 3.704 (2.7); 3.688 (2.3); 3.667 (1.4); 3.652 (1.0); 2.149 (198.9); 2.146 (196.5); 1.952 (81.7); 1.946 (127.4); 1.941 (152.3); 1.936 (119.1); 1.769 (0.9); 1.270 (0.7); 1.220 (0.4); 1.204 (0.5); 0.146 (0.5); 0.000 (84.3); -0.150 (0.4)
Example 133: ¾-NMR (400.0 MHz, CD3CN):
□□ 8.447 (8.0); 8.443 (8.3); 8.435 (8.3); 8.431 (8.1); 7.821 (9.6); 7.817 (10.9); 7.812 (5.8); 7.803 (11.1); 7.798 (12.8); 7.791 (16.0); 7.768 (12.5); 7.747 (7.7); 7.728 (3.2); 7.611 (4.4); 7.592 (6.9); 7.573
(3.0) ; 7.418 (9.6); 7.406 (9.7); 7.399 (9.0); 7.387 (8.5); 7.302 (2.3); 6.085 (2.1); 6.080 (2.2); 6.066
(2.2) ; 5.968 (2.1); 5.962 (2.1); 5.948 (2.1); 5.448 (6.5); 4.068 (0.4); 4.049 (0.4); 3.941 (1.1); 3.933 (1.2); 3.926 (1.2); 3.918 (1.2); 3.905 (2.4); 3.896 (2.4); 3.889 (2.4); 3.881 (2.3); 3.870 (1.0); 3.861
(1.1) ; 3.854 (1.1); 3.841 (2.7); 3.833 (2.9); 3.824 (5.0); 3.817 (3.1); 3.808 (4.5); 3.792 (3.1); 3.786 (1.7); 3.776 (3.2); 3.773 (3.3); 3.758 (2.8); 3.737 (1.2); 3.721 (1.0); 2.463 (0.5); 2.153 (317.7); 2.120 (1.4); 2.114 (1.9); 2.108 (2.4); 2.101 (1.6); 2.095 (0.9); 1.972 (3.2); 1.964 (12.7); 1.958 (31.4); 1.953 (150.7); 1.946 (269.4); 1.940 (355.2); 1.934 (242.1); 1.928 (122.5); 1.781 (0.8); 1.775 (1.5); 1.769 (2.0); 1.763 (1.4); 1.756 (0.7); 1.268 (1.1); 1.221 (0.5); 1.203 (0.9); 1.186 (0.5); 0.146 (1.7); 0.008 (15.6); -0.001 (374.2); -0.009 (13.9); -0.150 (1.6)
Example 134: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.957 (4.1); 8.934 (4.2); 7.786 (7.0); 7.782 (7.2); 7.696 (3.8); 7.689 (4.0); 7.672 (3.8); 7.666 (3.9); 7.648 (4.8); 7.627 (9.3); 7.606 (1.9); 7.599 (1.8); 7.586 (8.7); 7.564 (4.6); 7.301 (3.2); 7.288 (3.5); 7.280 (3.0); 7.267 (2.8); 6.576 (1.4); 5.759 (1.0); 5.175 (0.7); 5.158 (1.2); 5.136 (1.2); 5.123 (1.1); 5.106 (1.3); 5.084 (1.1); 5.066 (0.7); 3.330 (141.5); 2.676 (0.7); 2.672 (0.9); 2.667 (0.7); 2.525 (2.7); 2.511 (58.7); 2.507 (115.4); 2.503 (149.3); 2.498 (106.6); 2.334 (0.7); 2.329 (0.9); 2.325 (0.7); 1.278 (16.0); 1.260 (15.9); 1.235 (0.5); 0.008 (0.6); 0.000 (17.4); -0.008 (0.6)
Example 135: ¾-NMR (400.0 MHz, CD3CN):
□□ 8.766 (8.1); 8.756 (8.3); 7.904 (7.7); 7.884 (9.3); 7.804 (5.0); 7.787 (13.6); 7.773 (16.0); 7.753
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
6.965 (3.7); 6.958 (0.6); 5.448 (4.3); 4.209 (0.5); 4.193 (0.5); 4.172 (1.8); 4.156 (1.7); 4.141 (2.4); 4.125 (2.4); 4.104 (2.6); 4.088 (3.0); 4.085 (2.6); 4.069 (2.2); 4.048 (0.5); 4.033 (0.5); 2.167 (65.1); 2.114 (0.3); 2.108 (0.4); 1.972 (0.5); 1.965 (2.4); 1.959 (6.0); 1.953 (30.3); 1.947 (54.2); 1.941 (71.6); 1.935 (48.7); 1.929 (24.6); 1.876 (15.8); 1.815 (16.0); 1.769 (0.4); 1.437 (0.7); 0.146 (0.3); 0.008 (3.1); 0.000 (83.6); -0.009 (2.8); -0.150 (0.3)
Example 147: ¾-NMR (400.0 MHz, CD3CN):
□□ 7.957 (2.9); 7.955 (2.7); 7.937 (3.3); 7.934 (3.1); 7.700 (1.4); 7.697 (1.4); 7.681 (3.7); 7.678 (3.5); 7.663 (2.6); 7.659 (2.3); 7.629 (6.0); 7.623 (2.7); 7.607 (8.8); 7.588 (1.4); 7.584 (1.2); 7.531 (3.4); 7.529 (3.8); 7.526 (4.0); 7.524 (3.4); 7.415 (3.5); 7.409 (3.3); 7.393 (2.9); 7.388 (2.7); 7.344 (3.3); 7.340 (3.2); 7.325 (2.9); 7.322 (2.7); 7.097 (0.9); 5.448 (9.1); 4.207 (0.8); 4.190 (0.8); 4.170 (1.7); 4.154 (1.6); 4.137 (0.7); 4.121 (0.7); 4.108 (2.0); 4.101 (1.9); 4.093 (2.0); 4.085 (1.8); 4.072 (1.0); 4.055 (2.4); 4.039 (2.0); 4.018 (0.8); 4.003 (0.8); 2.159 (39.9); 1.972 (1.1); 1.965 (1.4); 1.959 (3.3); 1.953 (16.7); 1.947 (30.3); 1.941 (40.4); 1.934 (27.7); 1.928 (14.1); 1.898 (15.9); 1.837 (16.0); 1.436 (4.2); 1.204 (0.5); 0.008 (1.4); 0.000 (37.3); -0.009 (1.5)
Example 148: ¾-NMR (400.0 MHz, CD3CN):
□□ 8.396 (2.7); 8.391 (2.8); 8.384 (2.8); 8.379 (2.7); 7.644 (3.2); 7.639 (3.3); 7.625 (7.0); 7.620 (4.1); 7.603 (5.9); 7.529 (2.8); 7.527 (3.3); 7.524 (3.5); 7.521 (3.1); 7.409 (3.3); 7.403 (3.1); 7.387 (2.7); 7.382 (2.5); 7.358 (3.3); 7.346 (3.2); 7.339 (2.9); 7.327 (2.8); 7.040 (0.7); 4.306 (1.0); 4.289 (1.0); 4.269 (1.3); 4.252 (1.3); 4.232 (1.0); 4.215 (1.0); 4.196 (1.4); 4.179 (1.3); 4.058 (1.6); 4.043 (1.6); 4.021 (1.3); 4.007 (2.8); 3.992 (1.7); 3.970 (1.2); 3.956 (1.2); 2.469 (0.4); 2.465 (0.5); 2.460 (0.4); 2.165 (160.5); 2.136 (0.5); 2.120 (0.6); 2.114 (0.8); 2.108 (1.0); 2.102 (0.8); 2.096 (0.4); 1.965 (5.1); 1.959 (12.2); 1.953 (65.8); 1.947 (119.2); 1.941 (158.6); 1.935 (108.1); 1.929 (55.1); 1.915 (0.9); 1.898 (16.0); 1.837 (15.9); 1.781 (0.4); 1.775 (0.7); 1.769 (0.9); 1.763 (0.6); 1.757 (0.4); 0.146 (0.7); 0.019 (0.4); 0.008 (5.9); 0.000 (181.5); -0.009 (6.0); -0.149 (0.7)
Example 149: ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.024 (4.5); 9.010 (8.6); 8.994 (4.4); 8.316 (0.9); 8.035 (0.3); 7.831 (0.4); 7.819 (0.4); 7.805 (0.3); 7.767 (9.8); 7.747 (13.4); 7.726 (4.6); 7.708 (11.3); 7.689 (8.3); 7.674 (3.9); 7.658 (13.0); 7.637 (16.0); 7.616 (5.0); 7.515 (0.4); 7.512 (0.3); 7.482 (3.8); 7.477 (3.8); 7.454 (7.5); 7.430 (3.9); 7.427 (3.8); 7.363 (11.9); 7.345 (10.6); 7.249 (4.2); 7.227 (7.9); 7.207 (3.8); 4.151 (0.3); 4.111 (5.2); 4.095 (5.3); 4.076 (11.2); 4.060 (11.0); 4.040 (6.0); 4.024 (5.4); 3.517 (0.3); 3.474 (0.5); 3.466 (0.4); 3.441 (0.5); 3.427 (1.0); 3.403 (1.0); 3.392 (1.7); 3.385 (1.6); 3.372 (2.9); 3.337 (1532.0); 3.297 (1.7); 3.275 (0.7); 3.266 (0.6); 3.256 (0.7); 3.221 (0.7); 3.216 (0.7); 3.168 (0.3); 3.152 (0.4); 2.711 (1.7); 2.671 (3.6); 2.638 (0.3); 2.609 (0.4); 2.596 (0.7); 2.579 (0.7); 2.542 (349.9); 2.506 (480.8); 2.502 (607.2); 2.498 (460.4); 2.432 (0.7); 2.383 (0.5); 2.368 (1.9); 2.333 (3.0); 2.329 (3.8); 2.304 (0.4); 2.291 (0.3); 2.270 (0.3); 1.299 (0.5); 1.297 (0.6); 1.259 (0.7); 1.235 (3.3); 0.146 (0.5); 0.000 (75.7); -0.149 (0.3) Example 150: ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.167 (0.4); 9.137 (2.8); 9.121 (5.3); 9.106 (2.6); 8.316 (1.2); 7.780 (6.2); 7.762 (8.4); 7.751 (3.2);
Figure imgf000135_0001
Figure imgf000136_0001
7.521 (3.8); 7.517 (3.4); 7.500 (7.0); 7.483 (3.9); 7.479 (5.9); 7.472 (2.8); 7.463 (2.3); 7.448 (4.9); 7.425 (2.4); 7.419 (2.4); 7.241 (2.8); 7.236 (2.7); 7.220 (5.1); 7.215 (4.8); 7.199 (2.6); 7.194 (2.4); 7.162 (2.1); 7.155 (11.6); 7.136 (16.0); 7.115 (9.6); 7.108 (1.9); 4.136 (3.6); 4.121 (3.6); 4.101 (7.8); 4.085 (7.6); 4.066 (4.0); 4.050 (3.7); 3.333 (353.0); 3.306 (0.4); 3.290 (0.4); 2.711 (0.5); 2.676 (1.0); 2.671 (1.5); 2.667 (1.1); 2.560 (0.4); 2.542 (144.5); 2.525 (4.1); 2.51 1 (92.4); 2.507 (185.8); 2.502 (240.3); 2.498 (171.5); 2.493 (81.0); 2.455 (0.5); 2.447 (0.4); 2.441 (0.4); 2.368 (0.5); 2.333 (1.1); 2.329 (1.5); 2.325 (1.1); 2.008 (0.4); 1.989 (0.4); 1.298 (0.3); 1.258 (0.7); 1.235 (2.4); 0.854 (0.6); 0.008 (2.5); 0.000 (78.9); -0.009 (2.8)
Example 159: ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.017 (3.9); 9.002 (8.0); 8.985 (3.9); 7.882 (1 1.4); 7.880 (12.4); 7.872 (2.9); 7.861 (13.6); 7.859
(13.3) ; 7.466 (5.8); 7.463 (5.9); 7.447 (13.2); 7.445 (12.2); 7.428 (7.8); 7.426 (7.6); 7.389 (8.9); 7.365 (16.0); 7.341 (8.6); 7.194 (4.4); 7.190 (10.1); 7.183 (13.0); 7.179 (14.1); 7.173 (12.7); 7.164 (12.0); 7.160 (1 1.8); 7.155 (8.6); 7.150 (4.1); 4.086 (4.4); 4.070 (4.6); 4.052 (9.9); 4.036 (9.6); 4.017 (5.1); 4.001 (4.7); 3.375 (0.3); 3.333 (369.6); 3.314 (1.6); 3.302 (0.6); 2.71 1 (0.4); 2.680 (0.5); 2.676 (1.0); 2.671 (1.3); 2.667 (1.0); 2.542 (80.5); 2.524 (3.3); 2.511 (80.7); 2.507 (166.6); 2.502 (220.3); 2.498 (156.5); 2.493 (73.5); 2.368 (0.4); 2.338 (0.5); 2.334 (1.0); 2.329 (1.3); 2.324 (1.0); 1.235 (1.9); 0.008 (1.2); 0.000 (38.4); -0.009 (1.2)
Example 160: ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.192 (4.2); 9.177 (8.4); 9.161 (4.2); 8.033 (12.3); 8.013 (14.0); 7.798 (5.4); 7.796 (4.9); 7.780
(13.4) ; 7.777 (11.8); 7.761 (9.0); 7.758 (7.6); 7.710 (8.1); 7.706 (8.0); 7.689 (12.5); 7.687 (13.3); 7.670 (9.2); 7.667 (9.5); 7.648 (7.5); 7.626 (3.6); 7.484 (3.7); 7.478 (3.8); 7.455 (7.3); 7.426 (16.0); 7.407
(1 1.6) ; 7.404 (10.4); 7.246 (4.0); 7.242 (3.9); 7.225 (7.6); 7.220 (7.1); 7.203 (3.9); 7.199 (3.5); 5.326 (0.4); 4.114 (5.1); 4.099 (5.2); 4.079 (1 1.0); 4.063 (10.7); 4.043 (5.6); 4.028 (5.4); 3.370 (0.4); 3.331 (231.3); 3.304 (0.8); 2.711 (0.4); 2.671 (1.5); 2.542 (87.6); 2.506 (202.2); 2.502 (252.3); 2.498 (180.8); 2.443 (0.4); 2.368 (0.4); 2.329 (1.6); 2.008 (0.6); 1.990 (0.6); 1.972 (0.4); 1.237 (3.1); 0.870 (0.3); 0.854 (0.8); 0.837 (0.4); 0.000 (53.9); -0.009 (2.2)
Example 161 : ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.324 (4.4); 9.309 (8.3); 9.294 (4.2); 8.034 (1 1.2); 8.014 (12.4); 7.819 (5.1); 7.802 (1 1.6); 7.800
(1 1.7) ; 7.783 (7.6); 7.724 (7.1); 7.721 (7.6); 7.702 (10.5); 7.685 (4.6); 7.682 (4.4); 7.436 (11.3); 7.434 (1 1.7); 7.418 (10.7); 7.415 (10.6); 7.393 (9.0); 7.369 (16.0); 7.345 (8.6); 4.1 15 (4.7); 4.100 (5.1); 4.081 (10.3); 4.065 (10.1); 4.046 (5.4); 4.030 (4.9); 3.387 (0.3); 3.331 (189.3); 2.671 (1.5); 2.542 (71.9); 2.506 (193.7); 2.502 (244.4); 2.498 (190.8); 2.368 (0.4); 2.329 (1.5); 2.009 (0.6); 1.990 (0.6); 1.975 (0.4); 1.235 (3.1); 0.869 (0.3); 0.854 (0.8); 0.836 (0.4); 0.000 (50.2)
Example 162: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.945 (3.4); 8.929 (6.9); 8.914 (3.5); 7.685 (2.9); 7.668 (3.7); 7.663 (6.3); 7.647 (6.3); 7.642 (4.1); 7.630 (10.4); 7.628 (11.7); 7.61 1 (11.5); 7.608 (11.5); 7.478 (2.9); 7.473 (3.1); 7.450 (6.0); 7.428 (6.8); 7.421 (3.7); 7.412 (10.6); 7.409 (10.7); 7.393 (8.1); 7.390 (7.6); 7.365 (6.6); 7.361 (7.7); 7.346 (8.3); 7.341 (9.1); 7.327 (3.7); 7.322 (3.5); 7.242 (3.4); 7.237 (3.5); 7.224 (14.3); 7.220 (16.0); 7.205 (9.5); 7.201 (11.0); 4.104 (4.2); 4.088 (4.3); 4.069 (9.2); 4.053 (9.0); 4.034 (4.7); 4.018 (4.5); 3.333 (112.2); 2.712 (0.4); 2.676 (0.5); 2.671 (0.7); 2.558 (0.5); 2.542 (106.5); 2.524 (2.1); 2.507 (87.4); 2.502 (114.7); 2.498 (83.9); 2.368 (0.4); 2.333 (0.5); 2.329 (0.7); 2.325 (0.6); 1.258 (0.3); 1.235 (1.2); 0.008 (1.0); 0.000 (27.1); -0.009 (1.1)
Example 163: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.894 (2.1); 8.878 (4.1); 8.862 (2.1); 8.317 (1.0); 7.861 (6.4); 7.842 (6.5); 7.698 (1.7); 7.676 (3.6); 7.660 (3.6); 7.654 (2.3); 7.638 (1.9); 7.473 (1.9); 7.467 (1.9); 7.444 (4.1); 7.439 (5.3); 7.420 (8.6); 7.401 (4.0); 7.399 (3.7); 7.257 (0.4); 7.240 (2.1); 7.219 (3.8); 7.213 (3.6); 7.197 (1.9); 7.192 (1.8); 7.177 (2.7); 7.173 (4.1); 7.154 (16.0); 7.135 (11.5); 4.093 (2.5); 4.077 (2.6); 4.058 (5.6); 4.042 (5.2); 4.023 (2.8); 4.007 (2.6); 3.328 (403.1); 2.676 (1.7); 2.671 (2.4); 2.667 (1.7); 2.524 (6.1); 2.511 (139.0); 2.507 (284.6); 2.502 (375.6); 2.498 (270.7); 2.493 (131.5); 2.333 (1.8); 2.329 (2.4); 2.324 (1.8); 2.040 (0.4); 1.398 (0.4); 0.146 (0.3); 0.008 (2.4); 0.000 (75.7); -0.008 (2.8); -0.150 (0.4)
Example 164: ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.064 (3.1); 9.049 (6.2); 9.033 (3.1); 8.835 (0.4); 7.656 (0.9); 7.646 (9.1); 7.644 (8.6); 7.626 (10.7); 7.624 (9.6); 7.453 (3.9); 7.451 (3.6); 7.435 (10.4); 7.432 (9.1); 7.416 (7.8); 7.414 (6.5); 7.389 (7.5); 7.381 (7.8); 7.376 (8.7); 7.363 (16.0); 7.358 (11.5); 7.342 (10.5); 7.325 (1.7); 7.320 (1.6); 7.306 (0.7); 7.302 (0.7); 7.295 (0.6); 7.247 (9.1); 7.243 (8.6); 7.228 (7.8); 7.224 (7.0); 5.840 (0.5); 5.823 (0.7); 5.757 (1.5); 4.096 (3.7); 4.081 (3.9); 4.062 (8.1); 4.046 (7.9); 4.028 (4.2); 4.012 (3.9); 3.919 (0.4); 3.902 (0.5); 3.885 (0.7); 3.868 (0.6); 3.850 (0.3); 3.332 (168.7); 2.955 (0.3); 2.676 (0.6); 2.672 (0.8); 2.667 (0.6); 2.507 (94.4); 2.503 (118.3); 2.498 (84.7); 2.334 (0.6); 2.330 (0.7); 2.325 (0.6); 2.039 (0.5); 2.036 (0.5); 1.236 (0.8); 0.941 (0.5); 0.008 (1.2); 0.000 (26.5); -0.008 (1.2)
Example 165: ¾-NMR (400.0 MHz, CDC13):
□□ 8.753 (2.9); 8.743 (3.0); 7.703 (2.7); 7.684 (3.3); 7.571 (5.3); 7.550 (6.4); 7.540 (2.9); 7.528 (2.9);
7.521 (2.5); 7.509 (2.2); 7.448 (4.6); 7.445 (4.7); 7.326 (3.6); 7.321 (3.4); 7.304 (3.0); 7.299 (2.8); 7.263 (22.3); 5.942 (1.5); 5.302 (6.0); 4.353 (0.7); 4.338 (0.7); 4.316 (1.8); 4.301 (1.8); 4.284 (0.7); 4.276 (2.0); 4.270 (0.8); 4.261 (2.0); 4.248 (2.0); 4.239 (1.0); 4.233 (2.0); 4.220 (2.2); 4.205 (2.0); 4.184 (0.6); 4.169 (0.6); 4.129 (0.5); 4.111 (0.5); 2.046 (2.0); 1.919 (16.0); 1.859 (16.0); 1.569 (32.4); 1.426 (5.9); 1.277 (0.6); 1.260 (1.4); 1.242 (0.6); 0.007 (0.9); 0.000 (20.9)
Example 166: ¾-NMR (400.0 MHz, CD3CN):
□□ 8.795 (2.1); 8.789 (7.1); 8.785 (7.2); 8.779 (1.9); 7.594 (5.0); 7.573 (6.1); 7.528 (4.0); 7.525 (4.1);
7.522 (3.9); 7.379 (3.2); 7.374 (3.0); 7.358 (2.6); 7.352 (2.5); 4.244 (0.4); 4.228 (0.4); 4.207 (2.1); 4.191 (4.3); 4.175 (2.3); 4.155 (0.5); 4.142 (2.4); 4.134 (2.6); 4.126 (2.3); 4.118 (2.5); 2.133 (75.3); 2.120 (0.7); 2.113 (0.6); 2.107 (0.6); 2.101 (0.4); 1.964 (3.1); 1.958 (7.5); 1.952 (38.6); 1.946 (69.3); 1.940 (93.2); 1.934 (64.3); 1.927 (33.0); 1.915 (0.6); 1.881 (15.9); 1.821 (16.0); 1.774 (0.4); 1.768 (0.5); 1.762 (0.4); 0.146 (0.7); 0.008 (6.3); 0.000 (151.4); -0.009 (5.7); -0.150 (0.7)
lExample 167: ¾-NMR (400.0 MHz, CD3CN):
Figure imgf000139_0001
Figure imgf000140_0001
4.216 (0.7); 4.196 (1.7); 4.179 (1.7); 4.165 (0.7); 4.148 (0.7); 4.140 (2.0); 4.128 (2.0); 4.124 (2.2);
4.112 (1.8); 4.104 (1.0); 4.087 (1.3); 4.085 (2.3); 4.069 (2.2); 4.048 (0.9); 4.032 (0.8); 2.137 (32.7); 2.114 (0.3); 2.107 (0.4); 1.972 (0.7); 1.964 (1.7); 1.958 (4.0); 1.952 (21.6); 1.946 (39.1); 1.940 (52.9); 1.934 (36.9); 1.928 (19.2); 1.884 (15.9); 1.823 (16.0); 1.437 (2.3); 0.146 (0.7); 0.008 (6.0); 0.000 (157.1); -0.009 (6.4); -0.149 (0.7)
Example 176: ¾-NMR (400.0 MHz, CD3CN):
□□ 9.339 (5.8); 8.757 (7.4); 7.624 (5.0); 7.603 (6.1); 7.538 (2.9); 7.536 (3.2); 7.533 (3.4); 7.531 (3.0); 7.424 (3.3); 7.419 (3.1); 7.403 (2.7); 7.397 (2.5); 7.190 (0.8); 4.321 (1.0); 4.305 (1.0); 4.285 (1.5); 4.268 (1.4); 4.247 (1.0); 4.231 (1.0); 4.210 (1.5); 4.194 (1.5); 4.099 (1.6); 4.084 (1.6); 4.062 (1.2); 4.049 (2.3); 4.034 (1.7); 4.012 (1.2); 3.997 (1.2); 2.164 (35.6); 2.159 (45.4); 2.108 (0.3); 1.965 (1.7); 1.959 (4.0); 1.953 (22.0); 1.946 (40.0); 1.940 (54.3); 1.934 (37.6); 1.928 (19.4); 1.891 (16.0); 1.830 (16.0); 1.769 (0.3); 0.146 (0.7); 0.008 (5.5); 0.000 (150.2); -0.009 (5.6); -0.150 (0.7)
Example 177: ¾-NMR (400.0 MHz, CD3CN):
□□ 7.609 (4.9); 7.588 (5.9); 7.524 (4.1); 7.522 (4.3); 7.392 (3.3); 7.387 (3.2); 7.371 (2.7); 7.365 (2.6); 7.124 (1.8); 7.105 (3.7); 7.086 (3.0); 6.973 (7.9); 6.954 (6.0); 6.686 (1.2); 5.446 (0.8); 4.467 (1.2); 4.449 (1.2); 4.430 (1.5); 4.412 (1.4); 4.387 (1.2); 4.369 (1.2); 4.350 (1.5); 4.333 (1.4); 3.991 (1.5); 3.977 (1.5); 3.954 (1.3); 3.943 (2.2); 3.929 (1.6); 3.906 (1.3); 3.893 (1.3); 2.185 (0.4); 2.136 (58.2);
2.113 (0.7); 2.107 (0.7); 2.101 (0.5); 2.095 (0.3); 2.083 (0.7); 2.028 (43.8); 1.984 (0.4); 1.963 (2.5); 1.952 (26.7); 1.946 (48.1); 1.939 (64.1); 1.933 (46.8); 1.927 (25.8); 1.886 (16.0); 1.825 (15.9); 1.774 (0.3); 1.768 (0.4); 1.272 (0.4); 0.146 (0.8); 0.000 (157.3); -0.149 (0.8)
Example 178: ¾-NMR (400.0 MHz, -DMSO):
□□ 10.640 (0.7); 10.575 (1.2); 8.639 (1.6); 8.625 (2.9); 8.604 (2.6); 7.863 (2.2); 7.851 (3.9); 7.845
(2.4) ; 7.833 (3.9); 7.832 (3.9); 7.701 (2.5); 7.676 (4.7); 7.674 (4.9); 7.613 (0.4); 7.609 (0.4); 7.584
(1.5) ; 7.577 (0.8); 7.572 (1.0); 7.563 (4.7); 7.548 (15.7); 7.545 (16.0); 7.528 (1.0); 7.523 (0.9); 7.443 (2.7); 7.425 (5.9); 7.406 (3.6); 7.394 (0.4); 7.389 (0.5); 7.385 (0.4); 7.373 (0.6); 7.368 (0.6); 7.342 (0.9); 7.329 (0.5); 7.321 (0.5); 7.174 (4.3); 7.167 (2.2); 7.163 (2.5); 7.155 (5.2); 7.148 (3.4); 7.144
(3.6) ; 7.136 (1.4); 7.132 (1.2); 7.129 (1.8); 7.125 (2.0); 7.118 (3.7); 7.114 (3.2); 7.099 (3.3); 7.095
(2.7) ; 5.922 (2.4); 5.911 (2.3); 5.882 (1.2); 5.868 (1.3); 5.809 (2.3); 5.798 (2.5); 5.765 (1.3); 5.756 (3.4); 5.751 (1.4); 4.605 (0.5); 4.600 (0.5); 4.594 (0.6); 4.583 (1.0); 4.577 (0.8); 4.565 (1.0); 4.546 (0.9); 4.533 (1.0); 4.529 (1.0); 4.523 (0.8); 4.516 (1.0); 4.513 (0.9); 4.506 (0.6); 4.498 (0.5); 4.495 (0.6); 4.038 (0.5); 4.020 (0.5); 3.715 (1.0); 3.567 (1.8); 3.325 (78.2); 2.675 (0.4); 2.671 (0.6); 2.667 (0.4); 2.524 (1.7); 2.511 (35.3); 2.506 (68.7); 2.502 (89.8); 2.497 (66.5); 2.493 (33.3); 2.333 (0.5); 2.329 (0.6); 2.324 (0.5); 1.989 (2.1); 1.739 (3.6); 1.637 (1.9); 1.398 (2.6); 1.258 (11.1); 1.241 (11.0); 1.193 (5.6); 1.176 (5.8); 1.157 (0.7); 0.008 (0.8); 0.000 (19.3); -0.009 (0.8)
Example 179: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.667 (1.1); 8.645 (1.0); 7.696 (0.9); 7.676 (1.6); 7.674 (1.7); 7.632 (0.7); 7.620 (1.2); 7.614 (0.9); 7.602 (1.4); 7.600 (1.4); 7.584 (0.5); 7.563 (1.5); 7.541 (5.4); 7.525 (0.4); 7.520 (0.4); 7.432 (0.6); 7.429 (0.6); 7.413 (1.6); 7.410 (1.3); 7.395 (1.2); 7.392 (0.9); 7.362 (0.5); 7.354 (0.8); 7.350 (0.9); 7.343 (0.6); 7.335 (1.1); 7.331 (1.1); 7.324 (0.3); 7.316 (0.5); 7.311 (0.5); 7.253 (0.7); 7.249 (0.6); 7.235 (0.6); 7.231 (0.5); 7.192 (1.1); 7.188 (1.1); 7.173 (1.0); 7.169 (0.9); 5.918 (0.8); 5.908 (0.8); 5.856 (0.4); 5.841 (0.4); 5.805 (0.8); 5.794 (0.8); 5.739 (0.4); 5.725 (0.4); 4.601 (0.3); 4.584 (0.3); 4.551 (0.3); 4.533 (0.3); 4.038 (0.7); 4.020 (0.7); 3.324 (48.0); 2.506 (32.6); 2.502 (43.1); 2.498 (32.5); 1.989 (3.1); 1.398 (16.0); 1.252 (3.9); 1.235 (4.1); 1.193 (2.5); 1.175 (3.2); 1.157 (0.8); 0.008 (0.3); 0.000 (10.9); -0.008 (0.5)
Example 180: ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.115 (2.1); 9.105 (3.6); 9.095 (2.5); 9.082 (3.5); 9.017 (9.5); 9.011 (7.4); 8.964 (3.8); 8.958 (3.3); 8.949 (7.3); 8.943 (6.3); 8.316 (1.1); 7.710 (3.4); 7.693 (6.0); 7.573 (1.1); 7.559 (4.8); 7.552 (6.5); 7.546 (4.8); 7.538 (10.6); 7.525 (0.9); 7.520 (1.0); 7.508 (6.0); 7.503 (5.6); 7.487 (2.7); 7.482 (2.6); 5.958 (2.9); 5.947 (2.9); 5.924 (1.6); 5.913 (1.6); 5.845 (2.9); 5.833 (3.0); 5.808 (1.6); 5.796 (1.6); 4.656 (0.4); 4.645 (0.5); 4.635 (0.7); 4.629 (1.0); 4.618 (1.2); 4.612 (1.1); 4.607 (1.3); 4.600 (1.3); 4.595 (1.2); 4.589 (1.3); 4.577 (1.2); 4.570 (1.3); 4.558 (1.1); 4.553 (1.3); 4.541 (1.0); 4.536 (1.0);
4.531 (0.8); 4.519 (0.6); 3.361 (0.4); 3.325 (242.3); 2.676 (1.5); 2.671 (2.0); 2.667 (1.5); 2.541 (1.0); 2.525 (5.2); 2.507 (224.7); 2.502 (294.3); 2.498 (218.2); 2.494 (109.1); 2.333 (1.4); 2.329 (1.9); 2.324 (1.4); 1.398 (2.4); 1.274 (0.4); 1.249 (15.8); 1.232 (16.0); 1.196 (0.6); 1.179 (0.7); 1.146 (6.9); 1.129
(7.0) ; 0.008 (1.4); 0.000 (41.9); -0.008 (1.7)
Example 181 : ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.673 (0.9); 8.651 (0.9); 7.692 (0.6); 7.674 (1.4); 7.672 (1.3); 7.583 (0.4); 7.562 (1.0); 7.541 (0.8);
7.532 (4.1); 7.529 (3.8); 7.515 (0.4); 7.473 (0.4); 7.466 (0.5); 7.462 (0.6); 7.457 (0.7); 7.454 (0.8); 7.446 (1.5); 7.443 (1.6); 7.437 (0.8); 7.433 (0.8); 7.427 (0.6); 7.420 (1.2); 7.416 (1.1); 7.407 (0.4); 7.400 (0.5); 7.395 (0.6); 7.392 (0.5); 7.386 (0.8); 7.381 (0.6); 7.372 (0.6); 7.368 (1.1); 7.363 (0.9); 7.355 (0.3); 7.350 (0.5); 7.345 (0.4); 7.292 (0.5); 7.288 (0.5); 7.274 (0.4); 7.237 (0.9); 7.234 (0.9); 7.219 (0.8); 7.215 (0.7); 5.920 (0.6); 5.909 (0.6); 5.806 (0.6); 5.795 (0.7); 4.038 (0.7); 4.020 (0.7); 3.325 (14.9); 2.506 (13.4); 2.502 (17.3); 2.498 (13.1); 1.989 (2.8); 1.398 (16.0); 1.252 (3.1); 1.235 (3.4); 1.195 (1.4); 1.193 (1.4); 1.175 (1.9); 1.157 (0.8); 0.000 (4.6)
Example 182: ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.047 (1.8); 9.034 (3.8); 9.012 (3.4); 8.704 (4.4); 8.698 (13.3); 8.691 (10.4); 8.636 (4.8); 8.630
(4.3) ; 8.623 (10.3); 8.617 (8.8); 7.703 (2.9); 7.686 (6.5); 7.584 (1.5); 7.563 (4.8); 7.549 (3.3); 7.545
(3.1) ; 7.540 (3.0); 7.528 (1.4); 7.518 (11.7); 7.509 (7.8); 7.505 (7.0); 7.488 (1.7); 7.483 (1.7); 7.475 (0.4); 5.961 (3.1); 5.950 (3.0); 5.914 (1.4); 5.902 (1.4); 5.848 (3.1); 5.837 (3.2); 5.798 (1.4); 5.785
(1.4) ; 5.757 (1.3); 4.660 (0.4); 4.648 (1.0); 4.643 (0.8); 4.638 (1.0); 4.631 (1.3); 4.626 (1.3); 4.620 (1.1); 4.614 (1.1); 4.609 (1.4); 4.597 (1.1); 4.588 (1.2); 4.577 (1.1); 4.571 (1.3); 4.566 (1.0); 4.555 (1.1); 4.548 (0.9); 4.537 (0.7); 4.531 (0.4); 3.327 (97.5); 2.676 (0.6); 2.671 (0.9); 2.667 (0.7); 2.507 (98.2); 2.502 (127.6); 2.498 (94.7); 2.334 (0.6); 2.329 (0.8); 2.325 (0.6); 1.298 (0.4); 1.274 (15.9); 1.257 (16.0); 1.234 (1.4); 1.214 (0.3); 1.178 (6.0); 1.161 (6.0); 0.845 (0.4); 0.828 (0.4); 0.000 (10.4) Example 184: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.961 (2.4); 8.939 (2.5); 7.670 (5.1); 7.668 (5.3); 7.520 (0.8); 7.510 (0.6); 7.503 (2.0); 7.498 (2.1); 7.490 (16.0); 7.482 (4.1); 7.465 (1.9); 7.461 (1.9); 7.444 (0.8); 7.148 (0.9); 7.140 (5.2); 7.121 (6.8); 7.100 (4.4); 7.093 (0.8); 5.904 (2.8); 5.894 (2.7); 5.791 (2.7); 5.781 (2.8); 5.756 (0.8); 4.639 (0.5); 4.629 (0.5); 4.622 (0.6); 4.617 (0.6); 4.612 (0.6); 4.607 (0.6); 4.599 (0.6); 4.590 (0.6); 4.582 (0.3); 4.576 (0.6); 4.566 (0.5); 4.559 (0.7); 4.554 (0.7); 4.548 (0.6); 4.544 (0.6); 4.536 (0.6); 4.526 (0.5); 3.326 (71.3); 2.676 (0.4); 2.671 (0.5); 2.666 (0.4); 2.524 (1.4); 2.511 (28.2); 2.507 (56.4); 2.502 (73.9); 2.497 (53.1); 2.493 (25.4); 2.333 (0.3); 2.329 (0.5); 2.324 (0.3); 1.259 (12.7); 1.242 (12.5); 0.008 (2.2); 0.000 (61.4); -0.009 (2.1)
Example 185: ¾-NMR (400.0 MHz, d«-DMSO):
□□ 8.952 (0.4); 8.936 (2.0); 8.914 (1.9); 8.785 (2.1); 8.782 (2.1); 8.774 (2.0); 8.771 (2.0); 7.785 (1.2); 7.774 (1.0); 7.765 (3.2); 7.754 (3.7); 7.749 (3.5); 7.744 (3.6); 7.729 (1.0); 7.724 (0.9); 7.716 (0.5); 7.694 (3.8); 7.692 (3.8); 7.576 (0.3); 7.552 (11.3); 5.929 (1.8); 5.918 (1.7); 5.815 (1.7); 5.805 (1.8); 4.620 (0.4); 4.610 (0.4); 4.602 (0.5); 4.599 (0.5); 4.592 (0.5); 4.588 (0.5); 4.580 (0.5); 4.571 (0.4); 4.557 (0.5); 4.546 (0.4); 4.540 (0.5); 4.529 (0.5); 4.524 (0.5); 4.518 (0.4); 4.507 (0.4); 4.056 (1.2); 4.038 (3.7); 4.020 (3.8); 4.003 (1.3); 3.329 (97.2); 2.676 (0.4); 2.671 (0.5); 2.667 (0.3); 2.507 (55.8); 2.503 (71.4); 2.498 (52.7); 2.333 (0.3); 2.329 (0.4); 1.989 (16.0); 1.398 (9.7); 1.258 (8.5); 1.240 (8.6); 1.211 (0.3); 1.193 (4.4); 1.175 (8.5); 1.157 (4.2); 1.140 (0.9); 1.123 (0.9); 0.146 (0.4); 0.008 (4.0); 0.000 (85.0); -0.008 (3.7); -0.150 (0.4)
Example 186: ¾-NMR (601.6 MHz, d«-DMSO):
□□ 19.978 (0.7); 9.167 (4.3); 9.157 (8.7); 9.147 (4.4); 8.796 (9.6); 8.789 (9.8); 8.321 (0.6); 7.925 (16.0); 7.855 (7.9); 7.842 (10.8); 7.784 (8.4); 7.776 (8.5); 7.771 (6.7); 7.763 (6.2); 7.727 (7.5); 7.724
(7.5) ; 7.713 (9.3); 7.710 (9.2); 7.588 (15.7); 7.574 (13.1); 5.761 (1.5); 4.224 (3.8); 4.214 (4.3); 4.200 (8.9); 4.190 (8.6); 4.176 (4.6); 4.166 (4.1); 3.340 (71.0); 3.008 (3.2); 2.615 (1.1); 2.506 (133.1); 2.504 (178.8); 2.501 (139.7); 2.388 (1.1); 0.096 (0.6); 0.000 (112.4); -0.100 (0.6)
Example 187: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.997 (3.6); 8.981 (7.4); 8.966 (3.6); 8.316 (1.6); 7.910 (12.4); 7.906 (13.0); 7.767 (7.6); 7.748 (10.5); 7.725 (9.7); 7.721 (7.3); 7.704 (14.7); 7.699 (9.8); 7.689 (6.9); 7.658 (6.6); 7.639 (7.9); 7.620 (2.8); 7.586 (16.0); 7.564 (12.0); 7.366 (9.2); 7.347 (8.3); 4.210 (4.0); 4.194 (4.1); 4.174 (8.9); 4.159
(8.6) ; 4.139 (4.5); 4.123 (4.2); 3.325 (317.2); 2.675 (1.6); 2.671 (2.2); 2.666 (1.6); 2.524 (4.6); 2.506 (253.6); 2.502 (331.2); 2.497 (244.5); 2.333 (1.6); 2.329 (2.2); 2.324 (1.6); 1.989 (0.6); 1.398 (2.0); 0.146 (1.1); 0.008 (8.3); 0.000 (241.9); -0.008 (11.4); -0.150 (1.1)
Example 188: ¾-NMR (400.0 MHz, CD3CN):
□□ 8.755 (8.5); 8.744 (8.5); 7.852 (7.9); 7.832 (9.5); 7.694 (14.9); 7.668 (7.5); 7.656 (7.6); 7.648 (6.5); 7.636 (6.0); 7.607 (7.2); 7.602 (6.6); 7.586 (9.9); 7.582 (9.1); 7.478 (16.0); 7.457 (11.5); 7.229 (3.5); 6.037 (3.3); 6.029 (3.5); 6.020 (3.6); 6.012 (3.3); 5.921 (3.3); 5.913 (3.5); 5.904 (3.6); 5.896 (3.2); 3.981 (1.6); 3.973 (1.7); 3.966 (1.7); 3.958 (1.6); 3.945 (2.6); 3.936 (2.7); 3.929 (2.7); 3.921 (2.7); 3.915 (1.9); 3.907 (1.7); 3.899 (1.7); 3.891 (1.6); 3.878 (2.7); 3.870 (2.7); 3.863 (2.8); 3.855 (2.5); 3.829 (2.4); 3.813 (4.1); 3.796 (2.7); 3.772 (3.3); 3.756 (4.7); 3.739 (2.6); 3.719 (2.6); 3.703 (1.4); 2.462 (0.4); 2.145 (213.6); 2.120 (1.3); 2.114 (1.5); 2.108 (1.7); 2.101 (1.2); 2.095 (0.7); 1.964 (9.6); 1.952 (108.9); 1.946 (191.5); 1.940 (247.1); 1.934 (172.5); 1.928 (89.5); 1.781 (0.6); 1.775 (1.1); 1.768 (1.5); 1.762 (1.0); 1.756 (0.5); 1.270 (0.5); 0.000 (9.6)
Example 189: ¾-NMR (400.0 MHz, de-DMSO):
□□ 8.926 (2.7); 8.911 (5.4); 8.897 (2.8); 8.317 (0.3); 7.825 (7.7); 7.821 (10.1); 7.818 (8.7); 7.786 (5.9); 7.766 (8.0); 7.745 (2.7); 7.727 (6.7); 7.709 (4.9); 7.688 (6.0); 7.683 (5.8); 7.667 (12.4); 7.662 (9.3); 7.649 (6.2); 7.630 (2.3); 7.535 (13.5); 7.514 (10.6); 7.471 (7.1); 7.453 (6.3); 6.000 (2.0); 5.988 (2.4); 5.984 (3.0); 5.973 (2.1); 5.883 (2.0); 5.869 (4.0); 5.856 (2.2); 5.757 (4.6); 4.056 (1.2); 4.038 (3.6); 4.020 (3.7); 4.003 (1.2); 3.808 (0.4); 3.794 (0.5); 3.783 (2.6); 3.779 (2.7); 3.771 (3.4); 3.763 (4.5); 3.747 (2.2); 3.722 (4.3); 3.707 (7.1); 3.693 (3.2); 3.568 (1.3); 3.325 (59.0); 2.676 (0.5); 2.671 (0.7); 2.667 (0.5); 2.524 (1.5); 2.520 (2.5); 2.511 (39.2); 2.507 (81.8); 2.502 (110.6); 2.498 (82.6); 2.493 (41.8); 2.333 (0.5); 2.329 (0.7); 2.324 (0.5); 1.989 (16.0); 1.398 (3.6); 1.193 (4.3); 1.175 (8.5); 1.157 (4.2); 0.146 (0.5); 0.008 (4.1); 0.000 (124.2); -0.009 (5.5); -0.150 (0.5)
Example 190: ¾-NMR (400.0 MHz, CD3CN):
□□ 8.828 (16.0); 7.841 (0.7); 7.687 (2.5); 7.683 (3.6); 7.679 (2.5); 7.568 (1.7); 7.564 (1.6); 7.547 (2.5); 7.543 (2.4); 7.464 (4.5); 7.443 (3.0); 6.062 (0.8); 6.054 (0.9); 6.045 (0.9); 6.037 (0.9); 5.946 (0.8); 5.938 (0.9); 5.928 (0.9); 5.920 (0.8); 5.447 (1.0); 4.012 (0.4); 4.003 (0.5); 3.996 (0.5); 3.988 (0.5); 3.975 (0.7); 3.967 (0.7); 3.959 (0.7); 3.951 (0.7); 3.945 (0.5); 3.937 (0.4); 3.929 (0.4); 3.921 (0.4); 3.908 (0.8); 3.900 (0.7); 3.893 (0.8); 3.884 (0.7); 3.876 (0.7); 3.860 (1.2); 3.842 (0.8); 3.822 (1.3); 3.806 (1.6); 3.788 (0.8); 3.768 (0.7); 3.752 (0.4); 2.135 (51.2); 2.120 (0.4); 2.114 (0.5); 2.107 (0.6); 2.101 (0.4); 1.964 (3.0); 1.958 (7.9); 1.952 (40.7); 1.946 (72.9); 1.940 (97.0); 1.934 (66.3); 1.928 (33.6); 1.775 (0.4); 1.768 (0.6); 1.762 (0.4); 1.270 (0.6); 0.000 (4.1)
Example 191 : ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.117 (0.5); 9.101 (0.4); 9.078 (3.8); 9.063 (7.9); 9.047 (3.8); 8.461 (0.5); 8.456 (0.6); 8.448 (0.6); 8.444 (0.6); 8.372 (9.5); 8.366 (10.6); 8.361 (10.3); 8.355 (10.1); 8.316 (0.5); 8.054 (14.6); 7.933 (5.7); 7.913 (15.0); 7.890 (10.9); 7.879 (3.3); 7.876 (3.2); 7.869 (4.2); 7.842 (0.3); 7.748 (0.5); 7.743 (0.6); 7.729 (0.6); 7.724 (0.6); 7.499 (4.4); 7.493 (5.5); 7.480 (15.9); 7.474 (15.5); 7.466 (16.0); 7.454 (14.5); 7.447 (5.0); 7.435 (5.3); 4.292 (0.4); 4.272 (4.1); 4.256 (4.6); 4.237 (9.0); 4.221 (8.9); 4.202 (4.6); 4.186 (4.2); 4.056 (0.4); 4.039 (1.0); 4.021 (1.0); 4.003 (0.4); 3.325 (124.2); 2.676 (0.7); 2.672 (1.0); 2.667 (0.7); 2.525 (2.7); 2.511 (52.7); 2.507 (104.9); 2.503 (139.0); 2.498 (103.5); 2.494 (52.8); 2.334 (0.6); 2.330 (0.9); 2.325 (0.7); 1.989 (4.4); 1.235 (0.5); 1.193 (1.2); 1.176 (2.3); 1.158 (1.2); 0.146 (0.7); 0.008 (6.3); 0.000 (156.7); -0.009 (7.6); -0.150 (0.7)
Example 192: ¾-NMR (400.0 MHz, de-DMSO):
□□ 9.083 (0.3); 9.046 (2.6); 9.031 (5.4); 9.015 (2.7); 8.464 (0.4); 8.459 (0.4); 8.452 (0.4); 8.447 (0.4); 8.372 (6.4); 8.366 (7.4); 8.361 (7.2); 8.355 (7.1); 8.316 (1.0); 7.799 (8.5); 7.794 (9.1); 7.740 (0.4);
Figure imgf000145_0001
Figure imgf000146_0001
4.137 (0.8); 4.037 (0.4); 4.020 (0.4); 3.332 (413.9); 2.676 (1.3); 2.671 (1.8); 2.667 (1.4); 2.524 (4.7); 2.511 (98.0); 2.507 (200.8); 2.502 (267.3); 2.498 (201.5); 2.333 (1.2); 2.329 (1.7); 2.325 (1.3); 1.989 (1.4); 1.398 (7.7); 1.351 (2.4); 1.336 (1.3); 1.298 (0.5); 1.259 (1.0); 1.249 (2.1); 1.234 (3.8); 1.193 (0.5); 1.175 (0.8); 1.157 (0.5); 0.867 (0.4); 0.853 (0.7); 0.836 (0.5); 0.146 (1.5); 0.008 (11.7); 0.000 (317.7); -0.008 (16.0); -0.150 (1.5)
Example: in vivo preventive test on Alternaria brassicae (leaf spot on radish)
Solvent: 5% by volume of Dimethyl sulfoxide
10% by volume of Acetone
Emulsifier: 1 μΐ of Tween® 80 per mg of active ingredient
The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of radish are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Alternaria brassicae spores. The contaminated radish plants are incubated for 6 days at 20°C and at 100% relative humidity.
The test is evaluated 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 500 ppm of active ingredient: 10; 36; 42
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: 5; 13; 15; 21 ; 23 Example: in vivo preventive test on Botrytis cinerea (grey mould)
Solvent: by volume of Dimethyl sulfoxide
by volume of Acetone
Emulsifier: of Tween® 80 per mg of active ingredient
The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of gherkin are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Botrytis cinerea spores. The contaminated gherkin plants are incubated for 4 to 5 days at 17°C and at 90% relative humidity.
The test is evaluated 4 to 5 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 80% and 89%> at a concentration of 500 ppm of active ingredient: 39; 198
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: 20; 21 ; 23; 36; 37; 42; 84; 85; 86; 88; 199
Example: in vivo preventive test on Pyrenophora teres (net blotch on barley)
Solvent: 5% by volume of Dimethyl sulfoxide
10% by volume of Acetone
Emulsifier: 1 μΐ of Tween® 80 per mg of active ingredient
The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of barley are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores. The contaminated barley plants are incubated for 48 hours at 20°C and at 100% relative humidity and then for 12 days at 20°C and at 70-80% relative humidity.
The test is evaluated 14 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 500 ppm of active ingredient: 5; 22
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 500 ppm of active ingredient: 10; 21 ; 85
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: 1
Example: in vivo preventive test on Seytoria tritici (leaf spot on wheat)
Solvent: 5% by volume of Dimethyl sulfoxide
10% by volume of Acetone
Emulsifier: 1 μΐ of Tween® 80 per mg of active ingredient
The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of wheat are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Septoria tritici spores. The contaminated wheat plants are incubated for 72 hours at 18°C and at 100% relative humidity and then for 21 days at 20°C and at 90% relative humidity.
The test is evaluated 24 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 500 ppm of active ingredient: 87
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 500 ppm of active ingredient: 10; 15; 19; 20; 23
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: 21; 36; 37; 85; 86; 88; 196; 199
Example: in vivo preventive test on Syhaerotheca fuliginea (powdery mildew on cucurbits)
Solvent: 5% by volume of Dimethyl sulfoxide
10% by volume of Acetone
Emulsifier: 1 μΐ of Tween® 80 per mg of active ingredient
The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of gherkin are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Sphaerotheca fuliginea spores. The contaminated gherkin plants are incubated for 72 hours at 18°C and at 100% relative humidity and then for 12 days at 20°C and at 70-80% relative humidity.
The test is evaluated 15 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 500 ppm of active ingredient: 3; 23
In this test the following compounds according to the invention showed efficacy between 80% and 89%> at a concentration of 500 ppm of active ingredient: 22; 37
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: 4; 5; 10; 17; 20; 21 ; 36; 85; 88; 196; 199
Example: in vivo preventive test on Alternaria test (tomatoes)
Solvent: parts by weight of acetone
parts by weight of dimethylacetamide
Emulsifier: part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Alternaria solani. The plants are then placed in an incubation cabinet at approximately 20°C and a relative atmospheric humidity of 100%.
The test is evaluated 3 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 250 ppm of active ingredient: 20; 23
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 250 ppm of active ingredient: 5; 10; 13; 21
Example: in vivo preventive test on Venturia test (apples)
Solvent: parts by weight of acetone
parts by weight of dimethylacetamide
Emulsifier: part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causal agent of apple scab (Venturia inaequalis) and then remain for 1 day in an incubation cabinet at approximately 20°C and a relative atmospheric humidity of 100%.
The plants are then placed in a greenhouse at approximately 21°C and a relative atmospheric humidity of approximately 90%.
The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 250 ppm of active ingredient: 13
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 250 ppm of active ingredient: 20.
Example: in vivo preventive Blumeria test (barley)
Solvent: 49 parts by weight of N,N-dimethylacetamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.
After the spray coating has been dried, the plants are dusted with spores of Blumeria graminis f.sp. hordei.
The plants are placed in the greenhouse at a temperature of approximately 18°C and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.
The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 1000 ppm of active ingredient: 5; 15
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 1000 ppm of active ingredient: 10; 20; 21
Example: in vivo preventive Leptosphaeria nodorum test (wheat)
Solvent: 49 parts by weight of N,N-dimethylacetamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.
After the spray coating has been dried, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain for 48 hours in an incubation cabinet at approximately 20°C and a relative atmospheric humidity of approximately 100%.
The plants are placed in the greenhouse at a temperature of approximately 25°C and a relative atmospheric humidity of approximately 80%.
The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 1000 ppm of active ingredient: 23
Example: in vivo preventive Puccinia triticina test (wheat)
Solvent: 49 parts by weight of N,N-dimethylacetamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.
After the spray coating has been dried, the plants are sprayed with a spore suspension of Puccinia triticina. The plants remain for 48 hours in an incubation cabinet at approximately 20°C and a relative atmospheric humidity of approximately 100%.
The plants are placed in the greenhouse at a temperature of approximately 20°C and a relative atmospheric humidity of approximately 80%.
The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy between 70% and 79%> at a concentration of 500 ppm of active ingredient: 20
Example: Phytophthora infestans in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: sporocyste suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
A sporocyste suspension of P. infestans was prepared and diluted to the desired sporocyste density.
Fungicides were evaluated for their ability to inhibit sporocyste germination and mycelium growth in liquid culture assay. The compounds were added in the desired concentration to the culture medium with sporocystes. After 7 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 4
Example: Pythium ultimum in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: mycelial suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
Inoculum was prepared from a pre-culture of P. ultimum grown in liquid medium by homogenization using a blender. The concentration of ground mycelium in the inoculum was estimated and adjusted to the desired optical density (OD).
Fungicides were evaluated for their ability to inhibit mycelium growth in liquid culture assay. The compounds were added in the desired concentrations to culture medium containing the mycelial suspension. After 4 days of incubation, the fungicidal efficacy of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 7
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 4; 20; 21
Example: Altemaria alternata in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: spores suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
A spore suspension of A. alternata was prepared and diluted to the desired spore density.
Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assay. The compounds were added in the desired concentration to the culture medium with spores. After 5 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 20 ppm of active ingredient: 1 ; 22
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 7; 15; 19; 20; 23; 139
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 3; 4; 5; 10; 13; 14; 16; 17; 21 ; 199
Example: Botrytis cinerea in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: spore suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
A spore suspension of B. cinerea was prepared and diluted to the desired spore density.
Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assay. The compounds were added in the desired concentration to the culture medium with spores. After 5 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 20 ppm of active ingredient: 22
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 1; 5; 23
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 3; 4; 7; 8; 10; 13; 14; 15; 16; 17; 18; 19; 20; 21 ; 139; 198; 199
Example: Fusarium culmorum in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: spore suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
A spore suspension of F. culmorum was prepared and diluted to the desired spore density.
Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assay. The compounds were added in the desired concentration to the culture medium with spores. After 4 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 20 ppm of active ingredient: 3; 4; 6; 8; 19; 32
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 5; 13; 15; 21 ; 199
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 7; 14
Example: Leptnosphaeria nodorum in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: spore suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
A spore suspension of L. nodorum was prepared and diluted to the desired spore density.
Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assay. The compounds were added in the desired concentration to the culture medium with spores. After 6 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 20 ppm of active ingredient: 16; 18; 23
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 1; 4; 5; 6; 8; 13; 32; 139; 199
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 3; 7; 10; 14; 15; 17; 21
Example: Phytophtora cryptogea in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: mycelial suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
Inoculum was prepared from a pre-culture of P. cryptogea grown in liquid medium by homogenization using a blender. The concentration of ground mycelium in the inoculum was estimated and adjusted to the desired optical density (OD).
Fungicides were evaluated for their ability to inhibit mycelium growth in liquid culture assay. The compounds were added in the desired concentrations to culture medium containing the mycelial suspension. After 6 days of incubation, the fungicidal efficacy of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 4
Example: Pyricularia oryzae in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: spore suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
A spore suspension of P. oryzae was prepared and diluted to the desired spore density.
Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assay. The compounds were added in the desired concentration to the culture medium with spores. After 5 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 21; 23
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 1; 3; 4; 6; 7; 10; 14; 15; 16; 17; 19; 32
Example: Rhyzoctonia solani in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: mycelial suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
Inoculum was prepared from a pre-culture of R. solani grown in liquid medium by homogenization using a blender. The concentration of ground mycelium in the inoculum was estimated and adjusted to the desired optical density (OD).
Fungicides were evaluated for their ability to inhibit mycelium growth in liquid culture assay. The compounds were added in the desired concentrations to culture medium containing the mycelial suspension. After 5 days of incubation, the fungicidal efficacy of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 20 ppm of active ingredient: 10
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 14; 15; 17
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 3; 7; 19; 23
Example: Septoria tritici in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Bacteriological Peptone (Oxoid),
1.4g granulated Yeast Extract (Merck), QSP lliter
Inoculum: spore suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
A spore suspension of S. tritici was prepared and diluted to the desired spore density.
Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assay. The compounds were added in the desired concentration to the culture medium with spores. After 7 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 20 ppm of active ingredient: 1; 18; 198
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 4; 139
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 3; 5; 7; 8; 10; 13; 14; 15; 16; 17; 19; 20; 21; 22; 23; 199
Example: Ustilaso avenae in vitro cell test
Solvent: DMSO
Culture medium: 14.6g anhydrous D-glucose (VWR), 7.1g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
Inoculum: spore suspension
Fungicides were solubilized in DMSO and the solution used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was < 1%.
Inoculum was prepared from a pre-culture of U. avenae grown in liquid medium and diluted to the desired optical density (OD).
Fungicides were evaluated for their ability to inhibit mycelium growth in liquid culture assay. The compounds were added in the desired concentrations to culture medium containing the spore suspension. After 4 days of incubation, the fungicidal efficacy of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the fungicides with the absorbance in control wells without fungicides.
In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 20 ppm of active ingredient: 14
In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 20 ppm of active ingredient: 3; 7; 15; 16; 17; 18; 19; 23; 25

Claims

CLA IMS
1. Use of a compound of formula (I),
Figure imgf000168_0001
(I)
or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen or sulfur;
n represents 0, 1, 2, 3, 4 or 5;
X independently from each other X represents halogen, nitro, cyano, isonitrile, hydroxy, amino, sulfanyl, pentafluoro^6-sulfanyl, formyl, formyloxy, formylamino, (hydroxyimino)-Ci-C8-alkyl, (Ci- C8-alkoxyimino)-Ci-C8-alkyl, (C3-C8-alkenyloxyimino)-Ci-C8-alkyl, (C3-C8-alkynyloxyimino)-Ci-C8- alkyl, (benzyloxyimino)-Ci-C8-alkyl, carboxy, carbamoyl, N-hydroxycarbamoyl, carbamate, Ci-Ce- alkyl, Ci-Cs-halogenoalkyl having 1 to 9 halogen atoms, C2-Cs-alkenyl, C2-C8-halogenoalkenyl having 1 to 9 halogen atoms, C2-C8-alkynyl, C2-C8-halogenoalkynyl having 1 to 9 halogen atoms, G-Cs- alkoxy, Ci-Cs-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C8-alkylsulfanyl, Ci-Cs- halogenoalkylsulfanyl having 1 to 9 halogen atoms, Ci-Cs-alkylsulfinyl, Ci-Cs-halogenoalkylsulfinyl having 1 to 9 halogen atoms, Ci-Cs-alkylsulfonyl, G-Cs-halogenoalkylsulfonyl having 1 to 9 halogen atoms, Ci-C8-alkylamino, di-(Ci-C8-alkyl)-amino, C2-C8-alkenyloxy, C2-C8-halogenoalkenyloxy having 1 to 9 halogen atoms, C3-Cs-alkynyloxy, C2-C8-halogenoalkynyloxy having 1 to 9 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms, C4-C7-cycloalkenyl, C4-C7-halogenocycloalkenyl having 1 to 9 halogen atoms, (C3-C7-cycloalkyl)-Ci-C8-alkyl, (C3-C7- cycloalkyl)-C2-C8-alkenyl, (C3-C7-cycloalkyl)-C2-C8-alkynyl, tri-(Ci-C8-alkyl)-silyl, tri-(Ci-C8-alkyl)- silyl-Ci-C8-alkyl, Ci-Cs-alkylcarbonyl, Ci-C8-halogenoalkylcarbonyl having 1 to 9 halogen atoms, Ci-Cs-alkylcarbonyloxy, Ci-Cs-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms, Ci-Cs- alkylcarbonylamino, Ci-Cs-halogenoalkylcarbonylamino having 1 to 9 halogen atoms, Ci-Cs- alkoxycarbonyl, Ci-Cs-halogenoalkoxycarbonyl having 1 to 9 halogen atoms, Ci-Cs- alkyloxycarbonyloxy, Ci-Cs-halogenoalkoxycarbonyloxy having 1 to 9 halogen atoms, Ci-Cs- alkylcarbamoyl, di-Ci-Cs-alkylcarbamoyl, Ci-Cs-alkylaminocarbonyloxy, di-Ci-Cs- alkylaminocarbonyloxy, N-(Ci-C8-alkyl)-hydroxycarbamoyl, G-G-alkoxycarbamoyl, N-(G-G- alkyl)-Ci-C8-alkoxycarbamoyl, aryl-G-G-alkyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-C2-C8-alkenyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-G-G-alkynyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryloxy optionally substituted by 1 to 6 groups Q which can be the same or different, arylsulfanyl optionally substituted by 1 to 6 groups Q which can be the same or different, arylamino optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-Cs-alkyloxy optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-Cs-alkylsulfanyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-Cs-alkylamino optionally substituted by 1 to 6 groups Q which can be the same or different, pyridinyloxy which is optionally substituted by 1 to 4 groups Q; or
two substituents X together with the carbon atoms to which they are attached form a 5- or 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 4 groups Q which can be the same or different;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, G-G-alkyl, G-G-halogenoalkyl having 1 to 5 halogen atoms, G-G-alkoxy, G-G-alkylsulfanyl, or G-G-alkoxycarbonyl; or
Z2 and Z3 form together with the carbon atom to which they are attached a 3- to 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 6 groups Q which can be the same or different;
Q represents halogen, cyano, nitro, G-G-alkyl, G-G-halogenoalkyl having 1 to 9 halogen atoms, G- G-alkoxy, G-G-halogenoalkoxy having 1 to 9 halogen atoms, G-G-alkylsulfanyl, G-G- halogenoalkylsulfanyl having 1 to 9 halogen atoms, tri-(G-G-alkyl)-silyl, tri-(G-G-alkyl)-silyl-G- G-alkyl, G-G-alkoxyimino-G-G-alkyl, (benzyloxyimino)-G-G-alkyl;
A represents phenyl of formula A1
Figure imgf000169_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I), Y1 represents halogen, nitro, SH, SF5, CHO, OCHO, NHCHO, cyano, G-Cs-alkyl, G-Cg-halogenoalkyl having 1 to 5 halogen atoms, C2-C8-alkenyl, C2-C8-alkynyl, C3-C6-cycloalkyl, Cs-Ce-halogenocycloalkyl having 1 to 9 halogen atoms, Ci-Cs-alkylsulfanyl, -Ci-Cs-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C8-alkoxy, Ci-Cs-halogenoalkoxy having 1 to 5 halogen atoms, Ci-Cs-alkoxy-Ci-Cs-alkyl, C2- C8-alkenyloxy-Ci-C8-alkyl, Cs-Cs-alkynyloxy-G-Cs-alkyl, C2-Cs-alkenyloxy, C3-C8-alkynyloxy, Ci-Cs- alkoxycarbonyl, G-Cs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, G-Cs-alkylcarbonyloxy, G-Cs-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, Ci-Cs-alkylsulfinyl, Ci-Cs- halogenoalkylsulfinyl having 1 to 5 halogen atoms, G-Cs-alkylsulfonyl, Ci-Cs-halogenoalkylsulfonyl having 1 to 5 halogen atoms, Ci-Cs-alkylsulfonamide, tri-(Ci-C8)-alkylsilyl, aryl and aryloxy;
Y2, Y3, Y4 and Y5 independently from each other represent hydrogen or Y1; or
A represents a heterocycle of formula (A2)
Figure imgf000170_0001
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, G-Cs-alkyl, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, G-Cs-alkoxy or Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A3)
Figure imgf000170_0002
wherein
R4 to R6 independently from each other represent hydrogen, halogen, G-Cs-alkyl, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, G-Cs-alkoxy or G-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000171_0001
(A4) wherein
R9 to R1 1 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, amino, C1-C5- alkoxy, G-Cs-alkylsulfanyl, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or C1-C5- halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A5)
Figure imgf000171_0002
(A5) wherein
R and R independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, amino, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms, and
R14 represents hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, amino, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A6)
Figure imgf000171_0003
(A6) wherein
R represents hydrogen or substituted or unsubstitued Ci-Cs-alkyl, and R20 to R22 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A7)
Figure imgf000172_0001
(A7) wherein
R23 represents hydrogen, halogen, Ci-Cs-alkyl or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, and
R24 represents hydrogen or Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A8)
Figure imgf000172_0002
(A8) wherein
R25 represents hydrogen, halogen, Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, and
R26 represents hydrogen, Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A9)
Figure imgf000172_0003
wherein R29 represents hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, and
R30 represents hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms, amino, Ci-Cs-alkylamino or di-(C i- C5-alkyl)-amino; or
A represents a heterocycle of formula (A10)
Figure imgf000173_0001
(A10) wherein
R31 represents hydrogen or Ci-Cs-alkyl, and
R32 represents hydrogen, halogen, Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, and
R33 represents hydrogen, halogen, nitro, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A1 :)
Figure imgf000173_0002
(A11) wherein
R37 and R38 independently from each other represent hydrogen, halogen, G-Cs-alkyl, C1-C5 halogenoalkyl comprising 1 to 9 halogen atoms, Ci-Cs-alkoxy or a Ci-Cs-alkylsulfanyl, and
R represents hydrogen or Ci-Cs-alkyl; or A represents a heterocycle of formula (A12)
Figure imgf000174_0001
wherein
R40 and R41 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A13)
Figure imgf000174_0002
wherein
R42 and R43 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms or amino; or
A represents a heterocycle of formula (A14)
Figure imgf000174_0003
(A14) wherein
R44 and R45 independently from each other represent hydrogen, halogen, G-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A15)
Figure imgf000175_0001
(A15) wherein
R47 represents hydrogen, halogen, Ci-Cs-alkyl or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, and
R46 represents hydrogen, halogen, Ci-Cs-alkyl, C i- i-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-Cs-alkylsulfanyl; or
A represents a heterocycle of formula (A16)
Figure imgf000175_0002
(A16) wherein
R49 and R48 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy, G- C5-halogenoalkoxy comprising 1 to 9 halogen atoms or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A17)
Figure imgf000175_0003
(A17) wherein
R50 and R51 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl, G-Cs-alkoxy, G- C5-halogenoalkoxy comprising 1 to 9 halogen atoms or G-G-halogenoalkyl comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A18)
Figure imgf000176_0001
(A18) wherein
R52 represents hydrogen, halogen, Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A19)
Figure imgf000176_0002
(A19) wherein
R53 represents hydrogen, halogen, G-Cs-alkyl or G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A20)
Figure imgf000176_0003
(A20) wherein
R54 and R56 independently from each other represent hydrogen, halogen, Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms, and
R55 represents hydrogen or Ci-Cs-alkyl; or A represents a heterocycle of formula (A21)
Figure imgf000177_0001
(A21) wherein
R57 and R59 independently from each other represent hydrogen, halogen, G-Cs-alkyl or Ci-C halogenoalkyl comprising 1 to 9 halogen atoms, and
R58 represents hydrogen or Ci-Cs-alkyl; or
A represents a heterocycle of formula (A22)
Figure imgf000177_0002
*
(A22) wherein
R60 and R61 independently from each other represent hydrogen, halogen, C i-Cs-alkyl or Ci-C halogenoalkyl comprising 1 to 9 halogen atoms, and
R62 represents a hydrogen atom or Ci-Cs-alkyl; or
A represents a heterocycle of formula (A23)
Figure imgf000177_0003
(A23) wherein
R represents hydrogen, halogen, Ci-Cs-alkyl, cyano, G-Cs-alkoxy, G-Cs-alkylsulfanyl, C1-C5- halogenoalkyl comprising 1 to 9 halogen atoms, G-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms, amino, Ci-Cs-alkylamino or di(Ci-C5-alkyl)amino, and
R64 represents hydrogen or G-Cs-alkyl, and
R65 represents hydrogen, halogen, Ci-Cs-alkyl, C3-C5-cycloalkyl, G-Cs-halogenoalkyl comprising 1 to 9 halogen atoms, G-Cs-alkoxy, C3-Cs-alkynyloxy or G-Cs-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000178_0001
in which
R represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, G-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms and G-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, SCi-C4-alkylsulfinyl and G-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A25)
Figure imgf000178_0002
in which
R70 represents hydrogen, halogen, hydroxy, cyano, G-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, Ci-Cs-alkylsulfanyl, C2-Cs-alkenylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
R71, R72 and R73 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsuliinyl, Ci-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A )
Figure imgf000179_0001
in which
R , R , R and R independently from each other represent hydrogen, halogen, hydroxy, cyano, G- C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, G-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl and Ci-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A27)
Figure imgf000179_0002
in which
X1 represents -S-, -SO-, -SO2- and -CH2-, and
R represents Ci-C4-alkyl and G-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R and R independently from each other represent hydrogen and G-C4-alkyl; or
A represents a heterocycle of formula (A )
Figure imgf000179_0003
in which
R81 represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
A represents a heterocycle of formula (A )
Figure imgf000180_0001
in which
R represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A )
Figure imgf000180_0002
in which
R represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms;
A is a heterocycle of formula (A31)
Figure imgf000180_0003
in which
R represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
2. Use of a compound of formula 1 according to claim 1 or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen or sulfur;
n represents 0, 1, 2, 3 or 4;
X independently from each other X represents halogen, nitro, cyano, isonitrile, hydroxy, amino, sulfanyl, pentafluoro^6-sulfanyl, formyl, formyloxy, formylamino, (hydroxyimino)-Ci-C4-alkyl, (Ci- C4-alkoxyimino)-Ci-C4-alkyl, (C3-C4-alkenyloxyimino)-Ci-C4-alkyl, (C3-C4-alkynyloxyimino)-Ci-C4- alkyl, (benzyloxyimino)-Ci-C4-alkyl, carboxy, carbamoyl, N-hydroxycarbamoyl, carbamate, C1-C4- alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, C2-C4-alkenyl, C2-C4-halogenoalkenyl having 1 to 9 halogen atoms, C2-C4-alkynyl, C2-C4-halogenoalkynyl having 1 to 9 halogen atoms, C1-C4- alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfinyl, Ci-C4-halogenoalkylsulfinyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfonyl, Ci-C4-halogenoalkylsulfonyl having 1 to 9 halogen atoms, Ci-C4-alkylamino, di-(Ci-C4-alkyl)-amino, C2-C4-alkenyloxy, C2-C4-halogenoalkenyloxy having 1 to 9 halogen atoms, C3-C4-alkynyloxy, C2-C4-halogenoalkynyloxy having 1 to 9 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms, C4-C7-cycloalkenyl, C4-C7-halogenocycloalkenyl having 1 to 9 halogen atoms, (C3-C7-cycloalkyl)-Ci-C4-alkyl, (C3-C7- cycloalkyl)-C2-C4-alkenyl, (C3-C7-cycloalkyl)-C2-C4-alkynyl, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4-alkyl)- silyl-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-halogenoalkylcarbonyl having 1 to 9 halogen atoms, Ci-C4-alkylcarbonyloxy, Ci-C4-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms, O-C4- alkylcarbonylamino, Ci-C4-halogenoalkylcarbonylamino having 1 to 9 halogen atoms, O-C4- alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 9 halogen atoms, C1-C4- alkyloxycarbonyloxy, Ci-C4-halogenoalkoxycarbonyloxy having 1 to 9 halogen atoms, C1-C4- alkylcarbamoyl, di-Ci-C4-alkylcarbamoyl, Ci-C4-alkylaminocarbonyloxy, di-Ci-C4- alkylaminocarbonyloxy, N-(Ci-C4-alkyl)-hydroxycarbamoyl, Ci-C4-alkoxycarbamoyl, N-(Ci-C4- alkyl)-Ci-C4-alkoxycarbamoyl, aryl-Ci-C4-alkyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-C2-C4-alkenyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-C2-C4-alkynyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryloxy optionally substituted by 1 to 6 groups Q which can be the same or different, arylsulfanyl optionally substituted by 1 to 6 groups Q which can be the same or different, arylamino optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-C4-alkyloxy optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-C4-alkylsulfanyl optionally substituted by 1 to 6 groups Q which can be the same or different, aryl-Ci-C4-alkylamino optionally substituted by 1 to 6 groups Q which can be the same or different, pyridinyloxy which is optionally substituted by 1 to 4 groups Q; or two substituents X together with the carbon atoms to which they are attached form a 5- or 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 4 groups Q which can be the same or different;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, or Ci-C4-alkoxycarbonyl; or
Z2 and Z3 form together with the carbon atom to which they are attached a 3- to 6-membered, saturated carbocycle or saturated heterocycle, which is optionally substituted by 1 to 6 groups Q which can be the same or different;
Q represents halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, G- C4-alkoxy, G-C4-halogenoalkoxy having 1 to 9 halogen atoms, G-C4-alkylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 9 halogen atoms, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4-alkyl)-silyl-Ci- C4-alkyl, Ci-C4-alkoxyimino-Ci-C4-alkyl, (benzyloxyimino)-Ci-C4-alkyl;
A represents phenyl of formula A1
Figure imgf000182_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents halogen, nitro, SH, SF5, CHO, OCHO, NHCHO, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C3-C6-halogenocycloalkyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, -Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, G-C4-alkoxy-Ci-C4-alkyl, C2- C4-alkenyloxy-Ci-C4-alkyl, C3-C4-alkynyloxy-Ci-C4-alkyl, C2-C4-alkenyloxy, C3-C4-alkynyloxy, C1-C4- alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, G-C4-alkylcarbonyloxy, Ci-C4-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, G-C4-alkylsulfmyl, C1-C4- halogenoalkylsulfinyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfonyl, Ci-C4-halogenoalkylsulfonyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfonamide, tri-(Ci-C4)-alkylsilyl, aryl and aryloxy;
Y2, Y3, Y4 and Y5 independently from each other represent hydrogen or Y1; or A represents a heterocycle of formula (A2)
Figure imgf000183_0001
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A3)
Figure imgf000183_0002
(A3) wherein
R4 to R6 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000183_0003
(A4) wherein
R9 to R11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, amino, C1-C4- alkoxy, G-C4-alkylsulfanyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or C1-C4- halogenoalkoxy comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A5)
Figure imgf000184_0001
(A5) wherein
R12 and R13 independently from each other represent hydrogen, halogen, Ci-C i-alkyl, Ci-C4-alkoxy, amino, Ci-C i-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C i-halogenoalkoxy comprising 1 to 9 halogen atoms, and
R14 represents hydrogen, halogen, G-C4-alkyl, G-C4-alkoxy, amino, G-C4-halogenoalkyl comprising 1 to 9 halogen atoms or G-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000184_0002
in which
R represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, G-C4-alkylsulfanyl, G-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms and G-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, G-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, SCi-C4-alkylsulfinyl and Ci-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A25)
Figure imgf000184_0003
in which
R7 represents hydrogen, halogen, hydroxy, cyano, Ci-C i-alkyl, Ci-C i-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C2-C4-alkenylsulfanyl, C1-C4- halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
R71, R72 and R73 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A26)
Figure imgf000185_0001
in which
R7 , R75, R7 and R77 independently from each other represent hydrogen, halogen, hydroxy, cyano, Ci- C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl and Ci-C4-alkylsulfonyl; or
A represents a heterocycle of formula (A27)
Figure imgf000185_0002
in which
X1 represents -S-, -SO-, -SO2- and -CH2-, and
R represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R7 and R independently from each other represent hydrogen and Ci-C4-alkyl; or
A represents a heterocycle of formula (A )
Figure imgf000186_0001
in which
R represents hydrogen, halogen, Ci-C i-alkyl and Ci-C i-halogenoalkyl having 1 to 5 halogen atoms; A is a heterocycle of formula (A31)
Figure imgf000186_0002
in which
R represents hydrogen, halogen, Ci-C i-alkyl and Ci-C i-halogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
3. Use of a compound of formula (I) according to any of claims 1 to 2 or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen;
n represents 0, 1, 2 or 3;
X independently from each other X represents halogen, nitro, cyano, isonitrile, hydroxy, amino, formyl, formyloxy, formylaminocarboxy, carbamoyl, N-hydroxycarbamoyl, carbamate, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, C2-C4-alkenyl, C2-C4-halogenoalkenyl having 1 to 9 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, Ci-C4-halogenoalkylsulfanyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfinyl, C1-C4- halogenoalkylsulfinyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfonyl, Ci-C4-halogenoalkylsulfonyl having 1 to 9 halogen atoms, Ci-C4-alkylamino, di-(Ci-C4-alkyl)-amino, C2-C4-alkenyloxy, C2-C4- halogenoalkenyloxy having 1 to 9 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms, (C3-C7-cycloalkyl)-Ci-C4-alkyl, (C3-C7-cycloalkyl)-C2-C4-alkenyl, (C3-C7- cycloalkyl)-C2-C4-alkynyl, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4-alkyl)-silyl-Ci-C4-alkyl, G-C4- alkylcarbonyl, Ci-C4-halogenoalkylcarbonyl having 1 to 9 halogen atoms, Ci-C4-alkylcarbonyloxy, Ci-C4-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms, Ci-C4-alkoxycarbonyl, G-C4- halogenoalkoxycarbonyl having 1 to 9 halogen atoms, aryl-Ci-C4-alkyl optionally substituted by 1 to 6 groups Q which can be the same or different, pyridinyloxy which is optionally substituted by 1 to 4 groups Q; or
two substituents X together with the carbon atoms to which they are attached form a 5- or 6-membered, saturated carbocycle, which is optionally substituted by 1 to 4 groups Q which can be the same or different;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, or Ci-C4-alkoxycarbonyl; or
Z2 and Z3 form together with the carbon atom to which they are attached a 3- to 6-membered, saturated carbocycle, which is optionally substituted by 1 to 6 groups Q which can be the same or different;
Q represents halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, G- C4-alkoxy, G-C4-halogenoalkoxy having 1 to 9 halogen atoms, tri-(G-C4-alkyl)-silyl, tri-(G-C4- alkyl)-silyl-Ci-C4-alkyl;
A represents phenyl of formula A1
Figure imgf000187_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents halogen, nitro, CHO, OCHO, NHCHO, cyano, G-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-halogenocycloalkyl having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, -G-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, G-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfinyl, Ci-C4- halogenoalkylsulfinyl having 1 to 5 halogen atoms, Ci-C4-alkylsulfonyl, Ci-C4-halogenoalkylsulfonyl having 1 to 5 halogen atoms, tri-(Ci-C4)-alkylsilyl; Y2, Y3, Υ4 and Υ5 independently from each other represent hydrogen or Y1; or
A represents a heterocycle of formula (A2)
Figure imgf000188_0001
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, G-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A3)
Figure imgf000188_0002
(A3) wherein
R4 to R6 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000188_0003
(A4) wherein R9 to R11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, G- C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A5)
Figure imgf000189_0001
(A5) wherein
R12 and R13 independently from each other represent hydrogen, halogen, G-C4-alkyl, G-C4-alkoxy, amino, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or G-C4-halogenoalkoxy comprising 1 to 9 halogen atoms, and
R14 represents hydrogen, halogen, Ci-C4-alkyl, G-C4-alkoxy, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or G-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000189_0002
in which
R66 represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G-C4-alkoxy, and G-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A )
Figure imgf000190_0001
in which
R70 represents hydrogen, halogen, hydroxy, cyano,
Figure imgf000190_0002
Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
R71, R72 and R73 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A )
Figure imgf000190_0003
in which
R74, R75, R76 and R77 independently from each other represent hydrogen, halogen, hydroxy, cyano, Ci- C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A27)
Figure imgf000190_0004
in which
X1 represents -S-, -SO-, -SO2- and -CH2-, and
R represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R and R independently from each other represent hydrogen and Ci-C4-alkyl; or A represents a heterocycle of formula (A )
Figure imgf000191_0001
in which
R83 represents hydrogen, halogen, G-C i-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; A is a heterocycle of formula (A31)
Figure imgf000191_0002
in which
R represents hydrogen, halogen, G-C4-alkyl and G-C4-halogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
4. Use of a compound of formula (I) according to any of claims 1 to 3 or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen;
n represents 0, 1, 2 or 3;
X independently from each other X represents halogen, nitro, cyano, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 9 halogen atoms, G-C4-alkoxy, G-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, G-C4-halogenoalkylsulfanyl having 1 to 9 halogen atoms, C1-C4- alkylsulflnyl, Ci-C4-halogenoalkylsulfinyl having 1 to 9 halogen atoms, G-C4-alkylsulfonyl, C1-C4- halogenoalkylsulfonyl having 1 to 9 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms, (C3-C7-cycloalkyl)-Ci-C4-alkyl, tri-(Ci-C4-alkyl)-silyl, tri-(Ci-C4-alkyl)-silyl-Ci- C4-alkyl, G-C4-alkylcarbonyl, G-C4-halogenoalkylcarbonyl having 1 to 9 halogen atoms; or two substituents X together with the carbon atoms to which they are attached form a cyclopentyl or cyclohexyl;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy; or
Z2 and Z3 form together with the carbon atom to which they are attached a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
Q represents halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 9 halogen atoms, G- C4-alkoxy, G-C4-halogenoalkoxy having 1 to 9 halogen atoms;
A represents phenyl of formula A1
Figure imgf000192_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents halogen, nitro, cyano, G-C4-alkyl, G-C4-halogenoalkyl having 1 to 5 halogen atoms, G- C4-alkylsulfanyl, -G-C4-halogenoalkylsulfanyl having 1 to 5 halogen atoms, G-C4-alkoxy, C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-G-C4-alkyl, G-C4-alkoxycarbonyl, G-C4- halogenoalkoxycarbonyl having 1 to 5 halogen atoms, G-C4-alkylsulfinyl, G-C4-halogenoalkylsulfinyl having 1 to 5 halogen atoms, G-G-alkylsulfonyl, G-C4-halogenoalkylsulfonyl having 1 to 5 halogen atoms;
Y2, Y3, Y4 and Y5 independently from each other represent hydrogen or Y1; or A represents a heterocycle of formula (A2)
Figure imgf000192_0002
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, Ci-C ralkyl, Ci-C i-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A3)
Figure imgf000193_0001
(A3) wherein
R4 to R6 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms, Ci-C4-alkoxy or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000193_0002
(A4) wherein
R9 to R11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci- C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or A represents a heterocycle of formula (A5)
Figure imgf000194_0001
(A5) wherein
R and R independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, amino, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms, and
R14 represents hydrogen, halogen, Ci-C4-alkyl, G-C4-alkoxy, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms or Ci-C4-halogenoalkoxy comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000194_0002
in which
R represents hydrogen, halogen, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, and Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A25)
Figure imgf000194_0003
in which
R7 represents hydrogen, halogen, hydroxy, cyano, Ci-C t-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms and
R71, R72 and R73 independently from each other represent hydrogen, halogen, cyano, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A )
Figure imgf000195_0001
in which
R74, R75, R76 and R77 independently from each other represent hydrogen, halogen, hydroxy, cyano, Ci- C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A27)
Figure imgf000195_0002
in which
X1 represents -S-, -SO-, -SO2- and -CH2-, and
R78 represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and R79 and R80 independently from each other represent hydrogen and Ci-C4-alkyl; or A represents a heterocycle of formula (A30)
Figure imgf000195_0003
in which
R83 represents hydrogen, halogen, Ci-C i-alkyl and Ci-C rhalogenoalkyl having 1 to 5 halogen atoms; A is a heterocycle of formula (A31)
Figure imgf000196_0001
in which
R84 represents hydrogen, halogen, Ci-C i-alkyl and Ci-C rhalogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
5. Use of a compound of formula (I) according to any of claims 1 to 4 or an N-oxide, or an optically active isomer thereof, for control of phytopathogenic microorganisms in agriculture, wherein
T represents oxygen;
n represents 0, 1 or 2;
X independently from each other X represents halogen, nitro, cyano, Ci-C i-alkyl, C1-C4- halogenoalkyl having 1 to 9 halogen atoms, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 9 halogen atoms, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, G-C4-alkylsulfonyl, Ci-C4-alkylcarbonyl, C1-C4- halogenoalkylcarbonyl having 1 to 9 halogen atoms;
Z1, Z2 and Z3 independently represent hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, Ci-C4-alkoxy;
A represents phenyl of formula A1
Figure imgf000197_0001
(A1) wherein
* indicates the bond which connects A1 to the C=T moiety of the compounds of formula (I),
Y1 represents halogen, nitro, cyano, Ci-C i-alkyl, Ci-C i-halogenoalkyl having 1 to 5 halogen atoms, Ci- C4-alkylsulfanyl, Ci-C4-alkoxy, Ci-C4-halogenoalkoxy having 1 to 5 halogen atoms, Ci-C4-alkoxy-Ci- C4-alkyl, Ci-C4-alkoxycarbonyl, Ci-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, C1-C4- alkylsulfinyl, C i-C4-alkylsulfonyl;
Y2, Y3, Y4 and Y5 independently from each other represent hydrogen or Y1; or A represents a heterocycle of formula (A2)
Figure imgf000197_0002
(A2) wherein
R1 to R3 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A3)
Figure imgf000197_0003
(A3) wherein R4 to R6 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A4)
Figure imgf000198_0001
(A4) wherein
R9 to R11 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A5)
Figure imgf000198_0002
(A5) wherein
R12 and R13 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, C1-C4- halogenoalkyl comprising 1 to 9 halogen atoms, and
R14 represents hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl comprising 1 to 9 halogen atoms; or
A represents a heterocycle of formula (A24)
Figure imgf000198_0003
in which R represents hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R67, R68 and R69 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A25)
Figure imgf000199_0001
in which
R70 represents hydrogen, halogen, Ci-C4-alkyl, Ci-C4-halogenoalkyl having 1 to 5 halogen atoms, and
R71, R72 and R73 independently from each other represent hydrogen, halogen, Ci-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A26)
Figure imgf000199_0002
in which
R74, R75, R76 and R77 independently from each other represent hydrogen, halogen, G-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms; or
A represents a heterocycle of formula (A27)
Figure imgf000199_0003
in which
X represents -S-, and represents Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms,
R and R independently from each other represent hydrogen and Ci-C4-alkyl; or
A represents a heterocycle of formula (AJU)
Figure imgf000200_0001
in which
R represents hydrogen, halogen, Ci-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; A is a heterocycle of formula (A31)
Figure imgf000200_0002
in which
R84 represents hydrogen, halogen, G-C4-alkyl and Ci-C4-halogenoalkyl having 1 to 5 halogen atoms; wherein the * in formulae A1 to A31 indicates the bond which connects A1 to A31 to the C=T moiety of the compounds of formula (I).
6. Use of a composition at least one compound of the formula (I) according to Claim 1, 2, 3, 4 or 5, in addition to extenders and/or surfactants for the control of phytopathogenic microorganisms in agriculture.
7. Use of a compound of the formula (I) according to Claim 1, 2, 3, 4 or 5 or of a composition according to claim 6 for treatment of transgenic plants for the control of phytopathogenic microorganisms in agriculture..
8. Use of a compound of the formula (I) according to Claim 1, 2, 3, 4 or 5 or of a composition according to claim 6 for treatment of seed and of seed of transgenic plants for the control of phytopathogenic microorganisms in agriculture..
9. Use according to anyone of claims 1 to 8 for the control of phytopathogenic fungi in agriculture.
10. Process for producing compositions for controlling phytopathogenic microorganisms, wherein in that a compound of the formula (I) according to 1, 2, 3, 4 or 5 are mixed with extenders and/or surfactants.
11. Method for controlling phytopathogenic microorganisms, wherein a compound of formula (I) according to Claim 1, 2, 3, 4 or 5 is applied to the phytopathogenic microorganisms, their habitat, the plant, the seed thereof, plant parts, plant propagation material or the soil on which the plants are grown or intended to be grown.
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