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WO2014095637A1 - Composés imidazole et triazole substitués en [1,2,4] - Google Patents

Composés imidazole et triazole substitués en [1,2,4] Download PDF

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Publication number
WO2014095637A1
WO2014095637A1 PCT/EP2013/076551 EP2013076551W WO2014095637A1 WO 2014095637 A1 WO2014095637 A1 WO 2014095637A1 EP 2013076551 W EP2013076551 W EP 2013076551W WO 2014095637 A1 WO2014095637 A1 WO 2014095637A1
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Prior art keywords
alkyl
cycloalkyl
compounds
alkoxy
phenyl
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PCT/EP2013/076551
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English (en)
Inventor
Wassilios Grammenos
Ian Robert CRAIG
Nadege Boudet
Bernd Müller
Jochen Dietz
Erica May Wilson LAUTERWASSER
Jan Klaas Lohmann
Thomas Grote
Egon Haden
Ana Escribano Cuesta
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Basf Se
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Publication of WO2014095637A1 publication Critical patent/WO2014095637A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/68—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/84—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/10—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members

Definitions

  • the present invention relates to substituted [1 ,2,4]triazol and imidazole compounds and the N- oxides and the salts thereof for combating phytopathogenic fungi, and to the use and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound.
  • the invention also relates to processes for preparing these compounds, intermediates, processes for preparing such intermediates, and to compositions comprising at least one compound I.
  • EP 0 040 345 relates to 1 -hydroxyethyl-azole-derivatives, to processes for their preparation and to their use as fungicides.
  • EP 0 565 436 relates to triazole and imidazole derivatives as fungicides.
  • EP 0 390 022 relates to azolylcyclopropanes, processes for their preparation and their use as fungicides.
  • EP 0 345 639 relates to alpha-hydroxy-azolylethyloxiranes and their use as fungicides.
  • EP 0 052 424 relates to triazoles and imidazoles, their preparation and their use as plant fungicides.
  • EP 0 486 409 relates to triazolyl- and imidazolyl methyl allyl alcohols and their use as fungicides.
  • EP 0 043 419 relates to microbiocidal 1 -hydroxyethyl-azole-derivatives.
  • DE 3719326 A1 relates to a fungicidal combination of active ingredients, wherein one of the components is an azole compound, e.g. compound lld-13, that is, however, not substituted at the phenyls of the biphenyl unit.
  • an azole compound e.g. compound lld-13
  • Pestic. Sci. 1995, 44, 183-195 relates to the relationship between chemical structurs and bio- logical activity of certain triazole fungicides against Botrytis cinerea, e.g. compound 9, containing an unsubstituted biphenyl unit.
  • WO 2012/0220638 A1 relates to certain 5-iodotriazole derivatives.
  • WO 2010/1461 13 A1 relates to untifungal 1 ,2,4-triazolyl derivatives having a 5-sulfur substituent.
  • WO 2010/1461 14 A1 also relates to further triazole compounds carrying a sulfur substituent.
  • WO 2010/1461 15 A1 relates to still further triazole compounds carrying a sulfur substituent.
  • the fungicidal activity of the known fungi- cidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic harmful fungi.
  • A is CH or N
  • R D is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-Ce-haloalkynyl or CN;
  • X is CN or OR 3 , wherein
  • R 3 wherein the aliphatic moieties of R 3 are unsubstituted or carry one, two, three or up to the maximum possible number of identical or different substituents R 3a independently selected from halogen, CN, nitro, OH, Ci-C 4 -alkoxy, Ci-C 4 -halogenalkoxy, Cs-Cs-cycloalkyl and C3-C8- cycloalkyl-Ci-C 4 -alkyl;
  • R 3 wherein the cycloalkyl and/or phenyl moieties of R 3 are unsubstituted or carry one, two, three, four, five or up to the maximum number of identical or different substituents R 3b independently selected from halogen, CN, nitro, OH, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, C1-C4- halogenalkyl, Ci-C 4 -halogenalkoxy, Cs-Cs-cycloalkyl and C3-Cs-cycloalkyl-Ci-C 4 -alkyl;
  • R 6a ,R 66a are independently selected from hydrogen, halogen, CN, NO2, OH, SH, d-Ce- alkyl, Ci-C6-hydroxyalkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C1-C6- alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-Ce- alkylsulfonyl, Ci-C6-haloalkylsulfonyl, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-haloalkoxy- Ci-C6-alkyl, Ci-C6-alkoxy-Ci-C6-haloalkyl, Ci-C6-haloalkoxy- Ci-C6-alkyl, Ci-C6-
  • R L is independently selected from halogen, CN, N0 2 , OH, Ci-C6-alkyl, Ci-C6-alkoxy,
  • R La is independently selected from halogen, CN, N0 2 , OH, SH, NH 2 , Ci-C 6 -alkyl, Ci-C 6 - haloalkyi, C 3 -C8-cycloalkyl, C 3 -C8-halocycloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio and Ci-C6-haloalkylthio;
  • Z-Y stands for group Z 1 -Y, wherein Y is a triple bond and Z 1 is C 3 -C6-cycloalkyl
  • R 4 is independently selected from halogen, CN, N0 2 , OH, SH, Ci-C 4 -alkyl, CiCi-C 4 -alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl, C 3 -Cs- cycloalkyl, C 3 -C8-cycloalkyl-Ci-C 4 -alkyl, C 3 -C8-cycloalkyloxy, phenyl, phenoxy, a 5- or 6- membered heteroaryl, a 5- or 6-membered heteroaryloxy, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C 3 -C 6 -cycloalkyl), N(C 3 -C 6 -cycl
  • R 4a is independently selected from halogen, CN, NO2, OH, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 3 -C 3 - cycloalkyl, C 3 -C8-halocycloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -halogenalkoxy;
  • n 0, 1 , 2, 3 or 4;
  • m+n is 1 , 2, 3, 4, 5, 6, 7, 8 or 9;
  • Z is not 4-CI-phenyl if Y is a direct bond or -0-;
  • R 5 ,R 6 ,R 55 and R 66 are all hydrogen, X is OH, n is 0 and D is H;
  • D is H and A is N.
  • the compounds I can be obtained by various routes in analogy to prior art processes known and by the synthesis routes shown in the following schemes.
  • the process steps in any combination and the intermediates as far as novel are also part of the present invention.
  • a base e.g, LDA, BuLi, LH MDS, /-PrMgCI, EtMgl , NaH, KH, f-BuOK, f- BuOK, TMPLi, TMPZn
  • cyanogen halide such as Br-CN or CI-CN
  • a base organic or inorganic base such as K2CO3, NaOH, KOH or NEt.3, DBU
  • suitable solvent such as acetone, MeCN or THF.
  • an alkylation agent such as metyl iodide a base (organic or inorganic base such as K2CO3, NaOH, KOH or NEt.3, DBU) in a suitable solvent such as acetone, MeCN or THF.
  • an electrophile e.g. Mel, ethyl bromide, cyclopropyl bromide, 1 ,4-dibromobutane, propargyl bromide, methyl chloroformate, allyl bromide, acety
  • a reagent e.g. cyanuric trichloride, NaCN, tetrabutylammonium cyanide
  • an additive e.g. N-tosylimidazole, Bu 4 NI, Bu 4 NCI, Bu 4 NBr, TMSCI, DDQ, PPh 3
  • an inert organic solvent e.g
  • this reaction is carried out at temperatures between 25 and 200°C, preferably from 50 to 170°C, in an inert organic solvent preferably (e.g. THF, DME, Et20, DMF, NMP, DMSO, toluene, acetonitrile) in the presence of a base (e.g. NaH, KH, CS2CO3, NEt.3, DBU, NaOAc, KOAc, K2CO3, KOH, NaOH, f-BuOK, NaOEt) and/or a catalyst (e.g.
  • a base e.g. NaH, KH, CS2CO3, NEt.3, DBU, NaOAc, KOAc, K2CO3, KOH, NaOH, f-BuOK, NaOEt
  • a catalyst e.g.
  • These compounds can be prepared for example in analogy to methods described in: WO2010/101461 13, WO2010/1461 12, Organic Letters (2002), 4(14), 2445-2448, Journal of Medicinal Chemistr (1987), 30(6), 1054-1068.
  • Epoxide VI can be prepared from the reaction of alkene Via and a reagent (e.g. H2O2, m-CPBA, t-BuOOH, oxone) in an inert solvent (e.g. THF, DME, Et 2 0, DMF, NMP, DMSO, toluene, acetonitrile).
  • a reagent e.g. H2O2, m-CPBA, t-BuOOH, oxone
  • an inert solvent e.g. THF, DME, Et 2 0, DMF, NMP, DMSO, toluene, acetonitrile.
  • epoxides VI can be synthesized in one step procedure from ketone VIII (see below) using known methods (Journal of Organic Chemistry, 33(7), 2789-93; 1968; DE 3315681 A1 ; DE 4109277 A1 ; WO 2010023862 A1 ; Synthetic Communications, 15(8), 749-57; 1985; WO 2010051503 A1 ; ).
  • Alkene Via can be synthesized by the reaction of ketone VI II and reagent (e.g. Tebbe reagent, dihalogenemethane, methylmagnesium halide, phosphonium salts of type R3P-CHR 1 R 2 or phosphonate salts of type (RO) 3 P-CHR 1 R 2 ) in the present of base (e.g. TMEDA, f-BuOK, , LDA, BuLi, NaOMe, potassium bis(trimethylsilyl)amide) or/an additive (e.g. PbC , Zn, TiCU, CsF) in an inert solvent (e.g.
  • base e.g. TMEDA, f-BuOK, , LDA, BuLi, NaOMe, potassium bis(trimethylsilyl)amide
  • additive e.g. PbC , Zn, TiCU, CsF
  • an inert solvent e.g.
  • a deprotonated alkyne is reacted with pivaloyl chloride (see e.g. Journal of Organic Chemistry, 77(7), 3627-3633; 2012; Green Chemistry, 13(1 1 ), 3238-3247; 201 1 ; DE 3824434).
  • a base leads to epoxides, that can be o ened with triazole (see e.g. DE3824434) to obtain the desired compounds.
  • Ketone VIII can be synthesized for example by the reaction of a benzylic derivative XII and a f- butyl ketone Villa. This reaction takes places in the presence of a base (e.g.KOH, NaOH, BuLi, LDA, /-Pr 2 NH, f-BuOK, f-BuONa) in an inert organic solvent (e.g. THF, DME, Et 2 0, DMF, NMP, DMSO, toluene, acetonitrile) preferably.
  • a base e.g.KOH, NaOH, BuLi, LDA, /-Pr 2 NH, f-BuOK, f-BuONa
  • an inert organic solvent e.g. THF, DME, Et 2 0, DMF, NMP, DMSO, toluene, acetonitrile
  • a f-butyl metal species e.g. f-butyllithium; f- butylmagnesium bromide, di-f-butylmagnesium
  • ketone VII e.g. THF, DME, Et 2 0, DMF, NMP, DMSO, toluene, acetonitrile.
  • This reaction takes places by the formation of the corresponding metal species of Villa via insertion (e.g. Mg/ZnC , Li, Mg) or exchange reaction (e.g BuLi, Li-naphthalide) in an inert organ- ic solvent preferably (e.g. THF, DME, Et 2 0, DMF, NMP, DMSO, toluene, acetonitrile).
  • inert organ- ic solvent preferably (e.g. THF, DME, Et 2 0, DMF, NMP, DMSO, toluene, acetonitrile).
  • This reaction takes places by the formation of the correspond metal species of XX via insertion (e.g. Mg/ZnC , Li, Mg) or exchange reaction (e.g BuLi, Li-naphthalide) in an inert organic solvent preferably (e.g. THF, DME, Et 2 0, DMF, NMP, DMSO, toluene, acetonitrile).
  • insertion e.g. Mg/ZnC , Li, Mg
  • exchange reaction e.g BuLi, Li-naphthalide
  • an inert organic solvent preferably (e.g. THF, DME, Et 2 0, DMF, NMP, DMSO, toluene, acetonitrile).
  • Halide X can be obtained alcohol XI, in particular with methods to the skilled person (see also Organic Process Research & Development (2007), 1 1 (1 ), 156-159, Journal of Organometallic Chemistry (2003), 684(1 -2), 20-36) and following by the transformation of the alcohol in a halide (e.g. Tetrahedron Letters (2008), 49(7), 1 146-1 148, Tetrahedron Letters (2007), 48(2), 223- 226.). Ketones IX and alkohols XI are commercial available or literature known and/orcan be prepare din analogyto processes known to the skilled person. halogenating reagent ,
  • the N-oxides may be prepared from the inventive compounds according to conventional oxidation methods, e. g. by treating compounds I with an organic peracid such as metachloroper- benzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(1 1 ), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981 ) or oxone (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001 ).
  • the oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
  • C n -C m indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • Ci-C6-alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2- methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl,
  • C2-C4-alkyl refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1 -methylethyl (iso-propoyl), butyl, 1 -methylpropyl (sec. -butyl), 2-methylpropyl (iso-butyl), 1 ,1 -dimethylethyl (tert. -butyl).
  • Ci-C6-haloalkyl refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • Examples are "Ci-C2-haloalkyl” groups such as chloromethyl, bro- momethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 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,
  • Ci-C6-hydroxyalkyl refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by OH groups.
  • C2-C6-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.
  • Examples are “C2-C4-alkenyl” groups, such as ethenyl, 1 -propenyl, 2-propenyl (allyl), 1 -methylethenyl, 1 -butenyl, 2-butenyl,
  • C2-C6-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond.
  • Examples are "C2-C4- alkynyl” groups, such as ethynyl, prop-1 -ynyl, prop-2-ynyl (propargyl), but-1 -ynyl, but-2-ynyl, but-3-ynyl , 1 -methyl-prop-2-ynyl .
  • Cs-Cs-cycloalkyl refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • C3-C8-cycloalkyl-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical hav- ing 3 to 8 carbon atoms (as defined above).
  • Ci-C6-alkoxy refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group.
  • Examples are “C1-C4- alkoxy” groups, such as methoxy, ethoxy, n-propoxy, 1 -methylethoxy, butoxy, 1 - methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
  • Ci-C6-haloalkoxy refers to a Ci-C6-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • Examples are "Ci-C4-haloalkoxy” groups, such as OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoro- ethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-tri- chloro-"ethoxy, OC2F5, 2-fluoro
  • 2,3-difluoro -, propoxy 2 chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bro- mo-'propoxy, 3 bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1 -fluoromethyl-2-fluoroethoxy, 1 -chloromethyl-2-chloroethoxy, 1 -bromomethyl-2- bromo-'ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
  • phenyl-Ci-C6-alkyl refers to alkyl having 1 to 6 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a phenyl radical.
  • phenyl-C2-C6-alkenyl and “phenyl-C2-C6-alkynyl” refer to alkenyl and alkynyl, respectively, wherein one hydrogen atom of the aforementioned radicals is replaced by a phenyl radical.
  • Ci-C4-alkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group (as defined above).
  • Ci-C4-alkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C6-alkoxy group (as defined above).
  • Ci-C6-alkylthio refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as defined above) bonded via a sulfur atom. Accordingly, the term “Ci- C6-haloalkylthio” as used herein refers to straight-chain or branched haloalkyi group having 1 to 6 carbon atoms (as defined above) bonded through a sulfur atom, at any position in the haloalkyi group.
  • C 3 -C8-cycloalkyl-C 3 -C8-cycloalkyl refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above), which is substituted by a further cycloalkyl radical having 3 to 8 carbon atoms.
  • C 3 -C8-cycloalkoxy refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above), which is bonded via an oxygen.
  • the number of valence of carbon is 4, that of nitrogen is 3.
  • saturated or partially unsaturated 3-, 4- 5-, 6- or 7-membered carbocycle is to be understood as meaning both saturated or partially unsaturated carbocycles having 3, 4, 5, 6 or 7 ring members.
  • Examples include cyclopropyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptenyl, cycloheptadienyl, and the like.
  • saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroa- toms independently selected from the group of N, O and S is to be understood as meaning both saturated and partially unsaturated heterocycles, for example:
  • a 3- or 4-membered saturated heterocycle which contains 1 or 2 heteroatoms from the group consisting of N, O and S as ring members such as oxirane, aziridine, thiirane, oxetane, azet- idine, thiethane, [1 ,2]dioxetane, [1 ,2]dithietane, [1 ,2]diazetidine; and
  • a 5- or 6-membered saturated or partially unsaturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of N, O and S as ring members such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,
  • a 7-membered saturated or partially unsaturated heterocycle such as tetra- and hexahydroaze- pinyl, such as 2,3,4,5-tetrahydro[1 H]azepin-1 -,-2-,-3-,-4-,-5-,-6- or-7-yl, 3,4,5,6-tetra- hydro[2H]azepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -,-2-,-3-,-4-,-5-,-6- or-7- yl, 2,3,6,7-tetrahydro[1 H]azepin-1 -,-2-,-3-,-4-,-5-,-6- or-7-yl, hexahydroazepin-1 -,-2-,-3- or-4-yl, tetra- and hexahydrooxepinyl such as 2,3,4,5-tetrahydro[1 H
  • 5-or 6-membered heteroaryl refers to aromatic ring systems incuding besides carbon atoms, 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, for example,
  • a 5-membered heteroaryl such as pyrrol-1 -yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan- 2-yl, furan-3-yl, pyrazol-1 -yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1 -yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-
  • a 6-membered heteroaryl such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyri- dazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
  • Agriculturally acceptable salts of the inventive compounds encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of said compounds.
  • Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manga- nese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammoni- um, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phos- phonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting such inventive compound with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
  • the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or dia- stereomers and their mixtures are subject matter of the present invention.
  • a according to the invention is N or CH. According to one embodiment A is N. According to a further embodiment A is CH.
  • R D is hydrogen, halogen or SR D , wherein R D is hydrogen, CN, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl or
  • D is hydrogen.
  • D is halogen, in particular iodine.
  • D is SR D .
  • R D is H.
  • R D is CN.
  • X is OR 3 .
  • R 3 is hydrogen, Ci-C6-alkyl, C2-C6- alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyI, C3-C8-cycloalkyl-Ci-C6-alkyl, phenyl, phenyl-Ci-C4-alkyl, phenyl-C2-C4-alkenyl or phenyl-C2-C4-alkynyl; wherein the aliphatic moieties of R 3 may carry one, two, three or up to the maximum possible number of identical or different groups R 3a which independently of one another are selected from R 3a halogen, OH, CN, nitro, Ci-C4-alkoxy, C3- Ce-cycloalkyl, Cs-Cs-halocycloalkyl and Ci-C4-halogenalkoxy; and wherein the cycloalkyl and/or
  • R 3 is H.
  • R 3 is selected from Ci-C6-alkyl, C2-C6- alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyI, C3-Cs-cycloalkyl-Ci-C4-alkyl, phenyl, phenyl-Ci-C4-alkyl, phenyl-C2-C4-alkenyl and phenyl-C2-C4-alkynyl, wherein the R 3 are in each case unsubstituted or are substituted by R 3a and/or R 3b as defined and preferably defined herein. Specific embodiments thereof can be found in the below Table P3.
  • R 3 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH 3 , C 2 H 5 , CH(CH 3 ) 2 , CH2CH2CH3, CH2CH2CH2CH3, CH 2 CH(CH 3 ) 2 .
  • a further embodiment relates to compounds, wherein R 3 is Ci-C6-alkyl, in particular Ci-C4-alkyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 3a , as defined and preferably defined herein.
  • R 3 is C1-C6- haloalkyl, in particular Ci-C4-haloalkyl, more particularly Ci-C2-haloalkyl.
  • R 3 is Ci-C4-alkoxy-Ci-C6-alkyl, in particular Ci-C4-alkoxy-Ci-C4- alkyl, such as CH2OCH3 or CH2CH2OCH3.
  • R 3 is hydroxy-Ci-C6-alkyl, in particular hydroxyl-Ci-C4-alkyl, such as CH2CH2OH. Further specific embodiments thereof can be found in the below Table P3
  • R 3 is C3-C8-cycloalkyl-Ci-C6-alkyl, in particular C3-C6- cycloalkyl-Ci-C4-alkyl.
  • a further embodiment relates to compounds, wherein R 3 is C3-C8- cycloalkyl-Ci-C6-alkyl, in particular C3-C6-cycloalkyl-Ci-C4-alkyl, more particularly C3-C6- cycloalkyl-Ci-C2-alkyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 3a in the alkyl moiety and/or substituted by one, two, three four or five or up to the maximum possible number of identical or different groups R 3b in the cycloalkyl moiety.
  • R 3a and R 3b are in each case as defined and preferably defined herein. Specific embodiments thereof can be found in the below Table P3.
  • a further embodiment relates to compounds, wherein R 3 is C2-C6-alkenyl, in particular C2-C4-alkenyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 3a as defined and preferably defined herein.
  • R 3 is C3-C8-cycloalkyl-C 2 -C6-alkenyl or C3-C8-halocycloalkyl-C 2 -C6- alkenyl, in particular C3-C6-cycloalkyl-C 2 -C 4 -alkenyl or C3-C6-halocycloalkyl-C 2 -C 4 -alkenyl. Further specific embodiments thereof can be found in the below Table P3.
  • R 3 is C 2 -C6-alkynyl, in particular C 2 -C 4 -alkynyl, such as CH 2 C ⁇ CH or CH 2 C ⁇ CCH3.
  • a further embodiment relates to compounds, wherein R 3 is C 2 -C6- alkynyl, in particular C 2 -C 4 -alkynyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 3a , as defined and preferably defined herein.
  • R 3 is C 2 -C6-haloalkynyl, in particular C 2 -C 4 - haloalkynyl.
  • R 3 is C3-C8-cycloalkyl-C 2 -C6- alkynyl or C3-C8-halocycloalkyl-C 2 -C6-alkynyl, in particular C3-C6-cycloalkyl-C 2 -C 4 -alkynyl or C3- C6-halocycloalkyl-C 2 -C 4 -alkynyl. Specific embodiments thereof can be found in the below Table P3.
  • R 3 is phenyl-Ci-C 4 -alkyl, in particular phenyl-Ci-C 2 -alkyl, such as benzyl, wherein the alkyl moiety in each case is unsubstituted or carries one, two or three R 3a as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C 4 -alkoxy, in particular OCH3, and CN, and wherein the phenyl in each case is unsubstituted or carries one, two or three R 3b as as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C 4 -alkoxy, in particular OCH3, C1-C4- alkyl, in particular CH3 or C 2 H 5 , and CN. Specific embodiments thereof can be found in the below Table P3.
  • R 3 is phenyl-C 2 -C 4 -alkenyl, in particular phenyl-C 2 -C3- alkenyl, such as phenylethenyl, wherein the alkenyl moiety in each case is unsubstituted or carries one, two or three R 3a as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C 4 -alkoxy, in particular OCH3, and CN, and wherein the phenyl in each case is unsubstituted or carries one, two or three R 3b as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C 4 -alkoxy, in particular OCH 3 , Ci-C 4 -alkyl, in particular CH 3 or C 2 H 5 , and CN.
  • R 3 is phenyl-C 2 -C 4 -alkynyl, in particular phenyl-C 2 -C3- alkynyl, such as phenylethinyl, wherein the alkynyl moiety in each case is unsubstituted or carries one, two or three R 3a , as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C 4 -alkoxy, in particular OCH3, and CN, and wherein the phe- nyl in each case is unsubstituted or carries one, two or three R 3b as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C 4 -alkoxy, in particular OCH3, Ci-C 4 -alkyl, in particular CH3 or C 2 H 5 , and CN.
  • R 3 is Cs-Cs-cycloalkyl, in particular C3-C6-cycloalkyl, such as C3H5 (cyclopropyl), C 4 H 7 (cyclobutyl), cyclopentyl or cyclohexyl.
  • a further embodiment relates to compounds, wherein R 3 is Cs-Cs-cycloalkyl, in particular C3-C6-cycloalkyl, such as C3H5
  • R 3 is Cs-Cs-halocycloalkyl, in particular C3- C6-halocycloalkyl, such as halocyclopropyl, in particular 1 -F-cyclopropyl or 1 -CI-cyclopropyl.
  • R 3 is Cs-Cs-cycloalkyl-Cs-Cs-cycloalkyl, in particular C3-C6-cycloalkyl-C3-C6-cycloalkyl, wherein each of said cycloalkyl-cycloalkyi moieties is unsubstituted or carries one, two or three R 3b as defined and preferably defined herein.
  • R 3 is phenyl, wherein the phenyl is unsubstituted or carries one, two, three, four or five independently selected R 3b as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH3, Ci-C 4 -alkyl, in particular CH 3 or C 2 H 5 , and CN.
  • R 3 is selected from hydrogen, Ci-C6-alkyl, C2-C6- alkenyl and C2-C6-alkynyl, wherein the R 3 are in each case unsubstituted or are substituted by R 3a and/or R 3b as defined and preferably defined herein.
  • the substituents may also have the preferred meanings for the respective substituent as defined above. Specific embodiments thereof can be found in the below Table P3.
  • R 3 Particularly preferred embodiments of R 3 according to the invention are in Table P3 below, wherein each line of lines P3-1 to P3-88 corresponds to one particular embodiment of the invention, wherein P3-1 to P3-88 are also in any combination a preferred embodiment of the present invention.
  • R 6a ,R 66a are independently selected from hydrogen, halogen, CN, N0 2 , OH , SH, d-Ce-alkyl, Ci-C6-hydroxyalkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylsulfonyl, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-haloalkoxy-Ci-C6-alkyl, Ci-C6-alkoxy-Ci-C6-haloalkyl, Ci-C6-haloalkoxy-Ci-C6-
  • R 6a and R 66a together with the carbon atoms to which they are bound form a saturated or partially unsaturated three-, four-, five-, six- or seven-membered carbo- or heterocycle; wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the carbo- or heterocycle is unsubstituted or carries one, two, three or four substituents independently selected from halogen, CN, NO2, OH, SH, NH 2 , d-Ce-alkyl, d-Ce-haloalkyl,
  • R 5 ,R 6 ,R 55 ,R 66 are hydrogen.
  • R 6a and R 66a are preferably independently selected from the group consisting of hydrogen, halogen, CN, NO2, OH, SH, NH2, Ci-C6-alkyl,
  • Ci-C6-haloalkyl Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio and C1-C4- alkoxy-Ci-C4-alkyl.
  • R 6a and R 66a are independently selected from hydrogen, halogen, CN, N0 2 , OH, SH, NH 2 , Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy,
  • R 6a and R 66a are preferably selected from hydrogen, halogen, CN, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
  • R 6a and R 66a are selected from hydrogen, halogen, CN and Ci-C6-alkyl.
  • R 6a and R 66a are independently selected from hydrogen and halogen, in particular hydrogen and fluorine.
  • R 6a and R 66a are independently selected from hydrogen and Ci-C6-alkyl, in particular hydrogen and Ci-C4-alkyl, even more specifically hydrogen, methyl and ethyl.
  • R 6a and R 66a are independently selected from hydrogen, halogen, CN, (Ci-C 6 )-alkyl and (Ci-C 6 )-haloalkyl.
  • R 6a and R 66a are both hydrogen, taking into account the above proviso.
  • at least one of R 6a and R 66a is not hydrogen, in a particular embodiment thereof, the R 6a and/or R 66a that are not hydrogen is/are selected from halogen, CN, (Ci-Ce)-alkyl and (Ci-C6)-haloalkyl, more specifically selected from CI, Br, F, CN, (Ci-C4)-alkyl and (Ci-C4)-haloalkyl.
  • R 5 , R 6 , R 55 and R 66 together with the carbon atoms to which they are bound form a triple bond, taking into account the above proviso.
  • Each R 4 according to the present invention is independently selected from halogen, CN, NO2, OH , SH , d-Ce-alkyl, Ci-C 6 -alkoxy, Ci-C 6 -alkylthio, Ci-C 6 -alkylsulfinyl, Ci-C 6 -alkylsulfonyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, Cs-Cs-cycloalkyloxy, phenyl, phenoxy, a 5- or 6-membered heteroaryl, a 5- or 6-membered heteroaryloxy, N H2, N H(Ci-C 4 -alkyl), N(Ci-C 4 -alkyl) 2 , N H(C 3 -C 6 -cycloalkyl), N(C 3 -C 6 -
  • n 0, 1 , 2, 3 or 4.
  • n+n is 1 , 2, 3, 4, 5, 6, 7, 8 or 9.
  • n is 0. According to a further embodiment, n is 1.
  • n is 2 or 3. According to one specific embodiment thereof, n is 2, according to a further specific embodiment, n is 3.
  • one R 4 is attached to the 2-position (R 41 ).
  • n 1 , according to a further specific
  • n is 2.
  • one R 4 is attached to the 3-position (R 42 ).
  • n 1 , according to a further specific
  • n is 2.
  • one R 4 is attached to the 4-position (R 43 ).
  • n is 1 , according to a further specific
  • n is 2.
  • one R 4 is attached to the 5-position (R 44 ).
  • n is 1 , according to a further specific
  • n is 2.
  • n is 1 , 2 or 3 and one R 4 is in 2- or 6-position.
  • one R 4 is attached to the 6-position (R 45 ).
  • n is 1 , according to a further specific
  • n is 2. According to a further embodiment of the invention, two R 4 are attached in 2,3-position.
  • n is 2, according to a further specific
  • n 3.
  • two R 4 are attached in 2,4-position.
  • n is 2, according to a further specific
  • n 3.
  • two R 4 are attached in 2,5-position.
  • n is 2, according to a further specific
  • n 3.
  • two R 4 are attached in 2,6-position.
  • n is 2, according to a further specific
  • n 3.
  • two R 4 are attached in 3,4-position.
  • n is 2, according to a further specific
  • n 3.
  • two R 4 are attached in 3,5-position.
  • n is 2, according to a further specific
  • n 3.
  • two R 3 are attached in 3,6-position.
  • n is 2, according to a further specific
  • n 3.
  • R 4 (or R 41 , R 42 , R 43 , R 44 , R 45 , respectively) that is present in the inventive compounds
  • the following embodiments and preferences apply independently of the meaning of any other R 4 (or R 41 , R 42 , R 43 , R 44 , R 45 , respectively) that may be present in the phenyl ring.
  • R 4 is independently selected from F, CI, Br, CN, C1-C4- alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, S(Ci-C 4 -alkyl), S(0)(Ci-C 4 -alkyl) and S(0) 2 (Ci-C 4 -alkyl).
  • R 4 is halogen, in particular Br, F or CI, more specifically F or CI.
  • R 4 is CN
  • R 4 is Ci-C6-alkyl, in particular Ci-C 4 -alkyl, such as CH 3 .
  • R 4 is Ci-C6-haloalkyl, in particular Ci-C 4 -haloalkyl, such as CF 3 , CHF 2 , CH 2 F, CCI 3 , CHCI 2 or CH 2 CI.
  • R 4 is Ci-C6-alkoxy, in particular Ci-C 4 -alkoxy, more specifically Ci-C 2 -alkoxy such as OCH 3 or OCH 2 CH 3 .
  • R 4 is Ci-C6-haloalkoxy, in particular Ci-C 4 - haloalkoxy, more specifically Ci-C 2 -haloalkoxy such as OCF 3 , OCHF 2 , OCH 2 F, OCCI 3 , OCHCI 2 or OCH 2 CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHCI 2 .
  • R 4 is C 2 -C6-alkynyl or C 2 -C6-haloalkynyl, in particular C 2 -C 4 -alkynyl or C 2 -C 4 -haloalkynyl, such as C CH.
  • R 4 is selected from S(Ci-C 2 -alkyl), S(0)(Ci-C 2 -alkyl) and S(0) 2 (Ci-C 2 -alkyl), in particular SCH 3 , S(0)(CH 3 ) and S(0) 2 (CH 3 ).
  • R 4 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R 4a , as defined herein.
  • R 4 is unsubstituted phenoxy or phenoxy that is substituted by one, two, three or four R 4a , as defined herein.
  • R 4 is unsubstituted 5- or 6-membered heteroaryl.
  • R 4 is 5- or 6-membered heteroaryl that is substituted by one, two or three R 4a , as defined herein.
  • the heteroaryl in each case is 5-membered such as .
  • the heteroaryl in each case is 6-membered such as .
  • R 4 is unsubstituted 5- or 6-membered heteroaryloxy.
  • R 4 is 5- or 6-membered heteroaryloxy that is substituted by one, two or three R 4a , as defined herein.
  • the heteroaryloxy in each case is 5-membered.
  • the heteroaryloxy in each case is 6-membered.
  • R 4a is independently selected from halogen, CN, NO2, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C8- cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy, in particular selected from halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C2- alkoxy and Ci-C2-halogenalkoxy.
  • R 4a is independently selected from F, CI, CN, OH, CH3, halomethyl, cyclopropyl, halocyclopropyl, OCH3 and halogenmethoxy.
  • R 4 Particularly preferred embodiments of R 4 according to the invention are in Table P5 below, wherein each line of lines P5-1 to P5-17 corresponds to one particular embodiment of the invention, wherein P5-1 to P5-17 are also in any combination with one another a preferred embodiment of the present invention.
  • Table P5 wherein each line of lines P5-1 to P5-17 corresponds to one particular embodiment of the invention, wherein P5-1 to P5-17 are also in any combination with one another a preferred embodiment of the present invention.
  • P6a-3 4-CI P6a-22 2-SOCH 3 P6a-41 2,5-F 2
  • P6a-7 4-F P6a-26 2-S0 2 CH 3 P6a-45 5,6-F 2
  • P6a-1 1 4-CN P6a-30 2-C0 2 CH 3 P6a-49 2-CI-4-F
  • P6a-60 4-CHs P6a-100 4,5-(CH 2 CH 3 ) 2 P6a-140 2,4,6-(CH 3 ) 3
  • Z-Y is bound to the phenyl via Y, wherein Y is a direct bond or a divalent group selected from the group consisting of -0-, -S-, -SO-, SO2-, -NH-, -N(Ci-C 4 -alkyl)-, -CR 12 R 13 -, -CR 12 R 13 -
  • CR 14 R 15 -, -CR 16 CR 17 -and -C ⁇ C-; wherein R 12 ,R 13 ,R 14 ,R 15 ,R 16 and R 17 are independently selected from hydrogen, halogen, CN, nitro, OH, Ci-C 4 -alkyl, Ci-C 4 -halogenalkyl, Ci-C 4 -alkoxy and Ci-C 4 -halogenalkoxy.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is attached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • Y is a direct bond.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is at- tached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • Y is -0-.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is attached to the meta-position (3-position).
  • Z-Y is attached to the para- position (4-position).
  • Y is -S-.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is attached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • Y is -SO-.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is attached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • Y is -SO2-.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is attached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • Y is -NH-.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is at- tached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • Y is -N(Ci-C4-alkyl)-.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is attached to the meta-position (3-position).
  • Z-Y is at- tached to the para-position (4-position).
  • Y is -CR 12 R 13 -.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is at- tached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • R 12 and R 13 are independently selected from hydrogen, halogen, CN, nitro, OH , Ci-C4-alkyl, Ci- C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
  • R 12 and R 13 are independently selected from hydrogen and halogen, in particular hydrogen, fluorine and chlorine.
  • R 12 and R 13 are independently selected from hydrogen and Ci-C4-alkyl, in particular hydrogen, methyl and ethyl.
  • R 12 and R 13 are independently selected from hydrogen and Ci-C4-alkoxy, in particular hydrogen, methoxy and ethoxy.
  • R 12 and R 13 are independently selected from hydrogen and CN. In yet another preferred embodiment R 12 and R 13 are independently selected from hydrogen and OH.
  • Y is -CR 12 R 13 -CR 14 R 15 -.
  • Z-Y is attached to the ortho-position (2-position).
  • Z- Y is attached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • R 12 ,R 13 ,R 14 and R 15 are independently selected from hydrogen, halogen, CN, nitro, OH , C1-C4- alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
  • R 12 ,R 13 ,R 14 and R 15 are independently selected from hydrogen and halogen, in particular hydrogen, fluorine and chlorine. In a further preferred embodiment R 12 ,R 13 ,R 14 and R 15 are independently selected from hydrogen and Ci-C4-alkyl, in particular hydrogen, methyl and ethyl. In a preferred embodiment, R 12 ,R 13 ,R 14 and R 15 are independently selected from hydrogen and Ci-C4-alkoxy, in particular hydrogen, methoxy and ethoxy. In another preferred embodiment, R 12 ,R 13 ,R 14 and R 15 are independently selected from hydrogen and CN. In yet another preferred embodiment R 12 ,R 13 ,R 14 and R 15 are independently selected from hydrogen and OH.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is attached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • R 16 and R 17 are independently selected from hydrogen, halogen, CN, nitro, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
  • R 16 and R 17 are independently selected from hydrogen and halogen, in particular hydrogen, fluorine and chlorine. In a further preferred embodiment R 16 and R 17 are independently selected from hydrogen and Ci-C4-alkyl, in particular hydrogen, methyl and ethyl. In a preferred embodiment, R 16 and R 17 are independently selected from hydrogen and Ci-C4-alkoxy, in particular hydrogen, methoxy and ethoxy. In another preferred embodiment
  • R 16 and R 17 are independently selected from hydrogen and CN. In yet another preferred embodiment R 16 and R 17 are independently selected from hydrogen and OH.
  • Y is -C ⁇ C-.
  • Z-Y is attached to the ortho-position (2-position).
  • Z-Y is at- tached to the meta-position (3-position).
  • Z-Y is attached to the para-position (4-position).
  • R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 are independently selected from hydrogen, halogen, CN, nitro, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
  • R 12 ,R 13 ,R 14 ,R 15 ,R 16 and R 17 are independently selected from hydrogen and halogen, in particular hydrogen, fluorine and chlorine.
  • R 12 ,R 13 ,R 14 ,R 15 ,R 16 and R 17 are independently selected from hydrogen and C1-C4- alkyl, in particular hydrogen, methyl and ethyl.
  • R 12 ,R 13 ,R 14 ,R 15 ,R 16 and R 17 are independently selected from hydrogen and Ci-C4-alkoxy, in particular hydrogen, methoxy and ethoxy.
  • R 12 ,R 13 ,R 14 ,R 15 ,R 16 and R 17 are independently selected from hydrogen and CN.
  • yet another preferred embodiment
  • R 12 ,R 13 ,R 14 ,R 15 ,R 16 and R 17 are independently selected from hydrogen and OH.
  • Z is phenyl that is unsubstituted or substituted by (R L ) m .
  • R L there can be zero, one, two, three, four or five R L present, namely for m is 0, 1 , 2, 3, 4 or 5.
  • m is 0, 1 , 2, 3 or 4.
  • n has to be at least 1 , see above.
  • n is 0 with the above proviso, and n has to be at least 1 , see above.
  • m is 1 , 2, 3 or 4, in particular 1 , 2 or 3, more specifically 1 or 2. According to one specific embodiment thereof, m is 1 , according to a further specific embodiment, m is 2.
  • m is 2, 3 or 4.
  • m is 3.
  • one R L is attached to the para-position (4- position).
  • one R L is attached to the meta-position (3- position).
  • one R L is attached to the ortho-position (2- position).
  • two R L are attached in 2, 4-position.
  • two R L are attached in 2, 3-position.
  • two R L are attached in 2,5-position.
  • two R L are attached in 2,6-position.
  • two R L are attached in 3, 4-position.
  • two R L are attached in 3,5-position.
  • R L are attached in 2,4,6-position.
  • the following embodiments and preferences apply independently of the meaning of any other R L that may be present in the phenyl ring.
  • R La is independently selected R La , wherein R La is as defined and preferably defined herein.
  • R L is independently selected from halogen, CN, NO2, C1-C4- alkyl, Ci-C 4 -alkoxy, C2-C 4 -alkenyl, C2-C 4 -alkynyl, C 3 -C6-cycloalkyl, C 3 -C6-cycloalkyloxy, NH2, NH(Ci-C 42 -alkyl), N(Ci-C 2 -alkyl) 2 , S(Ci-C 2 -alkyl), S(0)(Ci-C 2 -alkyl), S(0) 2 (Ci-C 2 -alkyl),
  • each of R L is unsubstituted or further substituted by one, two, three or four independently selected R La , wherein R La is as defined and preferably defined herein.
  • R L is independently selected from F, CI, Br, CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, S(Ci-C 4 -alkyl), S(0)(Ci-C 4 -alkyl) and S(0) 2 (Ci- C 4 -alkyl).
  • R L is independently selected from halogen, in particular from Br, F and CI, more specifically from F and CI.
  • R L is CN. According to one further embodiment R L is NO2.
  • R L is OH
  • R L is SH.
  • R L is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH3.
  • Further appropriate alkyls are ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl.
  • R L is Ci-C6-haloalkyl, in particular Ci-C4-haloalkyl, such as CF 3 , CHF 2 , CH 2 F, CCI 3 , CHC or CH 2 CI.
  • R L is Ci-C6-alkyl, preferably Ci-C4-alkyl, substituted by OH, more preferably CH 2 OH, CH 2 CH 2 OH, CH 2 CH 2 CH 2 OH, CH(CH 3 )CH 2 OH,
  • R L is CH 2 CH(CH 3 )OH, CH 2 CH 2 CH 2 CH 2 OH.
  • R L is CH 2 OH.
  • R L is Ci-C6-alkyl, preferably Ci-C4-alkyl substituted by CN, more preferably CH 2 CN, CH 2 CH 2 CN, CH 2 CH 2 CH 2 CN, CH(CH 3 )CH 2 CN, CH 2 CH(CH 3 )CN, CH 2 CH- 2 CH 2 CH 2 CN.
  • R L is CH 2 CH 2 CN.
  • R 4 is CH(CH 3 )CN.
  • R L is Ci-C4-alkoxy-Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl.
  • R L is CH 2 OCH 3 .
  • R L is CH 2 CH 2 OCH 3 .
  • R L is CH(CH 3 )OCH 3 .
  • R L is CH(CH 3 )OCH 2 CH 3 .
  • R L is CH 2 CH 2 OCH 2 CH 3 .
  • R L is Ci-C4-haloalkoxy-Ci-C6- alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl.
  • R L is CH 2 OCF 3 .
  • R L is CH 2 CH 2 OCF 3 .
  • R L is
  • R L is CH 2 CH 2 OCCI 3 .
  • R L is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C 2 -alkoxy such as OCH 3 or OCH 2 CH 3 .
  • R L is Ci-C6-haloalkoxy, in particular C1-C4- haloalkoxy, more specifically Ci-C 2 -haloalkoxy such as OCF 3 , OCHF 2 , OCH 2 F, OCCI 3 , OCHCI 2 or OCH2CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHCI 2 .
  • R L is Ci-C4-alkoxy-C 2 -C6-alkenyl, more preferably Ci-C4-alkoxy-C 2 -C4-alkenyl.
  • R L is C1-C4- haloalkoxy-C 2 -C6-alkenyl, more preferably Ci-C4-haloalkoxy-C 2 -C4-alkenyl.
  • R L is
  • R L is C 3 -C8-cycloalkyl-C 2 -C6- alkenyl, preferably C3-C6-cycloalkyl-C2-C4-alkenyl.
  • R L is C3-C6-halocycloalkyl-C2-C4-alkenyl, preferably C3-C8-halocycloalkyl-C2-C6-alkenyl.
  • R L is C2-C6-alkynyl or C2-C6-haloalkynyl, in particular C 2 -C 4 -alkynyl or C 2 -C 4 -haloalkynyl, such as C ⁇ CH, CH 2 CCH or CH2CCCH3.
  • R L is C2-C6-alkynyl, preferably C2-C 4 -alkynyl, substituted by OH, more preferably, CCOH, CH 2 CCOH.
  • R L is CCOH.
  • R L is CH2CCOH.
  • R L is Ci-C 4 -alkoxy-C2-C6-alkynyl, more preferably Ci-C 4 -alkoxy-C2-C 4 -alkynyl.
  • R L is CCOCH3.
  • R L is CH2CCOCH3.
  • R L is Ci-C 4 -haloalkoxy-C2-C6-alkynyl, more preferably Ci-C 4 -haloalkoxy- C2-C 4 -alkynyl.
  • R L is CCOCF3.
  • R L is CH2CCOCF3.
  • R L is CCOCCI3.
  • R L is CH2CCOCCI3.
  • R L is C3-C8-cycloalkyl-C2-C6- alkynyl, preferably C3-C6-cycloalkyl-C2-C 4 -alkynyl.
  • R L is C3-C6-halocycloalkyl-C2-C 4 -alkynyl, preferably C3-C8-halocycloalkyl-C2-C6-alkynyl.
  • R L is Cs-Cs-cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl.
  • R L is cyclopropyl.
  • R L is cyclobutyl.
  • R 4 is cyclopentyl.
  • R L is cyclohexyl.
  • R L is Cs-Cs-cycloalkoxy, preferably C3-C6-cycloalkoxy.
  • R L is O-cyclopropyl.
  • R L is Cs-Cs-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl.
  • R L is fully or partially halogenated cyclopropyl.
  • R L is 1-CI-cyclopropyl.
  • R L is 2-CI-cyclopropyl.
  • R L is 1-F-cyclopropyl.
  • R L is 2-F-cyclopropyl.
  • R L is fully or partially halogenated cyclobutyl.
  • R L is 1-CI-cyclobutyl.
  • R L is 1-F-cyclobutyl. In a further special embodiment R L is 3,3-Cl2-cyclobutyl. In a further special embodiment R L is 3,3-F2-cyclobutyl. According to a specific embodiment R L is C3- Cs-cycloalkyl substituted by Ci-C 4 -alkyl, more preferably is C3-C6-cycloalkyl substituted by Ci- C 4 -alkyl. In a special embodiment R L is 1-CH3-cyclopropyl. According to a specific embodiment R L is Cs-Cs-cycloalkyl substituted by CN, more preferably is C3-C6-cycloalkyl substituted by CN.
  • R L is 1-CN-cyclopropyl.
  • R L is C3-C8-cycloalkyl-C3-C8-cycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-cycloalkyl.
  • R L is cyclopropyl-cyclopropyl.
  • R L is 2-cyclopropyl- cyclopropyl.
  • R L is C3-Cs-cycloalkyl-C3-Cs- halocycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-halocycloalkyl.
  • R L is C3-C8-cycloalkyl-Ci-C 4 -alkyl, preferably C3-C6- cycloalkyl-Ci-C 4 -alkyl.
  • R L is CH(CH3)(cyclopropyl).
  • R L is CH2-(cyclopropyl).
  • R L is C3-C8-cycloalkyl-Ci-C4-alkyl wherein the alkyl moiety can be substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein and the cycloalkyi moiety can be substituted by one, two, three or up to the maximum possible number of identical or different groups R b as defined and preferably herein.
  • R L is C3-C8-cycloalkyl-Ci-C4-haloalkyl, C3-C6-cycloalkyl-Ci- C4-haloalkyl.
  • R L is C3-C8-halocycloalkyl-Ci-C4-alkyl, C3-C6- halocycloalkyl-Ci-C4-alkyl.
  • R L is fully or partially halogenated cyclopro- pyl-Ci-C4-alkyl.
  • R L is 1 -CI-cyclopropyl-Ci-C4-alkyl.
  • R L is 1 -F-cyclopropyl-Ci-C4-alkyl.
  • R L is NH2.
  • R L is NH(Ci-C4-alkyl). According to a specific embodiment R L is NH(CH3). According to a specific embodiment R L is NH(CH2CH3). According to a specific embodiment R L is NH(CH2CH2CH3). According to a specific embodiment R L is
  • R L is NH(CH2CH2CH 2 CH 3 ). According to a specific embodiment R L is NH(C(CH 3 )3).
  • R L is N(Ci-C4-alkyl)2. According to a specific embodiment R L is N(CH3)2. According to a specific embodiment R L is N(CH2CH3)2. According to a specific embodiment R L is N(CH2CH2CH3)2. According to a specific embodiment R L is N(CH(CH3)2)2.
  • R L is N(CH2CH2CH2CH3)2. According to a specific embodiment R L is NH(C(CH 3 ) 3 )2.
  • R L is NH(C3-C8-cycloalkyl) preferably NH(C3-C6- cycloalkyl).
  • R L is NH(cyclopropyl).
  • R L is NH(cyclobutyl).
  • R L is NH(cyclopentyl).
  • R L is NH(cyclohexyl).
  • R L is N(C3-C8-cycloalkyl)2 preferably N(C3-C6- cycloalkyl)2. According to a specific embodiment R L is N(cyclopropyl)2. According to a specific embodiment R L is N(cyclobutyl)2. According to a specific embodiment R L is N(cyclopentyl)2.
  • R L is N(cyclohexyl)2.
  • R L is selected from S(Ci-C2-alkyl), S(0)(Ci-C2-alkyl) and S(0) 2 (Ci-C 2 -alkyl), in particular SCH 3 , S(0)(CH 3 ) and S(0) 2 (CH 3 ).
  • R L is selected from S(Ci-C 2 -haloalkyl), S(0)(Ci-C 2 -haloalkyl) and S(0) 2 (Ci-C 2 - haloalkyl), such as S0 2 CF 3 .
  • R L according to the invention are in Table PL below, wherein each line of lines PL-1 to PL-17 corresponds to one particular embodiment of the invention, wherein PL-1 to PL-17 are also in any combination with one another a preferred embodiment of the present invention.
  • Table PL below, wherein each line of lines PL-1 to PL-17 corresponds to one particular embodiment of the invention, wherein PL-1 to PL-17 are also in any combination with one another a preferred embodiment of the present invention.
  • Z is a five- membered heteroaryl which is unsubstituted or carries one, two or three independently selected radicals R L as defined or preferably defined below.
  • Z is a six-membered heteroaryl ahich is unsubstituted or carries one, two or three independently selected radicals R L as defined or preferably defined below.
  • Z is selected from the group consisting of pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazin-2-yl, pyridazin-3-yl, 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl; wherein said heteroaryl is unsubstituted or carrie one, two, three or four independently selected radicals R L as defined or preferably defined below.
  • Z is selected from the group consisting of pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyri- din-4-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl, 1 ,3,5-triazin-2-yl, and 1 ,2,4-triazin-3-yl; preferably Z is pyrimidin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl and thiazol-2-yl, that are unsubstituted or carry one, two, three or four independently selected radicals R L as defined or preferably defined below.
  • R L there can be zero, one, two, three, four or five R L present, namely for m is 0, 1 , 2, 3, 4 or 5.
  • the number of m also depends on the kind of heteroaryl.
  • m is 0, 1 , 2 or 3.
  • m is 0.
  • m is 1 , 2 or 3, in particular 1 or 2. According to one specific embodiment thereof, m is 1 , according to a further specific embodiment, m is 2.
  • Each R L is independently selected from halogen, CN, NO2, OH, Ci-C6-alkyl,
  • R La is independently selected R La , wherein R La is as defined and preferably defined herein.
  • R L is independently selected from F, CI, Br, CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, S(Ci-C 4 -alkyl), S(0)(Ci- C 4 -alkyl) and S(0) 2 (Ci-C 4 -alkyl).
  • R L is independently selected from halogen, in particular from Br, F and CI, more specifically from F and CI.
  • R L is CN
  • R L is N0 2 .
  • R L is OH
  • R L is SH.
  • R L is Ci-C6-alkyl, in particular Ci-C 4 -alkyl, such as CH3.
  • Further appropriate alkyls are ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl.
  • R L is Ci-C6-haloalkyl, in particular Ci-C 4 - haloalkyl, such as CF 3 , CHF 2 , CH 2 F, CCI 3 , CHCI 2 or CH 2 CI.
  • R L is Ci-C6-alkyl, preferably Ci-C 4 -alkyl, substituted by OH, more preferably CH 2 OH, CH 2 CH 2 OH, CH 2 CH 2 CH 2 OH,
  • R L is CH 2 OH.
  • R L is Ci-C6-alkyl, preferably Ci-C 4 - alkyl substituted by CN, more preferably CH 2 CN, CH 2 CH 2 CN, CH 2 CH 2 CH 2 CN,
  • R L is CH(CH 3 )CH 2 CN, CH 2 CH(CH 3 )CN, CH 2 CH 2 CH 2 CH 2 CN.
  • R L is CH 2 CH 2 CN.
  • R 4 is CH(CH 3 )CN.
  • R L is Ci-C 4 -alkoxy-Ci-C6-alkyl, more preferably Ci-C 4 -alkoxy-Ci- C 4 -alkyl.
  • R L is CH 2 OCH3.
  • R L is CH 2 CH 2 OCH 3 .
  • R L is CH(CH 3 )OCH 3 .
  • R L is CH(CH3)OCH2CH3.
  • R L is CH2CH2OCH2CH3.
  • R L is Ci-C4-haloalkoxy- Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl.
  • R L is CH2OCF3.
  • R L is CH2CH2OCF3.
  • R L is CH2OCCI3.
  • R L is CH2CH2OCCI3.
  • R L is Ci-C6-alkoxy, in particular C1-C4- alkoxy, more specifically Ci-C2-alkoxy such as OCH3 or OCH2CH3.
  • R L is Ci-C6-haloalkoxy, in particular C1-C4- haloalkoxy, more specifically Ci-C2-haloalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHC or OCH2CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHCI 2 .
  • R L is Ci-C4-alkoxy-C2-C6-alkenyl, more preferably Ci-C4-alkoxy-C2-C4-alkenyl.
  • R L is
  • R L is Ci-C4-haloalkoxy- C2-C6-alkenyl, more preferably Ci-C4-haloalkoxy-C2-C4-alkenyl.
  • R L is Cs-Cs-cycloalkyl- C2-C6-alkenyl, preferably C3-C6-cycloalkyl-C2-C4-alkenyl.
  • R L is C3-C6-halocycloalkyl-C2-C4-alkenyl, preferably Cs-Cs-halocycloalkyl- C2-C6-alkenyl.
  • R L is C2-C6-alkynyl or C2-C6-haloalkynyl, in particular C 2 -C 4 -alkynyl or C 2 -C 4 -haloalkynyl, such as C ⁇ CH, CH 2 CCH or CH2CCCH3.
  • R L is C2-C6-alkynyl, preferably C2-C4- alkynyl, substituted by OH, more preferably, CCOH, CH2CCOH.
  • R L is CCOH.
  • R L is CH2CCOH.
  • R L is Ci-C4-alkoxy-C2-C6-alkynyl, more preferably C1-C4- alkoxy-C2-C4-alkynyl.
  • R L is CCOCH3.
  • R L is CH2CCOCH3.
  • R L is C1-C4- haloalkoxy-C2-C6-alkynyl, more preferably Ci-C4-haloalkoxy-C2-C4-alkynyl.
  • R L is CCOCF3.
  • R L is CH2CCOCF3.
  • R L is CCOCCI3.
  • R L is CH2CCOCCI3.
  • R L is C3-C8-cycloalkyl-C2-C6- alkynyl, preferably C3-C6-cycloalkyl-C2-C4-alkynyl.
  • R L is C3-C6-halocycloalkyl-C2-C4-alkynyl, preferably C3-C8-halocycloalkyl-C2- C6-alkynyl.
  • R L is Cs-Cs-cycloalkyl, preferably cyclopropyl, cy- clobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl.
  • R L is cyclopropyl.
  • R L is cyclobutyl.
  • R 4 is cyclopentyl.
  • R L is cyclohexyl.
  • R L is C3-Cs-cycloalkoxy, preferably C3-C6- cycloalkoxy.
  • R L is O-cyclopropyl.
  • R L is Cs-Cs-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl.
  • R L is fully or partially halogenated cyclopropyl.
  • R L is 1 -CI-cyclopropyl.
  • R L is 2-CI-cyclopropyl.
  • R L is 1 -F-cyclopropyl.
  • R L is 2-F-cyclopropyl.
  • R L is fully or partially halogenated cyclobutyl.
  • R L is 1 -CI-cyclobutyl.
  • R L is 1 -F-cyclobutyl. In a further special embodiment R L is 3,3-Cl2-cyclobutyl. In a further special embodiment R L is 3,3-F2-cyclobutyl. According to a specific embodiment R L is Cs-Cs-cycloalkyl substituted by Ci-C4-alkyl, more preferably is C3-C6-cycloalkyl substituted by C1-C4- alkyl. In a special embodiment R L is 1 -CH3-cyclopropyl. According to a specific embodiment R L is Cs-Cs-cycloalkyl substituted by CN, more preferably is C3-C6-cycloalkyl substituted by CN.
  • R L is 1 -CN-cyclopropyl.
  • R L is Cs-Cs-cycloalkyl-Cs-Cs-cycloalkyl, preferably C3-C6- cycloalkyl-C3-C6-cycloalkyl.
  • R L is cyclopropyl-cyclopropyl.
  • R L is 2-cyclopropyl-cyclopropyl.
  • R L is Cs-Cs-cycloalkyl-Cs-Cs-halocycloalkyl, preferably C3-C6-cycloalkyl- C3-C6-halocycloalkyl.
  • R L is C3-C8-cycloalkyl-Ci-C4-alkyl, preferably C3- C6-cycloalkyl-Ci-C4-alkyl.
  • R L is CH(CH3)(cyclopropyl).
  • R L is CH2-(cyclopropyl).
  • R L is C3-C8-cycloalkyl-Ci-C4-alkyl wherein the alkyl moiety can be substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein and the cy- cloalkyl moiety can be substituted by one, two, three or up to the maximum possible number of identical or different groups R b as defined and preferably herein.
  • R L is C3-C8-cycloalkyl-Ci-C4-haloalkyl, C3-C6- cycloalkyl-Ci-C4-haloalkyl.
  • R L is C3-C8- halocycloalkyl-Ci-C4-alkyl, C3-C6-halocycloalkyl-Ci-C4-alkyl.
  • R L is fully or partially halogenated cyclopropyl-Ci-C4-alkyl.
  • R L is 1 -CI-cyclopropyl-Ci-C4-alkyl.
  • R L is 1 -F- cyclopropyl-Ci-C4-alkyl.
  • R L is NH2.
  • R L is NH(Ci-C4-alkyl). According to a specific embodiment R L is NH(CH3). According to a specific embodiment R L is NH(CH2CH3). According to a specific embodiment R L is NH(CH2CH2CH3). According to a specific embodiment R L is NH(CH(CH3)2). According to a specific embodiment R L is
  • R L is NH(C(CH 3 ) 3 ).
  • R L is N(Ci-C4-alkyl)2. According to a specific embodiment R L is N(CH3)2. According to a specific embodiment R L is N(CH2CH3)2.
  • R L is N(CH2CH2CH3)2. According to a specific embodiment R L is N(CH(CH3)2)2. According to a specific embodiment R L is
  • R L is NH(C(CH 3 ) 3 )2.
  • R L is NH(C3-C8-cycloalkyl) preferably NH(C3-C6- cycloalkyl).
  • R L is NH(cyclopropyl).
  • R L is NH(cyclobutyl).
  • R L is NH(cyclopentyl).
  • R L is NH(cyclohexyl).
  • R L is N(C3-C8-cycloalkyl)2 preferably N(C3-C6- cycloalkyl)2. According to a specific embodiment R L is N(cyclopropyl)2. According to a specific embodiment R L is N(cyclobutyl)2. According to a specific embodiment R L is N(cyclopentyl)2. According to a specific embodiment R L is N(cyclohexyl)2.
  • R L is
  • R L is
  • R L is selected from S(Ci-C2-alkyl), S(0)(Ci-C2- alkyl) and S(0) 2 (Ci-C 2 -alkyl), in particular SCH 3 , S(0)(CH 3 ) and S(0) 2 (CH 3 ).
  • R L is selected from S(Ci-C2-haloalkyl), S(0)(Ci-C2-haloalkyl) and S(0) 2 (Ci-C 2 -haloalkyl), such as SO2CF3.
  • R L present in the heteroaryl according to the invention are in Table PL above, wherein each line of lines PL-1 to PL-16 corresponds to one particular embodiment of the invention, wherein PL-1 to PL-16 are also in any combination with one another a preferred embodiment of the present invention.
  • More specific embodiments are compounds I.Ba, I.Bb, I.Bc, I.Bd, I. Be, I.Bf, I.Bg and I.Bh; wherein the numbering of the positions in the phenyls is as shown in compound I.Ba:
  • FIG. 1 (C3-C6)-cycloalkyl
  • R 5 ,R 6 ,R 55 ,R 66 are hydrogen (I.Ea), an unsubstituted double bond (I.Eb) or a triple bond (I.Ec).
  • the compounds of the formulae I.Ca-d, I.Da-d and I.Ea-f that are compiled in the Tables 1 i to 5i, Tables 1j to 5j, Tables 1 k to 5k, Tables 11 to 51, Tables 1 m to 5m, Tables 1 n to 5n, Tables 1 o to 5o, Ta- bles 1 p to 5p, Tables 1 q to 5q, Tables 1 r to 5r, Tables 1 s to 5s, Tables 1t to 5t, Tables 1 u to 5u and Tables 1 v to 5v below.
  • Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
  • Table 1 a Compounds of the formula I. Ba in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Ba.B-1 .D1 to I.Ba.B-1.D220).
  • Table 2a Compounds of the formula I.Ba in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corre- sponds in each case to one line of Table D (compounds I.Ba. B-2. D1 to I.Ba. B-2. D220).
  • Table 3a Compounds of the formula I.Ba in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Ba. B-3. D1 to I.Ba. B-3. D220).
  • Table 4a Compounds of the formula I.Ba in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Ba. B-37. D1 to I.Ba. B-37. D220).
  • Table 5a Compounds of the formula I.Ba in which X corresponds to line B-50 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corre- sponds in each case to one line of Table D (compounds I.Ba. B-50. D1 to I.Ba. B-50. D220).
  • Table 1 c Compounds of the formula I. Be in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Bc.B-1.D1 to I.Bc.B-1.D220).
  • Table 2c Compounds of the formula I. Be in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Bc.B-2.D1 to I.Bc.B-2.D220).
  • Table 3c Compounds of the formula I. Be in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Bc.B-3.D1 to I.Bc.B-3.D220).
  • Table 4c Compounds of the formula I. Be in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Bc.B-37.D1 to I.Bc.B-37.D220).
  • Table 5c Compounds of the formula I. Be in which X corresponds to line B-50 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Bc.B-50.D1 to I.Bc.B-50.D220).
  • Table 1 Compounds of the formula I. Be in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I. Be. B-1 .E1 to I. Be. B-1 .E220).
  • Table 2e Compounds of the formula I. Be in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I. Be. B-2. E1 to I.Be.B-2.E220).
  • Table 3e Compounds of the formula I. Be in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I. Be. B-3. E1 to I.Be.B-3.E220).
  • Table 4e Compounds of the formula I.
  • Table 5e Compounds of the formula I. Be in which X corresponds to line B-50 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corre- sponds in each case to one line of Table E (compounds I. Be. B-50. E1 to I.Be.B-50.E220).
  • Table 1 g Compounds of the formula I.Bg in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Bg. B-1 .E1 to I.Bg. B-1 .E220).
  • Table 2g Compounds of the formula I.Bg in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Bg. B-2. E1 to I.Bg. B-2. E220).
  • Table 3g Compounds of the formula I.Bg in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Bg. B-3. E1 to I.Bg. B-3. E220).
  • Table 4g Compounds of the formula I.Bg in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Bg. B-37. E1 to I.Bg. B-37. E220).
  • Table 1 i Compounds of the formula I.Ca in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Ca. B-1 .D1 to I.Ca. B-1 .D220).
  • Table 2i Compounds of the formula I.Ca in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Ca. B-2. D1 to I.Ca. B-2. D220).
  • Table 3i Compounds of the formula I.Ca in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Ca. B-3. D1 to I.Ca. B-3. D220).
  • Table 4i Compounds of the formula I.Ca in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Ca.B-37.D1 to I.Ca. B-37. D220).
  • Table 5i Compounds of the formula I.Ca in which X corresponds to line B-50 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Ca. B-50. D1 to I.Ca. B-50. D220).
  • Table 1j Compounds of the formula I.Cb in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Cb.B-1 .D1 to I.Cb. B-1 .D220).
  • Table 2j Compounds of the formula I.Cb in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Cb.B-2.D1 to I.Cb. B-2. D220).
  • Table 3j Compounds of the formula I.Cb in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Cb.B-3.D1 to I.Cb. B-3. D220).
  • Table 4j Compounds of the formula I .Cb in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Cb.B-37.D1 to I.Cb.B-37.D220).
  • Table 5j Compounds of the formula I.Cb in which X corresponds to line B-50 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Cb.B-50.D1 to I.Cb.B-50.D220).
  • Table 1 k Compounds of the formula I.Cc in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Cc.B-1 .E1 to I.Cc. B-1 .E220).
  • Table 2k Compounds of the formula I.Cc in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Cc.B-2.E1 to I.Cc. B-2. E220).
  • Table 4k Compounds of the formula I.Cc in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Cc.B-37.E1 to I.Cc. B-37. E220).
  • Table 11 Compounds of the formula I.Cd in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Cd. B-1 .E1 to I.Cd. B-1.E220).
  • Table 2I Compounds of the formula I.Cd in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Cd. B-2. E1 to I.Cd. B-2. E220).
  • Table 3I Compounds of the formula I.Cd in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Cd. B-3. E1 to I.Cd. B-3. E220).
  • Table 4I Compounds of the formula I.Cd in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Cd. B-37. E1 to I.Cd. B-37. E220).
  • Table 51 Compounds of the formula I.Cd in which X corresponds to line B-50 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Cd. B-50. E1 to I.Cd. B-50. E220).
  • Table 1 m Compounds of the formula I. Da in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I. Da. B-1 .D1 to I. Da. B-1 .D220).
  • Table 2m Compounds of the formula I. Da in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I. Da. B-2. D1 to I.Da.B-2.D220).
  • Table 4m Compounds of the formula I. Da in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I. Da. B-37. D1 to I.Da.B-37.D220).
  • Table 4n Compounds of the formula I.Db in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D (compounds I.Db.B-37.D1 to I.Db.B-37.D220).
  • Table 1 o Compounds of the formula I.Dc in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Dc.B-1 .E1 to I.Dc. B-1 .E220).
  • Table 3o Compounds of the formula I.Dc in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Dc.B-3.E1 to I.Dc. B-3. E220).
  • Table 4o Compounds of the formula I.Dc in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Dc.B-37.E1 to I.Dc. B-37. E220).
  • Table 4p Compounds of the formula I.Dd in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E (compounds I.Dd. B-37. E1 to I.Dd. B-37. E220).
  • Table 1 Compounds of the formula I.Eb in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D2 (compounds I.Eb. B-1.D2-1 to I.Eb. B-1 .D2-44).
  • Table 2r Compounds of the formula I.Eb in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D2 (compounds I.Eb. B-2. D2-1 to I.Eb. B-2. D2-44).
  • Table 3r Compounds of the formula I.Eb in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D2 (compounds I.Eb. B-3. D2-1 to I.Eb. B-3. D2-44).
  • Table 4r Compounds of the formula I.Eb in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D2 (compounds I.Eb. B-37. D2-1 to I.Eb. B-37. D2-44).
  • Table 1 s Compounds of the formula I.Ec in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D2 (compounds I.Ec.B-1 .D2-1 to I.Ec.B-1.D2-44).
  • Table 2 Compounds of the formula I.Ec in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D2 (compounds I.Ec.B-2.D2-1 to I.Ec.B-2.D2-44).
  • Table 3 Compounds of the formula I.Ec in which X corresponds to line B-3 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D2 (compounds I.Ec.B-3.D2-1 to I.Ec.B-3.D2-44).
  • Table 4 Compounds of the formula I.Ec in which X corresponds to line B-37 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D2 (compounds I.Ec.B-37.D2-1 to I.Ec.B-37.D2-44).
  • Table 5 Compounds of the formula I.Ec in which X corresponds to line B-50 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table D2 (compounds I.Ec.B-50.D2-1 to I.Ec.B-50.D2-44).
  • Table 1 u Compounds of the formula I.Ee in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E1 (compounds I.Ee. B-1. E1 -1 to I.Ee. B-1 .E1 -44).
  • Table 2 u Compounds of the formula I.Ee in which X corresponds to line B-2 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E1 (compounds I.Ee. B-2. E1 -1 to I.Ee. B-2. E1 -44).
  • Table 1 v Compounds of the formula I.Ef in which X corresponds to line B-1 of Table B and the meaning for the combination of (R 4 ) n and (R L ) m for each individual compound corresponds in each case to one line of Table E1 (compounds I. Ef.B-1 .E1 -1 to I.Ef.B-1 .E1 -44).
  • the compounds I and the compositions according to the invention, respectively, are suitable as fungicides.
  • the present invention relates to the use of compounds of formula I, the N-oxides and the agriculturally acceptable salts thereof or of the compositions of the invention for combating phytopathogenic fungi.
  • the present invention also encompasses a method for combating harmful fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I or with a composition comprising according to the invention.
  • Plasmo- diophoromycetes Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti).
  • Some are systemi- cally effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides.
  • they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • compounds I and compositions thereof are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
  • The- se young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • treatment of plant propagation materials with compounds I and compositions thereof, respectively is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g.
  • auxin herbi- cides such as dicamba or 2,4-D
  • bleacher herbicides such as hydroxylphenylpyruvate di
  • herbicides e. bromoxynil or ioxynil herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from anoth- er class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci.
  • cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield ® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ -endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • VIP1 , VIP2, VIP3 or VIP3A vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins pro- prised by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdyster- oid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ).
  • Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coelop- tera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called "pathogenesis- related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Er- winia amylvora).
  • PR proteins pathogenesis- related proteins
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lysozym e. g. potato
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e. g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • the compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
  • Albugo spp. white rust on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Altemaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassi- cae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A.retemata), tomatoes (e. g. A. solani or A.retemata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A.
  • Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e.g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) gram- inis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botry- otinia fuckeliana: grey mold) on fruits and berries (e.
  • strawberries vegetables
  • vegetables e. g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • Bremia lactucae downy mildew
  • Ceratocystis syn. Ophiostoma
  • Cercospora spp. rot or wilt
  • corn e.g. Gray leaf spot: C. zeae-maydis
  • sugar beets e. g. C.
  • sa- sakii sheath blight
  • Corynespora cassiicola leaf spots
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.
  • lirio- dendri teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D.
  • phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyr- enophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formiti- poria (syn. Phellinus) punctata, F.
  • Phaeomoniella chlamydospora (earlier Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa
  • Elsinoe spp. on pome fruits £. pyri
  • soft fruits £. veneta: anthracnose
  • vines £. ampelina: anthracnose
  • Entyloma oryzae leaf smut
  • E. pisi such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F.
  • cucurbits e. g. E. cichoracearum
  • cabbages rape (e. g. E. cruciferarum)
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella
  • fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas
  • Peronospora spp. downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica);
  • Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P.
  • phaseoli, teleomorph Diaporthe phaseolorum
  • Phy- soderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • paprika and cucurbits e. g. P. capsici
  • soybeans e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew
  • Puccinia spp. rusts on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P.
  • Pyrenophora anamorph: Drechslera
  • tritici-repentis tan spot
  • P. feres net blotch
  • Pyricularia spp. e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals
  • Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum);
  • Ramularia spp. e. g. R.
  • collo-cygni Roso-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R.
  • S. reiliana head smut
  • Sphaerotheca fuliginea powdery mildew
  • Spongospora subterranea powdery scab
  • Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lepto- sphaeria [syn. Phaeosphaeria] nodorum) on wheat
  • Synchytrium endobioticum on potatoes potato wart disease
  • Taphrina spp. e. g. T.
  • deformans leaf curl disease
  • T. pruni plum pocket
  • plums Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U.
  • occulta stem smut
  • Uromyces spp. rust
  • vegetables such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae)
  • Ustilago spp. loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane
  • Venturia spp. scab
  • apples e. g. V. inaequalis
  • pears Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
  • the compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • the term "protection of materials” is to be understood to denote the protection of technical and non- living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, colling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
  • the method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms.
  • the term "stored products” is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired.
  • Stored products of crop plant origin such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment.
  • stored products are timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.
  • Stored products of animal origin are hides, leather, furs, hairs and the like.
  • the combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.
  • Preferably "stored products” is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
  • the compounds I and compositions thereof may be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • the compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
  • the compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be pro- tected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
  • the invention also relates to compositions comprising one compound I according to the invention.
  • such composition further comprises an auxiliary as defined below.
  • the term "effective amount” used denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materi- als and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
  • compositions e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene, alkylated
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e.g. cellulose, starch
  • fertilizers
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • a compound I and 5-15 wt% wetting agent e.g. alcohol alkoxylates
  • a water-soluble solvent e.g. alcohols
  • a compound I and 1 -10 wt% dispersant e. g. polyvinylpyrrolidone
  • organic solvent e.g. cyclohexanone
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e.g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e.g. aromatic hydrocarbon
  • a compound I In an agitated ball mill, 20-60 wt% of a compound I are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1 -2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • 0.1 -2 wt% thickener e.g. xanthan gum
  • a compound I 50-80 wt% of a compound I are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active sub- stance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • Water-dispersible powders and water-soluble powders (WP, SP, WS) 50-80 wt% of a compound I are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -3 wt% wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • a compound I In an agitated ball mill, 5-25 wt% of a compound I are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -5 wt% thickener e.g. carboxymethylcellulose
  • wt% of a compound I are added to 5-30 wt% organic solvent blend (e.g. fatty acid dime- thylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alcohol ethoxylate and ar- ylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • organic solvent blend e.g. fatty acid dime- thylamide and cyclohexanone
  • surfactant blend e.g. alcohol ethoxylate and ar- ylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g.
  • diphenylmethene-4,4'-diisocyanatae are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol).
  • a protective colloid e.g. polyvinyl alcohol.
  • the addition of a polyamine results in the formation of polyurea microcapsules.
  • the monomers amount to 1 -10 wt%.
  • the wt% relate to the total CS composition.
  • Dustable powders (DP, DS)
  • a compound I 1 -10 wt% of a compound I are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%.
  • solid carrier e.g. finely divided kaolin
  • a compound I 0.5-30 wt% of a compound I is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt%.
  • solid carrier e.g. silicate
  • Granulation is achieved by extrusion, spray-drying or fluidized bed.
  • organic solvent e.g. aromatic hydrocarbon
  • compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • compound I or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne des composés de formule (I), les variables étant définies dans la description et les revendications, leurs méthodes de préparation et leur utilisations.
PCT/EP2013/076551 2012-12-21 2013-12-13 Composés imidazole et triazole substitués en [1,2,4] WO2014095637A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9815798B2 (en) 2014-03-26 2017-11-14 Basf Se Substituted [1,2,4]triazole and imidazole compounds as fungicides
US10053432B2 (en) 2013-12-12 2018-08-21 Basf Se Substituted [1,2,4]triazole and imidazole compounds
US10112913B2 (en) 2014-05-13 2018-10-30 Basf Se Substituted [1,2,4]triazole and imidazole compounds as fungicides
US10450279B2 (en) 2014-06-06 2019-10-22 Basf Se Substituted [1,2,4]triazole compounds

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US4507140A (en) * 1980-11-19 1985-03-26 Imperial Chemical Industries Plc Triazole and imidazole compounds useful as fungicides and plant growth regulators
DE3719326A1 (de) * 1987-06-10 1989-01-05 Bayer Ag Fungizide wirkstoffkombination
US5691363A (en) * 1994-04-28 1997-11-25 Uniroyal Chemical Company, Inc. Fungicidal azole derivatives
WO2010146115A1 (fr) * 2009-06-18 2010-12-23 Basf Se Composés de triazole portant un substituant de soufre
WO2010146113A1 (fr) * 2009-06-18 2010-12-23 Basf Se Derives triazolyle antifongiques 1, 2, 4 ayant un substituant 5-soufre
WO2010146114A1 (fr) * 2009-06-18 2010-12-23 Basf Se Composés de triazole portant un substituant soufré
US20120220638A1 (en) * 2010-08-26 2012-08-30 Bayer Cropscience Ag 5-Iodotriazole derivatives

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4507140A (en) * 1980-11-19 1985-03-26 Imperial Chemical Industries Plc Triazole and imidazole compounds useful as fungicides and plant growth regulators
DE3719326A1 (de) * 1987-06-10 1989-01-05 Bayer Ag Fungizide wirkstoffkombination
US5691363A (en) * 1994-04-28 1997-11-25 Uniroyal Chemical Company, Inc. Fungicidal azole derivatives
WO2010146115A1 (fr) * 2009-06-18 2010-12-23 Basf Se Composés de triazole portant un substituant de soufre
WO2010146113A1 (fr) * 2009-06-18 2010-12-23 Basf Se Derives triazolyle antifongiques 1, 2, 4 ayant un substituant 5-soufre
WO2010146114A1 (fr) * 2009-06-18 2010-12-23 Basf Se Composés de triazole portant un substituant soufré
US20120220638A1 (en) * 2010-08-26 2012-08-30 Bayer Cropscience Ag 5-Iodotriazole derivatives

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10053432B2 (en) 2013-12-12 2018-08-21 Basf Se Substituted [1,2,4]triazole and imidazole compounds
US9815798B2 (en) 2014-03-26 2017-11-14 Basf Se Substituted [1,2,4]triazole and imidazole compounds as fungicides
US10112913B2 (en) 2014-05-13 2018-10-30 Basf Se Substituted [1,2,4]triazole and imidazole compounds as fungicides
US10450279B2 (en) 2014-06-06 2019-10-22 Basf Se Substituted [1,2,4]triazole compounds

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