WO2015150135A1 - Substituted 1,4-dithiine derivatives and their use as fungicides - Google Patents

Substituted 1,4-dithiine derivatives and their use as fungicides Download PDF

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Publication number
WO2015150135A1
WO2015150135A1 PCT/EP2015/056063 EP2015056063W WO2015150135A1 WO 2015150135 A1 WO2015150135 A1 WO 2015150135A1 EP 2015056063 W EP2015056063 W EP 2015056063W WO 2015150135 A1 WO2015150135 A1 WO 2015150135A1
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Prior art keywords
cio
alkyl
compounds
formula
haloalkyl
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PCT/EP2015/056063
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French (fr)
Inventor
Wassilios Grammenos
Nadege Boudet
Bernd Müller
Maria Angelica QUINTERO PALOMAR
Ana Escribano Cuesta
Erica May Wilson LAUTERWASSER
Jan Klaas Lohmann
Thomas Grote
Manuel KRETSCHMER
Marcus Fehr
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Basf Se
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Publication of WO2015150135A1 publication Critical patent/WO2015150135A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains three hetero rings
    • C07D513/14—Ortho-condensed systems

Definitions

  • the present invention relates to com ounds of the formula I
  • the present invention relates to a process for preparing compounds of the formula I.
  • compositions comprising at least one compound of formula I a N-oxide or an agriculturally acceptable salt thereof.
  • the present invention relates to the use of a compound of the formula I and/or of an agriculturally acceptable salt thereof or of the compositions for combating phytopathogenic fungi.
  • the present invention relates to 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.
  • the present invention relates to seed, coated with at least one compound of the formula I and/or an agriculturally acceptable salt thereof or with a composition in an amount of from 0.1 to 10 kg per 100 kg of seed.
  • WO 91/08510 relates to organic optical elements and nonlinear optical devices and disclosed substituted 1 ,4-dithiine derivatives. An application in crop protection is not mentioned.
  • the present invention relates, to the compounds of the formula I
  • R 1 and R 2 independently of one another are
  • Ci-Cio-alkyl Ci-Cio-haloalkyl
  • a 1 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl;
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy; or
  • R 1 and R 2 together with the C atom to which these radicals are attached may also form a five or six membered heterocycle, where the heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S as ring members and may furthermore contain one or two CO, SO or SO2 groups as ring members;
  • a 1A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; and
  • Ci-Cio-alkyl Ci-Cio-haloalkyl
  • a 3 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl;
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, C1-C10- haloalkoxy; and
  • I is 0, 1 or 2;
  • k 0, 1 or 2;
  • the present invention provides a process for preparing compounds of the formula I.
  • an agrochemical composition comprising at least one compound of formula I an N-oxide or an agriculturally acceptable salt thereof.
  • R 1 and R 2 independently of one another are
  • Ci-Cio-alkyl Ci-Cio-haloalkyl
  • a 1 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl;
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cy- ano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy; or
  • R 1 and R 2 together with the C atom to which these radicals are attached may also form a five or six membered heterocycle, where the heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S as ring members and may furthermore contain one or two CO, SO or SO2 groups as ring members;
  • a 1A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl,
  • Ci-Cio-alkyl Ci-Cio-haloalkyl
  • a 3 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl;
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, C1-C10- haloalkoxy; and
  • I is 0, 1 or 2;
  • k is O, 1 or 2; and the N-oxides and the agriculturally acceptable salts thereof and/or of an agriculturally acceptable salt thereof or of the compositions, as defined in any of the claims 8 or 9, for combating phytopathogenic fungi.
  • the present invention provides 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.
  • the present invention provides seed, coated with at least one compound of the formula I and/or an agriculturally acceptable salt thereof or with a composition in an amount of from 0.1 to 10 kg per 100 kg of seed.
  • the prefix C x -C y denotes the number of possible carbon atoms in the particular case.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • alkyl and the alkyl moieties of composite groups such as, for example, alkoxy, alkylamino, alkoxycarbonyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 10 carbon atoms, for example Ci-Cio-akyl, such as methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 - methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 - methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethyl
  • haloalkyl straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above.
  • the alkyl groups are substituted at least once or completely by a particular halogen atom, preferably fluorine, chlorine or bromine.
  • the alkyl groups are partially or fully halogenated by different halogen atoms; in the case of mixed halogen substitutions, the combination of chlorine and fluorine is preferred.
  • (Ci-C3)-haloalkyl more preferably (Ci-C2)-haloalkyl, such as chloromethyl, bromomethyl, 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, 2,2,2-trichloroethyl, pentafluoroethyl or 1 ,1 ,1 -trifluoroprop- 2-yl;
  • cycloalkyl and also the cycloalkyl moieties in composite groups mono- or bicyclic saturated hydrocarbon groups having 3 to 10, in particular 3 to 6, carbon ring members, for example C3-C6- cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1 .1 ]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
  • optionally substituted Cs-Cs-cycloalkyl means a cyclo- alkyl radical having from 3 to 8 carbon atoms, in which at least one hydrogen atom, for example 1 , 2, 3, 4 or 5 hydrogen atoms, is/are replaced by substituents which are inert under the conditions of the reaction.
  • substituents which are inert under the conditions of the reaction.
  • inert substituents are CN, Ci-C6-alkyl, Ci-C4-haloalkyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, and Ci-C4-alkoxy-Ci-C6-alkyl;
  • halocycloalkyl and the halocycloalkyl moieties in halocycloalkoxy, halocycloalkylcarbonyl and the like monocyclic saturated hydrocarbon groups having 3 to 10 carbon ring members (as mentioned above) in which some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
  • alkoxy an alkyl group as defined above which is attached via an oxygen, preferably having 1 to 10, more preferably 2 to 6, carbon atoms.
  • Examples are: methoxy, ethoxy, n-propoxy, 1 -methyl- ethoxy, butoxy, 1 -methylpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy, and also for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethyl- propoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1 -
  • Examples are OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHC , OCCI 3 , chlorofluoro- methoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 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-trichloroethoxy, OC2F5, 2- fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3- chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-
  • 5-, 6-membered heterocycle which contains 1 , 2, 3 or 4 heteroatoms from the group consisting of O, N and S as ring members, and may furthermore contain one or two CO, SO, SO2 groups as ring members, where the heterocycle in question may be attached via a carbon atom or, if pre- sent, via a nitrogen atom.
  • a five- or six-membered saturated or partially unsaturated heterocycle which comprises one, two, three or four heteroatoms from the group consisting of O, N and S as ring members: for example monocyclic saturated or partially unsaturated heterocycles which, in addition to carbon ring members, comprise one, two or three nitrogen atoms and/or one oxygen or sul- fur atom or one or two oxygen and/or sulfur atoms, for example 2-tetrahydrofuranyl, 3- tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3- isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,
  • a five- or six-membered aromatic heterocycle which contains one, two, three or four heteroatoms from the group consisting of oxygen, nitrogen and sulfur, for example 5-membered heteroaryl which is attached via carbon and contains one to three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, such as 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4- imidazolyl, 1 ,2,4-oxadiazol-3-
  • Ci-Cio-alkoxy-Ci-Cio-alkyl Ci-Cio-alkyl (as defined above) where one hydrogen atom is replaced by a Ci-Cio-alkoxy group as defined above;
  • Ci-Cio-alkyl (as defined above) where one hydrogen atom is replaced by a NA 1 A 2 group as defined above; mono-(Ci-Cio-alkyl)amino: group of the formula NA 1 A 2 group in which A 1 or A 2 is an Ci-Cio-alkyl group as defined above.
  • di-(Ci-Cio-alkyl)amino group of the formula NA 1 A 2 group in which each A 1 and A 2 are an C1-C10- alkyl group as defined above.
  • hydroxyl OH group which is attached via an O atom
  • cyano CN group which is attached via an C atom
  • the compound of the formula I-A can be oxided according to conventional oxidation methods, e. g. by treating with an organic peracid such as metachloroperbenzoic 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.
  • an organic peracid such as metachloroperbenzoic 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.
  • the precursor (III) may be obtained by various routes in analogy to prior art processes known from JOC, 1980, 45(25), 5122-30.
  • precursors IV are commercially available.
  • Precursors IV in which R 1 and R 2 together form the rin can be prepared employing a preparative procedure known from Mendeleev Comm. 1 1 (4), 152-
  • inventive compounds cannot be directly obtained by the routes described above, they can be prepared by derivatization of other inventive compounds.
  • 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 metachloroperbenzoic 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 ).
  • an organic peracid such as metachloroperbenzoic 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
  • the oxidation may lead to pure mono-N-oxides or to a composition of different N-oxides, which can be separated by conventional methods such as chromatography. If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
  • 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 manganese, 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 sul
  • 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, prefera- bly 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.
  • k in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment, 0. k in the compounds according to the invention or the compounds used according to the invention is, according to one further embodiment, 1 . k in the com- pounds according to the invention or the compounds used according to the invention is, according to one further embodiment, 2.
  • I in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment, 0. 1 in the compounds according to the invention or the com- pounds used according to the invention is, according to one further embodiment, 1 . 1 in the compounds according to the invention or the compounds used according to the invention is, according to one further embodiment, 2.
  • R 1 in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment H, halogen, CN or NO2.
  • R 1 is H.
  • R 1 is CN.
  • R 1 is NO2.
  • R 1 is CI.
  • R 1 is Br.
  • R 1 is F.
  • R 1 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment Ci-Cio-alkyl or Ci-Cio-haloalkyl.
  • R 1 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl.
  • R 1 is methyl.
  • R 1 is ethyl.
  • R 1 is propyl.-ln a further special embodiment R 1 is i-propyl.
  • R 1 is 1 -methylpropyl.
  • R 1 is n-butyl.
  • R 1 is i-butyl. In a further special embodiment R 1 is t-butyl. In a further special embodiment R 1 is n-pentyl. In a further special embodiment R 1 is n-hexyl.
  • R 1 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, in particular fully or partially halogenated methyl.
  • R 1 is CF3.
  • R 1 is CHF2.
  • R 1 is CFH2.
  • R 1 is CH2CF3.
  • R 1 is CCI3.
  • R 1 is CHC .
  • R 1 is CCIH2.
  • a 1 is H.
  • a 1 is Ci-Cio-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • a 1 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i- propyl, n-butyl, i-butyl or t-butyl, in particular fully or partially halogenated methyl.
  • a 1 is C3-Cio-cycloalkyl, preferrably cyclopropyl, cyclobutyl or cyclopentyl, in particular cyclopropyl or cyclobutyl.
  • a 1 is C3-Cio-halocycloalkyl, preferrably fully or partially halogenated cyclopropyl, cyclobutyl or cyclopentyl, in particular fully or partially halogenated cyclopropyl.
  • a 1 is NH2.
  • a 1 is mono-(Ci-Cio-alkyl)amino.
  • a 1 is di- (Ci-Cio-alkyl)amino.
  • a 1 is phenyl. According to a further embodiment A 1 is benzyl. According to a further embodiment A 1 is naphthyl.
  • phenyl, benzyl and naphthyl may carry one, two, three or four identical or different substituents selected from the group consisting of CI, I, F, Br, preferably CI, F.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methyl, ethyl, propyl, butyl, preferably methyl.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of partially or fully halogenated methyl, ethyl, propyl, butyl, preferably partially or fully halogenated methyl, in particular CF3.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, preferably methoxy.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of partially or fully halogenated methoxy, ethoxy, propoxy, butoxy, preferably partially or fully halogenated methoxy, in particular OCF3.
  • R 2 in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment H, halogen, CN or NO2.
  • R 2 is H.
  • R 2 is CN.
  • R 2 is NO2.
  • R 2 is CI.
  • R 2 is Br.
  • R 2 is F.
  • R 2 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment Ci-Cio-alkyl or Ci-Cio-haloalkyl.
  • R 2 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl.
  • R 2 is methyl.
  • R 2 is ethyl.
  • R 2 is propyl.-ln a further special embodiment R 2 is i-propyl.
  • R 2 is 1 -methylpropyl.
  • R 2 is n-butyl.
  • R 2 is i-butyl. In a further special embodiment R 2 is t-butyl. In a further special embodiment R 2 is n-pentyl. In a further special embodiment R 2 is n-hexyl.
  • R 2 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, in particular fully or partially halogenated methyl.
  • R 2 is CF3.
  • R 2 is CHF2.
  • R 2 is CFH2.
  • R 2 is CH2CF3.
  • R 2 is CCI3.
  • R 2 is CHC .
  • R 2 is CCIH2.
  • a 1 is H.
  • a 1 is Ci-Cio-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • a 1 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i- propyl, n-butyl, i-butyl or t-butyl, in particular fully or partially halogenated methyl.
  • a 1 is C3-Cio-cycloalkyl, preferrably cyclopropyl, cyclobutyl or cyclopentyl, in particular cyclopropyl or cyclobutyl.
  • a 1 is C3-Cio-halocycloalkyl, preferrably fully or partially halogenated cyclopropyl, cyclobutyl or cyclopentyl, in particular fully or partially halogenated cyclopropyl.
  • a 1 is NH2.
  • a 1 is mono-(Ci-Cio-alkyl)amino.
  • a 1 is di- (C-i-Cio-alkyl)amino.
  • a 1 is phenyl. According to a further embodiment A 2 is benzyl. According to a further embodiment A 1 is naphthyl.
  • phenyl, benzyl and naphthyl may carry one, two, three or four iden- tical or different substituents selected from the group consisting of CI, I, F, Br, preferably CI, F.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methyl, ethyl, propyl, butyl, preferably methyl.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of par- tially or fully halogenated methyl, ethyl, propyl, butyl, preferably partially or fully halogenated methyl, in particular CF3.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, preferably methoxy.
  • the above mentioned groups may carry one, two, three or four identical or different substituents se- lected from the group consisting of partially or fully halogenated methoxy, ethoxy, propoxy, butoxy, preferably partially or fully halogenated methoxy, in particular OCF3.
  • R 1 and R 2 form five membered saturated ring including O as ring member. According to one further embodiment R 1 and R 2 form five membered saturated ring including N as ring member. According to one embodiment R 1 and R 2 form five membered aromatic ring including N and S as ring members.
  • R 1 and R 2 together with the C atom to which these radicals are attached form the ring
  • # means C atoms to which R 1 and R 2 are attached.
  • R 1 and R 2 together with the C atom to which these radicals are attached form the ring
  • # means C atoms to which R 1 and R 2 are attached and
  • R 4 is selected from H, Ci-Cio-alkyl, Ci-Cio-alkoxy, CH 2 -0-Ci-Cio-alkyl.
  • R 4 in the compounds according to the invention or the compounds used according to the invention is, according to an embodiment, H.
  • R 4 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment, Ci-Cio-alkyl.
  • R 4 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl.
  • R 4 is methyl.
  • R 4 is ethyl.
  • R 4 is propyl.-ln a further special embodiment R 4 is i-propyl.
  • R 4 is 1 -methylpropyl.
  • R 4 is n-butyl.
  • R 4 is i-butyl. In a further special embodiment R 4 is t-butyl. In a further special embodiment R 4 is n-pentyl. In a further special embodiment R 4 is n-hexyl.
  • R 4 is Ci-Cio-alkoxy.
  • R 4 is OCH3.
  • R 4 is OCH2CH3.
  • R 4 is OCH2CH2CH3.
  • R 4 is OCH(CH 3 )2.
  • R 4 is OCH2CH2CH2CH3.
  • R 4 is OCH(CH2CH3)2.
  • R 4 is OC(CH3)3.
  • R 4 is OCH 2 CH(CH 3 )2.
  • R 4 is OCH2CH2CH2CH2CH2CH3.
  • R 4 is O CH2CH2CH2CH2CH2CH3.
  • R 4 is O CH2CH2CH2CH2CH2CH3.
  • R 4 is O CH2CH2CH2CH2CH2CH3.
  • R 4 is O CH2CH2CH2CH2CH2CH3.
  • R 4 is CH2-0-Ci-Cio-alkyl, preferrerably Chb-O-methyl, Chb-O-ethyl, CH 2 -0-n-propyl, CH 2 -0-i-propyl, CH 2 -0-n-butyl, CH 2 -0-i-butyl, CH 2 -0-t-butyl, in particular CH2-O- methyl, CH2-0-ethyl.
  • R 4 is Chb-O-methyl.
  • R 4 is Chb-O-ethyl.
  • R 4 is Chb-O-propyl.-ln a further special embodiment R 4 is Chb-O-i-propyl. In a further special embodiment R 4 is Chb-O-l -methylpropyl. In a further special embodiment R 4 is Ch -O-n- butyl. In a further special embodiment R 4 is Ch -O-i-butyl. In a further special embodiment R 4 is Chb-O-t-butyl. In a further special embodiment R 4 is CH2-0-n-pentyl. In a further special embodiment R 4 is CH 2 -0-n-hexyl.
  • R 1 and R 2 together with the C atom to which these radicals are attached form the ring wherein # means C atoms to which R 1 and R 2 are attached and
  • R 5 in the compounds according to the invention or the compounds used according to the invention is, according to an embodiment, H.
  • R 5 in the compounds according to the invention or the compounds used according to the invention is, according to an embodiment, CI, F or Br.
  • R 5 is CI. .
  • R 5 is F.
  • R 5 is Br.
  • R 5 in the compounds according to the invention or the compounds used according to the invention is, according to an embodiment, CN.
  • R 5 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment, Ci-Cio-alkyl.
  • R 5 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl.
  • R 5 is methyl.
  • R 5 is ethyl.
  • R 5 is propyl.-ln a further special embodiment R 5 is i-propyl.
  • R 5 is 1 -methylpropyl.
  • R 5 is n-butyl.
  • R 5 is i-butyl. In a further special embodiment R 5 is t-butyl. In a further special embodiment R 5 is n-pentyl. In a further special embodiment R 5 is n-hexyl.
  • a 5A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C 3 -Cio-cycloalkyl, C3-C10- halocycloalkyl, N H2, mono-(Ci-Cio-alkyl)amino
  • a 5A is H or Ci-Cio-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • a 5A is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl, in particular fully or partially halogenated methyl.
  • a 5A is C3-Cio-cycloalkyl, preferrably cyclopropyl, cyclobutyl or cyclopentyl, in particular cyclopropyl or cyclobutyl.
  • a 5A is C3-Cio-halocycloalkyl, preferrably fully or partially halogenated cyclopropyl, cyclobutyl or cyclopentyl, in particular fully or partially halogenated cyclopropyl.
  • a 5A is N H2.
  • a 5A is mono-(Ci-Cio- alkyl)amino.
  • a 5A is di-(Ci-Cio-alkyl)amino.
  • a 5A is phenyl. According to a further embodiment A 5 is benzyl. Ac- cording to a further embodiment A 5A is naphthyl.
  • R 1 and R 2 together with the C atom to which these radicals are attached form the ring wherein # means C atoms to which R 1 and R 2 are attached.
  • R 1 and R 2 are not H and CN.
  • R 3 in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment H, halogen, CN or NO2.
  • R 3 is H.
  • R 3 is CN.
  • R 3 is NO2.
  • R 3 is CI.
  • R 3 is Br.
  • R 3 is F.
  • R 3 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment Ci-Cio-alkyl or Ci-Cio-haloalkyl.
  • R 3 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl.
  • R 3 is methyl.
  • R 3 is ethyl.
  • R 3 is propyl.-ln a further special embodiment R 3 is i-propyl.
  • R 3 is 1 -methylpropyl. In a further special embodiment R 3 is n-butyl. In a further special embodiment R 3 is i-butyl. In a further special embodiment R 3 is t-butyl. In a further special embodiment R 3 is n-pentyl. In a further special embodiment R 3 is n-hexyl.
  • R 3 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, in particular fully or partially halogenated methyl.
  • R 3 is CF3.
  • R 3 is CHF2.
  • R 3 is CFH2.
  • R 3 is CH2CF3.
  • R 3 is CCI3.
  • R 3 is CHC .
  • R 3 is CCIH2.
  • a 3 is H. or Ci-Cio-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • a 3 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl, in particular fully or partially halogenated methyl.
  • a 3 is C3-Cio-cycloalkyl, prefer- rably cyclopropyl, cyclobutyl or cyclopentyl, in particular cyclopropyl or cyclobutyl.
  • a 3 is C3-Cio-halocycloalkyl, preferrably fully or partially halogenated cyclopropyl, cyclobutyl or cyclopentyl, in particular fully or partially halogenated cyclopropyl.
  • a 3 is NH2.
  • a 3 is mono-(Ci-Cio-alkyl)amino.
  • a 3 is di-(Ci-Cio-alkyl)amino.
  • a 4 is phenyl. According to a further embodiment A 4 is benzyl. According to a further embodiment A 4 is naphthyl.
  • phenyl, benzyl and naphthyl may carry one, two, three or four identical or different substituents selected from the group consisting of CI, I, F, Br, preferably CI, F.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methyl, ethyl, propyl, butyl, preferably methyl.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of partially or fully halogenated methyl, ethyl, propyl, butyl, preferably partially or fully halogenated methyl, in particular CF3.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, preferably methoxy.
  • the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of partially or fully halogenated methoxy, ethoxy, propoxy, butoxy, preferably partially or fully halogenated methoxy, in particular OCF3.
  • R 1 and R 2 are in Table A below, wherein each line of lines A-1 to A-293 corresponds to one particular embodiment of the invention, wherein A-1 to A-293 are also in any combination a preferred embodiment of the present invention.
  • the exception as deifned above will be considered.
  • the groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question.
  • the present invention relates to compounds of the formula I.A
  • the present invention relates to compounds of the formula I.B
  • the present invention relates to compounds of the formula I.C
  • the present invention relates to compounds of the formula I.D
  • 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 com- positions 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.
  • the compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, 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. pota- toes), 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.
  • These 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. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • 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 another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors.
  • ALS inhibitors 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 nema- todes, 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 produced 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 blockers of
  • 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 arthropods, 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 cultivars capable of synth
  • 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).
  • 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) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g.
  • strawberries strawberries
  • vegetables e. g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • Bremia lactucae downy mildew
  • Ceratocystis syn. Ophiostoma
  • spp. rot or wilt
  • broad- leaved trees and evergreens e. g. C. ulmi (Dutch elm disease) on elms
  • Cercospora spp. Cer- cospora leaf spots
  • corn e. g. Gray leaf spot: C. zeae-maydis
  • sugar beets e. g. C.
  • sasakii 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.
  • liriodendri 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: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. D.
  • tritici-repentis tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (£. pyri), soft fruits (£. veneta: anthracnose) and vines (£.
  • ampelina anthracnose
  • Entyloma oryzae leaf smut
  • Epicoccum spp. black mold
  • Erysiphe spp. potowdery mildew
  • sugar beets £. betae
  • vegetables e. g. E. pisi
  • cucurbits e. g. E. cichoracearum
  • cabbages e. g. E. cruciferarum
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn.
  • G. sabinae rust on pears
  • Helminthosporium spp. syn. Drechslera, teleomorph: Cochliobolus
  • Hemileia spp. e. g. H. vastatrix (coffee leaf rust) on coffee
  • Isariopsis clavispora syn. Cladosporium vitis
  • Macrophomina phaseolina syn. phaseoli
  • root and stem rot on soybeans and cotton
  • Microdochium syn. Fusarium
  • nivale pink snow mold
  • Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. 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);
  • Monilinia spp. e. g. la
  • 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.
  • 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, cooling 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 Coni- ophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Ser- pula 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 pro- Roud forms.
  • the compounds I and compositions thereof, respectively, 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 protected from fungal attack with a fungicidally effective amount of the active substances.
  • the ap- plication 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 agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
  • An agrochemical composition comprises a fungicidally effective amount of a compound I.
  • effective amount 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 materials 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.
  • 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, benzyl alcohol, 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, al
  • lactates carbonates, fatty acid es- ters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e. g. N-methyl pyrroli- done, fatty acid dimethyl amides; 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, star
  • 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 emulsifier, 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 alkylaryl sul- fonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin 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 alkyl naphthalenes, 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-substituted 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-substituted 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 vinyl pyrroli- done, vinyl alcohols, or vinyl acetate.
  • 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 polyvinyl amines or polyethylene amines.
  • Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity them- selves, and which improve the biological performance of the compound I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxiliaries. 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, carboxymethyl cellulose), inorganic 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 polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, 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. polyvinyl pyrrolidone
  • organic solvent e. g. cyclohexanone
  • emulsifiers e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e. g. aromatic hydro- carbon
  • 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. polyvinyl alcohol) 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, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • 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. carboxymethyl cellulose) 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. carboxymethyl cellulose
  • wt% of a compound I are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide 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 dimethyl amide 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 results in the formation of poly(meth)acrylate micro- capsules.
  • 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 isocya- nate 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 xiii) 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.
  • 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).
  • 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, onto plant propagation material, especially seeds include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods.
  • 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.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • a pesticide is generally a chemical or biological agent (such as pestidal active ingredient, compound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests.
  • Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease.
  • pesticides includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
  • Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/).
  • Biopesticides are typically created by growing and concentrating naturally occurring organisms and/or their metabolites including bacteria and other microbes, fungi, viruses, nematodes, proteins, etc. They are often considered to be important components of integrated pest management (IPM) programs.
  • IPM integrated pest management
  • Biopesticides fall into two major classes, microbial and biochemical pesticides:
  • Microbial pesticides consist of bacteria, fungi or viruses (and often include the me- tabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classed as microbial pesticides, even though they are multi-cellular.
  • Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1 ) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and option- ally a further active component 3) as defined herein.
  • pesticides II e. g. pesticidally-active substances and biopesticides
  • the compounds I in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
  • strobilurins azoxystrobin (A.1 .1 ), coumethoxy- strobin (A.1.2), coumoxystrobin (A.1 .3), dimoxystrobin (A.1.4), enestroburin (A.1 .5), fenaminstrobin (A.1 .6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1 .8), kresox- im-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1 .17) and 2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(
  • - inhibitors of complex II e. g. carboxamides: benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'- trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H-pyrazo
  • respiration inhibitors e. g. complex I, uncouplers: diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthi- ofam (A.4.12);
  • fentin salts such as fentin-acetate (A.4.8), fentin chloride (A
  • C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1.1 ), bitertanol (B.1.2), bromuconazole (B.1 .3), cyproconazole (B.1 .4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole (B.1 .8), fenbuconazole (B.1 .9), fluquinconazole (B.1.10), flusilazole (B.1 .1 1 ), flutriafol (B.1 .12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1.15), metconazole (B.1 .17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclo
  • Delta14-reductase inhibitors aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spirox- amine (B.2.8);
  • Inhibitors of 3-keto reductase fenhexamid (B.3.1 );
  • phenylamides or acyl amino acid fungicides benalaxyl (C.1.1 ), benalaxyl-M (C.1 .2), kiral- axyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (mefenoxam, C.1 .5), ofurace (C.1 .6), oxadixyl (C.1.7);
  • hymexazole C.2.1
  • octhilinone C.2.2
  • oxolinic acid C.2.3
  • bupirimate C.2.4
  • 5-fluorocytosine C.2.5
  • 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine C.2.6
  • 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine C.2.7
  • tubulin inhibitors such as benzimidazoles, thiophanates: benomyl (D1.1 ), carbendazim (D1 .2), fuberidazole (D1.3), thiabendazole (D1 .4), thiophanate-methyl (D1.5); triazolopyrim- idines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine (D1 .6);
  • diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);
  • - methionine synthesis inhibitors anilino-pyrimidines: cyprodinil (E.1 .1 ), mepanipyrim (E.1.2), pyrimethanil (E.1 .3);
  • blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hy- drochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);
  • fluoroimid F.1 .1
  • iprodione F.1 .2
  • procymidone F.1 .3
  • vinclozolin F.1 .4
  • fenpiclonil F.1.5
  • fludioxonil F.1 .6
  • quinoxyfen F.2.1 ;
  • edifenphos (G.1.1 ), iprobenfos (G.1 .2), pyrazophos (G.1.3), isoprothiolane (G.1 .4);
  • dicloran G.2.1
  • quintozene G.2.2
  • tecnazene G.2.3
  • tolclofos-methyl G.2.4
  • biphenyl G.2.5
  • chloroneb G.2.6
  • etridiazole G.2.7
  • dimethomorph G.3.1
  • flumorph G.3.2
  • mandipropamid G.3.3
  • pyrimorph G.3.4
  • benthiavalicarb G.3.5
  • propamocarb (G.4.1 );
  • oxathiapiprolin G.5.1
  • 2- ⁇ 3-[2-(1 - ⁇ [3,5-bis(di- fluoromethyl-1 H-pyrazol-1 -yl]acetyl ⁇ piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5- yl ⁇ phenyl methanesulfonate G.5.2
  • 2- ⁇ 3-[2-(1 - ⁇ [3, 5-bis(difluoromethyl)-1 H-pyrazol-1 - yl]acetyl ⁇ piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate G.5.3
  • ferbam H.2.1
  • mancozeb H.2.2
  • maneb H.2.3
  • metam H.2.4
  • metiram H.2.5
  • propineb H.2.6
  • thiram H.2.7
  • zineb H.2.8
  • ziram H.2.9
  • organochlorine compounds e. g. phthalimides, sulfamides, chloronitriles: anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid
  • guanidine H.4.1
  • dodine H.4.2
  • dodine free base H.4.3
  • guazatine H.4.4
  • guazatine-acetate H.4.5
  • iminoctadine H.4.6
  • iminoctadine-triacetate H.4.7
  • iminoctadine-tris(albesilate) H.4.8
  • dithianon H.4.9
  • 2,6-dimethyl-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone H.4.10
  • - melanin synthesis inhibitors pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (1.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);
  • abscisic acid (M.1.1 ), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dime- thipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gib- berellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione, prohexadi- one-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithio
  • acetochlor N.1.1
  • alachlor butachlor, dimethachlor, dimethenamid (N.1 .2), flufenacet (N.1.3), mefenacet (N.1 .4), metolachlor (N.1 .5), metazachlor (N.1 .6), napropa- mide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
  • - aryloxyphenoxypropionates clodinafop (N.3.1 ), cyhalofop-butyl, fenoxaprop (N.3.2), flua- zifop (N.3.3), haloxyfop (N.3.4), metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
  • - (thio)carbamates asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham (N.5.1 ), prosulfocarb, pyributicarb, thiobencarb, triallate;
  • acifluorfen N.8.1
  • aclonifen bifenox
  • diclofop ethoxyfen
  • fomesafen lac- tofen
  • lac- tofen oxyfluorfen
  • imidazolinones imazamethabenz, imazamox (N.10.1 ), imazapic (N.10.2), imazapyr (N.10.3), imazaquin (N.10.4), imazethapyr (N.10.5);
  • - phenoxy acetic acids clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D) (N.1 1.1 ), 2,4- DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
  • - pyrazines chloridazon (N.1 1.1 ), flufenpyr-ethyl, fluthiacet, norflurazon, pyridate; - pyridines: aminopyralid, clopyralid (N.12.1 ), diflufenican, dithiopyr, fluridone, fluroxypyr (N.12.2), picloram (N.12.3), picolinafen (N.12.4), thiazopyr;
  • - sulfonyl ureas amidosulfuron, azimsulfuron, bensulfuron (N.13.1 ), chlorimuron-ethyl (N.13.2), chlorsulfuron, cinosulfuron, cyclosulfamuron (N.13.3), ethoxysulfuron, flazasulfu- ron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron (N.13.4), mesosulfuron (N.13.5), metazosulfuron, metsulfuron-methyl (N.13.6), nicosulfuron (N.13.7), oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron (N.13.8), sul- fometuron,
  • ametryn ametryn, atrazine (N.14.1 ), cyanazine, dimethametryn, ethiozin, hexazinone (N.14.2), metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
  • ureas chlorotoluron, daimuron, diuron (N.15.1 ), fluometuron, isoproturon, linuron, metha- benzthiazuron, tebuthiuron;
  • acetolactate synthase inhibitors bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam (N.16.1 ), flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrim- isulfan, pyrithiobac, pyroxasulfone (N.16.2), pyroxsulam;
  • ethofumesate etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac (N.17.7), quinmerac (N.17.8), mesotrione (N.17.9), methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil (N.17.10), sulcotrione (N.
  • organo(thio)phosphates acephate (0.1 .1 ), azamethiphos (0.1 .2), azinphos-methyl (0.1.3), chlorpyrifos (0.1 .4), chlorpyrifos-methyl (0.1.5), chlorfenvinphos (0.1.6), diazinon (0.1.7), dichlorvos (0.1 .8), dicrotophos (0.1 .9), dimethoate (0.1 .10), disulfoton (0.1.1 1 ), ethion (0.1.12), fenitrothion (0.1 .13), fenthion (0.1 .14), isoxathion (0.1 .15), malathion (0.1.16), methamidophos (0.1 .17), methidathion (0.1 .18), methyl-parathion (0.1.19), mevinphos (0.1.20), monocrotophos (0.1.21 ), oxydemeton-methyl (0.1.22), paraoxon (0.1.23),
  • chitin synthesis inhibitors benzoylureas: chlorfluazuron (0.4.1 ), cyramazin (0.4.2), diflubenzuron (0.4.3), flucycloxuron (0.4.4), flufenoxuron
  • pyriproxyfen O.4.20
  • methoprene 0.4.21
  • fenoxycarb 0.4.22
  • d lipid biosynthesis inhibitors: spirodiclofen (0.4.23), spiromesifen (0.4.24), spirotetramat (0.4.24);
  • - nicotinic receptor agonists/antagonists compounds clothianidin (0.5.1 ), dinotefuran (0.5.2), flupyradifurone (0.5.3), imidacloprid (0.5.4), thiamethoxam (0.5.5), nitenpyram (0.5.6), acetamiprid (0.5.7), thiacloprid (0.5.8), 1 -2-chloro-thiazol-5-ylmethyl)-2-nitrimino- 3,5-dimethyl-[1 ,3,5]triazinane (0.5.9);
  • endosulfan (0.6.19, ethiprole (0.6.2), fipronil (0.6.3), vaniliprole (0.6.4), pyrafluprole (0.6.5), pyriprole (0.6.6), 5-amino-1 -(2,6-dichloro-4-methyl- phenyl)-4-sulfinamoyl-1 H-pyrazole-3-carbothioic acid amide (0.6.7);
  • acaricides fenazaquin (0.8.1 ), pyrida- ben (0.8.2), tebufenpyrad (0.8.3), tolfenpyrad (0.8.4), flufenerim (0.8.5);
  • cryomazine (0.12.1 );
  • chlorantraniliprole 0.15.1
  • cyantraniliprole 0.15.2
  • flu- bendiamide 0.15.3
  • N-[4-chloro-2-[(di- ethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(triflu- oromethyl)pyrazole-3-carboxamide 0.15.5
  • component 2 The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
  • the compounds described by l UPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141
  • EP-A 152 031 EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP-
  • the present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if desired one suitable solvent or solid carrier.
  • agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if desired one suitable solvent or solid carrier.
  • fungicide e. g. one or more fungicide from the groups A) to K
  • the order of application is not essential for working of the present invention.
  • the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1 .5 hours to 5 days, even more preferred from 2 hours to 1 dayln the binary mixtures and compositions according to the invention the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active components used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1.
  • the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1000:1 to 1 :1 , often in the range of from 100: 1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1.
  • the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1 :1 to 1 :1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
  • the ternary mixtures i.e.
  • compositions according to the invention comprising the component 1 ) and component 2) and a compound III (component 3), the weight ratio of component 1 ) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4: 1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1.
  • any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1 ).
  • mixtures comprising as component 2) at least one active substance selected from group A), which is particularly selected from (A.1 .1 ), (A.1 .4), (A.1 .8), (A.1 .9), (A.1.12), (A.1 .13), (A.1.14), (A.1 .17), (A.1.19), (A.1.21 ), (A.2.1 ), (A.2.2), (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.8), (A.3.9), (A.3.12), (A.3.14), (A.3.15), (A.3.16), (A.3.19), (A.3.20), (A.3.21 ), (A.3.22), (A.3.23), (A.3.24), (A.3.25), (A.3.26), (A.3.27); (A.4.5), (A.4.6), (A.4.8), (A.4.9) and (A.4.1 1 ).
  • mixtures as component 2) at least one active substance selected from group B), which is particularly selected from (B.1.4), (B.1 .5), diniconazole (B.1 .6), (B.1 .8),
  • mixtures comprising as component 2) at least one active substance selected from group C), which is particularly selected from (C.1 .4), C.1.5), (C.1 .6), and (C.2.4).
  • mixtures comprising as component 2) at least one active substance selected from group D), which is particularly selected from (D1 .1 ), (D1.2), (D1.4), (D1 .5); (D2.2), (D2.4), (D2.5), (D2.6) and (D2.7);
  • mixtures comprising as component 2) at least one active substance selected from group E), which is particularly selected from (E.1.1 ), (E.1.2), and (E.1 .3);
  • mixtures comprising as component 2) at least one active substance selected from group F), which is particularly selected from (F.1.2), (F.1 .4), (F.1 .5), (F.1.6) and (F.2.1 ).
  • mixtures comprising as component 2) at least one active substance selected from group H), which is and particularly selected from (H.1 .2), (H.1.3), copper oxychlo- ride (H.1 .4), (H.1.5), (H.1.6); (H.2.2), (H.2.5), (H.2.7), (H.3.2), (H.3.3), (H.3.4), (H.3.5), (H.3.6), (H.3.12); (H.4.2), (H.4.6), dithianon (H.4.9) and (H.4.10).
  • group H is and particularly selected from (H.1 .2), (H.1.3), copper oxychlo- ride (H.1 .4), (H.1.5), (H.1.6); (H.2.2), (H.2.5), (H.2.7), (H.3.2), (H.3.3), (H.3.4), (H.3.5), (H.3.6), (H.3.12); (H.4.2), (H.4.6), dithianon (H.4.9) and (H.4.10).
  • mixtures comprising as component 2) at least one active substance selected from group I), which is particularly selected from (I.2.3) and (1.2.5).
  • mixtures comprising as component 2) at least one active substance selected from group J), which is particularly selected from (J.1.1 ), (J.1 .2), (J.1.3), (J.1 .4), (J.1 .6), (J.1 .7), (J.1.8) and (J.1.9).
  • mixtures comprising as component 2) at least one active substance selected from group K), which is particularly selected from (K.1.4), (K.1.5), (K.1.8), (K.1.12), (K.1.14), (K.1 .15), (K.1.19) and(K.1 .22).
  • mixtures comprising as pesticide II a biopesticide selected from the isoflavones formonennitin, hesperetin and naringenin.
  • the present invention furthermore relates to compositions comprising one compound I (component 1 ) and one pesticide II (component 2), which pesticide II is selected from the column "Co. 2" of the lines C-1 to C-593 of Table C.
  • a further embodiment relates to the compositions C-1 to C-593 listed in Table C, where a row of Table C corresponds in each case to a fungicidal composition comprising as active components one of the in the present specification individualized compounds of formula I (component 1 ) and the respective pesticide II from groups A) to O) (component 2) stated in the row in question.
  • the compositions described comprise the active components in synergistically effec- tive amounts.
  • Table C Compositions comprising as active components one individualized compound I (I) (in Column Co. 1 ) and as component 2) (in Column Co. 2) one pesticide from groups A) to O)
  • the mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient (auxiliary) by usual means, e. g. by the means given for the compositions of compounds I.
  • the mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomy- cetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is refered to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I, respectively.
  • Example 1 Synthesis of lsothiazolo[1 ,2][1 ,4]dithiino[3,4-c]pyrazine-3,6,7-tricarbonitrile Upon cooling with an ice/water bath 1 ,32 g (10 mmol) (5-cyano-3-sodiosulfanyl-isothiazol-4- yl)sulfanyl sodium have been added to a solution of 1 g (5,03 mmol) 5,6-dichloropyrazine-2,3- dicarbonitrile in 20 ml dimethyl formamide ( according to Journal of Organic Chemistry, 45(25), 5122-30; 1980).
  • Example 1 Activity against the grey mold Botrytis cinerea in the microtiterplate test
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
  • Example 2 Activity against the late blight pathogen Phytophthora infestans in the microtiter test
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Phytophtora infestans containing a pea juice-based aqueous nutrient medium or DDC medium was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C.
  • the MTPs were measured at 405 nm 7 days after the inoculation.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
  • Example 4 Activity against leaf blotch on wheat caused by Septoria tritici
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
  • the measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.

Abstract

The present invention relates to substituted thiadiazoles and the salts thereof and the use of these compounds for combating phytopathogenic fungi,and to seeds coated with at least one such compound.

Description

Substituted 1 ,4-dithiine derivatives and their use as fungicides
Description The present invention relates to com ounds of the formula I
Figure imgf000002_0001
and the N-oxides and the agriculturally acceptable salts thereof.
Furthermore the present invention relates to a process for preparing compounds of the formula I.
Furthermore the present invention relates to agrochemical compositions, comprising at least one compound of formula I a N-oxide or an agriculturally acceptable salt thereof.
Furthermore the present invention relates to the use of a compound of the formula I and/or of an agriculturally acceptable salt thereof or of the compositions for combating phytopathogenic fungi.
Furthermore the present invention relates to 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.
Furthermore the present invention relates to seed, coated with at least one compound of the formula I and/or an agriculturally acceptable salt thereof or with a composition in an amount of from 0.1 to 10 kg per 100 kg of seed.
WO 91/08510 relates to organic optical elements and nonlinear optical devices and disclosed substituted 1 ,4-dithiine derivatives. An application in crop protection is not mentioned.
Accordingly, it was an object of the present invention to find novel substituted 1 ,4-dithiine compounds which preferably have improved properties, such as improved fungicidal action.
Surprisingly, this object is achieved by the use of the inventive substituted 1 ,4-dithiine com- pounds of formula I having favorable fungicidal activity against phytopathogenic fungi.
Accordingly, the present invention relates, to the compounds of the formula I
Figure imgf000002_0002
wherein
R1 and R2 independently of one another are
H, halogen, CN, N02; or Ci-Cio-alkyl, Ci-Cio-haloalkyl; or
a radical of the formula -C(=0)A1 or -C(=0)OA1 , where
A1 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl;
wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy; or
R1 and R2 together with the C atom to which these radicals are attached may also form a five or six membered heterocycle, where the heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S as ring members and may furthermore contain one or two CO, SO or SO2 groups as ring members;
wherein the above mentioned rings may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, CH2-0-Ci-Cio-alkyl; or a radical of the formula -C(=0)A1A, - C(=0)OA1A, where
A1A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; and
R3 is
H, halogen, CN, NO2; or
Ci-Cio-alkyl, Ci-Cio-haloalkyl; or
a radical of the formula -C(=0)A3 or -C(=0)OA3, where
A3 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl;
wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, C1-C10- haloalkoxy; and
I is 0, 1 or 2; and
k is 0, 1 or 2;
and the N-oxides and the agriculturally acceptable salts thereof with the proviso that
if I is 0 and k is 0 and R1 and R2 is H R3 cannot be H and
if I is 0 and k is 0 and R1 and R2 is CN R3 cannot be CN.
Furthermore the present invention provides a process for preparing compounds of the formula I.
Furthermore the present invention provides an agrochemical composition, comprising at least one compound of formula I an N-oxide or an agriculturally acceptable salt thereof.
Furthermore the present invention provides compounds of the formula I
Figure imgf000004_0001
wherein
R1 and R2 independently of one another are
H, halogen, CN, NO2; or
Ci-Cio-alkyl, Ci-Cio-haloalkyl; or
a radical of the formula -C(=0)A1 or -C(=0)OA1 , where
A1 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl;
wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cy- ano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy; or
R1 and R2 together with the C atom to which these radicals are attached may also form a five or six membered heterocycle, where the heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S as ring members and may furthermore contain one or two CO, SO or SO2 groups as ring members;
wherein the above mentioned rings may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, CH2-0-Ci-Cio-alkyl; or a radical of the formula -C(=0)A1A, - C(=0)OA1A, where
A1A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl,
NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; and
R3 is
H, halogen, CN, NO2; or
Ci-Cio-alkyl, Ci-Cio-haloalkyl; or
a radical of the formula -C(=0)A3 or -C(=0)OA3, where
A3 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl;
wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, C1-C10- haloalkoxy; and
I is 0, 1 or 2; and
k is O, 1 or 2; and the N-oxides and the agriculturally acceptable salts thereof and/or of an agriculturally acceptable salt thereof or of the compositions, as defined in any of the claims 8 or 9, for combating phytopathogenic fungi. Furthermore the present invention provides 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.
Furthermore the present invention provides seed, coated with at least one compound of the formula I and/or an agriculturally acceptable salt thereof or with a composition in an amount of from 0.1 to 10 kg per 100 kg of seed.
The terms used for organic groups in the definition of the variables are, for example the expression "halogen", collective terms which represent the individual members of these groups of organic units.
The prefix Cx-Cy denotes the number of possible carbon atoms in the particular case.
The term "halogen" refers to fluorine, chlorine, bromine and iodine.
alkyl and the alkyl moieties of composite groups such as, for example, alkoxy, alkylamino, alkoxycarbonyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 10 carbon atoms, for example Ci-Cio-akyl, such as methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 - methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 - methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2- ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl and 1 -ethyl-2- methylpropyl; heptyl, octyl, 2-ethylhexyl and positional isomers thereof; nonyl, decyl and positional isomers thereof;
haloalkyl: straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above. In one embodiment, the alkyl groups are substituted at least once or completely by a particular halogen atom, preferably fluorine, chlorine or bromine. In a further embodi- ment, the alkyl groups are partially or fully halogenated by different halogen atoms; in the case of mixed halogen substitutions, the combination of chlorine and fluorine is preferred. Particular preference is given to (Ci-C3)-haloalkyl, more preferably (Ci-C2)-haloalkyl, such as chloromethyl, bromomethyl, 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, 2,2,2-trichloroethyl, pentafluoroethyl or 1 ,1 ,1 -trifluoroprop- 2-yl;
cycloalkyl and also the cycloalkyl moieties in composite groups: mono- or bicyclic saturated hydrocarbon groups having 3 to 10, in particular 3 to 6, carbon ring members, for example C3-C6- cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Ex- amples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1 .1 ]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl. In this connection, optionally substituted Cs-Cs-cycloalkyl means a cyclo- alkyl radical having from 3 to 8 carbon atoms, in which at least one hydrogen atom, for example 1 , 2, 3, 4 or 5 hydrogen atoms, is/are replaced by substituents which are inert under the conditions of the reaction. Examples of inert substituents are CN, Ci-C6-alkyl, Ci-C4-haloalkyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, and Ci-C4-alkoxy-Ci-C6-alkyl;
halocycloalkyl and the halocycloalkyl moieties in halocycloalkoxy, halocycloalkylcarbonyl and the like: monocyclic saturated hydrocarbon groups having 3 to 10 carbon ring members (as mentioned above) in which some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
alkoxy: an alkyl group as defined above which is attached via an oxygen, preferably having 1 to 10, more preferably 2 to 6, carbon atoms. Examples are: methoxy, ethoxy, n-propoxy, 1 -methyl- ethoxy, butoxy, 1 -methylpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy, and also for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethyl- propoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2- trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1 -ethyl-1-methylpropoxy or 1 -ethyl-2-methylpropoxy; haloalkoxy: alkoxy as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyi, in particular by fluorine, chlorine or bromine. Examples are OCH2F, OCHF2, OCF3, OCH2CI, OCHC , OCCI3, chlorofluoro- methoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 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-trichloroethoxy, OC2F5, 2- fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3- chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1 -(CH2F)-2-fluoroethoxy, 1 -(CH2CI)-2- chloroethoxy, 1 -(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or no- nafluorobutoxy; and also 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, un- decafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluo- rohexoxy;
5-, 6-membered heterocycle which contains 1 , 2, 3 or 4 heteroatoms from the group consisting of O, N and S as ring members, and may furthermore contain one or two CO, SO, SO2 groups as ring members, where the heterocycle in question may be attached via a carbon atom or, if pre- sent, via a nitrogen atom. In particular:
a five- or six-membered saturated or partially unsaturated heterocycle which comprises one, two, three or four heteroatoms from the group consisting of O, N and S as ring members: for example monocyclic saturated or partially unsaturated heterocycles which, in addition to carbon ring members, comprise one, two or three nitrogen atoms and/or one oxygen or sul- fur atom or one or two oxygen and/or sulfur atoms, for example 2-tetrahydrofuranyl, 3- tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3- isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,
5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4- oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4- imidazolidinyl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin-5-yl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3-yl, 1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2- yl, 1 ,3,4-triazolidin-2-yl, 2,3-d ihyd rofur-2-yl , 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4- dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4- dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin- 3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4- yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3- yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2- isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1 -yl, 2,3- dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5- yl, 3,4-dihydropyrazol-1 -yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4- dihydropyrazol-5-yl, 4,5-dihydropyrazol-1 -yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4- yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3- dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3- yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1 ,3-dioxan-5-yl, 2- tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexa- hydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4-hexahydrotriazin-3-yl and also the corresponding -ylidene radicals;
a five- or six-membered aromatic heterocycle (= heteroaromatic radical) which contains one, two, three or four heteroatoms from the group consisting of oxygen, nitrogen and sulfur, for example 5-membered heteroaryl which is attached via carbon and contains one to three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, such as 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4- imidazolyl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl, 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-thiadiazol- 5-yl, 1 ,2,4-triazol-3-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,3,4-thiadiazol-2-yl and 1 ,3,4-triazol-2-yl; 5- membered heteroaryl which is attached via nitrogen and contains one to three nitrogen atoms as ring members, such as pyrrol-1 -yl, pyrazol-1 -yl, imidazol-1 -yl, 1 ,2,3-triazol-1 -yl and 1 ,2,4-triazol-1 -yl; 6-membered heteroaryl, which contains one, two or three nitrogen atoms as ring members, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl;
Ci-Cio-alkoxy-Ci-Cio-alkyl: Ci-Cio-alkyl (as defined above) where one hydrogen atom is replaced by a Ci-Cio-alkoxy group as defined above;
amino-Ci-Cio-alkyl: Ci-Cio-alkyl (as defined above) where one hydrogen atom is replaced by a NA1A2 group as defined above; mono-(Ci-Cio-alkyl)amino: group of the formula NA1A2 group in which A1 or A2 is an Ci-Cio-alkyl group as defined above.
di-(Ci-Cio-alkyl)amino: group of the formula NA1A2 group in which each A1 and A2 are an C1-C10- alkyl group as defined above.
hydroxyl: OH group which is attached via an O atom;
cyano: CN group which is attached via an C atom;
nitro: NO2 group which is attached via an N atom.
The compounds of the formula l-A according to the invention in which k = 0 and I =0 can be prepared by different routes analogously to processes known per se of the prior art as follows: Scheme 1 :
Figure imgf000008_0001
l-A (R3= CN)
According to the above mentioned route a precursor II can be converted into the corresponding compounds of the formula (III) (for details see: Journal of Organic Chemistry, 45(25), 5122-30; 1980).
This can be coupled with the precursors (IV) in DMF at about 5°C to about 50°C preferably at about 10°C to about 30°C providing efficient access to the corresponding compounds of the formula l-A (for details see: US 5,633,219).
The compounds of the formulae l-B according to the invention in which k = 1 and I = 0, l-C in which k = 0 and I = 1 , l-D in which k = 1 and I = 1 , l-E in which k = 2 and I = 2 can be prepared by different routes analogously to processes known per se of the prior art as follows: Scheme 2:
Figure imgf000009_0001
I-A
According to the above mentioned route the compound of the formula I-A can be oxided according to conventional oxidation methods, e. g. by treating with an organic peracid such as metachloroperbenzoic 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 using ammonium cerium(IV) nitrate in the presence of a catalytic amount of KBr or NaBr ) (for details see: Catalysis Communications, 9(8), 1739-1744; 2008; Monatshefte fuer Chemie, 139(8), 895-899; 2008) giving the corresponding compounds of the formula IB, IC, ID, IE.
The precursor (III) may be obtained by various routes in analogy to prior art processes known from JOC, 1980, 45(25), 5122-30.
Some of precursors IV are commercially available.
Precursors IV in which R1 and R2 together form the ring
Figure imgf000009_0002
can be prepared employing a preparative procedure known from Org. & Biomolecular Chem., 10(36), 7392 - 7401 (2012).
Precursors IV in which R1 and R2 together form the rin
Figure imgf000009_0003
can be prepared employing a preparative procedure known from Mendeleev Comm. 1 1 (4), 152-
153 (2001 ).
If individual inventive compounds cannot be directly obtained by the routes described above, they can be prepared by derivatization of other inventive compounds.
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 metachloroperbenzoic 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 composition of different N-oxides, which can be separated by conventional methods such as chromatography. If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
In the following, the intermediate compounds are further described. A skilled person will readily understand that the preferences for the substituents, also in particular the ones given in the tables below for the respective substituents, given herein in connection with compounds I apply for the intermediates accordingly. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein.
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 manganese, 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 sulfoxonium ions, prefer- ably tri(Ci-C4-alkyl)sulfoxonium. 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, prefera- bly of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The 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.
Depending on the substitution pattern, 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.
In the following, particular embodiments of the inventive compounds are described. Therein, specific meanings of the respective substituents are further detained, wherein the meanings are in each case on their own but also in any combination with one another, particular embodiments of the present invention.
Furthermore, in respect of the variables, generally, the embodiments of the compounds I also apply to the intermediates.
k in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment, 0. k in the compounds according to the invention or the compounds used according to the invention is, according to one further embodiment, 1 . k in the com- pounds according to the invention or the compounds used according to the invention is, according to one further embodiment, 2.
I in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment, 0. 1 in the compounds according to the invention or the com- pounds used according to the invention is, according to one further embodiment, 1 . 1 in the compounds according to the invention or the compounds used according to the invention is, according to one further embodiment, 2.
R1 in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment H, halogen, CN or NO2. In a special embodiment of the invention, R1 is H. In a further special embodiment of the invention, R1 is CN. In a further special embodiment of the invention, R1 is NO2. In a further special embodiment of the invention, R1 is CI. In a further special embodiment of the invention, R1 is Br. In a further special embodiment of the invention, R1 is F.
R1 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment Ci-Cio-alkyl or Ci-Cio-haloalkyl.
According to one embodiment R1 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl. In a special embodiment of the invention, R1 is methyl. In a further special embodiment of the invention, R1 is ethyl. In a further special embodiment of the invention, R1 is propyl.-ln a further special embodiment R1 is i-propyl. In a further spe- cial embodiment R1 is 1 -methylpropyl. In a further special embodiment R1 is n-butyl. In a further special embodiment R1 is i-butyl. In a further special embodiment R1 is t-butyl. In a further special embodiment R1 is n-pentyl. In a further special embodiment R1 is n-hexyl.
According to a further embodiment R1 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, in particular fully or partially halogenated methyl. In a special embodiment of the invention, R1 is CF3. In a further special embodiment of the invention, R1 is CHF2. In a further special embodiment R1 is CFH2. In a further special embodiment of the invention, R1 is CH2CF3. In a further special embodiment R1 is CCI3. In a further special embodiment R1 is CHC . In a further special embodiment R1 is CCIH2.
R1 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment, a radical of the a radical of the formula -C(=0)A1, or - C(=0)OA1, where A1 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; wherein the above mentioned groups may carry one, two, three or four identical or different sub- stituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy.
According to one embodiment A1 is H. According to a further embodiment A1 is Ci-Cio-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. According to a further embodiment A1 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i- propyl, n-butyl, i-butyl or t-butyl, in particular fully or partially halogenated methyl. According to a further embodiment A1 is C3-Cio-cycloalkyl, preferrably cyclopropyl, cyclobutyl or cyclopentyl, in particular cyclopropyl or cyclobutyl. According to a further embodiment A1 is C3-Cio-halocycloalkyl, preferrably fully or partially halogenated cyclopropyl, cyclobutyl or cyclopentyl, in particular fully or partially halogenated cyclopropyl. According to a further embodiment A1 is NH2. According to a further embodiment A1 is mono-(Ci-Cio-alkyl)amino. According to a further embodiment A1 is di- (Ci-Cio-alkyl)amino.
According to one embodiment A1 is phenyl. According to a further embodiment A1 is benzyl. According to a further embodiment A1 is naphthyl.
According to one embodiment phenyl, benzyl and naphthyl may carry one, two, three or four identical or different substituents selected from the group consisting of CI, I, F, Br, preferably CI, F. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methyl, ethyl, propyl, butyl, preferably methyl. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of partially or fully halogenated methyl, ethyl, propyl, butyl, preferably partially or fully halogenated methyl, in particular CF3. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, preferably methoxy. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of partially or fully halogenated methoxy, ethoxy, propoxy, butoxy, preferably partially or fully halogenated methoxy, in particular OCF3.
In a specific embodiment of the invention R1 is -CHO. In a further specific embodiment of the invention R1 is -C(=0)OH. In a further specific embodiment of the invention R1 is -C(=0)NH2. In a further specific embodiment of the invention R1 is -C(=0)OCi-Cio-alkyl. In a further specific embodiment of the invention R1 is -C(=0)NHCi-Cio-alkyl. In a further specific embodiment of the invention R1 is -C(=0)N(Ci-Cio-alkyl)2.
R2 in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment H, halogen, CN or NO2. In a special embodiment of the invention, R2 is H. In a further special embodiment of the invention, R2 is CN. In a further special embodiment of the invention, R2 is NO2. In a further special embodiment of the invention, R2 is CI. In a further special embodiment of the invention, R2 is Br. In a further special embodiment of the invention, R2 is F.
R2 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment Ci-Cio-alkyl or Ci-Cio-haloalkyl.
According to one embodiment R2 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl. In a special embodiment of the invention, R2 is methyl. In a further special embodiment of the invention, R2 is ethyl. In a further special embodiment of the invention, R2 is propyl.-ln a further special embodiment R2 is i-propyl. In a further special embodiment R2 is 1 -methylpropyl. In a further special embodiment R2 is n-butyl. In a further special embodiment R2 is i-butyl. In a further special embodiment R2 is t-butyl. In a further special embodiment R2 is n-pentyl. In a further special embodiment R2 is n-hexyl.
According to a further embodiment R2 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, in particular fully or partially halogenated methyl. In a special embodiment of the invention, R2 is CF3. In a further special embodiment of the invention, R2 is CHF2. In a further special embodiment R2 is CFH2. In a further special embodiment of the invention, R2 is CH2CF3. In a further special embodiment R2 is CCI3. In a further special embodiment R2 is CHC . In a further special embodiment R2 is CCIH2.
R2 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment, a radical of the a radical of the formula -C(=0)A2, or - C(=0)OA1, where A1 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; wherein the above mentioned groups may carry one, two, three or four identical or different sub- stituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy.
According to one embodiment A1 is H. According to a further embodiment A1 is Ci-Cio-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. According to a further embodiment A1 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i- propyl, n-butyl, i-butyl or t-butyl, in particular fully or partially halogenated methyl. According to a further embodiment A1 is C3-Cio-cycloalkyl, preferrably cyclopropyl, cyclobutyl or cyclopentyl, in particular cyclopropyl or cyclobutyl. According to a further embodiment A1 is C3-Cio-halocycloalkyl, preferrably fully or partially halogenated cyclopropyl, cyclobutyl or cyclopentyl, in particular fully or partially halogenated cyclopropyl. According to a further embodiment A1 is NH2. According to a further embodiment A1 is mono-(Ci-Cio-alkyl)amino. According to a further embodiment A1 is di- (C-i-Cio-alkyl)amino.
According to one embodiment A1 is phenyl. According to a further embodiment A2 is benzyl. According to a further embodiment A1 is naphthyl.
According to one embodiment phenyl, benzyl and naphthyl may carry one, two, three or four iden- tical or different substituents selected from the group consisting of CI, I, F, Br, preferably CI, F. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methyl, ethyl, propyl, butyl, preferably methyl. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of par- tially or fully halogenated methyl, ethyl, propyl, butyl, preferably partially or fully halogenated methyl, in particular CF3. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, preferably methoxy. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents se- lected from the group consisting of partially or fully halogenated methoxy, ethoxy, propoxy, butoxy, preferably partially or fully halogenated methoxy, in particular OCF3.
In a specific embodiment of the invention R2 is -CHO. In a further specific embodiment of the invention R2 is -C(=0)OH. In a further specific embodiment of the invention R2 is -C(=0)NH2. In a further specific embodiment of the invention R2 is -C(=0)OCi-Cio-alkyl. In a further specific em- bodiment of the invention R2 is -C(=0)NHCi-Cio-alkyl. In a further specific embodiment of the invention R2 is -C(=0)N(Ci-Cio-alkyl)2. R1 and R2 in the compounds according to the invention or the compounds used according to the invention, together with the C atom to which these radicals are attached may also form a five or six membered heterocycle, where the heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S as ring members and may furthermore contain one or two CO, SO or SO2 groups as ring members; wherein the above mentioned rings may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Chb-O-Ci-Cio-alkyl; or a radical of the formula -C(=0)A1A, -C(=0)OA1A, where A1A is hydrogen, Ci-Cio-alkyl, Ci-Cio- haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio- alkyl)amino, phenyl, benzyl, napthyl.
According to one embodiment R1 and R2 form five membered saturated ring including O as ring member. According to one further embodiment R1 and R2 form five membered saturated ring including N as ring member. According to one embodiment R1 and R2 form five membered aromatic ring including N and S as ring members.
According to one embodiment R1 and R2 together with the C atom to which these radicals are attached form the ring
Figure imgf000014_0001
wherein # means C atoms to which R1 and R2 are attached.
According to one further embodiment R1 and R2 together with the C atom to which these radicals are attached form the ring
Figure imgf000014_0002
wherein # means C atoms to which R1 and R2 are attached and
R4 is selected from H, Ci-Cio-alkyl, Ci-Cio-alkoxy, CH2-0-Ci-Cio-alkyl.
R4 in the compounds according to the invention or the compounds used according to the invention is, according to an embodiment, H.
R4 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment, Ci-Cio-alkyl.
According to one embodiment R4 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl. In a special embodiment of the invention, R4 is methyl. In a further special embodiment of the invention, R4 is ethyl. In a further special embodiment of the invention, R4 is propyl.-ln a further special embodiment R4 is i-propyl. In a further special embodiment R4 is 1 -methylpropyl. In a further special embodiment R4 is n-butyl. In a further special embodiment R4 is i-butyl. In a further special embodiment R4 is t-butyl. In a further special embodiment R4 is n-pentyl. In a further special embodiment R4 is n-hexyl.
According to a further embodiment R4 is Ci-Cio-alkoxy. In a special embodiment of the invention, R4 is OCH3. In a further special embodiment of the invention, R4 is OCH2CH3. In a further special embodiment of the invention, R4 is OCH2CH2CH3. In a further special embodiment of the invention, R4 is OCH(CH3)2. In a further special embodiment of the invention, R4 is OCH2CH2CH2CH3. In a further special embodiment of the invention, R4 is OCH(CH2CH3)2. In a further special embodiment of the invention, R4 is OC(CH3)3. In a further special embodiment of the invention, R4 is OCH2CH(CH3)2. In a further special embodiment of the invention, R4 is OCH2CH2CH2CH2CH3. In a further special embodiment of the invention, R4 is O CH2CH2CH2CH2CH2CH3.
According to one embodiment R4 is CH2-0-Ci-Cio-alkyl, preferrerably Chb-O-methyl, Chb-O-ethyl, CH2-0-n-propyl, CH2-0-i-propyl, CH2-0-n-butyl, CH2-0-i-butyl, CH2-0-t-butyl, in particular CH2-O- methyl, CH2-0-ethyl. In a special embodiment of the invention, R4 is Chb-O-methyl. In a further special embodiment of the invention, R4 is Chb-O-ethyl. In a further special embodiment of the invention, R4 is Chb-O-propyl.-ln a further special embodiment R4 is Chb-O-i-propyl. In a further special embodiment R4 is Chb-O-l -methylpropyl. In a further special embodiment R4 is Ch -O-n- butyl. In a further special embodiment R4 is Ch -O-i-butyl. In a further special embodiment R4 is Chb-O-t-butyl. In a further special embodiment R4 is CH2-0-n-pentyl. In a further special embodiment R4 is CH2-0-n-hexyl.
According to one further embodiment R1 and R2 together with the C atom to which these radicals are attached form the ring
Figure imgf000015_0001
wherein # means C atoms to which R1 and R2 are attached and
R5 is selected from H, halogen, CN, Ci-Cio-alkyl; or is a radical of the formula -C(=0)A5A, - C(=0)OA5A, where A5A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl.
R5 in the compounds according to the invention or the compounds used according to the invention is, according to an embodiment, H.
R5 in the compounds according to the invention or the compounds used according to the invention is, according to an embodiment, CI, F or Br. In a special embodiment of the invention, R5 is CI. . In a further special embodiment of the invention, R5 is F. In a further special embodiment of the invention, R5 is Br. R5 in the compounds according to the invention or the compounds used according to the invention is, according to an embodiment, CN.
R5 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment, Ci-Cio-alkyl.
According to one embodiment R5 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl. In a special embodiment of the invention, R5 is methyl. In a further special embodiment of the invention, R5 is ethyl. In a further special embodiment of the invention, R5 is propyl.-ln a further special embodiment R5 is i-propyl. In a further special embodiment R5 is 1 -methylpropyl. In a further special embodiment R5 is n-butyl. In a further special embodiment R5 is i-butyl. In a further special embodiment R5 is t-butyl. In a further special embodiment R5 is n-pentyl. In a further special embodiment R5 is n-hexyl.
R5 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment, a radical of the a radical of the formula -C(=0)A5A, or - C(=0)OA5A, where A5A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, N H2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl. According to one embodiment A5A is H or Ci-Cio-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. According to a further embodiment A5A is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl, in particular fully or partially halogenated methyl. According to a further embodiment A5A is C3-Cio-cycloalkyl, preferrably cyclopropyl, cyclobutyl or cyclopentyl, in particular cyclopropyl or cyclobutyl. According to a further embodiment A5A is C3-Cio-halocycloalkyl, preferrably fully or partially halogenated cyclopropyl, cyclobutyl or cyclopentyl, in particular fully or partially halogenated cyclopropyl. According to a further embodiment A5A is N H2. According to a further embodiment A5A is mono-(Ci-Cio- alkyl)amino. According to a further embodiment A5A is di-(Ci-Cio-alkyl)amino.
According to one embodiment A5A is phenyl. According to a further embodiment A5 is benzyl. Ac- cording to a further embodiment A5A is naphthyl.
In a specific embodiment of the invention R5 is -CHO. In a further specific embodiment of the invention R5 is -C(=0)OH. In a further specific embodiment of the invention R5 is -C(=0)N H2. In a further specific embodiment of the invention R5 is -C(=0)OCi-Cio-alkyl. In a further specific embodiment of the invention R5 is -C(=0)N HCi-Cio-alkyl. In a further specific embodiment of the invention R5 is -C(=0)N(Ci-Cio-alkyl)2.
According to one further embodiment R1 and R2 together with the C atom to which these radicals are attached form the ring
Figure imgf000016_0001
wherein # means C atoms to which R1 and R2 are attached.
In the compounds according to the invention R1 and R2 are not H and CN.
R3 in the compounds according to the invention or the compounds used according to the invention is, according to one embodiment H, halogen, CN or NO2. In a special embodiment of the invention, R3 is H. In a further special embodiment of the invention, R3 is CN. In a further special embodiment of the invention, R3 is NO2. In a further special embodiment of the invention, R3 is CI. In a further special embodiment of the invention, R3 is Br. In a further special embodiment of the invention, R3 is F.
R3 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment Ci-Cio-alkyl or Ci-Cio-haloalkyl. According to one embodiment R3 is Ci-Cio-alkyl, preferrerably methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, in particular methyl, ethyl. In a special embodiment of the invention, R3 is methyl. In a further special embodiment of the invention, R3 is ethyl. In a further special embodiment of the invention, R3 is propyl.-ln a further special embodiment R3 is i-propyl. In a further spe- cial embodiment R3 is 1 -methylpropyl. In a further special embodiment R3 is n-butyl. In a further special embodiment R3 is i-butyl. In a further special embodiment R3 is t-butyl. In a further special embodiment R3 is n-pentyl. In a further special embodiment R3 is n-hexyl.
According to a further embodiment R3 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, in particular fully or partially halogenated methyl. In a special embodiment of the invention, R3 is CF3. In a further special embodiment of the invention, R3 is CHF2. In a further special embodiment R3 is CFH2. In a further special embodiment of the invention, R3 is CH2CF3. In a further special embodiment R3 is CCI3. In a further special embodiment R3 is CHC . In a further special embodiment R3 is CCIH2.
R3 in the compounds according to the invention or the compounds used according to the invention is, according to a further embodiment, a radical of the a radical of the formula -C(=0)A4, or - C(=0)OA4, where A3 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy.
According to one embodiment A3 is H. or Ci-Cio-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. According to a further embodiment A3 is Ci-Cio-haloalkyl; preferrably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl, in particular fully or partially halogenated methyl. According to a further embodiment A3 is C3-Cio-cycloalkyl, prefer- rably cyclopropyl, cyclobutyl or cyclopentyl, in particular cyclopropyl or cyclobutyl. According to a further embodiment A3 is C3-Cio-halocycloalkyl, preferrably fully or partially halogenated cyclopropyl, cyclobutyl or cyclopentyl, in particular fully or partially halogenated cyclopropyl. According to a further embodiment A3 is NH2. According to a further embodiment A3 is mono-(Ci-Cio-alkyl)amino. According to a further embodiment A3 is di-(Ci-Cio-alkyl)amino.
According to one embodiment A4 is phenyl. According to a further embodiment A4 is benzyl. According to a further embodiment A4 is naphthyl.
According to one embodiment phenyl, benzyl and naphthyl may carry one, two, three or four identical or different substituents selected from the group consisting of CI, I, F, Br, preferably CI, F. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methyl, ethyl, propyl, butyl, preferably methyl. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of partially or fully halogenated methyl, ethyl, propyl, butyl, preferably partially or fully halogenated methyl, in particular CF3. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, preferably methoxy. According to a further embodiment the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of partially or fully halogenated methoxy, ethoxy, propoxy, butoxy, preferably partially or fully halogenated methoxy, in particular OCF3.
In a specific embodiment of the invention R3 is -CHO. In a further specific embodiment of the in- vention R3 is C(=0)OH. In a further specific embodiment of the invention R3 is -C(=0)NH2. In a further specific embodiment of the invention R3 is -C(=0)OCi-Cio-alkyl. In a further specific embodiment of the invention R3 is -C(=0)NHCi-Cio-alkyl. In a further specific embodiment of the invention R3 is -C(=0)N(Ci-Cio-alkyl)2.
Particularly preferred embodiments of R1 and R2 according to the invention are in Table A below, wherein each line of lines A-1 to A-293 corresponds to one particular embodiment of the invention, wherein A-1 to A-293 are also in any combination a preferred embodiment of the present invention. With regard to the compounds according to the invention the exception as deifned above will be considered. The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question.
According to one embodiment, the present invention relates to compounds of the formula I.A
Figure imgf000018_0001
Here, the variables are as defined elsewhere herein for formula I, or as defined as being preferred for formula I.
According to one embodiment, the present invention relates to compounds of the formula I.B
Figure imgf000018_0002
Here, the variables are as defined elsewhere herein for formula I, or as defined as being preferred for formula I.
According to one embodiment, the present invention relates to compounds of the formula I.C
Figure imgf000018_0003
Here, the variables are as defined elsewhere herein for formula I, or as defined as being preferred for formula I.
According to one embodiment, the present invention relates to compounds of the formula I.D
Figure imgf000019_0001
Here, the variables are as defined elsewhere herein for formula I, or as defined as being preferred for formula I.
According to one embodiment, th compounds of the formula I.E
Figure imgf000019_0002
Here, the variables are as defined elsewhere herein for formula I, or as defined as being preferred for formula I.
Preference is given to the compounds I according to the invention compiled in Tables 1 a to 14a, 1 b to 14 b, 1 c to 14c, 1 d to 14d, 1 e to 14e below with the proviso as defined above. The groups mentioned for a substituent in the tables are furthermore per se, independently of the
combination in which they are mentioned, a particularly preferred aspect of the substituent in question.
Table 1 a
Compounds of the formula I. A in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is H (compounds I.A.1 a.A-1 to I.A.1 a.A-294).
Table 2a
Compounds of the formula I.A in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CI (compounds I.A.2a.A-1 to I.A.2a.A-294).
Table 3a
Compounds of the formula I.A in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CH3 (compounds I.A.3a.A-1 to I.A.3a.A- 294).
Table 4a
Compounds of the formula I.A in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is CH2CH3 (compounds I.A.4a.A-1 to
I.A.4a.A-294).
Table 5a
Compounds of the formula I.A in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CF3 (compounds I.A.5a.A-1 to I.A.5a.A- 294).
Table 6a
Compounds of the formula I.A in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)OH (compounds I.A.6a.A-1 to I.A.6a.A-294).
Table 7a
Compounds of the formula I .A in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)OCH3 (compounds I.A.7a.A-1 to I.A.7a.A-294).
Compounds of the formula I. A in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OCH2CH3 (compounds I.A.8a.A-1 to I.A.8a.A-294).
Table 8a
Compounds of the formula I .A in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)NH2 (compounds I.A.9a.A-1 to I.A.9a.A-294).
Table 9a
Compounds of the formula I. A in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)NHCH3 (compounds I.A.10a.A-1 to I.A.10a.A-294).
Table 10a
Compounds of the formula I .A in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)NHCH2CH3 (compounds I.A.1 1 a.A- 1 to I.A.1 1 a.A-294).
Table 1 1 a
Compounds of the formula I. A in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)N(CH3)2 (compounds I.A.12a.A-1 to I.A.12a.A-294).
Table 12a
Compounds of the formula I .A in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)N(CH2CH3)2 (compounds I.A.13a.A- 1 to I.A.13a. A-294).
Table 13a
Compounds of the formula I .A in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CN (compounds I.A.14a.A-1 to I.A.14a.A- 294).
Table 1 b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is H (compounds I.B.1 b.A-1 to I.B.1 b.A-294).
Table 2b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CI (compounds I.B.2b.A-1 to I.B.2b.A-294). Table 3b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CH3 (compounds I.B.3b.A-1 to I.B.3b.A- 294).
Table 4b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CH2CH3 (compounds I.B.4b.A-1 to I.B.4b.A-294).
Table 5b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CF3 (compounds I.B.5b.A-1 to I.B.5b.A- 294).
Table 6b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)OH (compounds I.B.6b.A-1 to I.B.6b.A-294).
Table 7b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OCH3 (compounds I.B.7b.A-1 to I.B.7b.A-294).
Table 8b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OCH2CH3 (compounds I.B.8b.A-1 to I.B.8b.A-294).
Table 9b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)NH2 (compounds I.B.9b.A-1 to I.B.9b.A-294).
Table 10b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)NHCH3 (compounds I.B.10b.A-1 to I.B.1 Ob.A-294).
Table 1 1 b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)NHCH2CH3 (compounds I.B.1 1 b.A- 1 to I.B.1 1 b.A-294).
Table 12b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)N(CH3)2 (compounds I.B.12b.A-1 to I.B.12b.A-294). Table 13b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)N(CH2CH3)2 (compounds I.B.13b.A- 1 to I.B.13b.A-294).
Table 14b
Compounds of the formula I.B in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CN (compounds I.B.14b.A-1 to I.B.14b.A- 294).
Table 1 c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is H (compounds I.C.1 c.A-1 to I.C.1 c.A-294).
Table 2c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CI (compounds I.C.2c.A-1 to I.C.2c.A-294). Table 3c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CH3 (compounds I.C.3c.A-1 to I.C.3c.A- 294).
Table 4c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CH2CH3 (compounds I.C.4c.A-1 to
I.C.4C.A-294).
Table 5c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is CF3 (compounds I.C.5c.A-1 to I.C.5c.A- 294).
Table 6c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OH (compounds I.C.6c.A-1 to I.C.6C.A-294).
Table 7c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OCH3 (compounds I.C.7c.A-1 to I.C.7C.A-294).
Table 8c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OCH2CH3 (compounds I.C.8c.A-1 to I.C.8C.A-294).
Table 9c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)NH2 (compounds I.C.9c.A-1 to I.C.9C.A-294).
Table 10c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)NHCH3 (compounds I.C.10c.A-1 to I.C.10C.A-294).
Table 1 1 c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)NHCH2CH3 (compounds I.C.1 1 c.A- 1 to I.C.1 1 C.A-294).
Table 12c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)N(CH3)2 (compounds I.C.12c.A-1 to I.C.12C.A-294).
Table 13c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)N(CH2CH3)2 (compounds I.C.13c.A- 1 to I.C.13C.A-294).
Table 14c
Compounds of the formula I.C in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CN (compounds I.C.14c.A-1 to I.C.14c.A- 294).
Table 1 d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is H (compounds I.D.1 d.A-1 to I.D.1 d.A-294).
Table 2d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CI (compounds I.D.2d.A-1 to I.D.2d.A- 294).
Table 3d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CH3 (compounds I.D.3d.A-1 to I.D.3d.A- 294).
Table 4d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CH2CH3 (compounds I.D.4d.A-1 to
I.D.4d.A-294).
Table 5d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is CF3 (compounds I.D.5d.A-1 to I.D.5d.A- 294).
Table 6d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)OH (compounds I.D.6d.A-1 to I.D.6d.A-294).
Table 7d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OCH3 (compounds I.D.7d.A-1 to I.D.7d.A-294).
Table 8d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OCH2CH3 (compounds I.D.8d.A-1 to I.D.8d.A-294).
Table 9d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)NH2 (compounds I.D.9d.A-1 to I.D.9d.A-294).
Table 10d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)NHCH3 (compounds I.D.10d.A-1 to I.D.10d.A-294).
Table 1 1 d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)NHCH2CH3 (compounds I.D.1 1 d.A- 1 to I.D.1 1 d.A-294).
Table 12d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)N(CH3)2 (compounds I.D.12d.A-1 to I.D.12d.A-294).
Table 13d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)N(CH2CH3)2 (compounds I.D.13d.A- 1 to I.D.13d.A-294).
Table 14d
Compounds of the formula I.D in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CN (compounds I.D.14d.A-1 to I.D.14d.A- 294). Table 1 e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is H (compounds I.E.1 e.A-1 to I.E.1 e.A-294).
Table 2e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CI (compounds I.E.2e.A-1 to I.E.2e.A-294).
Table 3e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CH3 (compounds I.E.3e.A-1 to I.E.3e.A- 294).
Table 4e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CH2CH3 (compounds I.E.4e.A-1 to
I.E.4e.A-294).
Table 5e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CF3 (compounds I.E.5e.A-1 to I.E.5e.A- 294).
Table 6e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OH (compounds I.E.6e.A-1 to I.E.6e.A-294).
Table 7e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)OCH3 (compounds I.E.7e.A-1 to I.E.7e.A-294).
Table 8e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)OCH2CH3 (compounds I.E.8e.A-1 to I.E.8e.A-294).
Table 9e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)NH2 (compounds I.E.9e.A-1 to I.E.9e.A-294).
Table 10e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)NHCH3 (compounds I.E.10e.A-1 to I.E.1 Oe.A-294).
Table 1 1 e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)NHCH2CH3 (compounds I.E.1 1 e.A- 1 to I.E.1 1 e.A-294).
Table 12e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corre- sponds in each case to one row of Table A and R3 is -C(=0)N(CH3)2 (compounds I.E.12e.A-1 to I.E.12e.A-294).
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is -C(=0)N(CH2CH3)2 (compounds I.E.13e.A- 1 to I.E.13e.A-294).
Table 13e
Compounds of the formula I.E in which the combination of R1 and R2 for a compound corresponds in each case to one row of Table A and R3 is CN (compounds I.E.14e.A-1 to I.E.14e.A- 294294).
Table A
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
The compounds I and the compositions according to the invention, respectively, are suitable as fungicides.
Consequently, according to a further aspect, the present invention relates to the use of compounds of formula I, the N-oxides and the agriculturally acceptable salts thereof or of the com- positions of the invention for combating phytopathogenic fungi.
Accordingly, 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.
The compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, 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. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cu- cumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
Preferably, compounds I and compositions thereof, respectively 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.
The term "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. pota- toes), 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.
These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
Preferably, 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.
The term "cultivated 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. Typically, 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. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbi- cides such as dicamba or 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxy- genase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. 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 another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several 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. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tol- erant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cul- tivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, Bayer CropScience, Germany).
Furthermore, 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 δ-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 nema- todes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced 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 blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention 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. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, 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. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the CrylAb toxin), YieldGard® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme phosphinothri- cin-N-acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard® I (cotton cultivars producing the CrylAc toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Pro- tecta®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. 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).
Furthermore, 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. Examples of such 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). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
Furthermore, 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.
Furthermore, 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).
Furthermore, 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. altemata), tomatoes (e. g. A. solani or A. altemata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; 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) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad- leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cer- cospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helmin- thosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. gramini- cola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; 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.) on fruit trees, vines (e. g. C. liriodendri, 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: Pyrenophora) 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 Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (£. pyri), soft fruits (£. veneta: anthracnose) and vines (£. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (£. betae), vegetables (e. g. 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. turci- cum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme ) and F. tucumani- ae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. 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) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P.
megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad- leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby trans- mitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yal- lundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; 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. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. feres (net blotch) on barley; 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 (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. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sa- rocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) no- dorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; 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) on peaches and T. pruni (plum pocket) on 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) on rye; Uromyces spp. (rust) on 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) on apples (e. g. V. inaequalis) and pears; and 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, cooling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coni- ophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Ser- pula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following 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. According to the present invention, 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. Also falling under the definition of stored products is 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 pro- cessed forms.
The compounds I and compositions thereof, respectively, 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.
The term "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. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
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 protected from fungal attack with a fungicidally effective amount of the active substances. The ap- plication 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 agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
An agrochemical composition comprises a fungicidally effective amount of a compound I. The term "effective amount" 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 materials 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.
The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for 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. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e. g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The 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, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e. g. cyclohexanone; esters, e. g. lactates, carbonates, fatty acid es- ters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e. g. N-methyl pyrroli- done, fatty acid dimethyl amides; 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.
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 emulsifier, 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. Examples of sulfonates are alkylaryl sul- fonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin 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 alkyl naphthalenes, 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-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of 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. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinyl pyrroli- done, vinyl alcohols, or vinyl acetate. 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 polyvinyl amines or polyethylene amines.
Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity them- selves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. 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, carboxymethyl cellulose), inorganic 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 (e. g. in red, blue, or green) 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 polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I and 5-15 wt% wetting agent (e. g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e. g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I and 1 -10 wt% dispersant (e. g. polyvinyl pyrrolidone) are dissolved in organic solvent (e. g. cyclohexanone) ad 100 wt%. Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound I and 5-10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e. g. aromatic hydro- carbon) ad 100 wt%. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I and 1 -10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e. g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion. v) Suspensions (SC, OD, FS)
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. polyvinyl alcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
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, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) 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.
viii) Gel (GW, GF)
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. carboxymethyl cellulose) 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.
ix) Microemulsion (ME)
5-20 wt% of a compound I are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide 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.
x) Microcapsules (CS)
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 results in the formation of poly(meth)acrylate micro- capsules. Alternatively, 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 isocya- nate monomer (e. g. diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). The addition of a polyamine (e. g. hexameth- ylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1 - 10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1 -10 wt% of a compound I are ground finely and mixed intimately with solid carrier (e. g. finely divided kaolin) ad 100 wt%.
xii) Granules (GR, FG)
0.5-30 wt% of a compound I is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or fluidized bed.
xiii) Ultra-low volume liquids (UL)
1 -50 wt% of a compound I are dissolved in organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%.
The compositions types i) to xiii) 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).
For the purposes of treatment of plant propagation materials, particularly seeds, 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. 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, onto plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods. Preferably, 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.
When employed in plant protection, 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.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
A pesticide is generally a chemical or biological agent (such as pestidal active ingredient, compound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term pesticides includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/).
Biopesticides are typically created by growing and concentrating naturally occurring organisms and/or their metabolites including bacteria and other microbes, fungi, viruses, nematodes, proteins, etc. They are often considered to be important components of integrated pest management (IPM) programs.
Biopesticides fall into two major classes, microbial and biochemical pesticides:
(1 ) Microbial pesticides consist of bacteria, fungi or viruses (and often include the me- tabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classed as microbial pesticides, even though they are multi-cellular.
(2) Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area. According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
When living microorganisms, such as pesticides from groups L1 ), L3) and L5), form part of such kit, it must be taken care that choice and amounts of the components (e. g. chemical pesticidal agents) and of the further auxiliaries should not influence the viability of the microbial pesticides in the composition mixed by the user. Especially for bactericides and solvents, compatibility with the respective microbial pesticide has to be taken into account.
Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1 ) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and option- ally a further active component 3) as defined herein.
Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.
The following list of pesticides II (e. g. pesticidally-active substances and biopesticides), in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
A) Respiration inhibitors
- Inhibitors of complex III at Q0 site (e. g. strobilurins): azoxystrobin (A.1 .1 ), coumethoxy- strobin (A.1.2), coumoxystrobin (A.1 .3), dimoxystrobin (A.1.4), enestroburin (A.1 .5), fenaminstrobin (A.1 .6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1 .8), kresox- im-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1 .17) and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylidene- aminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide (A.1 .18), pyribencarb
(A.1.19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21 ), fenamidone (A.1.21 ); methyl-A/-[2-[(1 ,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1.22), 1 -[3-chloro-2-[[1 -(4-chlorophenyl)-1 H-pyrazol-3-yl]oxymethyl]phenyl]-4-methyl- tetrazol-5-one (A.1 .23), 1 -[3-brorno-2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-4- methyl-tetrazol-5-one (A.1 .24), 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl- phenyl]-4-methyl-tetrazol-5-one (A.1 .25), 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3- fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1 .26), 1 -[2-[[1 -(2,4-dichlorophenyl)pyrazol-3- yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1 .27),
1 -[2-[[4-(4-chlorophenyl)thiazol-2-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1.28), 1 -[3-chloro-2-[[4-(p-tolyl)thiazol-2-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.29), 1 -[3-cyclopropyl-2-[[2-methyl-4-(1 -methylpyrazol-3-yl)phenoxy]methyl]phenyl]- 4-methyl-tetrazol-5-one (A.i .30), 1 -[3-(difluoromethoxy)-2-[[2-methyl-4-(1 -methylpyrazol- 3-yl)phenoxy]methyl]phenyl]-4-methyl-tetrazol-5-one (A.1.31 ), 1 -methyl-4-[3-methyl- 2-[[2-methyl-4-(1 -methylpyrazol-3-yl)phenoxy]methyljphenyl]tetrazol-5-one (A.1 ,32), 1 -me- thyl-4-[3-methyl-2-[[1 -[3-(trif!uoromethyl)phenyl]-ethylideneamino]oxymethyl]pheny
5-one (A.1.33), (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-A/,3- dimethyl-pent-3-enamide (A.1 .34), (Z,2£)-5-[1 -(4-chlorophenyl)pyrazol-3-yl]oxy-2- methoxyimino-A/.3-dimethyl-pent-3-enarnide (A.1.35), (Z,2£)-5-[1 -(4-chloro-2-f!uoro- phenyl)pyrazol-3-yl]oxy-2-methoxyimino-A/,3-dimethyl-pent-3-enamide (A.1.36);
inhibitors of complex III at Q, site: cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)- 8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan- 7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.4), [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.5), [(3S,6S,7R,8R)-8-benzyl-3-[[3- (1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5- dioxonan-7-yl] 2-methylpropanoate (A.2.6); (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2- pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2- methylpropanoate (A.2.7); 3S,6S,7R,8R)-8-benzyl-3-[3-[(isobutyryloxy)methoxy]-4- methoxypicolinamido]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl isobutyrate (A.2.8); [2-[[(7R,8R,9S)- 7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-dioxo-1 ,5-dioxonan-3-yl]carbamoyl]-4- methoxy-3-pyridyl]oxymethyl 2-methylpropanoate (A.2.9)
- inhibitors of complex II (e. g. carboxamides): benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'- trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide (A.3.19), N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole- 4-carboxamide (A.3.20), 3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.21 ), 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.22), 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.23), 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.24), 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.25), N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carboxamide
(A.3.26), N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl- pyrazole-4-carboxamide (A.3.27);
- other respiration inhibitors (e. g. complex I, uncouplers): diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthi- ofam (A.4.12);
B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1.1 ), bitertanol (B.1.2), bromuconazole (B.1 .3), cyproconazole (B.1 .4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole (B.1 .8), fenbuconazole (B.1 .9), fluquinconazole (B.1.10), flusilazole (B.1 .1 1 ), flutriafol (B.1 .12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1.15), metconazole (B.1 .17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1 .20), penconazole (B.1.21 ), propiconazole (B.1 .22), prothioconazole
(B.1.23), simeconazole (B.1 .24), tebuconazole (B.1.25), tetraconazole (B.1 .26), triadimefon (B.1 .27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), 1 -[re/-(2S;3R)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazolo (B.1.31 ), 2- [re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol (B.1 .32), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.33), 1 -[4- (4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1 -yl)ethanol (B.1 .34), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.35),
2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .36), 2-[4-(4-chloro- phenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .37), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1.38), 2-[2-chloro- 4-(4-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.39), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.40), 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1 .41 ); imidazoles: imazalil (B.1 .42), pefurazoate (B.1 .43), prochloraz (B.1.44), triflumizol (B.1 .45); pyrimidines, pyridines and piperazines: fenarimol (B.1.46), nuarimol (B.1.47), pyrifenox (B.1.48), triforine (B.1.49), [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1 .50), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol (B.1.51 );
Delta14-reductase inhibitors: aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spirox- amine (B.2.8);
Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1 ), benalaxyl-M (C.1 .2), kiral- axyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (mefenoxam, C.1 .5), ofurace (C.1 .6), oxadixyl (C.1.7);
- others: hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine (C.2.7);
D)lnhibitors of cell division and cytoskeleton
- tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl (D1.1 ), carbendazim (D1 .2), fuberidazole (D1.3), thiabendazole (D1 .4), thiophanate-methyl (D1.5); triazolopyrim- idines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine (D1 .6);
- other cell division inhibitors: diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil (E.1 .1 ), mepanipyrim (E.1.2), pyrimethanil (E.1 .3);
- protein synthesis inhibitors: blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hy- drochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);
F) Signal transduction inhibitors
- MAP / histidine kinase inhibitors: fluoroimid (F.1 .1 ), iprodione (F.1 .2), procymidone (F.1 .3), vinclozolin (F.1 .4), fenpiclonil (F.1.5), fludioxonil (F.1 .6);
- G protein inhibitors: quinoxyfen (F.2.1 );
G) Lipid and membrane synthesis inhibitors
- Phospholipid biosynthesis inhibitors: edifenphos (G.1.1 ), iprobenfos (G.1 .2), pyrazophos (G.1.3), isoprothiolane (G.1 .4);
- lipid peroxidation: dicloran (G.2.1 ), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
- phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb
(G.3.6), valifenalate (G.3.7) and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester (G.3.8);
- compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1 );
- fatty acid amide hydrolase inhibitors: oxathiapiprolin (G.5.1 ), 2-{3-[2-(1 -{[3,5-bis(di- fluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5- yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3, 5-bis(difluoromethyl)-1 H-pyrazol-1 - yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3);
H) lnhibitors with Multi Site Action
- inorganic active substances: Bordeaux mixture (H.1 .1 ), copper acetate (H.1.2), copper hydroxide (H.1.3), copper oxychloride (H.1 .4), basic copper sulfate (H.1 .5), sulfur (H.1.6);
- thio- and dithiocarbamates: ferbam (H.2.1 ), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);
- organochlorine compounds (e. g. phthalimides, sulfamides, chloronitriles): anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid
(H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12);
- guanidines and others: guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);
I) Cell wall synthesis inhibitors
- inhibitors of glucan synthesis: validamycin (1.1.1 ), polyoxin B (1.1 .2);
- melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (1.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);
J) Plant defence inducers
- acibenzolar-S-methyl (J.1.1 ), probenazole (J.1 .2), isotianil (J.1 .3), tiadinil (J.1 .4), prohexa- dione-calcium (J.1.5); phosphonates: fosetyl (J.1 .6), fosetyl-aluminum (J.1 .7), phosphorous acid and its salts (J.1 .8), potassium or sodium bicarbonate (J.1.9);
K) Unknown mode of action
- bronopol (K.1.1 ), chinomethionat (K.1.2), cyflufenamid (K.1 .3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclomezine (K.1 .7), difenzoquat (K.1.8), difenzoquat- methylsulfate (K.1.9), diphenylamin (K.1 .10), fenpyrazamine (K.1.1 1 ), flumetover (K.1.12), flusulfamide (K.1 .13), flutianil (K.1 .14), methasulfocarb (K.1 .15), nitrapyrin (K.1 .16), nitrothal- isopropyl (K.1.18), oxathiapiprolin (K.1 .19), tolprocarb (K.1.20), oxin-copper (K.1.21 ), pro- quinazid (K.1 .22), tebufloquin (K.1.23), tecloftalam (K.1 .24), triazoxide (K.1.25), 2-butoxy-6- iodo-3-propylchromen-4-one (K.1.26), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5- [2-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yljetha- none (K.1 .27), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 - yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1.28), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -yloxy)phenyl]- 4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1.29), N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide (K.1.30), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.31 ), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N- ethyl-N-methyl formamidine (K.1 .32), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl- propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.33), N'-(5-difluoromethyl-2-methyl-4-(3- trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester (K.1 .35), 3-[5-(4-methylphenyl)-2,3- dimethyl-isoxazolidin-3-yl]-pyridine (K.1 .36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine (pyrisoxazole) (K.1 .37), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide (K.1.38), 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole (K.1.39), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy- acetamide, ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41 ), pentyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2- pyridyl]carbamate (K.1 .42), 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro- phenyl]propan-2-ol (K.1 .43), 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phen-yl]propan- 2-o\ (K.1 .44), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1 .45), 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline (K.1.46), 3-(4,4,5-trifluoro- 3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1 .47), 9-fluoro-2,2-dimethyl-5-(3- quinolyl)-3H-1 ,4-benzoxazepine (K.1.48);
M) Growth regulators
abscisic acid (M.1.1 ), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dime- thipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gib- berellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione, prohexadi- one-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate,
2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole;
N) Herbicides
- acetamides: acetochlor (N.1.1 ), alachlor, butachlor, dimethachlor, dimethenamid (N.1 .2), flufenacet (N.1.3), mefenacet (N.1 .4), metolachlor (N.1 .5), metazachlor (N.1 .6), napropa- mide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
- amino acid derivatives: bilanafos, glyphosate (N.2.1 ), glufosinate (N.2.2), sulfosate (N.2.3);
- aryloxyphenoxypropionates: clodinafop (N.3.1 ), cyhalofop-butyl, fenoxaprop (N.3.2), flua- zifop (N.3.3), haloxyfop (N.3.4), metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- Bipyridyls: diquat, paraquat (N.4.1 );
- (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham (N.5.1 ), prosulfocarb, pyributicarb, thiobencarb, triallate;
- cyclohexanediones: butroxydim, clethodim (N.6.1 ), cycloxydim (N.6.2), profoxydim
(N.6.3), sethoxydim (N.6.4), tepraloxydim (N.6.5), tralkoxydim;
- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin (N.7.1 ), prodiamine (N.7.2), trifluralin (N.7.3);
- diphenyl ethers: acifluorfen (N.8.1 ), aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lac- tofen, oxyfluorfen;
- hydroxybenzonitriles: bomoxynil (N.9.1 ), dichlobenil, ioxynil;
- imidazolinones: imazamethabenz, imazamox (N.10.1 ), imazapic (N.10.2), imazapyr (N.10.3), imazaquin (N.10.4), imazethapyr (N.10.5);
- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D) (N.1 1.1 ), 2,4- DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
- pyrazines: chloridazon (N.1 1.1 ), flufenpyr-ethyl, fluthiacet, norflurazon, pyridate; - pyridines: aminopyralid, clopyralid (N.12.1 ), diflufenican, dithiopyr, fluridone, fluroxypyr (N.12.2), picloram (N.12.3), picolinafen (N.12.4), thiazopyr;
- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron (N.13.1 ), chlorimuron-ethyl (N.13.2), chlorsulfuron, cinosulfuron, cyclosulfamuron (N.13.3), ethoxysulfuron, flazasulfu- ron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron (N.13.4), mesosulfuron (N.13.5), metazosulfuron, metsulfuron-methyl (N.13.6), nicosulfuron (N.13.7), oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron (N.13.8), sul- fometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron (N.13.9), tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6- dimethoxy-pyrimidin-2-yl)urea;
- triazines: ametryn, atrazine (N.14.1 ), cyanazine, dimethametryn, ethiozin, hexazinone (N.14.2), metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
- ureas: chlorotoluron, daimuron, diuron (N.15.1 ), fluometuron, isoproturon, linuron, metha- benzthiazuron, tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam (N.16.1 ), flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrim- isulfan, pyrithiobac, pyroxasulfone (N.16.2), pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarba- zone,benfluresate, benzofenap, bentazone (N.17.1 ), benzobicyclon, bicyclopyrone, broma- cil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl (N.17.2), chlorthal, cinmethylin (N.17.3), clomazone (N.17.4), cumyluron, cyprosulfamide, dicamba (N.17.5), difenzoquat, diflufenzopyr (N.17.6), Drechslera monoceras, endothal,
ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac (N.17.7), quinmerac (N.17.8), mesotrione (N.17.9), methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil (N.17.10), sulcotrione (N.17.1 1 ), sulfentrazone, terbacil, tefuryltrione, tembotrione, thien- carbazone, topramezone (N.17.12), (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4- trifluoromethyl-3,6-dihydro-2H-pyrimidin-1 -yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2- cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro- pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)- pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino- 2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester;
Insecticides
- organo(thio)phosphates: acephate (0.1 .1 ), azamethiphos (0.1 .2), azinphos-methyl (0.1.3), chlorpyrifos (0.1 .4), chlorpyrifos-methyl (0.1.5), chlorfenvinphos (0.1.6), diazinon (0.1.7), dichlorvos (0.1 .8), dicrotophos (0.1 .9), dimethoate (0.1 .10), disulfoton (0.1.1 1 ), ethion (0.1.12), fenitrothion (0.1 .13), fenthion (0.1 .14), isoxathion (0.1 .15), malathion (0.1.16), methamidophos (0.1 .17), methidathion (0.1 .18), methyl-parathion (0.1.19), mevinphos (0.1.20), monocrotophos (0.1.21 ), oxydemeton-methyl (0.1.22), paraoxon (0.1.23), parathion (0.1.24), phenthoate (0.1 .25), phosalone (0.1.26), phosmet (0.1 .27), phosphamidon (0.1 .28), phorate (0.1 .29), phoxim (0.1 .30), pirimiphos-methyl (0.1.31 ), profenofos (0.1 .32), prothiofos (0.1.33), sulprophos (0.1 .34), tetrachlorvinphos (0.1.35), terbufos (0.1 .36), triazophos (0.1.37), trichlorfon (0.1 .38);
- carbamates: alanycarb (0.2.1 ), aldicarb (0.2.2), bendiocarb (0.2.3), benfuracarb (0.2.4), carbaryl (0.2.5), carbofuran (0.2.6), carbosulfan (0.2.7), fenoxycarb (0.2.8), furathiocarb (0.2.9), methiocarb (0.2.10), methomyl (0.2.1 1 ), oxamyl (0.2.12), pirimicarb (0.2.13), propoxur (0.2.14), thiodicarb (0.2.15), triazamate (0.2.16);
- pyrethroids: allethrin (0.3.1 ), bifenthrin (0.3.2), cyfluthrin (0.3.3), cyhalothrin (0.3.4), cy- phenothrin (0.3.5), cypermethrin (0.3.6), alpha-cypermethrin (0.3.7), beta-cypermethrin (0.3.8), zeta-cypermethrin (0.3.9), deltamethrin (0.3.10), esfenvalerate (0.3.1 1 ), etofenprox (0.3.1 1 ), fenpropathrin (0.3.12), fenvalerate (0.3.13), imiprothrin (0.3.14), lambda- cyhalothrin (0.3.15), permethrin (0.3.16), prallethrin (0.3.17), pyrethrin I and II (0.3.18), resmethrin (0.3.19), silafluofen (O.3.20), tau-fluvalinate (0.3.21 ), tefluthrin (0.3.22), tetrame- thrin (0.3.23), tralomethrin (0.3.24), transfluthrin (0.3.25), profluthrin (0.3.26), dimefluthrin (0.3.27);
- insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron (0.4.1 ), cyramazin (0.4.2), diflubenzuron (0.4.3), flucycloxuron (0.4.4), flufenoxuron
(0.4.5), hexaflumuron (0.4.6), lufenuron (0.4.7), novaluron (0.4.8), teflubenzuron (0.4.9), triflumuron (0.4.10); buprofezin (0.4.1 1 ), diofenolan (0.4.12), hexythiazox (0.4.13), etox- azole (0.4.14), clofentazine (0.4.15); b) ecdysone antagonists: halofenozide (0.4.16), methoxyfenozide (0.4.17), tebufenozide (0.4.18), azadirachtin (0.4.19); c) juvenoids:
pyriproxyfen (O.4.20), methoprene (0.4.21 ), fenoxycarb (0.4.22); d) lipid biosynthesis inhibitors: spirodiclofen (0.4.23), spiromesifen (0.4.24), spirotetramat (0.4.24);
- nicotinic receptor agonists/antagonists compounds: clothianidin (0.5.1 ), dinotefuran (0.5.2), flupyradifurone (0.5.3), imidacloprid (0.5.4), thiamethoxam (0.5.5), nitenpyram (0.5.6), acetamiprid (0.5.7), thiacloprid (0.5.8), 1 -2-chloro-thiazol-5-ylmethyl)-2-nitrimino- 3,5-dimethyl-[1 ,3,5]triazinane (0.5.9);
- GABA antagonist compounds: endosulfan (0.6.19, ethiprole (0.6.2), fipronil (0.6.3), vaniliprole (0.6.4), pyrafluprole (0.6.5), pyriprole (0.6.6), 5-amino-1 -(2,6-dichloro-4-methyl- phenyl)-4-sulfinamoyl-1 H-pyrazole-3-carbothioic acid amide (0.6.7);
- macrocyclic lactone insecticides: abamectin (0.7.1 ), emamectin (0.7.2), milbemectin (0.7.3), lepimectin (0.7.4), spinosad (0.7.5), spinetoram (0.7.6);
- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin (0.8.1 ), pyrida- ben (0.8.2), tebufenpyrad (0.8.3), tolfenpyrad (0.8.4), flufenerim (0.8.5);
- METI II and III compounds: acequinocyl (0.9.1 ), fluacyprim (0.9.2), hydramethylnon (0.9.3);
- Uncouplers: chlorfenapyr (0.10.1 ); - oxidative phosphorylation inhibitors: cyhexatin (0.1 1 .1 ), diafenthiuron (0.1 1 .2), fenbutatin oxide (0.1 1 .3), propargite (0.1 1 .4);
- moulting disruptor compounds: cryomazine (0.12.1 );
- mixed function oxidase inhibitors: piperonyl butoxide (0.13.1 );
- sodium channel blockers: indoxacarb (0.14.1 ), metaflumizone (0.14.2);
- ryanodine receptor inhibitors: chlorantraniliprole (0.15.1 ), cyantraniliprole (0.15.2), flu- bendiamide (0.15.3), N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (0.15.4); N-[4-chloro-2-[(di- ethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(triflu- oromethyl)pyrazole-3-carboxamide (0.15.5); N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanyli- dene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-car- boxamide (0.15.6); N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (0.15.7); N-[4,6-di- chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(di- fluoromethyl)pyrazole-3-carboxamide (0.15.8); N-[4,6-dibromo-2-[(di-2-propyl-lambda-4-sul- fanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbox- amide (0.15.9); N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-cyano- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (0.15.10); N-[4,6- dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(tri- fluoromethyl)pyrazole-3-carboxamide (0.15.1 1 );
- others: benclothiaz (0.16.1 ), bifenazate (0.16.2), artap (0.16.3), flonicamid (0.16.4), pyridalyl (0.16.5), pymetrozine (0.16.6), sulfur (0.16.7), thiocyclam (0.16.8), cyenopyrafen (0.16.9), flupyrazofos (O.16.10), cyflumetofen (0.16.1 1 ), amidoflumet (0.16.12), imicyafos (0.16.13), bistrifluron (0.16.14), pyrifluquinazon (0.16.15) and
1 ,1 '-[(3S,4R,4aR,6S,6aS, 12R, 12aS, 12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-
1 ,3,4,4a,5,6,6a, 12, 12a, 12b-decahydro-12-hydroxy-4,6a, 12b-trimethyl-1 1 -oxo-9-(3-pyridinyl)- 21-1, 1 1 H-naphtho[2, 1 -b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester (0.16.16); tioxazafen (0.16.17).
The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by l UPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141
317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP-
A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244,
JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272;
US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404;
WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ;
WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388;
WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325;
WO 06/87343; WO 07/82098; WO 07/90624, WO 1 1/028657, WO2012/168188, WO 2007/006670, WO 201 1/77514; WO13/047749, WO 10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009,
WO 13/024010 and WO 13/047441 , WO 13/162072, WO 13/092224, WO 1 1/135833). The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if desired one suitable solvent or solid carrier. Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Furthermore, combating harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to K), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to K).
By applying compounds I together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures).
This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or seperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance ap- plied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.
When applying compound I and a pesticide II sequentially the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1 .5 hours to 5 days, even more preferred from 2 hours to 1 dayln the binary mixtures and compositions according to the invention the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active components used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1.
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1000:1 to 1 :1 , often in the range of from 100: 1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1.
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1 :1 to 1 :1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2. In the ternary mixtures, i.e. compositions according to the invention comprising the component 1 ) and component 2) and a compound III (component 3), the weight ratio of component 1 ) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4: 1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1.
Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1 ).
These ratios are also suitable for inventive mixtures applied by seed treatment.
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group A), which is particularly selected from (A.1 .1 ), (A.1 .4), (A.1 .8), (A.1 .9), (A.1.12), (A.1 .13), (A.1.14), (A.1 .17), (A.1.19), (A.1.21 ), (A.2.1 ), (A.2.2), (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.8), (A.3.9), (A.3.12), (A.3.14), (A.3.15), (A.3.16), (A.3.19), (A.3.20), (A.3.21 ), (A.3.22), (A.3.23), (A.3.24), (A.3.25), (A.3.26), (A.3.27); (A.4.5), (A.4.6), (A.4.8), (A.4.9) and (A.4.1 1 ).
Preference is given to mixtures as component 2) at least one active substance selected from group B), which is particularly selected from (B.1.4), (B.1 .5), diniconazole (B.1 .6), (B.1 .8),
(B.1.10), (B.1 .1 1 ), (B.1.12), (B.1.17), (B.1 .18), (B.1.21 ), (B.1 .22), (B.1 .23), (B.1.25), (B.1 .26), (B.1.27), (B.1 .28), (B.1 .29), uni (B.1.31 ), (B.1.32), (B.1 .33), (B.1.34), (B.1.35), (B.1.36), (B.1.37), (B.1 .38), (B.1.39), (B.1.40), (B.1.41 ), (B.1 .42), (B.1.44), (B.1 .46), (B.1.49) and (B.1 .50; (B.2.2), (B.2.4), (B.2.5), (B.2.6), piperalin (B.2.7), (B.2.8); and (B.3.1 ).
Preference is given to mixtures comprising as component 2) at least one active substance selected from group C), which is particularly selected from (C.1 .4), C.1.5), (C.1 .6), and (C.2.4).
Preference is given to mixtures comprising as component 2) at least one active substance selected from group D), which is particularly selected from (D1 .1 ), (D1.2), (D1.4), (D1 .5); (D2.2), (D2.4), (D2.5), (D2.6) and (D2.7);
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group E), which is particularly selected from (E.1.1 ), (E.1.2), and (E.1 .3);
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group F), which is particularly selected from (F.1.2), (F.1 .4), (F.1 .5), (F.1.6) and (F.2.1 ).
Preference is also given to mixtures as component 2) at least one active substance selected from group G), which is particularly selected from (G.3.1 ), (G.3.2), (G.3.3), (G.3.4), (G.3.5), (G.3.6), (G.4.1 ) and (G.5.1 ).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group H), which is and particularly selected from (H.1 .2), (H.1.3), copper oxychlo- ride (H.1 .4), (H.1.5), (H.1.6); (H.2.2), (H.2.5), (H.2.7), (H.3.2), (H.3.3), (H.3.4), (H.3.5), (H.3.6), (H.3.12); (H.4.2), (H.4.6), dithianon (H.4.9) and (H.4.10).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group I), which is particularly selected from (I.2.3) and (1.2.5).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group J), which is particularly selected from (J.1.1 ), (J.1 .2), (J.1.3), (J.1 .4), (J.1 .6), (J.1 .7), (J.1.8) and (J.1.9).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group K), which is particularly selected from (K.1.4), (K.1.5), (K.1.8), (K.1.12), (K.1.14), (K.1 .15), (K.1.19) and(K.1 .22).
Preference is also given to mixtures comprising as pesticide II a biopesticide selected from the isoflavones formonennitin, hesperetin and naringenin.
Accordingly, the present invention furthermore relates to compositions comprising one compound I (component 1 ) and one pesticide II (component 2), which pesticide II is selected from the column "Co. 2" of the lines C-1 to C-593 of Table C.
A further embodiment relates to the compositions C-1 to C-593 listed in Table C, where a row of Table C corresponds in each case to a fungicidal composition comprising as active components one of the in the present specification individualized compounds of formula I (component 1 ) and the respective pesticide II from groups A) to O) (component 2) stated in the row in question. Preferably, the compositions described comprise the active components in synergistically effec- tive amounts.
Table C: Compositions comprising as active components one individualized compound I (I) (in Column Co. 1 ) and as component 2) (in Column Co. 2) one pesticide from groups A) to O)
[which is coded e. g. as (A.1 .1 ) for azoxystrobin as defined above].
Figure imgf000059_0001
Figure imgf000059_0002
Figure imgf000059_0003
Mixt Co.1 Co.2 Mixt Co.1 Co.2 Mixt Co.1 Co.2
C-46 (I) (A.3.1) C-86 (I) (B.1.2) C-126 (I) (B.1.42)
C-47 (I) (A.3.2) C-87 (I) (B.1.3) C-127 (I) (B.1.43)
C-48 (I) (A.3.3) C-88 (I) (B.1.4) C-128 (I) (B.1.44)
C-49 (I) (A.3.4) C-89 (I) (B.1.5) C-129 (I) (B.1.45)
C-50 (I) (A.3.5) C-90 (I) (B.1.6) C-130 (I) (B.1.46)
C-51 (I) (A.3.6) C-91 (I) (B.1.7) C-131 (I) (B.1.47)
C-52 (I) (A.3.7) C-92 (I) (B.1.8) C-132 (I) (B.1.48)
C-53 (I) (A.3.8) C-93 (I) (B.1.9) C-133 (I) (B.1.49)
C-54 (I) (A.3.9) C-94 (I) (B.1.10) C-134 (I) (B.1.50)
C-55 (I) (A.3.10) C-95 (I) (B.1.11) C-135 (I) (B.1.51)
C-56 (I) (A.3.11) C-96 (I) (B.1.12) C-136 (I) (B.2.1)
C-57 (I) (A.3.12) C-97 (I) (B.1.13) C-137 (I) (B.2.2)
C-58 (I) (A.3.13) C-98 (I) (B.1.14) C-138 (I) (B.2.3)
C-59 (I) (A.3.14) C-99 (I) (B.1.15) C-139 (I) (B.2.4)
C-60 (I) (A.3.15) C-100 (I) (B.1.16) C-140 (I) (B.2.5)
C-61 (I) (A.3.16) C-101 (I) (B.1.17) C-141 (I) (B.2.6)
C-62 (I) (A.3.17) C-102 (I) (B.1.18) C-142 (I) (B.2.7)
C-63 (I) (A.3.18) C-103 (I) (B.1.19) C-143 (I) (B.2.8)
C-64 (I) (A.3.19) C-104 (I) (B.1.20) C-144 (I) (B.3.1)
C-65 (I) (A.3.20) C-105 (I) (B.1.21) C-145 (I) (C.1.1)
C-66 (I) (A.3.21) C-106 (I) (B.1.22) C-146 (I) (C.1.2)
C-67 (I) (A.3.22) C-107 (I) (B.1.23) C-147 (I) (C.1.3)
C-68 (I) (A.3.23) C-108 (I) (B.1.24) C-148 (I) (C.1.4)
C-69 (I) (A.3.24) C-109 (I) (B.1.25) C-149 (I) (C.1.5)
C-70 (I) (A.3.25) C-110 (I) (B.1.26) C-150 (I) (C.1.6)
C-71 (I) (A.3.26) C-111 (I) (B.1.27) C-151 (I) (C.1.7)
C-72 (I) (A.3.27) C-112 (I) (B.1.28) C-152 (I) (C.2.1)
C-73 (I) (A.4.1) C-113 (I) (B.1.29) C-153 (I) (C.2.2)
C-74 (I) (A.4.2) C-114 (I) (B.1.30) C-154 (I) (C.2.3)
C-75 (I) (A.4.3) C-115 (I) (B.1.31) C-155 (I) (C.2.4)
C-76 (I) (A.4.4) C-116 (I) (B.1.32) C-156 (I) (C.2.5)
C-77 (I) (A.4.5) C-117 (I) (B.1.33) C-157 (I) (C.2.6)
C-78 (I) (A.4.6) C-118 (I) (B.1.34) C-158 (I) (C.2.7)
C-79 (I) (A.4.7) C-119 (I) (B.1.35) C-159 (I) (D.1.1)
C-80 (I) (A.4.8) C-120 (I) (B.1.36) C-160 (I) (D.1.2)
C-81 (I) (A.4.9) C-121 (I) (B.1.37) C-161 (I) (D.1.3)
C-82 (I) (A.4.10) C-122 (I) (B.1.38) C-162 (I) (D.1.4)
C-83 (I) (A.4.11) C-123 (I) (B.1.39) C-163 (I) (D.1.5)
C-84 (I) (A.4.12) C-124 (I) (B.1.40) C-164 (I) (D.1.6)
C-85 (I) (B.1.1) C-125 (I) (B.1.41) C-165 (I) (D.2.1) Mixt Co.1 Co.2 Mixt Co.1 Co.2 Mixt Co.1 Co.2
C-166 (I) (D.2.2) C-206 (I) (G.3.6) C-246 (I) (H.4.8)
C-167 (I) (D.2.3) C-207 (I) (G.3.7) C-247 (I) (H.4.9)
C-168 (I) (D.2.4) C-208 (I) (G.3.8) C-248 (I) (H.4.10)
C-169 (I) (D.2.5) C-209 (I) (G.4.1) C-249 (I) (1.1.1)
C-170 (I) (D.2.6) C-210 (I) (G.5.1) C-250 (I) (1.1.2)
C-171 (I) (D.2.7) C-211 (I) (G.5.2) C-251 (I) (1.2.1)
C-172 (I) (E.1.1) C-212 (I) (G.5.3) C-252 (I) (I.2.2)
C-173 (I) (E.1.2) C-213 (I) (H.1.1) C-253 (I) (I.2.3)
C-174 (I) (E.1.3) C-214 (I) (H.1.2) C-254 (I) (I.2.4)
C-175 (I) (E.2.1) C-215 (I) (H.1.3) C-255 (I) (I.2.5)
C-176 (I) (E.2.2) C-216 (I) (H.1.4) C-256 (I) (J.1.1)
C-177 (I) (E.2.3) C-217 (I) (H.1.5) C-257 (I) (J.1.2)
C-178 (I) (E.2.4) C-218 (I) (H.1.6) C-258 (I) (J.1.3)
C-179 (I) (E.2.5) C-219 (I) (H.2.1) C-259 (I) (J.1.4)
C-180 (I) (E.2.6) C-220 (I) (H.2.2) C-260 (I) (J.1.5)
C-181 (I) (E.2.7) C-221 (I) (H.2.3) C-261 (I) (J.1.6)
C-182 (I) (E.2.8) C-222 (I) (H.2.4) C-262 (I) (J.1.7)
C-183 (I) (F.1.1) C-223 (I) (H.2.5) C-263 (I) (J.1.8)
C-184 (I) (F.1.2) C-224 (I) (H.2.6) C-264 (I) (J.1.9)
C-185 (I) (F.1.3) C-225 (I) (H.2.7) C-265 (I) (K.1.1)
C-186 (I) (F.1.4) C-226 (I) (H.2.8) C-266 (I) (K.1.2)
C-187 (I) (F.1.5) C-227 (I) (H.2.9) C-267 (I) (K.1.3)
C-188 (I) (F.1.6) C-228 (I) (H.3.1) C-268 (I) (K.1.4)
C-189 (I) (F.2.1) C-229 (I) (H.3.2) C-269 (I) (K.1.5)
C-190 (I) (G.1.1) C-230 (I) (H.3.3) C-270 (I) (K.1.6)
C-191 (I) (G.1.2) C-231 (I) (H.3.4) C-271 (I) (K.1.7)
C-192 (I) (G.1.3) C-232 (I) (H.3.5) C-272 (I) (K.1.8)
C-193 (I) (G.1.4) C-233 (I) (H.3.6) C-273 (I) (K.1.9)
C-194 (I) (G.2.1) C-234 (I) (H.3.7) C-274 (I) (K.1.10)
C-195 (I) (G.2.2) C-235 (I) (H.3.8) C-275 (I) (K.1.11)
C-196 (I) (G.2.3) C-236 (I) (H.3.9) C-276 (I) (K.1.12)
C-197 (I) (G.2.4) C-237 (I) (H.3.10) C-211 (I) (K.1.13)
C-198 (I) (G.2.5) C-238 (I) (H.3.11) C-278 (I) (K.1.14)
C-199 (I) (G.2.6) C-239 (I) (H.4.1) C-279 (I) (K.1.15)
C-200 (I) (G.2.7) C-240 (I) (H.4.2) C-280 (I) (K.1.16)
C-201 (I) (G.3.1) C-241 (I) (H.4.3) C-281 (I) (K.1.17)
C-202 (I) (G.3.2) C-242 (I) (H.4.4) C-282 (I) (K.1.18)
C-203 (I) (G.3.3) C-243 (I) (H.4.5) C-283 (I) (K.1.19)
C-204 (I) (G.3.4) C-244 (I) (H.4.6) C-284 (I) (K.1.20)
C-205 (I) (G.3.5) C-245 (I) (H.4.7) C-285 (I) (K.1.21) Mixt Co.1 Co.2 Mixt Co.1 Co.2 Mixt Co.1 Co.2
C-286 (I) (K.1.22) C-326 (I) (M.1.14) C-366 (I) (N.1.4)
C-287 (I) (K.1.23) C-327 (I) (M.1.15) C-367 (I) (N.1.5)
C-288 (I) (K.1.24) C-328 (I) (M.1.16) C-368 (I) (N.2.1)
C-289 (I) (K.1.25) C-329 (I) (M.1.17) C-369 (I) (N.2.2)
C-290 (I) (K.1.26) C-330 (I) (M.1.18) C-370 (I) (N.2.3)
C-291 (I) (K.1.27) C-331 (I) (M.1.19) C-371 (I) (N.3.1)
C-292 (I) (K.1.28) C-332 (I) (M.1.20) C-372 (I) (N.3.2)
C-293 (I) (K.1.29) C-333 (I) (M.1.21) C-373 (I) (N.3.3)
C-294 (I) (K.1.30) C-334 (I) (M.1.22) C-374 (I) (N.3.4)
C-295 (I) (K.1.31) C-335 (I) (M.1.23) C-375 (I) (N.4.1)
C-296 (I) (K.1.32) C-336 (I) (M.1.24) C-376 (I) (N.5.1)
C-297 (I) (K.1.33) C-337 (I) (M.1.25) C-377 (I) (N.6.1)
C-298 (I) (K.1.34) C-338 (I) (M.1.26) C-378 (I) (N.6.2)
C-299 (I) (K.1.35) C-339 (I) (M.1.27) C-379 (I) (N.6.3)
C-300 (I) (K.1.36) C-340 (I) (M.1.28) C-380 (I) (N.6.4)
C-301 (I) (K.1.37) C-341 (I) (M.1.29) C-381 (I) (N.6.5)
C-302 (I) (K.1.38) C-342 (I) (M.1.30) C-382 (I) (N.7.1)
C-303 (I) (K.1.39) C-343 (I) (M.1.31) C-383 (I) (N.7.2)
C-304 (I) (K.1.40) C-344 (I) (M.1.32) C-384 (I) (N.7.3)
C-305 (I) (K.1.41) C-345 (I) (M.1.33) C-385 (I) (N.8.1)
C-306 (I) (K.1.42) C-346 (I) (M.1.34) C-386 (I) (N.9.1)
C-307 (I) (K.1.43) C-347 (I) (M.1.35) C-387 (I) (N.10.1)
C-308 (I) (K.1.44) C-348 (I) (M.1.36) C-388 (I) (N.10.2)
C-309 (I) (K.1.45) C-349 (I) (M.1.37) C-389 (I) (N.10.3)
C-310 (I) (K.1.46) C-350 (I) (M.1.38) C-390 (I) (N.10.4)
C-311 (I) (K.1.47) C-351 (I) (M.1.39) C-391 (I) (N.10.5)
C-312 (I) (K.1.48) C-352 (I) (M.1.40) C-392 (I) (N.11.1)
C-313 (I) (M.1.1) C-353 (I) (M.1.41) C-393 (I) (N.12.1)
C-314 (I) (M.1.2) C-354 (I) (M.1.42) C-394 (I) (N.12.2)
C-315 (I) (M.1.3) C-355 (I) (M.1.43) C-395 (I) (N.12.3)
C-316 (I) (M.1.4) C-356 (I) (M.1.44) C-396 (I) (N.12.4)
C-317 (I) (M.1.5) C-357 (I) (M.1.45) C-397 (I) (N.13.1)
C-318 (I) (M.1.6) C-358 (I) (M.1.46) C-398 (I) (N.13.2)
C-319 (I) (M.1.7) C-359 (I) (M.1.47) C-399 (I) (N.13.3)
C-320 (I) (M.1.8) C-360 (I) (M.1.48) C-400 (I) (N.13.4)
C-321 (I) (M.1.9) C-361 (I) (M.1.49) C-401 (I) (N.13.5)
C-322 (I) (M.1.10) C-362 (I) (M.1.50) C-402 (I) (N.13.6)
C-323 (I) (M.1.11) C-363 (I) (N.1.1) C-403 (I) (N.13.7)
C-324 (I) (M.1.12) C-364 (I) (N.1.2) C-404 (I) (N.13.8)
C-325 (I) (M.1.13) C-365 (I) (N.1.3) C-405 (I) (N.13.9) Mixt Co.1 Co.2 Mixt Co.1 Co.2 Mixt Co.1 Co.2
C-406 (I) (N.14.1) C-446 (I) (0.1.24) C-486 (I) (0.3.10)
C-407 (I) (N.14.2) C-447 (I) (0.1.25) C-487 (I) (0.3.11)
C-408 (I) (N.15.1) C-448 (I) (0.1.26) C-488 (I) (0.3.12)
C-409 (I) (N.16.1) C-449 (I) (0.1.27) C-489 (I) (0.3.13)
C-410 (I) (N.16.2) C-450 (I) (0.1.28) C-490 (I) (0.3.14)
C-411 (I) (N.17.1) C-451 (I) (0.1.29) C-491 (I) (0.3.15)
C-412 (I) (N.17.2) C-452 (I) (0.1.30) C-492 (I) (0.3.16)
C-413 (I) (N.17.3) C-453 (I) (0.1.31) C-493 (I) (0.3.17)
C-414 (I) (N.17.4) C-454 (I) (0.1.32) C-494 (I) (0.3.18)
C-415 (I) (N.17.5) C-455 (I) (0.1.33) C-495 (I) (0.3.19)
C-416 (I) (N.17.6) C-456 (I) (0.1.34) C-496 (I) (O.3.20)
C-417 (I) (N.17.7) C-457 (I) (0.1.35) C-497 (I) (0.3.21)
C-418 (I) (N.17.8) C-458 (I) (0.1.36) C-498 (I) (0.3.22)
C-419 (I) (N.17.9) C-459 (I) (0.1.37) C-499 (I) (0.3.23)
C-420 (I) (N.17.10) C-460 (I) (0.1.38) C-500 (I) (0.3.24)
C-421 (I) (N.17.11) C-461 (I) (0.2.1) C-501 (I) (0.3.25)
C-422 (I) (N.17.12) C-462 (I) (0.2.2) C-502 (I) (0.3.26)
C-423 (I) (0.1.1) C-463 (I) (0.2.3) C-503 (I) (0.3.27)
C-424 (I) (0.1.2) C-464 (I) (0.2.4) C-504 (I) (0.4.1)
C-425 (I) (0.1.3) C-465 (I) (0.2.5) C-505 (I) (0.4.2)
C-426 (I) (0.1.4) C-466 (I) (0.2.6) C-506 (I) (0.4.3)
C-427 (I) (0.1.5) C-467 (I) (0.2.7) C-507 (I) (0.4.4)
C-428 (I) (0.1.6) C-468 (I) (0.2.8) C-508 (I) (0.4.5)
C-429 (I) (0.1.7) C-469 (I) (0.2.9) C-509 (I) (0.4.6)
C-430 (I) (0.1.8) C-470 (I) (0.2.10) C-510 (I) (0.4.7)
C-431 (I) (0.1.9) C-471 (I) (0.2.11) C-511 (I) (0.4.8)
C-432 (I) (0.1.10) C-472 (I) (0.2.12) C-512 (I) (0.4.9)
C-433 (I) (0.1.11) C-473 (I) (0.2.13) C-513 (I) (0.4.10)
C-434 (I) (0.1.12) C-474 (I) (0.2.14) C-514 (I) (0.4.11)
C-435 (I) (0.1.13) C-475 (I) (0.2.15) C-515 (I) (0.4.12)
C-436 (I) (0.1.14) C-476 (I) (0.2.16) C-516 (I) (0.4.13)
C-437 (I) (0.1.15) C-477 (I) (0.3.1) C-517 (I) (0.4.14)
C-438 (I) (0.1.16) C-478 (I) (0.3.2) C-518 (I) (0.4.15)
C-439 (I) (0.1.17) C-479 (I) (0.3.3) C-519 (I) (0.4.16)
C-440 (I) (0.1.18) C-480 (I) (0.3.4) C-520 (I) (0.4.17)
C-441 (I) (0.1.19) C-481 (I) (0.3.5) C-521 (I) (0.4.18)
C-442 (I) (0.1.20) C-482 (I) (0.3.6) C-522 (I) (0.4.19)
C-443 (I) (0.1.21) C-483 (I) (0.3.7) C-523 (I) (O.4.20)
C-444 (I) (0.1.22) C-484 (I) (0.3.8) C-524 (I) (0.4.21)
C-445 (I) (0.1.23) C-485 (I) (0.3.9) C-525 (I) (0.4.22) Mixt Co.1 Co. 2 Mixt Co.1 Co. 2 Mixt Co.1 Co. 2
C-526 (I) (0.4.23) C-550 (I) (0.8.1 ) C-574 (I) (0.15.8)
C-527 (I) (0.4.24) C-551 (I) (0.8.2) C-575 (I) (0.15.9)
C-528 (I) (0.5.1 ) C-552 (I) (0.8.3) C-576 (I) (O.15.10)
C-529 (I) (0.5.2) C-553 (I) (0.8.4) C-577 (I) (0.15.1 1 )
C-530 (I) (0.5.3) C-554 (I) (0.8.5) C-578 (I) (0.16.1 )
C-531 (I) (0.5.4) C-555 (I) (0.9.1 ) C-579 (I) (0.16.2)
C-532 (I) (0.5.5) C-556 (I) (0.9.2) C-580 (I) (0.16.3)
C-533 (I) (0.5.6) C-557 (I) (0.9.3) C-581 (I) (0.16.4)
C-534 (I) (0.5.7) C-558 (I) (O.10.1 ) C-582 (I) (0.16.5)
C-535 (I) (0.5.8) C-559 (I) (0.1 1.1 ) C-583 (I) (0.16.6)
C-536 (I) (0.5.9) C-560 (I) (0.1 1.2) C-584 (I) (0.16.7)
C-537 (I) (0.6.1 ) C-561 (I) (0.1 1.3) C-585 (I) (0.16.8)
C-538 (I) (0.6.2) C-562 (I) (0.1 1.4) C-586 (I) (0.16.9)
C-539 (I) (0.6.3) C-563 (I) (0.12.1 ) C-587 (I) (O.16.10)
C-540 (I) (0.6.4) C-564 (I) (0.13.1 ) C-588 (I) (0.16.1 1 )
C-541 (I) (0.6.5) C-565 (I) (0.14.1 ) C-589 (I) (0.16.12)
C-542 (I) (0.6.6) C-566 (I) (0.14.2) C-590 (I) (0.16.13)
C-543 (I) (0.6.7) C-567 (I) (0.15.1 ) C-591 (I) (0.16.14)
C-544 (I) (0.7.1 ) C-568 (I) (0.15.2) C-592 (I) (0.16.15)
C-545 (I) (0.7.2) C-569 (I) (0.15.3) C-593 (I) (0.16.16)
C-546 (I) (0.7.3) C-570 (I) (0.15.4) C-594 (I) (0.16.17)
C-547 (I) (0.7.4) C-571 (I) (0.15.5)
C-548 (I) (0.7.5) C-572 (I) (0.15.6)
C-549 (I) (0.7.6) C-573 (I) (0.15.7)
The mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient (auxiliary) by usual means, e. g. by the means given for the compositions of compounds I.
Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.
The mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomy- cetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is refered to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I, respectively.
Synthesis examples
Example 1 - Synthesis of lsothiazolo[1 ,2][1 ,4]dithiino[3,4-c]pyrazine-3,6,7-tricarbonitrile Upon cooling with an ice/water bath 1 ,32 g (10 mmol) (5-cyano-3-sodiosulfanyl-isothiazol-4- yl)sulfanyl sodium have been added to a solution of 1 g (5,03 mmol) 5,6-dichloropyrazine-2,3- dicarbonitrile in 20 ml dimethyl formamide ( according to Journal of Organic Chemistry, 45(25), 5122-30; 1980).
The reaction mixture has been stirred for 5 hours at room temperature. Subsequently some further (5-cyano-3-sodiosulfanyl-isothiazol-4-yl)sulfanyl sodium has been added and stirring has been continued for 5 days at room temperature. Afterwards water has been added and a yellow solid precipitated. Upon addition of methyl-t-butylether the mixture has been stirred for about 30 min. Then the solid was filtered off and washed with water and pentane. After drying in a stream of nitrogen 0.97 g of the title compound was obtained as yellow crystals (mp = 268°C).
3C-NMR (DMSO-de, δ in ppm): 155.15; 153.56; 152.89, 131 .45; 129.38; 129.26; 128.47;
1 13.32; 1 13.31 ; 109.41
According to the procedure as described above following compounds can be prepared:
Table I
Figure imgf000065_0001
Figure imgf000065_0002
Microtest
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. Example 1 - Activity against the grey mold Botrytis cinerea in the microtiterplate test
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
Compounds 1-1 , I-2, I-3, I-4 and I-5, respectively, showed a growth of 1 % at 31 ppm.
Example 2 - Activity against the late blight pathogen Phytophthora infestans in the microtiter test
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Phytophtora infestans containing a pea juice-based aqueous nutrient medium or DDC medium was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Compounds 1-1 , I-2, I-3, I-4 and I-5, respectively, showed a growth of 14 % and less at 31 ppm.
Example 3 - Activity against rice blast Pyricularia oryzae in the microtiterplate test
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
Compounds I-2, I-3, I-4 and I-5, respectively, showed a growth of 9 % and less at 31 ppm.
Example 4 - Activity against leaf blotch on wheat caused by Septoria tritici
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
Compounds 1-1 , I-2, I-3, I-4, respectively, showed a growth of 9 % and less at 31 ppm.
The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.

Claims

Claims
1 . Compounds of the formula I
Figure imgf000067_0001
wherein
R1 and R2 independently of one another are
H, halogen, CN, NO2; or
Ci-Cio-alkyl, Ci-Cio-haloalkyl; or
a radical of the formula -C(=0)A1 or -C(=0)OA1 , where
A1 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C1-C10- alkoxy, Ci-Cio-haloalkoxy; or
R1 and R2 together with the C atom to which these radicals are attached may also form a five or six membered heterocycle, where the heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S as ring members and may furthermore contain one or two CO, SO or SO2 groups as ring members;
wherein the above mentioned rings may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, cyano, nitro,
NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Chb-O-Ci-do-alkyl; or a radical of the formula -C(=0)A1A, -C(=0)OA1A, where
A1A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; and
R3 is
H, halogen, CN, NO2; or
Ci-Cio-alkyl, Ci-Cio-haloalkyl; or
a radical of the formula -C(=0)A3 or -C(=0)OA3, where
A3 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl,
NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C1-C10- alkoxy, Ci-Cio-haloalkoxy; and
I is 0, 1 or 2; and
k is 0, 1 or 2;
and the N-oxides and the agriculturally acceptable salts thereof with the proviso that if I is 0 and k is 0 and R1 and R2 is H R3 cannot be H and
if I is 0 and k is 0 and R1 and R2 is CN R3 cannot be CN.
The compounds according to claim 1 where
R1 and R2 together with the C atom to which these radicals are attached form the ring
Figure imgf000068_0001
wherein # means C atoms to which R1 and R2 are attached.
The compounds according to claim 1 where
R1 and R2 together with the C atom to which these radicals are attached form the ring
Figure imgf000068_0002
wherein # means C atoms to which R1 and R2 are attached and
R4 is selected from H, Ci-Cio-alkyl, Ci-Cio-alkoxy, CH2-0-Ci-Cio-alkyl.
The compounds according to claim 1 where
R1 and R2 together with the C atom to which these radicals are attached form the ring
Figure imgf000068_0003
wherein # means C atoms to which R1 and R2 are attached and
R5 is selected from H, halogen, CN, Ci-Cio-alkyl; or
is a radical of the formula -C(=0)A5A, -C(=0)OA5A, where
A5A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl. The compounds according to claim 1 where
R1 and R2 together with the C atom to which these radicals are attached form
Figure imgf000069_0001
wherein # means C atoms to which R1 and R2 are attached
6. The compounds of any one of claims 1 to 5 where I is 0.
7. The compounds of any one of claims 1 to 6, where k is 0.
8. A composition, comprising one compound of formula I, as defined in any of the claims 1 to 7, or a N-oxide or an agriculturally acceptable salt thereof.
9. The composition according to claim 8, comprising additionally a further active substance. 10. An use of a compound of the formula I
Figure imgf000069_0002
wherein
R1 and R2 independently of one another are
H, halogen, CN, NO2; or
Ci-Cio-alkyl, Ci-Cio-haloalkyl; or
a radical of the formula -C(=0)A1 or -C(=0)OA1, where
A1 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, N H2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, N H2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C1-C10- alkoxy, Ci-Cio-haloalkoxy; or
R1 and R2 together with the C atom to which these radicals are attached may also form a five or six membered heterocycle, where the heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S as ring members and may furthermore contain one or two CO, SO or SO2 groups as ring members;
wherein the above mentioned rings may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, cyano, nitro, N H2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Chb-O-Ci-Cio-alkyl; or a radical of the formula -C(=0)A1A, -C(=0)OA1A, where A1A is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; and
R3 is
H, halogen, CN, NO2; or
Ci-Cio-alkyl, Ci-Cio-haloalkyl; or
a radical of the formula -C(=0)A3 or -C(=0)OA3, where
A3 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C1-C10- alkoxy, Ci-Cio-haloalkoxy; and
I is 0, 1 or 2; and
k is 0, 1 or 2;
and the N-oxides and the agriculturally acceptable salts thereof and/or of an
agriculturally acceptable salt thereof or of the compositions, as defined in any of the claims 8 or 9, for combating phytopathogenic fungi.
The use according to claiml 0 where
k is 0; and
I is 0; and
R1 and R2 independently of one another are CN; and
R3 is CN.
The use according to claiml 0 where
k is 0; and
I is 0; and
R1 and R2 independently of one another are CN; and
R3 is
H, halogen, NO2; or
Ci-Cio-alkyl, Ci-Cio-haloalkyl; or
a radical of the formula -C(=0)A3 or -C(=0)OA3, where
A3 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, NH2, mono-(Ci-Cio-alkyl)amino, di-(Ci-Cio-alkyl)amino, phenyl, benzyl, naphthyl; wherein the above mentioned groups may carry one, two, three or four identical or different substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci- Cio-alkoxy, Ci-Cio-haloalkoxy.
13. The use according to claim 10 where
R1 and R2 together with the C atom to which these radicals are attached form a ring as defined in any of claims 2 to 5; and
R3 is CN.
14. A method for combating phytopathogenic 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, as defined in any of the claims 1 to 7 or with a composition, as defined in any of the claims 8 or 9.
15. Seed, coated with at least one compound of the formula I, as defined in any of the
claims 1 to 7, and/or an agriculturally acceptable salt thereof or with a composition, as defined in any of the claims 8 or 9, in an amount of from 0.1 to 10 kg per 100 kg of seed.
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