WO2019214979A1 - Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi - Google Patents

Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi Download PDF

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WO2019214979A1
WO2019214979A1 PCT/EP2019/060875 EP2019060875W WO2019214979A1 WO 2019214979 A1 WO2019214979 A1 WO 2019214979A1 EP 2019060875 W EP2019060875 W EP 2019060875W WO 2019214979 A1 WO2019214979 A1 WO 2019214979A1
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alkyl
methyl
phenyl
compounds
hydrogen
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PCT/EP2019/060875
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French (fr)
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Christine WIEBE
Wassilios Grammenos
Georg Christoph RUDOLF
Maria Angelica QUINTERO PALOMAR
Marcus Fehr
Tobias MENTZEL
Ian Robert CRAIG
Thomas Grote
Jan Klaas Lohmann
Michael Seet
Bernd Mueller
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms

Definitions

  • the present invention relates to trifluoromethyloxadiazoles of the formula I, or the N-oxides, or the agriculturally useful salts thereof, and to the use thereof for controlling phytopathogenic fungi; to a method for combating phytopathogenic harmful fungi, which process comprises treating the fungi, the plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof; and to agrochemical compositions comprising at least one compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof; and to agrochemical compositions further comprising seeds.
  • the compounds according to the invention differ from those described in the closest prior art in the divalent moiety“-CR 3 (-X-R 4 )-“.
  • the present invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof,
  • A is phenyl or a 6-membered aromatic heterocycle; wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 or 2 nitrogen atoms as ring member atoms; and wherein the phenyl ring or the aromatic heterocycle is unsubstituted or substituted with 1 , 2, 3 or 4 identical or different groups R A ; wherein
  • R A is halogen, cyano, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy or
  • X is O or S
  • Y is O or S
  • R 1 is hydrogen, Ci-C 6 -alkyl, C2-C6-alkenyl, C3-C6-alkynyl, Ci-C6-alkoxyimino-Ci-C4-alkyl, C 2 - C6-alkenyloxyimino-Ci-C4-alkyl, C2-C6-alkynyloxyimino-Ci-C4-alkyl, C3-Cn-cycloalkyl, C3- Cn-cycloalkenyl, C3-Cn-cycloalkyl-Ci-C4-alkyl, phenyl-Ci-C4-alkyl, heterocyclyl-Ci-C 4 - alkyl, heteroaryl-Ci-C4-alkyl, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle, wherein the ring member atoms of said mono- or bicycl
  • any of the aliphatic or cyclic groups R 1 are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different groups R 1a ; wherein R 1a is halogen, cyano, Ci-C 6 -alkyl, Ci-C 6 -alkoxy or Ci-C 6 -haloalkoxy;
  • R 2 is hydrogen, formyl, Ci-C 6 -alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C 6 -alkoxy,
  • R 2a is independently selected from the group consisting of hydrogen, OH, Ci-C 6 -alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkenyl, Ci-C 6 -alkoxy, Ci-C 4 -alkoxy-Ci-C 4 -alkyl and Ci-C 6 -alkylthio;
  • any of the aliphatic or cyclic groups in R 2 are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, hydroxy, oxo, cyano, Ci-C 6 -alkyl,
  • R 3 , R 4 independently of each other are selected from the group consisting of hydrogen and Ci-C 4 -alkyl.
  • Agriculturally acceptable salts of the compounds of the formula I 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 the compounds I.
  • 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 be substituted with one to four Ci-C 4 -alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium,
  • trimethylbenzylammonium furthermore phosphonium ions, sulfonium ions, preferably tri(C-i-C 4 - alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C 4 -alkyl)sulfoxonium.
  • Anions of acceptable 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 a compound I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Stereoisomers of the formula I can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers arising from restricted rotation about a single bond of asymmetric groups and geometric isomers. They also form part of the subject matter of the present invention.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers, e.g. a racemate, individual
  • the embodiments of the intermediates obtained during preparation of compounds I correspond to the embodiments of the compounds of formula I.
  • the term“ compounds I” refers to compounds of the formula I.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • Ci-C 6 -alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 - methylpropyl, 2-methylpropyl, and 1 ,1 -dimethylethyl.
  • C2-C6-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1 -propenyl, 2- propenyl (allyl), 1 -methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-
  • C2-C6-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, 1 -propynyl,
  • Ci-C 6 -haloalkyl refers to a straight-chained or branched alkyl group having 1 to 6 carbon atoms (as defined above), wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl,
  • Ci-C 6 -alkoxy refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as defined above) which is bonded via an oxygen, at any position in the alkyl group, for example methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2- methylpropoxy or 1 ,1-dimethylethoxy.
  • Ci-C 6 -haloalkoxy refers to a Ci-C 6 -alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example, OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chlorofluoromethoxy, 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-d
  • C 3 -Cn-cycloalkyl-Ci-C 4 -alkyl, heterocyclyl-Ci-C 4 -alkyl, phenyl-Ci-C 4 -alkyl or heteroaryl-Ci-C 4 -alkyl refer to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl, heterocyclyl, phenyl or heteroaryl radical respectively.
  • Ci-C 4 -alkoxy-Ci-C 4 -alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C 4 -alkoxy group (as defined above).
  • C2-C6-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2- propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-
  • C2-C6-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, 1-propynyl,
  • 2-propynyl (propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl.
  • Cs-Cs-cycloalkyl refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members such as cyclopropyl (C 3 H 5 ), cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • C3-Cn-cycloalkyl refers to a monocyclic, bicyclic or tricyclic saturated univalent hydrocarbon radical having 3 to 11 carbon ring members that is connected through one of the ring carbon atoms by substitution of one hydrogen atom, such as cyclopropyl (C 3 H 5 ), cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[1.1.0]butyl, bicyclo[2.1.0]pentyl, bicyclo[1.1.1]pentyl, bicyclo[3.1.0]hexyl, bicyclo[2.1.1 ]hexyl, norcaranyl (bicyclo[4.1.0]heptyl) and norbornyl (bicyclo[2.2.1]heptyl).
  • C2-C6-alkenyloxyimino-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms, wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced
  • aliphatic refers to compounds or radicals composed of carbon and hydrogen and which are non-aromatic compounds.
  • An“alicyclic” compound or radical is an organic compound that is both aliphatic and cyclic. They contain one or more all-carbon rings which may be either saturated or unsaturated, but do not have aromatic character.
  • cyclic moiety or“cyclic group” refer to a radical which is an alicyclic ring or an aromatic ring, such as, for example, phenyl or heteroaryl.
  • any of the aliphatic or cyclic groups R 1 are unsubstituted or substituted with...” refers to aliphatic groups, cyclic groups and groups, which contain an aliphatic and a cyclic moiety in one group, such as in, for example, C3-Cn-cycloalkyl-Ci-C4-alkyl or phenyl-C-i- C4-alkyl; therefore, a group which contains an aliphatic and a cyclic moiety both of these moieties may be substituted or unsubstituted independently of each other.
  • phenyl refers to an aromatic ring systems incuding six carbon atoms (commonly referred to as benzene ring. In association with the group A the term“phenyl” is to be interpreted as a benzene ring or phenylene ring, which is attached to both, the oxadiazole moiety and the group“-CR 3 (-X-R 4 )-“.
  • heteroaryl refers to aromatic monocyclic or polycyclic ring systems incuding besides carbon atoms 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S.
  • saturated 3- to 7-membered carbocycle is to be understood as meaning monocyclic saturated carbocycles having 3, 4 or 5 carbon ring members. Examples include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
  • 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle wherein the ring member atoms of said mono- or bicyclic heterocycle include besides carbon atoms further 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S”, is to be understood as meaning both, aromatic mono- and bicyclic heteroaromatic ring systems, and also saturated and partially unsaturated heterocycles, for example:
  • a 3- or 4-membered saturated heterocycle which contains 1 or 2 heteroatoms from the group consisting of N, O and S as ring members such as oxirane, aziridine, thiirane, oxetane, azetidine, thiethane, [1 ,2]dioxetane, [1 ,2]dithietane, [1 ,2]diazetidine;
  • a 5- or 6-membered saturated or partially unsaturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of N, O and S as ring members such as 2-tetrahydro- furanyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,
  • hexahydroazepinyl such as 2,3,4,5-tetrahydro[1 H]azepin-1-,-2-,-3-,-4-,-5-,-6- or-7-yl, 3, 4, 5, 6- tetrahydro[2H]azepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -,-2-, -3-, -4-, -5-, -6- or-7-yl, 2,3,6,7-tetrahydro[1 H]azepin-1-,-2-,-3-,-4-,-5-,-6- or-7-yl, hexahydroazepin-1-,-2-,-3- or- 4-yl, tetra- and hexahydrooxepinyl such as 2,3,4,5-tetrahydro[1 H]oxepin-2-,-3-,-4-,-5-,-6- or-7-yl,
  • the term“5- or 6-membered heteroaryl” or the term”5- or 6-membered aromatic heterocycle” refer to aromatic ring systems incuding besides carbon atoms, 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, for example, a 5-membered heteroaryl such as pyrrol-1 -yl, pyrrol-2 -yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, iso
  • group A is phenyl, which is unsubstituted or substituted with 1 , 2,
  • A is phenyl, which is unsubstituted or substituted with 1 , 2, 3 or 4 identical or different groups R A as defined or preferably defined herein and wherein the group - CR 3 (-X-R 4 )- is attached to the phenyl ring in aie/a-position with regard to the oxadiazole group.
  • A is a 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 or 2 nitrogen atoms as ring member atoms; and wherein the aromatic heterocycle is unsubstituted or substituted with 1 or 2 identical or different groups R A as defined or preferably defined herein; particularly R A is chlorine, fluorine or methyl.
  • A is a 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 or 2 nitrogen atoms as ring member atoms; and wherein the aromatic heterocycle is unsubstituted or substituted with 1 or 2 identical or different groups R A as defined or preferably defined herein; particularly R A is chlorine, fluorine or methyl; and wherein the group -CR 3 (-X-R 4 )- is attached to the 6-membered aromatic heterocycle in /?ara-position with regard to the oxadiazole group.
  • the invention relates to compounds of the formula I, wherein the moiety A is defined as in sub
  • A denotes the position, which is bound to the oxadiazole moiety and #2 denotes the position, which is connected to the group -CR 3 (-X-R 4 )- of compounds of the formula I; and wherein A is unsubstituted or substituted with 1 or 2 identical or different groups R A and wherein R A is as defined or preferably defined herein.
  • a as defined in any one of subformulae (A.1 ) to (A.5) is unsubstituted or substituted with 1 or 2 identical or different groups R A ; and wherein R A is chlorine, fluorine or methyl.
  • a as defined in any one of subformulae (A.1 ) to (A.5) is unsubstituted.
  • R A is independently selected from the group consisting of halogen, Ci-C 6 -alkyl or C 3 -Cs-cycloalkyl.
  • R A is independently selected from the group consisting of halogen, methyl or ethyl, more preferably chlorine, fluorine or methyl. More preferably R A is independently selected from the group consisting of halogen, in particular R A is fluorine.
  • Embodiment X.1 X is O.
  • Embodiment Y.1 Y is O.
  • Embodiment XY.1 X is O and Y is O.
  • Embodiment XY.2 X is O and Y is S.
  • Embodiment XY.3 X is S and Y is O.
  • Embodiment XY.4 X is S and Y is S.
  • Embodiment XY.5 Embodiment XY.1 and Embodiment XY.2.
  • Embodiment XY.6 Embodiment XY.3 and Embodiment XY.4.
  • R 1 is hydrogen, Ci-C 6 -alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C 6 -alkoxyimino- Ci-C4-alkyl, C2-C6-alkenyloxyimino-Ci-C4-alkyl, C2-C6-alkynyloxyimino-Ci-C4-alkyl, Cs-Cs- cycloalkyl, C 3 -Cs-cycloalkenyl, C 3 -C8-cycloalkyl-Ci-C4-alkyl, phenyl-Ci-C4-alkyl, heteroaryl-Ci- C4-alkyl-, phenyl, or a 5- or 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member
  • Ci-C 6 -haloalkyl Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy and C 3 -Cs-cycloalkyl.
  • Embodiment 1 .2 R 1 is hydrogen, Ci-C 6 -alkyl, C2-C6-alkenyl, C 3 -C 6 -alkynyl or C 3 -Cn-cycloalkyl.
  • Embodiment 1 .4 R 1 is phenyl or heteroaryl; and wherein the heteroaryl group is a 5- or 6- membered aromatic heterocycle, wherein the ring includes besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein any of the cyclic groups are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy and Cs-Cs-cycloalkyl.
  • the heteroaryl group is a 5- or 6- membered aromatic heterocycle, wherein the ring includes besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N
  • Embodiment 1 .5 R 1 is C3-Cn-cycloalkyl or C3-Cn-cycloalkenyl; and wherein the cyclic group is unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, oxo, cyano, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy and Cs-Cs-cycloalkyl.
  • Embodiment 1 .6 R 1 is Ci-C 6 -alkyl; and wherein the alkyl group is unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, oxo, cyano, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy and Cs-Cs-cycloalkyl.
  • Embodiment 1 .7 R 1 is difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2- chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, 3,3,3- trifluoropropyl, CH2CF2CF3 or CF 2 CF 2 CF 5 , CH(CH 3 )CF 3 , CH2CF2CH3, CH 2 C(CH 3 )2F,
  • R 1 is selected from the group consisting of radicals R 1 .1 to R 1 .26 below, particularly from R 1 .1 to R 1 .18, which are further unsubstituted or substituted with 1 or 2 radicals selected from the group consisting of methyl, ethyl, oxo, hydroxyl and halogen; and wherein “#C” indicates the carbon atom, which is attached to the remainder of the compounds of formula
  • R 1a is selected from the group consisting of halogen, oxo, cyano,
  • R 1a is selected from the group consisting of fluorine, chlorine, oxo, cyano, methyl, ethyl, methoxy, trifluoromethyl, trifluoromethoxy, difluoromethyl,
  • R 1a is selected from the group consisting of halogen, oxo, Ci-C 6 -alkyl and Cs-Cs-cycloalkyl; particularly from oxo, methyl, ethyl, fluorine and chlorine; more particularly from fluorine and chlorine.
  • R 2 is hydrogen, formyl, Ci-C 6 -alkyl, Ci-C 6 -alkoxy, C 2 -C 6 -alkenyl, propargyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkenyl, C 3 -Cs-cycloalkyl-Ci-C 4 -alkyl, phenyl or -N(R 2a ) 2 ; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1 , 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C 6 -alkyl and Ci-C 6 -alkoxy; more preferably from halogen, in particular the radical is fluorine; and wherein R 2a is independently selected from the group consisting of hydrogen, OH, Ci-C 6 -alkyl, C 2 -C 6 -alkoxy, C 2
  • R 2 is -N(R 2a ) 2 , wherein R 2a is independently selected from the group consisting of hydrogen, OH, Ci-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Cs-Cs-cycloalkyl and Ci-C 6 -alkoxy.
  • R 2a is independently selected from the group consisting of hydrogen, OH, methyl, ethyl, /7-propyl, /so-propyl, methoxy, ethoxy, propoxy, vinyl, allyl propargyl, cyclopropyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Cs-Cs-cycloalkyl and Ci-C 6 -alkoxy.
  • R 2 is methylamino or dimethylamino.
  • R 2 is hydrogen, formyl, Ci-C 6 -alkyl, Ci-C 6 -alkoxy, C 2 -C 6 -alkenyl, propargyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkenyl, C 3 -Cs-cycloalkyl-Ci-C 4 -alkyl, phenyl, C 1 -C 6 - alkylamino or diCi-C 6 -alkylamino; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1 , 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C 6 -alkyl and
  • R 2 is hydrogen, formyl, Ci-C 6 -alkyl, Ci-C 6 -alkoxy, C 2 -C 6 -alkenyl, propargyl, Cs-Cs-cycloalkyl, Ci-C 6 -alkylamino or diC-i-C 6 -alkylamino.
  • R 2 is hydrogen, formyl, methyl, ethyl, /7-propyl, /so-propyl, methoxy, ethyoxy, propyloxy, cyclopropyl, cyclopropyl-CH 2 -, allyl, phenyl, 4-F-phenyl, 2-F-phenyl, C 1 -C 6 - alkylamino or diCi-C 6 -alkylamino.
  • R 2 is hydrogen, formyl, methyl, ethyl, /7-propyl, /so-propyl, methoxy, ethyoxy, propyloxy, cyclopropyl, cyclopropyl-CH 2 -, allyl, propargyl, Ci-C 6 -alkylamino or diCi-C 6 - alkylamino.
  • R 2 is hydrogen, formyl, Ci-C 6 -alkyl, Ci-C 6 -alkoxy, C2-C6-alkenyl, propargyl, Ci-C 6 -alkylamino or diCi-C 6 -alkylamino.
  • R 2 is hydrogen, formyl, methy, ethyl, methoxy, ethoxy, propyloxy, methylamino or dimethylamino.
  • R 2 is hydrogen
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, Ci-C 6 -alkyl, C2-C6-alkenyl, C3-C6-alkynyl or C3-Cn-cycloalkyl.
  • Embodiment 12.2 R 1 is hydrogen, Ci-C 6 -alkyl, C2-C6-alkenyl, C3-C6-alkynyl, or C3-Cn-cycloalkyl and R 2 is hydrogen.
  • Embodiment 12.3 R 1 is hydrogen, methyl, ethyl, /7-propyl, /so-propyl, /7-butyl, /so-butyl, sec- butyl, tert- butyl, cyclopropyl, or bicyclo[1 .1 1 ]pentan-1 -yl and R 2 is hydrogen.
  • Embodiment 3.1 R 3 and R 4 independently of each other are hydrogen, methyl or ethyl.
  • Embodiment 3.2 R 3 and R 4 are both hydrogen.
  • Embodiment 3.3 R 3 is hydrogen and R 4 is methyl.
  • Embodiment 3.4 R 3 and R 4 are both methyl.
  • the embodiments E.1 to E.48 listed in Table E represent preferred combinations of the embodiments, which are defined herein above for each of the variables X and Y (Embodiments XY.1 to XY.4), R 1 and R 2 (Embodiments 12.1 to 12.3), R 3 and R 4 (Embodiments 3.1 to 3.4).
  • the invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof, wherein
  • A is a group selected from subformulae (A.1 ) to (A.5); and wherein the phenyl ring or the aromatic heterocycle is unsubstituted or substituted with 1 or 2 identical or different groups R A ; wherein
  • R A is halogen, cyano, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy or
  • X is O or S
  • Y is O or S
  • R 1 is hydrogen, Ci-C 6 -alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxyimino-Ci-C4-alkyl, C2- C6-alkenyloxyimino-Ci-C4-alkyl, C2-C6-alkynyloxyimino-Ci-C4-alkyl, Cs-Cs-cycloalkyl, C3- Cs-cycloalkenyl, C3-C8-cycloalkyl-Ci-C4-alkyl, phenyl-Ci-C4-alkyl, heteroaryl-Ci-C4-alkyl-, phenyl, or a 5- or 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle
  • R 2 is hydrogen, formyl, Ci-C 6 -alkyl, Ci-C 6 -alkoxy, C2-C6-alkenyl, propargyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkenyl, C3-C8-cycloalkyl-Ci-C4-alkyl, phenyl, Ci-C 6 -alkylamino or diCi-C 6 - alkylamino; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1 , 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C 6 -alkyl and
  • R 3 , R 4 independently of each other are hydrogen, methyl or ethyl.
  • the invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof, wherein A is a group selected from subformulae (A.1) to (A.5); and wherein the phenyl ring or the aromatic heterocycle is unsubstituted or substituted with 1 or 2 identical or different groups R A ; wherein
  • R A is halogen, cyano, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy or
  • X is O
  • Y is O or S
  • R 1 and R 2 are as defined in any one of Embodiments 12.1 , 12.2 or 12.3 as defined above;
  • R 3 , R 4 independently of each other are hydrogen, methyl or ethyl.
  • the invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof, wherein
  • A is a phenyl ring; and wherein the phenyl ring is unsubstituted or substituted with 1 or 2 identical or different groups R A ; wherein
  • R A is halogen, cyano, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy or
  • X is O
  • Y is O or S
  • R 1 is hydrogen, Ci-C 6 -alkyl, C2-C6-alkenyl, C3-C6-alkynyl or C3-Cn-cycloalkyl;
  • R 2 is hydrogen
  • R 3 , R 4 independently of each other are hydrogen, methyl or ethyl.
  • the invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof, wherein
  • A is a phenyl ring; and wherein the phenyl ring is unsubstituted or substituted with 1 or 2 identical or different groups R A ; wherein
  • R A is halogen, cyano, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy or
  • X is O
  • Y is O
  • R 1 is hydrogen, methyl, ethyl, /7-propyl, /se-propyl, /7-butyl, /se-butyl, sec-butyl, tert- butyl, cyclopropyl or bicyclo[1.1.1]pentan-1-yl;
  • R 2 , R 3 , R 4 are hydrogen.
  • the invention relates to compounds of the formula 1.1 or to compounds of the formula 1.2, or the N-oxides, or the agriculturally acceptable salts thereof,
  • n 0, 1 or 2; and wherein the meaning of the variables R 3 , R 4 , X, Y, R 1 and R 2 are as defined herein for compounds of the formula I or as defined in embodiments E.1 to E.48 in Table E; and wherein R A is as defined or preferably defined herein for compounds of the formula I.
  • a preferred embodiment relates to compounds of the formula 1.1 or to compounds of the formula 1.2 as defined above, wherein the meaning of the variables R 3 , R 4 , X, Y, R 1 and R 2 are as defined herein for compounds of the formula I or as defined in embodiments E.1 to E.48 in Table E; and wherein n is 0 or 1 and R A is halogen, Ci-C 6 -alkyl or Cs-Cs-cycloalkyl; in particular R A is fluorine.
  • the invention relates to compounds of the formula 1.1 , or the N-oxides, or the agriculturally acceptable salts thereof, wherein:
  • n O or l ;
  • R A is fluorine
  • X is O
  • Y is O or S
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, Ci-C 6 -alkyl, C2-C6- alkenyl, C3-C6-alkynyl or C3-Cn-cycloalkyl;
  • R 3 , R 4 independently of each other are hydrogen, methyl or ethyl.
  • the invention relates to compounds of the formula 1.1 , or the N-oxides, or the agriculturally acceptable salts thereof, wherein:
  • n O or l ;
  • R A is fluorine; in particular the fluorine atom is attached to the ortho- position of the phenyl ring with regard to the oxadiazole group;
  • X is O
  • Y is O or S
  • R 1 is hydrogen, Ci-C 6 -alkyl, C2-C6-alkenyl, C3-C6-alkynyl or C3-Cn-cycloalkyl;
  • R 2 is hydrogen
  • R 3 , R 4 independently of each other are hydrogen, methyl or ethyl.
  • the invention relates to compounds of the formula 1.1 , or the N-oxides, or the agriculturally acceptable salts thereof, wherein:
  • n O or l ;
  • R A is fluorine; in particular the fluorine atom is attached to the ortho- position of the phenyl ring with regard to the oxadiazole group;
  • X is O
  • Y is O
  • R 1 is hydrogen, methyl, ethyl, /7-propyl, /se-propyl, /7-butyl, /se-butyl, sec-butyl, tert- butyl, cyclopropyl or bicyclo[1.1.1]pentan-1-yl;
  • R 2 , R 3 , R 4 are hydrogen.
  • the present invention relates to compounds of the formulae I .A, I.B, I.C, I.D, I.E, I.F, I.G and I.H, wherein the radicals R 1 , R 2 and R 4 are as defined or preferably defined herein:
  • Table 1 Compounds of the formula I. A, in which R 1 , R 2 and R 4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.A.A-1 to I.A.A- 1364). This means, for example, that a compound of the formula I. A, wherein R 1 is
  • Table 2 Compounds of the formula I.B, in which R 1 , R 2 and R 4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.B.A-1 to I.B.A- 1364).
  • Table 3 Compounds of the formula I.C, in which R 1 , R 2 and R 4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.C.A-1 to I.C.A- 1364)
  • Table 4 Compounds of the formula I.D, in which R 1 , R 2 and R 4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.D.A-1 to I.D.A- 1364).
  • Table 5 Compounds of the formula I.E, in which R 1 , R 2 and R 4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.E.A-1 to I.E.A- 1364).
  • Table 6 Compounds of the formula I.F, in which R 1 , R 2 and R 4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.F.A-1 to I.F.A- 1364).
  • Table 7 Compounds of the formula I.G, in which R 1 , R 2 and R 4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.G.A-1 to I.G.A- 1364).
  • Table 8 Compounds of the formula I.H, in which R 1 , R 2 and R 4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.H.A-1 to I.H.A- 1364).
  • the compounds of the formula I according to the invention may be present in a reversible equilibrium with the corresponding covalently hydrated forms at the CF3-oxadiazole motif (for example, the compounds of formula l-l and formula l-ll as shown below, wherein A is phenyl).
  • This dynamic equilibrium may be important for the biological activity of the compounds of the formula I.
  • the designations of the variables in compounds of the formula I of the present invention apply generally to the compounds of Formula l-l and Formula l-ll.
  • compounds of the formula I can be prepared by reacting amidines of type II with trifluoroacetic anhydride in an organic solvent, for example dichloromethane, or an ethereal solvent at temperatures between 0°C and 100°C, preferably at room temperature, as previously described in WO 2013/008162.
  • an organic solvent for example dichloromethane, or an ethereal solvent at temperatures between 0°C and 100°C, preferably at room temperature, as previously described in WO 2013/008162.
  • Compounds of type II can be accessed by treating nitriles of type III with hydroxylamine or its hydrochloride salt in an organic solvent, preferably an alcoholic solvent such as methanol, at a temperature between 0°C and 100°C and in the presence of a base, preferably an inorganic base, most preferably potassium carbonate (for precedents see for example WO 2009/074950, WO 2006/013104, EP 1932843). If appropriate, water may be added to enhance solubility of the reactants. The reaction is best performed at elevated temperatures, most preferably in the range between
  • Compounds of the formula III can be prepared by reacting a compound of the formula IV, for example with a carboxylic acid chloride or anhydride, with compounds of type V, wherein LG in compounds V is chlorine or a carboxylate, in an organic solvent and in the presence of a base as described in J. Org. Chem. 2015, 80, 511 1 -5124.
  • compound III can be obtained by reacting compound V with the carboxylic acid IV (LG is OH) using peptide coupling reaction conditions such as 1-ethyl-3-(3-dimethylamino-propyl)carbodiimid (EDC) or its salts and hydroxybenzotriazole as described in Bioorganic & Medicinal Chemistry Letters 2010, 20(15), 4550-4554.
  • peptide coupling reaction conditions such as 1-ethyl-3-(3-dimethylamino-propyl)carbodiimid (EDC) or its salts and hydroxybenzotriazole as described in Bioorganic & Medicinal Chemistry Letters 2010, 20(15), 4550-4554.
  • Compounds of the formula V can be prepared from compounds of type VI by Grignard reaction with the corresponding magnesium bromide in an anhydrous ethereal solvent (e.g. THF).
  • anhydrous ethereal solvent e.g. THF
  • Compounds of the formula VI can be prepared from compounds of the formula VII by lithiation using butyl lithium in a solvent such as hexane at room temperature.
  • the solution containing the lithiated species of compound VII may then be added at -78°C to a suitable electrophile, for example ethyl chloro(oxo)acetate.
  • a suitable electrophile for example ethyl chloro(oxo)acetate.
  • the chloro(oxo)acetate is prediluted, for example in THF.
  • compounds VI can be prepared by oxidation of the hydroxy-ester VIII with an oxidizing agent such as oxalyl chloride and dimethylsulfoxide or by heating with manganese dioxide in a solvent such as toluene or dichloromethane as described in WO 9950257.
  • an oxidizing agent such as oxalyl chloride and dimethylsulfoxide
  • manganese dioxide in a solvent such as toluene or dichloromethane as described in WO 9950257.
  • Compounds of type XI can be accessed by treating nitriles of type XII with hydroxylamine or its hydrochloride salt in an organic solvent, preferably an alcoholic solvent such as methanol, at a temperature between 0°C and 100°C and in the presence of a base, preferably an inorganic base, most preferably potassium carbonate (for precedents see for example WO 2009/074950, WO 2006/013104, EP 1932843). If appropriate, water may be added to enhance solubility of the reactants. The reaction is best performed at elevated temperatures, most preferably in the range between
  • Compounds of formula XII can be prepared by treating from Compounds of type XIII with the respective amine in an organic solvent (e.g. toluene) as described in Journal of the chem.
  • an organic solvent e.g. toluene
  • Compounds of formula XIII can be prepared by treating compounds of type V with triethylamine, methansulphonylchloride, the respective thiole in an organic solvent, for example in dichloromethane, as described in WO 2003/055482.
  • 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, 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.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g.
  • potatoes which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
  • 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 mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
  • Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, to create mutations at a specific locus of a plant genome.
  • Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.
  • Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination.
  • one or more genes are integrated into the genome of a plant to add a trait or improve a trait.
  • transgenic plants These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants.
  • the process of plant transformation usually produces several transformation events, wich differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
  • Herbicide tolerance has been created by using mutagenesis as well as using genetic
  • Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield®.
  • ALS acetolactate synthase
  • Herbicide tolerance has been created via the use of transgenes to glyphosate, glufosinate, 2,4- D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitors and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.
  • transgenes to glyphosate, glufosinate, 2,4- D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitors and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.
  • HPPD 4-hydroxyphenylpyruvate dioxygenase
  • Transgenes wich have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601 , gat4621 , goxv247; for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 , aad-12; for tolerance to dicamba: dmo; for tolerance to oxynil herbicies: bxn; for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA; for tolerance to ALS inhibitors: csr1-2; and for tolerance to HPPD inhibitors: hppdPF, W336, avhppd-03.
  • Transgenic corn events comprising herbicide tolerance genes include, but are not limited to, DAS40278, MON801 , MON802, MON809, MON810, MON832, MON8741 1 , MON87419, MON87427, MON88017, MON89034, NK603, GA21 , MZHGOJG, HCEM485, VCO-01981-5, 676, 678, 680, 33121 , 4114, 59122, 98140, Bt10, Bt176, CBH-351 , DBT418, DLL25, MS3,
  • Transgenic soybean events comprising herbicide tolerance genes include, but are not limited to, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704- 21 , A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
  • Transgenic cotton events comprising herbicide tolerance genes include, but are not limited to, 19-51 a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN1021 1 , BXN10215, BXN10222, BXN 10224, MON1445, MON1698, MON88701 , MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
  • Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1 , HCN10, HCN28, HCN92, MS1 , MS8, PHY14, PHY23, PHY35, PHY36, RF1 , RF2 and RF3.
  • Transgenes which have most frequently been used are toxin genes of Bacillus spp. and synthetic variants thereof, like cry1A, crylAb, cry1Ab-Ac, crylAc, cry1A.105, cry1 F, cry1 Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1 , cry34Ab1 , cry35Ab1 , cry9C, vip3A(a), vip3Aa20.
  • genes of plant origin such as genes coding for protease inhibitors, like CpTI and pinll, have been transferred to other plants.
  • a further approach uses transgenes such as dvsnf7 to produce double-stranded RNA in plants.
  • Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA include, but are not limited to, Bt10, Bt1 1 , Bt176, MON801 , MON802, MON809, MON810, MON863, MON87411 , MON88017, MON89034, 33121 , 41 14, 5307, 59122, TC1507, TC6275, CBH-351 , MIR162, DBT418 and MZIR098.
  • Transgenic soybean events comprising genes for insecticidal proteins include, but are not limited to, MON87701 , MON87751 and DAS-81419.
  • Transgenic cotton events comprising genes for insecticidal proteins include, but are not limited to, SGK321 , MON531 , MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BN LA-601 , Eventl , COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281- 24-236, 3006-210-23, GHB119 and SGK321.
  • transgene athb17 being present for example in corn event MON87403, or by using the transgene bbx32, being present for example in the soybean event MON87712.
  • Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1 , Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
  • transgene cspB comprised by the corn event MON87460 and by using the transgene Hahb-4, comprised by soybean event IND-00410-5.
  • Preferred combinations of traits are combinations of herbicide tolerance traits to different groups of herbicides, combinations of insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, combinations of herbicide tolerance with one or several types of insect resistance, combinations of herbicide tolerance with increased yield as well as combinations of herbicide tolerance and tolerance to abiotic conditions.
  • CERA Cera-gmc.org/GMCropDatabase
  • effects which are specific to a cultivated plant comprising a certain gene or event may result in effects which are specific to a cultivated plant comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
  • 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), A Hern aria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauciox A. porri), oilseed rape ⁇ A. brass icicoia or brassicae ), sugar beets ⁇ A. tenuis ), fruits (e.g. A. grandis ), rice, soybeans, potatoes and tomatoes (e. g. A. soiani, A. grandis or A. alternate), tomatoes (e. g. A. soiani ox A. aiternata) and wheat (e.g. A.
  • B. oryzae ox ⁇ rice and turfs Biumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeiianar. grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages); B. squamosa ox B. aiiii on onion family), oilseed rape, ornamentals (e.g.
  • Ciadobotryum syn. Dactyiium
  • spp. e.g. C. mycophilum
  • Cochiioboius anamorph: Heiminthosporium of Bipoiaris
  • spp. leaf spots
  • C. coccodes. black dot beans (e. g. C. Hndemuthianum ), soybeans (e. g. C. truncatumox C. gloeosporioides ), vegetables (e.g. C. lagenariumox C. capsid), fruits (e.g. C. acutatum ), coffee (e.g. C. coffeanumox C. kahawae) and C. gloeosporioides on various crops; Corticium spp., e. g. C.
  • sasakii sheath blight
  • Corynespora cassiicoia leaf spots
  • Cycioconium spp. e. g. C. oieaginumox ⁇ olive trees
  • Heiminthosporium, teleomorph Pyrenophora
  • corn 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. Pheiiinus) punctata, F. mediterranea,
  • Phaeomonieiia chiamydospora (formerly Phaeoacremonium chiamydosporum)
  • Microdochium (syn. Fusarium) nivaie (pink snow mold) on cereals (e. g. wheat or barley);
  • Microsphaera diffusa (powdery mildew) on soybeans; Moniiinia spp., e. g. M. iaxa, M. fructicoia and M. fructigena (syn. Moniiia spp:. bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaereiia spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicda (anamorph: Zymoseptoria M/c/formerly Septoria triticr. Septoria blotch) on wheat or M. fijiensis (syn. Pseudocercospora fijiensis. black Sigatoka disease) and M.
  • Moniiinia spp. e. g. M. iaxa, M. fructicoia and M. fructigena (syn. Moniiia
  • meibomiae (soybean rust) on soybeans; Phiaiophora spp. e. g. on vines (e. g. P. tracheiphiia and P. tetraspora ) and soybeans (e. g. P. gregata. stem rot); Phoma Hngam (syn. Leptosphaeria biglobosa and L macula ns. root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp.
  • Physoderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • paprika and cucurbits e. g. P. capsici
  • soybeans e. g. P. megasperma, syn. P. sojae
  • potatoes and tomatoes e. g. P. infestans. late blight
  • broad-leaved trees e. g. P. ramorum.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P.
  • Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits (e. g. P. ieucotricha on apples) and curcurbits ( P xanthii) ⁇ , Poiymyxa spp., e. g. on cereals, such as barley and wheat ( P graminis ) and sugar beets ( P betae) and thereby transmitted viral diseases; Pseudocercosporeiia herpotrichoides ⁇ syn. Ocuiimacuia yaiiundae,
  • Pseudoperonospora downy mildew
  • P. cubensis on cucurbits or P. hum Hi on hop
  • Pseudopezicuia tracheiphiia red fire disease or .rotbrenner’, anamorph
  • Phiaiophora 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. recondite (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. a spa rag ion asparagus; Pyrenopeziza spp., e.g. P.
  • R. soiani(roo ⁇ and stem rot) on soybeans e.g. R. soiani (sheath blight) on rice or R. cereaiis (Rhizoctonia spring blight) on wheat or barley;
  • Rhizopus stoionifer black mold, soft rot
  • strawberries carrots, cabbage, vines and tomatoes
  • Rhynchosporium secaiis and R. commune scald
  • Sarociadium oryzae and S. attenuatum (sheath rot) on rice
  • Scierotinia spp. stem rot or white mold
  • vegetables S. minorand S. scierotiorum
  • field crops such as oilseed rape, sunflowers (e. g. S. scierotiorum) and soybeans, S. roifsii ⁇ syn.
  • Sphaceiotheca spp. (smut) on corn e. g. S. reiiiana, syn. Ustiiago reiiiana. head smut
  • sorghum und sugar cane e.g. S. turcicum, syn. Heiminthosporium turcicum
  • smut Sphaceiotheca spp.
  • Sphaerotheca fuiiginea (syn. Podosphaera xanthii. 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: Leptosphaeria [syn.
  • sugar beets e. g. U. betae or U. beticoia
  • on pulses e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae
  • Ustiiago spp. loose smut
  • corn e. g. U. maydis corn smut
  • sugar cane e. g. V. inaequaiis
  • Verticiiiium spp. wilt
  • various plants such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. iongisporum on oilseed rape, V. dahiiae on strawberries, oilseed rape, potatoes and tomatoes, and V. fungicoia on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. iongisporum on oilseed rape, V. dahiiae on strawberries, oilseed rape, potatoes and tomatoes, and V. fungicoia on
  • the compounds I, their mixtures with other active compounds as defined herein and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases: Puccinia spp. (rusts) on various plants, for example, but not limited to P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondite (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. sorghi (common rust) on maize, P. poiysora (southern rust) on maize; P.
  • Puccinia spp. rusts
  • rusts rusts
  • P. triticina brown or leaf rust
  • P. striiformis stripe or yellow rust
  • P. hordei dwarf rust
  • Fungicide-resistant strains of the above-mentioned phytopathgenic fungi have been reported, with strains resistant to one or more fungicides from various fungicidal mode of action classes being observed including but not limited to beta-tubulin assembly inhibitors, sterol
  • DMI demethylation-inhibitors
  • Qol quinone-outside-inhibitors
  • SDHI succinate dehydrogenase inhibitors
  • compounds I are useful to control phytopathogenic fungi comprising at least one of the following mutations: E198A/G/K or F200Y in the beta-tubulin gene conferring resistance to beta-tubulin assembly inhibitors (Phytopathol (2008) 98: 397-404), I365N/S, V368F, Q369H/P, N373S, T447S in the histidine kinase gene Os1 conferring resistance to MAP / histidin kinase inhibitors (dicarboximides; ibida); G143A, G137R or F129L in the mitochondrial cytochrome B Gene (Phytopathol (2003) 93: 891-900; Pest Manag Sci (2016) 72: 121 1-1215) resulting in resistance to Qol; V136A, Y137F (homologous to
  • 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.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis s p p .
  • Aureobasidium pullulans Sderophoma spp., Chaetomium spp., Humico/a spp., Petrie I la spp., Trichurus spp. Basidiomycetes such as Coniophora spp., Corioius spp., Gioeophyiium spp., Lentinus spp., P/eurotus spp., Poria spp., Serpuia spp.
  • yeast fungi are worthy of note: Candida s . 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.
  • 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
  • stored products is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
  • the compounds I and compositions thereof, 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 application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
  • the invention also relates to 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
  • compositions are prepared in a known manner, such as described by Mollet and
  • 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 esters, gamma-butyrolactone; fatty acids; phosphonates;
  • 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 colloid, 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 sulfonates, 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
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinyl pyrrolidone, 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 themselves, 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
  • 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 hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 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.
  • 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
  • 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, fluidized 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
  • 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 arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce
  • organic solvent blend e. g. fatty acid dimethyl amide and cyclohexanone
  • surfactant blend e. g. alcohol ethoxylate and arylphenol 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 microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocyanate monomer (e. g. diphenylmethene-4,4’-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol).
  • a polyamine e. g.
  • hexamethylenediamine 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)
  • 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%, more preferably between 1 and 70%, and in particular between 10 and 60%, 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.
  • 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.
  • the term“pesticide” 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 e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
  • 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 composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the composition according to the invention usually from a predosage device, a
  • 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.
  • 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.
  • 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 optionally 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:
  • Inhibitors of complex III at Q 0 site azoxystrobin (A.1.1 ), coumethoxystrobin (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), kresoxim-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), trifloxy- strobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)- 2-me
  • respiration inhibitors diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone (A.4.7); organometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1); silthiofam (A.4.12);
  • - C14 demethylase inhibitors triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromu- conazole (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.1.11 ), 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
  • benalaxyl (C.1.1 ), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);
  • nucleic acid synthesis inhibitors 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), 5-fluoro- 2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8);
  • tubulin inhibitors benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D1.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), pyridachlometyl (D.1.6), /V-ethyl-2-[(3-ethynyl-8-methyl- 6-quinolyl)oxy]butanamide (D.1.8), /V-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2- methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/V-(2- fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/V-(2-fluoroethyl)-2- methoxy-acetamide (D.1.1 1)
  • diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7),
  • cyprodinil E.1.1
  • mepanipyrim E.1.2
  • pyrimethanil E.1.3
  • blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydro- chloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6);
  • fluoroimid F.1.1
  • iprodione F.1.2
  • procymidone F.1.3
  • vinclozolin F.1.4
  • fludioxonil F.1.5
  • 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
  • zinc thiazole G.2.8
  • 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
  • propamocarb (G.4.1 );
  • oxathiapiprolin G.5.1
  • fluoxapiprolin G.5.3
  • 4-[1-[2- [3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-/V-tetralin-1-yl-pyridine-2- carboxamide G.5.4
  • 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/V- tetralin-1-yl-pyridine-2-carboxamide G.5.5
  • 4-[1-[2-[3-(difluoromethyl)-5-(tri- fluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/V-tetralin-1-yl-pyridine-2-carboxamide G.5.6
  • organochlorine compounds 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.3.11 );
  • 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 A/,5A L [1 ,4]di- thiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2A/,6A)-tetraone (H.4.10);
  • abscisic acid (M.1.1 ), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, /V-6-benzyl adenine, paclobutrazol, prohexadione, prohexadione-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithio
  • Lipid biosynthesis inhibitors alloxydim, alloxydim-sodium, butroxydim, clethodim,
  • clodinafop clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop- methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop- butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P- methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl,
  • N.2 ALS inhibitors amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethamet- sulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron- methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfu- ron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, meta- zosulfuron, metsulfuron, metsulfuron-methyl, nic
  • Photosynthesis inhibitors amicarbazone; chlorotriazine; ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, pro- pazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn, trietazin; chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, sidu- ron, tebuthiuron, thiadiazuron, desmedipham, karbutilat, phenmedipham, phenmedipham- ethyl, bromofenoxim, brom
  • N.4 protoporphyrinogen-IX oxidase inhibitors acifluorfen, acifluorfen-sodium, azafenidin, ben- carbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlor- methoxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pen- tyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen
  • N.5 Bleacher herbicides beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone,
  • norflurazon picolinafen, 4-(3-trifluoromethyhphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (180608-33-7); benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquintrione, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone; aclonifen, amitrole, flumeturon;
  • N.6 EPSP synthase inhibitors glyphosate, glyphosate-isopropylammonium, glyposate- potassium, glyphosate-trimesium (sulfosate);
  • Glutamine synthase inhibitors bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P, glufosinate-ammonium;
  • Mitosis inhibitors benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pen- dimethalin, prodiamine, trifluralin; amiprophos, amiprophos-methyl, butamiphos; chlorthal, chlorthal-dimethyl, dithiopyr, thiazopyr, propyzamide, tebutam; carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, propham;
  • N.10 VLCFA inhibitors acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethen- amid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, prop- isochlor, thenylchlor, flufenacet, mefenacet, diphenamid, naproanilide, napropamide, napro- pamide-M, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, isoxazoline compounds of the formulae 11.1 , II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9
  • N.1 1 Cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam, 1 -cyclohexyl-5-pentafluorphenyloxy-14-[1 ,2,4,6]thiatriazin-3-ylamine (175899-01 - 1 );
  • N.12 Decoupler herbicides dinoseb, dinoterb, DNOC and its salts
  • N.13 Auxinic herbicides 2,4-D and its salts and esters, clacyfos, 2,4-DB and its salts and
  • esters aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-dimethylammonium, aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopy- ralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, fluroxypyr, fluroxypyr-butometyl, fluroxypyr- meptyl, halauxifen and its salts and esters (943832-60-8); MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, meco- prop-P and its salts and esters, picloram and
  • N.14 Auxin transport inhibitors diflufenzopyr, diflufenzopyr-sodium, naptalam, naptalam- sodium;
  • Acetylcholine esterase (AChE) inhibitors aldicarb (0.1 .1 ), alanycarb (0.1.2), bendiocarb (0.1.3), benfuracarb (0.1 .4), butocarboxim (0.1.5), butoxycarboxim (0.1.6), carbaryl (0.1.7), carbofuran (0.1.8), carbosulfan (0.1.9), ethiofencarb (0.1 .10), fenobucarb (0.1 .1 1 ), formetanate (0.1 .12), furathiocarb (0.1.13), isoprocarb (0.1.14), methiocarb (0.1.15), methomyl (0.1 .16), metolcarb (0.1.17), oxamyl (0.1 .18), pirimicarb (0.1 .19), propoxur (0.1.20), thiodicarb (0.1.21 ), thiofanox (0.1 .22), trimethacarb (0.1 .23
  • GABA-gated chloride channel antagonists endosulfan (0.2.1 ), chlordane (0.2.2), ethiprole (0.2.3), fipronil (0.2.4), flufiprole (0.2.5), pyrafluprole (0.2.6), pyriprole (0.2.7);
  • Nicotinic acetylcholine receptor agonists (nAChR): acetamiprid (0.4.1), clothianidin (0.4.2), cycloxaprid (0.4.3), dinotefuran (0.4.4), imidacloprid (0.4.5), nitenpyram (0.4.6), thiacloprid (0.4.7), thiamethoxam (0.4.8), 4,5-dihydro-/V-nitro-1-(2-oxiranylmethyl)-1 TT-imidazol ⁇ -amine (0.4.9), (2£)-1-[(6-chloropyridin-3-yl)methyl]-/V : -nitro-2-pentylidene- hydrazinecarboximidamide (0.4.10), 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5- propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridine (0.4.1 1), nicotine (0.4.
  • Nicotinic acetylcholine receptor allosteric activators spinosad (0.5.1 ), spinetoram (0.5.2); Chloride channel activators: abamectin (0.6.1), emamectin benzoate (0.6.2), ivermectin (0.6.3), lepimectin (0.6.4), milbemectin (0.6.5);
  • Juvenile hormone mimics hydroprene (0.7.1 ), kinoprene (0.7.2), methoprene (0.7.3), fenoxycarb (0.7.4), pyriproxyfen (0.7.5);
  • miscellaneous non-specific (multi-site) inhibitors methyl bromide (0.8.1 ) and other alkyl halides, chloropicrin (0.8.2), sulfuryl fluoride (0.8.3), borax (0.8.4), tartar emetic (0.8.5); Chordotonal organ TRPV channel modulators: pymetrozine (0.9.1), pyrifluquinazon (0.9.2), flonicamid (0.9.3);
  • Mite growth inhibitors clofentezine (0.10.1 ), hexythiazox (0.10.2), diflovidazin (0.10.3), etoxazole (0.10.4);
  • frane/ensis (0.1 1.1), Bacillus sphaericus (0.1 1.2), Bacillus thuringiensis subsp. aizawai (0.1 1.3), Bacillus thuringiensis subsp. kurstaki (0L 1.4), Bacillus thuringiensis subsp.
  • Inhibitors of mitochondrial ATP synthase diafenthiuron (0.12.1), azocyclotin (0.12.2), cyhexatin (0.12.3), fenbutatin oxide (0.12.4), propargite (0.12.5), tetradifon (0.12.6);
  • Nicotinic acetylcholine receptor (nAChR) channel blockers bensultap (0.14.1 ), cartap hydrochloride (0.14.2), thiocyclam (0.14.3), thiosultap sodium (0.14.4);
  • Inhibitors of the chitin biosynthesis type 0 bistrifluron (0.15.1 ), chlorfluazuron (0.15.2), diflubenzuron (0.15.3), flucycloxuron (0.15.4), flufenoxuron (0.15.5), hexaflumuron
  • Inhibitors of the chitin biosynthesis type 1 buprofezin (0.16.1);
  • halofenozide (0.18.3), fufenozide (0.18.4), chromafenozide (0.18.5);
  • Mitochondrial complex III electron transport inhibitors hydramethylnon (0.20.1), acequinocyl (0.20.2), fluacrypyrim (0.20.3), bifenazate (0.20.4);
  • Mitochondrial complex I electron transport inhibitors fenazaquin (0.21.1 ), fenpyroximate (0.21.2), pyrimidifen (0.21.3), pyridaben (0.21.4), tebufenpyrad (0.21.5), tolfenpyrad (0.21.6), rotenone (0.21.7);
  • Inhibitors of the of acetyl CoA carboxylase spirodiclofen (0.23.1 ), spiromesifen (0.23.2), spirotetramat (0.23.3), spiropidion (0.23.4);
  • Mitochondrial complex IV electron transport inhibitors aluminium phosphide (0.24.1), calcium phosphide (0.24.2), phosphine (0.24.3), zinc phosphide (0.24.4), cyanide (0.24.5);5 Mitochondrial complex II electron transport inhibitors: cyenopyrafen (0.25.1), cyflumetofen (0.25.2);
  • insecticidal active compounds of unknown or uncertain mode of action afidopyropen (0.28.1), afoxolaner (0.28.2), azadirachtin (0.28.3), amidoflumet (0.28.4), benzoximate (0.28.5), broflanilide (0.28.6), bromopropylate (0.28.7), chinomethionat (0.28.8), cryolite (0.28.9), dicloromezotiaz (0.28.10), dicofol (0.28.1 1), flufenerim (0.28.12), flometoquin (0.28.13), fluensulfone (0.28.14), fluhexafon (0.28.15), fluopyram (0.28.16), fluralaner (0.28.17), metoxadiazone (0.28.18), piperonyl butoxide (0.28.19), pyflubumide (0.28.20), pyridalyl (0.28.21 ), tioxazafen
  • component 2 The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: https://www.alanwood.net/pesticides/); these substances are commercially available.
  • the compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968;
  • 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
  • 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).
  • 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 day.
  • 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 :10,000 to 10,000:1 , often 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 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 ).
  • the present invention furthermore relates to mixtures comprising one compound of the formula I (component 1 , a group represented by the expression“(I)”) and one pesticide II (component 2), wherein pesticide II is an active ingredient selected from the groups A) to O) defined above.
  • compositions described in Table B comprise the active components in synergistically effective amounts.
  • B-1 (I) + (A.1 .1 ), B-2: (I) + (A.1.2), B-3: (I) + (A.1 .3), B-4: (I) + (A.1.4), B-5: (I) + (A.1.5), B-6: (I)
  • B-1 12 (I) + (B.1 .28), B-1 13: (I) + (B.1 .29), B-1 14: (I) + (B.1 .30), B-1 15: (I) + (B.1.31 ), B-1 16: (I) + (B.1 .32), B-1 17: (I) + (B.1 .37), B-1 18: (I) + (B.1.38), B-1 19: (I) + (B.1 .39), B-120: (I)
  • B-320 (I) + (K.1.41), B-321 : (I) + (K.1.42), B-322: (I) + (K.1.43), B-323: (I) + (K.1.44), B-324: (I) + (K.1.45), B-325: (I) + (K.1.46), B-326: (I) + (K.1.47), B-327: (I) + (K.1.48), B-328: (I)
  • B-329 (I) + (K.1.50), B-330: (I) + (K.1.51), B-331 : (I) + (K.1.52), B-332: (I) + (K.1.53), B-333: (I) + (K.1.54), B-334: (I) + (0.1.1), B-335: (I) + (0.1.2), B-336: (I) + (0.1.3), B-337: (I) + (0.1.4), B-338: (I) + (0.1.5), B-339: (I) + (0.1.6), B-340: (I) + (0.1.7), B-341 : (I) + (0.1.8), B-342: (I) + (0.1.9), B-343: (I) + (0.1.10), B-344: (I) + (0.1.11), B-345: (I) + (0.1.12), B-346: (I) + (0.1.13), B-347: (I) + (0.1.14), B-348
  • B-412 (I) + (0.1.79), B-413: (I) + (0.1.80), B-414: (I) + (0.1.81), B-415: (I) + (0.1.82), B-416: (I) + (0.1.83), B-417: (I) + (0.1.84), B-418: (I) + (0.1.85), B-419: (I) + (0.1.86), B-420: (I) + (0.1.87), B-421 : (I) + (0.1.88), B-422: (I) + (0.1.89), B-423: (I) + (0.1.90), B-424: (I) +
  • B-425 (I) + (0.2.1), B-426: (I) + (0.2.2), B-427: (I) + (0.2.3), B-428: (I) + (0.2.4), B- 429: (I) + (0.2.5), B-430: (I) + (0.2.6), B-431 : (I) + (0.2.7), B-432: (I) + (0.3.1), B-433: (I) + (0.3.2), B-434: (I) + (0.3.3), B-435: (I) + (0.3.4), B-436: (I) + (0.3.5), B-437: (I) + (0.3.6), B-438: (I) + (0.3.7), B-439: (I) + (0.3.8), B-440: (I) + (0.3.9), B-441 : (I) + (0.3.10), B-442: (I) + (0.3.11), B-443: (I) + (0.3.12), B-444: (I) + (0.3.13), B-445
  • B-452 (I) + (0.3.21), B-453: (I) + (0.3.22), B-454: (I) + (0.3.23), B-455: (I) + (0.3.24), B-456: (I) + (0.3.25), B-457: (I) + (0.3.26), B-458: (I) + (0.3.27), B-459: (I) + (0.3.28), B-460: (I) + (0.3.29), B-461 : (I) + (0.3.30), B-462: (I) + (0.3.31), B-463: (I) + (0.3.32), B-464: (I) +
  • B-465 (I) + (0.3.34), B-466: (I) + (0.3.35), B-467: (I) + (0.3.36), B-468: (I) + (0.3.37), B-469: (I) + (0.3.38), B-470: (I) + (0.3.39), B-471 : (I) + (0.3.40), B-472: (I) + (0.3.41), B-473: (I) + (0.3.42), B-474: (I) + (0.3.43), B-475: (I) + (0.3.44), B-476: (I) + (0.3.45), B-477: (I) +
  • B-478 (I) + (0.3.47), B-479: (I) + (0.3.48), B-480: (I) + (0.3.49), B-481 : (I) + (0.3.50), B-482: (I) + (0.3.51), B-483: (I) + (0.3.52), B-484: (I) + (0.4.1), B-485: (I) + (0.4.2), B-486: (I) + (0.4.3), B-487: (I) + (0.4.4), B-488: (I) + (0.4.5), B-489: (I) + (0.4.6), B-490: (I) + (0.4.7), B-491: (I) + (0.4.8), B-492: (I) + (0.4.9), B-493: (I) + (0.4.10), B-494: (I) + (0.4.11), B-495: (I) +
  • B-496 (I) + (0.4.13), B-497: (I) + (0.4.14), B-498: (I) + (0.4.15), B-499: (I) + (0.5.1), B-500: (I) + (0.5.2), B-501: (I) + (0.6.1), B-502: (I) + (0.6.2), B-503: (I) + (0.6.3), B-504: (I) + (0.6.4), B-505: (I) + (0.6.5), B-506: (I) + (0.7.1), B-507: (I) + (0.7.2), B-508: (I) + (0.7.3), B-509: (I) + (0.7.4), B-510: (I) + (0.7.5), B-511: (I) + (0.8.1), B-512: (I) + (0.8.2), B-513: (I) + (0.8.3), B-514: (I) + (0.8.4), B-515: (I) + (0.8.5), B-5
  • B-532 (I) + (0.11.10)
  • B-533 (I) + (0.11.11)
  • B-534 (I) + (0.11.12)
  • B-535 (I) + (0.11.13)
  • B-536 (I) + (0.12.1)
  • B-537 (I) + (0.12.2)
  • B-538 (I) + (0.12.3)
  • B-539 (I) +
  • B-540 (I) + (0.12.5), B-541 : (I) + (0.12.6), B-542: (I) + (0.13.1), B-543: (I) + (0.13.2), B-544: (I) + (0.13.3), B-545: (I) + (0.14.1), B-546: (I) + (0.14.2), B-547: (I) + (0.14.3), B-548: (I) + (0.14.4), B-549: (I) + (0.15.1), B-550: (I) + (0.15.2), B-551 : (I) + (0.15.3), B-552: (I) +
  • B-626 I) + (0.28.15), B-627 (I) + (0.28.16), B-628 (I) + (0.28.17), B-629 (l) + (0.28.18), B-630 (I) + (0.28.19), B-631 (I) + (0.28.20), B-632 (I) + (0.28.21 ), B-633 (l) + (0.28.22), B-634 (I) + (0.28.23), B-635 (I) + (0.28.24), B-636 (I) + (0.28.25), B-637 (l) + (0.28.26), B-638 (I) + (0.28.27), B-639 (I) + (0.28.28), B-640 (I) + (0.28.29), B-641 (l) + (0.28.30), B-642 (I) + (0.28.31 ), B-643 (I) + (0.28.42), B-644 (I) + (0.28.43), B-645 (l)
  • B-686 (I) + (D.2.8), B-687: (I) + (G.2.8), B-688: (I) + (K.1 .56), B-689: (I) + (0.4.16), B-690: (I) + (0.4.17), B-691 : (I) + (0.4.18), B-692: (I) + (0.4.19), B-693: (I) + (0.4.20), B-694: (I) + (0.4.21 ), B-695: (I) + (0.28.83), B-696: (I) + (0.28.84), B-697: (I) + (0.28.85), B-698: (I) + (0.28.86), B-699: (I) + (0.28.87), B-700: (I) + (0.28.88), B-701 : (I) + (0.28.89), B-702: (I) +
  • B-703 (I) + (0.28.91 ), B-704: (I) + (0.28.92), B-705: (I) + (0.28.93).
  • 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.
  • 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
  • the compounds of the formula I can be prepared according to the methods outlined below.
  • ethyl 2-(4-cyanophenyl)-2-hydroxy-acetate (0.50 g), which can be prepared as described in European Journal of Organic Chemistry 2008, (34), 5692-5695, in tetrahydrofuran (5 ml.) was added ethylamine (0.79 mg, 70% in water, 5 eq.). The mixture was stirred overnight. Hydroxylamine hydrochloride (0.34 g, 2 eq.) in L/,/V-dimethylformamide (0.5 ml.) was added and the mixture was stirred at 70°C for 3 hours. Trifluoroacetic anhydride (2.0 g, 4 eq.) was then added dropwise to the mixture.
  • HPLC High Performance Liquid Chromatography; HPLC-column Kinetex XB C18 1 ,7m (50 x 2,1 mm); eluent: acetonitrile / water + 0.1 % trifluoroacetic acid (gradient from 5:95 to 100 : 0 in 1 .5 min at 60°C, flow gradient from 0.8 to 1.0 ml/min in 1 .5 min).
  • the spray solutions were prepared in several steps:
  • the stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml. This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.
  • Leaves of pot-grown soybean seedlings were inoculated with spores of Phakopsora pachyrhizi. To ensure the success of the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 20 to 24°C for 24 hours. The next day the plants were cultivated for 3 days in a greenhouse chamber at 23 to 27°C and a relative humidity between 60 and 80%. Then the plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. Then the trial plants were cultivated for 14 days in a greenhouse chamber at 23 to 27°C and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • Leaves of pot-grown soybean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 2 days in a greenhouse chamber at
  • the plants were inoculated with spores of Phakopsora pachyrhizi. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24°C for
  • the trial plants were cultivated for fourteen days in a greenhouse chamber at 23 to 27°C and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • the first two developed leaves of pot-grown wheat seedling were dusted with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to 24°C for 24 hours. The next day the plants were cultivated for 3 days in a greenhouse chamber at 20 to 24°C and a relative humidity between 65 and 70%. Then the plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants could air-dry. Then the trial plants were cultivated for 8 days in a greenhouse chamber at 20 to 24°C and a relative humidity between 65 and 70%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • the first two developed leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below.
  • the next day the plants were inoculated with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to 24°C for 24 hours. Then the trial plants were cultivated for 6 days in a greenhouse chamber at 20 to 24°C and a relative humidity between 65 and 70%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

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Abstract

The present invention relates to trifluoromethyloxadiazoles of the formula I, or the N-oxides, or the agriculturally useful salts thereof, and to the use thereof for controlling phytopathogenic fungi; to a method for combating phytopathogenic harmful fungi, which process comprises treating the fungi, the plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof; and to agrochemical compositions comprising at least one compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof; and to agrochemical compositions further comprising seeds.

Description

Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
The present invention relates to trifluoromethyloxadiazoles of the formula I, or the N-oxides, or the agriculturally useful salts thereof, and to the use thereof for controlling phytopathogenic fungi; to a method for combating phytopathogenic harmful fungi, which process comprises treating the fungi, the plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof; and to agrochemical compositions comprising at least one compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof; and to agrochemical compositions further comprising seeds.
Similar 5-trifluoromethyl-1 ,2,4-oxadiazoles are known as fungicides from WO 2017/076742 A1 and WO 2018/065414 A1.
In many cases, in particular at low application rates, the fungicidal activity of known fungicidal compounds is unsatisfactory. Based on this, it was an objective of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic fungi. Another object of the present invention is to provide fungicides with improved toxicological properties or with improved environmental fate properties. This objective is achieved by the oxadiazole compounds of the formula I, or the N-oxides, or their agriculturally useful salts for controlling phytopathogenic fungi.
The compounds according to the invention differ from those described in the closest prior art in the divalent moiety“-CR3(-X-R4)-“.
Accordingly, the present invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof,
Figure imgf000002_0001
wherein:
A is phenyl or a 6-membered aromatic heterocycle; wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 or 2 nitrogen atoms as ring member atoms; and wherein the phenyl ring or the aromatic heterocycle is unsubstituted or substituted with 1 , 2, 3 or 4 identical or different groups RA; wherein
RA is halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy or
Ci-C6-haloalkoxy;
X is O or S;
Y is O or S;
R1 is hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl, Ci-C6-alkoxyimino-Ci-C4-alkyl, C2- C6-alkenyloxyimino-Ci-C4-alkyl, C2-C6-alkynyloxyimino-Ci-C4-alkyl, C3-Cn-cycloalkyl, C3- Cn-cycloalkenyl, C3-Cn-cycloalkyl-Ci-C4-alkyl, phenyl-Ci-C4-alkyl, heterocyclyl-Ci-C4- alkyl, heteroaryl-Ci-C4-alkyl, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle, wherein the ring member atoms of said mono- or bicyclic heterocycle include besides carbon atoms further 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein 1 or 2 carbon ring member atoms of the heterocycle may be replaced by 1 or 2 groups independently selected from C(=0) and C(=S); and wherein the heterocyclyl group in heterocyclyl-Ci-C4-alkyl is a 3- to 10-membered saturated, partially unsaturated, mono- or bicyclic heterocycle, wherein the ring member atoms of said mono- or bicyclic heterocycle include besides carbon atoms further 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein 1 or 2 carbon ring member atoms of the heterocycle may be replaced by 1 or 2 groups independently selected from C(=0) and C(=S); and wherein the heteroaryl group in heteroaryl-Ci-C4-alkyl is a 5- or 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S;
and wherein any of the aliphatic or cyclic groups R1 are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different groups R1a; wherein R1a is halogen, cyano, Ci-C6-alkyl, Ci-C6-alkoxy or Ci-C6-haloalkoxy;
R2 is hydrogen, formyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy,
Cs-Cs-cycloalkyl, Cs-Cs-cycloalkenyl, C3-C8-cycloalkyl-Ci-C4-alkyl, phenyl-Ci-C4-alkyl, phenyl, pyridinyl, C(=0)-(Ci-C6-alkyl), C(=0)-(C3-C8-cycloalkyl),
C(=0)-(Ci-C6-alkoxy) or -N(R2a)2; wherein
R2a is independently selected from the group consisting of hydrogen, OH, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkenyl, Ci-C6-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl and Ci-C6-alkylthio;
and wherein any of the aliphatic or cyclic groups in R2 are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, hydroxy, oxo, cyano, Ci-C6-alkyl,
Ci-C6-alkoxy and Cs-Cs-cycloalkyl;
R3, R4 independently of each other are selected from the group consisting of hydrogen and Ci-C4-alkyl.
Agriculturally acceptable salts of the compounds of the formula I 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 the compounds I. 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 be substituted with one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium,
trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C-i-C4- alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of acceptable 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 a compound I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
Compounds of the formula I can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers arising from restricted rotation about a single bond of asymmetric groups and geometric isomers. They also form part of the subject matter of the present invention. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, e.g. a racemate, individual
stereoisomers, or as an optically active form.
Compounds of the formula I can be present in different crystal modifications whose biological activity may differ. They also form part of the subject matter of the present invention.
In respect of the variables, the embodiments of the intermediates obtained during preparation of compounds I correspond to the embodiments of the compounds of formula I. The term“ compounds I” refers to compounds of the formula I.
In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term“Cn-Cm” indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
The term“halogen” refers to fluorine, chlorine, bromine and iodine.
The term“oxo” refers to an oxygen atom =0, which is bound to a carbon atom or sulfur atom, thus forming, for example, a ketonyl -C(=0)- or sulfinyl -S(=0)- group.
The term“Ci-C6-alkyl” refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 - methylpropyl, 2-methylpropyl, and 1 ,1 -dimethylethyl.
The term“C2-C6-alkenyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1 -propenyl, 2- propenyl (allyl), 1 -methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-
1 -propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl.
The term“C2-C6-alkynyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, 1 -propynyl,
2-propynyl (propargyl), 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl.
The term“Ci-C6-haloalkyl” refers to a straight-chained or branched alkyl group having 1 to 6 carbon atoms (as defined above), wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl,
bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, 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 and pentafluoroethyl, 2- fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3- chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3- trichloropropyl, CH2-C2F5, CF2-C2F5, CF(CFs)2, 1-(fluoromethyl)-2-fluoroethyl, l-(chloromethyl)- 2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl.
The term“Ci-C6-alkoxy” refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as defined above) which is bonded via an oxygen, at any position in the alkyl group, for example methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2- methylpropoxy or 1 ,1-dimethylethoxy.
The term“Ci-C6-haloalkoxy” refers to a Ci-C6-alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example, OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chlorofluoromethoxy, 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 nonafluorobutoxy.
The terms“C3-Cn-cycloalkyl-Ci-C4-alkyl, heterocyclyl-Ci-C4-alkyl, phenyl-Ci-C4-alkyl or heteroaryl-Ci-C4-alkyl” refer to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl, heterocyclyl, phenyl or heteroaryl radical respectively.
The term“Ci-C4-alkoxy-Ci-C4-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group (as defined above).
The term“C2-C6-alkenyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2- propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-
1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.
The term“C2-C6-alkynyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, 1-propynyl,
2-propynyl (propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl.
The term“Cs-Cs-cycloalkyl” refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members such as cyclopropyl (C3H5), cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
The term“C3-Cn-cycloalkyl” refers to a monocyclic, bicyclic or tricyclic saturated univalent hydrocarbon radical having 3 to 11 carbon ring members that is connected through one of the ring carbon atoms by substitution of one hydrogen atom, such as cyclopropyl (C3H5), cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[1.1.0]butyl, bicyclo[2.1.0]pentyl, bicyclo[1.1.1]pentyl, bicyclo[3.1.0]hexyl, bicyclo[2.1.1 ]hexyl, norcaranyl (bicyclo[4.1.0]heptyl) and norbornyl (bicyclo[2.2.1]heptyl). Further examples of bicyclic or tricyclic cycloalkyl radicals are found herein as embodiments R1.1 to R1.26. The term "Ci-C6-alkoxyimino-Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms, wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced by a divalent C1-C6- alkoxyimino radical (Ci-C6-alkyl-0-N=) as defined above.
The term "C2-C6-alkenyloxyimino-Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms, wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced
by a divalent C2-C6-alkenyloxyimino radical (C2-C6-alkenyl-0-N=).
The term "C2-C6-alkynyloxyimino-Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms, wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced by a divalent C2-C6-alkynyloxyimino radical (C2-C6-alkynyl-0-N=).
The term“formyl” refers to a group -C(=0)H.
The term“aliphatic" refers to compounds or radicals composed of carbon and hydrogen and which are non-aromatic compounds. An“alicyclic” compound or radical is an organic compound that is both aliphatic and cyclic. They contain one or more all-carbon rings which may be either saturated or unsaturated, but do not have aromatic character.
The terms“cyclic moiety” or“cyclic group” refer to a radical which is an alicyclic ring or an aromatic ring, such as, for example, phenyl or heteroaryl.
The term“and wherein any of the aliphatic or cyclic groups R1 are unsubstituted or substituted with...” refers to aliphatic groups, cyclic groups and groups, which contain an aliphatic and a cyclic moiety in one group, such as in, for example, C3-Cn-cycloalkyl-Ci-C4-alkyl or phenyl-C-i- C4-alkyl; therefore, a group which contains an aliphatic and a cyclic moiety both of these moieties may be substituted or unsubstituted independently of each other.
The term“phenyl” refers to an aromatic ring systems incuding six carbon atoms (commonly referred to as benzene ring. In association with the group A the term“phenyl” is to be interpreted as a benzene ring or phenylene ring, which is attached to both, the oxadiazole moiety and the group“-CR3(-X-R4)-“.
The term“heteroaryl”, unless defined otherwise, refers to aromatic monocyclic or polycyclic ring systems incuding besides carbon atoms 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S.
The term“saturated 3- to 7-membered carbocycle" is to be understood as meaning monocyclic saturated carbocycles having 3, 4 or 5 carbon ring members. Examples include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
The term "3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle, wherein the ring member atoms of said mono- or bicyclic heterocycle include besides carbon atoms further 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S”, is to be understood as meaning both, aromatic mono- and bicyclic heteroaromatic ring systems, and also saturated and partially unsaturated heterocycles, for example:
a 3- or 4-membered saturated heterocycle which contains 1 or 2 heteroatoms from the group consisting of N, O and S as ring members such as oxirane, aziridine, thiirane, oxetane, azetidine, thiethane, [1 ,2]dioxetane, [1 ,2]dithietane, [1 ,2]diazetidine;
and a 5- or 6-membered saturated or partially unsaturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of N, O and S as ring members such as 2-tetrahydro- furanyl, 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-dihydrofur-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-pyrrol in-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-hexahydropyridazinyl, 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; and
a 7-membered saturated or partially unsaturated heterocycle such as tetra- and
hexahydroazepinyl, such as 2,3,4,5-tetrahydro[1 H]azepin-1-,-2-,-3-,-4-,-5-,-6- or-7-yl, 3, 4, 5, 6- tetrahydro[2H]azepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -,-2-, -3-, -4-, -5-, -6- or-7-yl, 2,3,6,7-tetrahydro[1 H]azepin-1-,-2-,-3-,-4-,-5-,-6- or-7-yl, hexahydroazepin-1-,-2-,-3- or- 4-yl, tetra- and hexahydrooxepinyl such as 2,3,4,5-tetrahydro[1 H]oxepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,4,7-tetrahydro[1 H]oxepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,6,7-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5- ,-6- or-7-yl, hexahydroazepin-1-,-2-,-3- or-4-yl, tetra- and hexahydro-1 ,3-diazepinyl, tetra- and hexahydro-1 ,4-diazepinyl, tetra- and hexahydro-1 ,3-oxazepinyl, tetra- and hexahydro-1 ,4- oxazepinyl, tetra- and hexahydro-1 ,3-dioxepinyl, tetra- and hexahydro-1 ,4-dioxepinyl and the corresponding -ylidene radicals.
The term“5- or 6-membered heteroaryl” or the term”5- or 6-membered aromatic heterocycle” refer to aromatic ring systems incuding besides carbon atoms, 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, for example, a 5-membered heteroaryl such as pyrrol-1 -yl, pyrrol-2 -yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1 ,2,4-triazolyl- 1 -yl, 1 ,2,4-triazol-3-yl 1 ,2,4-triazol-5-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl and 1 ,2,4- thiadiazol-3-yl, 1 ,2,4-thiadiazol-5-yl; or a 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
In respect of the variables, the embodiments of the intermediates correspond to the
embodiments of the compounds I. Preference is given to those compounds I and, where applicable, also to compounds of all subformulae provided herein, e. g. formulae 1.1 , I.2, 1.A, I.B, I.C, I.D, I.E, I.F, I.G and I.H, wherein the variables have independently of each other or more preferably in combination (any possible combination of 2 or more substituents as defined herein) the following meanings:
In one aspect of the invention group A is phenyl, which is unsubstituted or substituted with 1 , 2,
3 or 4 identical or different groups RA as defined or preferably defined herein and wherein the group -CR3(-X-R4)- is attached to the phenyl ring in para- position with regard to the oxadiazole group.
In one aspect of the invention A is phenyl, which is unsubstituted or substituted with 1 , 2, 3 or 4 identical or different groups RA as defined or preferably defined herein and wherein the group - CR3(-X-R4)- is attached to the phenyl ring in aie/a-position with regard to the oxadiazole group.
In one embodiment A is a 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 or 2 nitrogen atoms as ring member atoms; and wherein the aromatic heterocycle is unsubstituted or substituted with 1 or 2 identical or different groups RA as defined or preferably defined herein; particularly RA is chlorine, fluorine or methyl.
In a further embodiment A is a 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 or 2 nitrogen atoms as ring member atoms; and wherein the aromatic heterocycle is unsubstituted or substituted with 1 or 2 identical or different groups RA as defined or preferably defined herein; particularly RA is chlorine, fluorine or methyl; and wherein the group -CR3(-X-R4)- is attached to the 6-membered aromatic heterocycle in /?ara-position with regard to the oxadiazole group.
In one embodiment the invention relates to compounds of the formula I, wherein the moiety A is defined as in sub
Figure imgf000008_0001
(A.1 ) (A.2) (A3) (A.4) (A.5) wherein #1 denotes the position, which is bound to the oxadiazole moiety and #2 denotes the position, which is connected to the group -CR3(-X-R4)- of compounds of the formula I; and wherein A is unsubstituted or substituted with 1 or 2 identical or different groups RA and wherein RA is as defined or preferably defined herein. In another embodiment A as defined in any one of subformulae (A.1 ) to (A.5) is unsubstituted or substituted with 1 or 2 identical or different groups RA; and wherein RA is chlorine, fluorine or methyl. In a preferred embodiment A as defined in any one of subformulae (A.1 ) to (A.5) is unsubstituted.
In a preferred embodiment, RA is independently selected from the group consisting of halogen, Ci-C6-alkyl or C3-Cs-cycloalkyl. In another preferred embodiment, RA is independently selected from the group consisting of halogen, methyl or ethyl, more preferably chlorine, fluorine or methyl. More preferably RA is independently selected from the group consisting of halogen, in particular RA is fluorine.
Further embodiments with regard to the meaning of groups X and Y are as follows:
Embodiment X.1 : X is O.
Embodiment Y.1 : Y is O.
Embodiment XY.1 : X is O and Y is O.
Embodiment XY.2: X is O and Y is S.
Embodiment XY.3: X is S and Y is O.
Embodiment XY.4: X is S and Y is S.
Embodiment XY.5: Embodiment XY.1 and Embodiment XY.2.
Embodiment XY.6: Embodiment XY.3 and Embodiment XY.4.
Further embodiments with regard to the meaning of radical R1 are as follows:
Embodiment 1.1 : R1 is hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxyimino- Ci-C4-alkyl, C2-C6-alkenyloxyimino-Ci-C4-alkyl, C2-C6-alkynyloxyimino-Ci-C4-alkyl, Cs-Cs- cycloalkyl, C3-Cs-cycloalkenyl, C3-C8-cycloalkyl-Ci-C4-alkyl, phenyl-Ci-C4-alkyl, heteroaryl-Ci- C4-alkyl-, phenyl, or a 5- or 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein the heteroaryl group in heteroaryl-Ci-C4- alkyl is a 5- or 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein any of the aliphatic or cyclic groups R1 are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C6-alkyl,
Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and C3-Cs-cycloalkyl.
Embodiment 1 .2: R1 is hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl or C3-Cn-cycloalkyl. Embodiment 1 .3: R1 is hydrogen, methyl, ethyl, /7-propyl, /so-propyl, /7-butyl, /iso-butyl, sec-butyl, tert- butyl, cyclopropyl or bicyclo[1.1.1 ]pentan-1 -yl.
Embodiment 1 .4: R1 is phenyl or heteroaryl; and wherein the heteroaryl group is a 5- or 6- membered aromatic heterocycle, wherein the ring includes besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein any of the cyclic groups are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and Cs-Cs-cycloalkyl.
Embodiment 1 .5: R1 is C3-Cn-cycloalkyl or C3-Cn-cycloalkenyl; and wherein the cyclic group is unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, oxo, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and Cs-Cs-cycloalkyl.
Embodiment 1 .6: R1 is Ci-C6-alkyl; and wherein the alkyl group is unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, oxo, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and Cs-Cs-cycloalkyl.
Embodiment 1 .7: R1 is difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2- chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, 3,3,3- trifluoropropyl, CH2CF2CF3 or CF2CF2CF5, CH(CH3)CF3, CH2CF2CH3, CH2C(CH3)2F,
CH2CH(CH3)CF3 0r CH2C(CH3)2CF3.
Embodiment 1 .8: R1 is Ci-C6-alkoxyimino-Ci-C4-alkyl, C2-C6-alkenyloxyimino-Ci-C4-alkyl or C2-C6-a I ky ny I oxy i m i n o-C 1 -C4-a I ky I .
Embodiment 1 .9: R1 is selected from the group consisting of radicals R1.1 to R1.26 below, particularly from R1.1 to R1.18, which are further unsubstituted or substituted with 1 or 2 radicals selected from the group consisting of methyl, ethyl, oxo, hydroxyl and halogen; and wherein “#C” indicates the carbon atom, which is attached to the remainder of the compounds of formula
Figure imgf000010_0001
R1.15 R1.16 R1.17 R1.18 R1.19 R1.20 R1.21
Figure imgf000011_0001
In one embodiment R1a is selected from the group consisting of halogen, oxo, cyano,
Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and Cs-Cs-cycloalkyl.
In another aspect of the invention R1a is selected from the group consisting of fluorine, chlorine, oxo, cyano, methyl, ethyl, methoxy, trifluoromethyl, trifluoromethoxy, difluoromethyl,
difluoromethoxy and cyclopropyl.
In a preferred aspect of the invention R1a is selected from the group consisting of halogen, oxo, Ci-C6-alkyl and Cs-Cs-cycloalkyl; particularly from oxo, methyl, ethyl, fluorine and chlorine; more particularly from fluorine and chlorine.
In one aspect of the invention R2 is hydrogen, formyl, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, propargyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkenyl, C3-Cs-cycloalkyl-Ci-C4-alkyl, phenyl or -N(R2a)2; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1 , 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C6-alkyl and Ci-C6-alkoxy; more preferably from halogen, in particular the radical is fluorine; and wherein R2a is independently selected from the group consisting of hydrogen, OH, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and Ci-C6-alkoxy.
In one aspect of the invention R2 is -N(R2a)2, wherein R2a is independently selected from the group consisting of hydrogen, OH, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and Ci-C6-alkoxy. Preferably R2a is independently selected from the group consisting of hydrogen, OH, methyl, ethyl, /7-propyl, /so-propyl, methoxy, ethoxy, propoxy, vinyl, allyl propargyl, cyclopropyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and Ci-C6-alkoxy.
In a more preferred aspect R2 is methylamino or dimethylamino.
In a further embodiment R2 is hydrogen, formyl, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, propargyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkenyl, C3-Cs-cycloalkyl-Ci-C4-alkyl, phenyl, C1-C6- alkylamino or diCi-C6-alkylamino; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1 , 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C6-alkyl and
Ci-C6-alkoxy.
In yet another embodiment R2 is hydrogen, formyl, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, propargyl, Cs-Cs-cycloalkyl, Ci-C6-alkylamino or diC-i-C6-alkylamino.
In a further embodiment R2 is hydrogen, formyl, methyl, ethyl, /7-propyl, /so-propyl, methoxy, ethyoxy, propyloxy, cyclopropyl, cyclopropyl-CH2-, allyl, phenyl, 4-F-phenyl, 2-F-phenyl, C1-C6- alkylamino or diCi-C6-alkylamino.
In one embodiment R2 is hydrogen, formyl, methyl, ethyl, /7-propyl, /so-propyl, methoxy, ethyoxy, propyloxy, cyclopropyl, cyclopropyl-CH2-, allyl, propargyl, Ci-C6-alkylamino or diCi-C6- alkylamino. In another embodiment R2 is hydrogen, formyl, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, propargyl, Ci-C6-alkylamino or diCi-C6-alkylamino.
In a further embodiment R2 is hydrogen, formyl, methy, ethyl, methoxy, ethoxy, propyloxy, methylamino or dimethylamino.
In a special embodiment R2 is hydrogen.
Embodiment 12.1 : R1 and R2 are independently selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl or C3-Cn-cycloalkyl.
Embodiment 12.2: R1 is hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl, or C3-Cn-cycloalkyl and R2 is hydrogen.
Embodiment 12.3: R1 is hydrogen, methyl, ethyl, /7-propyl, /so-propyl, /7-butyl, /so-butyl, sec- butyl, tert- butyl, cyclopropyl, or bicyclo[1 .1 1 ]pentan-1 -yl and R2 is hydrogen.
Further embodiments with regard to the meaning of radicals R3 and R4 are as follows:
Embodiment 3.1 : R3 and R4 independently of each other are hydrogen, methyl or ethyl.
Embodiment 3.2: R3 and R4 are both hydrogen.
Embodiment 3.3: R3 is hydrogen and R4 is methyl.
Embodiment 3.4: R3 and R4 are both methyl.
In further aspects of the present invention, the embodiments E.1 to E.48 listed in Table E represent preferred combinations of the embodiments, which are defined herein above for each of the variables X and Y (Embodiments XY.1 to XY.4), R1 and R2 (Embodiments 12.1 to 12.3), R3 and R4 (Embodiments 3.1 to 3.4).
Table E:
Figure imgf000012_0002
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000013_0002
In one embodiment, the invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof, wherein
A is a group selected from subformulae (A.1 ) to (A.5); and wherein the phenyl ring or the aromatic heterocycle is unsubstituted or substituted with 1 or 2 identical or different groups RA; wherein
RA is halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy or
Ci-C6-haloalkoxy;
X is O or S;
Y is O or S;
R1 is hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxyimino-Ci-C4-alkyl, C2- C6-alkenyloxyimino-Ci-C4-alkyl, C2-C6-alkynyloxyimino-Ci-C4-alkyl, Cs-Cs-cycloalkyl, C3- Cs-cycloalkenyl, C3-C8-cycloalkyl-Ci-C4-alkyl, phenyl-Ci-C4-alkyl, heteroaryl-Ci-C4-alkyl-, phenyl, or a 5- or 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein the heteroaryl group in heteroaryl-Ci-C4-alkyl is a 5- or 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein any of the aliphatic or cyclic groups R1 are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and Cs-Cs-cycloalkyl;
R2 is hydrogen, formyl, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, propargyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkenyl, C3-C8-cycloalkyl-Ci-C4-alkyl, phenyl, Ci-C6-alkylamino or diCi-C6- alkylamino; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1 , 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, Ci-C6-alkyl and
Ci-C6-alkoxy
R3, R4 independently of each other are hydrogen, methyl or ethyl.
In one embodiment, the invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof, wherein A is a group selected from subformulae (A.1) to (A.5); and wherein the phenyl ring or the aromatic heterocycle is unsubstituted or substituted with 1 or 2 identical or different groups RA; wherein
RA is halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy or
Ci-C6-haloalkoxy;
X is O;
Y is O or S;
R1 and R2 are as defined in any one of Embodiments 12.1 , 12.2 or 12.3 as defined above;
R3, R4 independently of each other are hydrogen, methyl or ethyl.
In another embodiment, the invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof, wherein
A is a phenyl ring; and wherein the phenyl ring is unsubstituted or substituted with 1 or 2 identical or different groups RA; wherein
RA is halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy or
Ci-C6-haloalkoxy;
X is O;
Y is O or S;
R1 is hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl or C3-Cn-cycloalkyl;
R2 is hydrogen;
R3, R4 independently of each other are hydrogen, methyl or ethyl.
In another embodiment, the invention relates to compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof, wherein
A is a phenyl ring; and wherein the phenyl ring is unsubstituted or substituted with 1 or 2 identical or different groups RA; wherein
RA is halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy or
Ci-C6-haloalkoxy;
X is O;
Y is O;
R1 is hydrogen, methyl, ethyl, /7-propyl, /se-propyl, /7-butyl, /se-butyl, sec-butyl, tert- butyl, cyclopropyl or bicyclo[1.1.1]pentan-1-yl;
R2, R3, R4 are hydrogen.
In one embodiment, the invention relates to compounds of the formula 1.1 or to compounds of the formula 1.2, or the N-oxides, or the agriculturally acceptable salts thereof,
Figure imgf000014_0001
wherein n is 0, 1 or 2; and wherein the meaning of the variables R3, R4, X, Y, R1 and R2 are as defined herein for compounds of the formula I or as defined in embodiments E.1 to E.48 in Table E; and wherein RA is as defined or preferably defined herein for compounds of the formula I.
A preferred embodiment relates to compounds of the formula 1.1 or to compounds of the formula 1.2 as defined above, wherein the meaning of the variables R3, R4, X, Y, R1 and R2 are as defined herein for compounds of the formula I or as defined in embodiments E.1 to E.48 in Table E; and wherein n is 0 or 1 and RA is halogen, Ci-C6-alkyl or Cs-Cs-cycloalkyl; in particular RA is fluorine.
In a further embodiment, the invention relates to compounds of the formula 1.1 , or the N-oxides, or the agriculturally acceptable salts thereof, wherein:
n is O or l ;
RA is fluorine;
X is O;
Y is O or S;
R1 and R2 are independently selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C6- alkenyl, C3-C6-alkynyl or C3-Cn-cycloalkyl;
R3, R4 independently of each other are hydrogen, methyl or ethyl.
In a further embodiment, the invention relates to compounds of the formula 1.1 , or the N-oxides, or the agriculturally acceptable salts thereof, wherein:
n is O or l ;
RA is fluorine; in particular the fluorine atom is attached to the ortho- position of the phenyl ring with regard to the oxadiazole group;
X is O;
Y is O or S;
R1 is hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl or C3-Cn-cycloalkyl;
R2 is hydrogen;
R3, R4 independently of each other are hydrogen, methyl or ethyl.
In a further embodiment, the invention relates to compounds of the formula 1.1 , or the N-oxides, or the agriculturally acceptable salts thereof, wherein:
n is O or l ;
RA is fluorine; in particular the fluorine atom is attached to the ortho- position of the phenyl ring with regard to the oxadiazole group;
X is O;
Y is O;
R1 is hydrogen, methyl, ethyl, /7-propyl, /se-propyl, /7-butyl, /se-butyl, sec-butyl, tert- butyl, cyclopropyl or bicyclo[1.1.1]pentan-1-yl;
R2, R3, R4 are hydrogen. In one embodiment, the present invention relates to compounds of the formulae I .A, I.B, I.C, I.D, I.E, I.F, I.G and I.H, wherein the radicals R1, R2 and R4 are as defined or preferably defined herein:
Figure imgf000016_0001
Preference is given to compounds of the formula I, which are compiled in Tables 1 to 8 below, and which may be used according to the invention.
Table 1 : Compounds of the formula I. A, in which R1, R2 and R4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.A.A-1 to I.A.A- 1364). This means, for example, that a compound of the formula I. A, wherein R1 is
bicyclo[1 .1 .1]pentan-1 yl, R2 is hydrogen and R4 is hydrogen (corresponding to the definition in line A-341 in Table A) is named I.A.A-341 .
Table 2: Compounds of the formula I.B, in which R1, R2 and R4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.B.A-1 to I.B.A- 1364).
Table 3: Compounds of the formula I.C, in which R1, R2 and R4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.C.A-1 to I.C.A- 1364)
Table 4: Compounds of the formula I.D, in which R1, R2 and R4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.D.A-1 to I.D.A- 1364).
Table 5: Compounds of the formula I.E, in which R1, R2 and R4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.E.A-1 to I.E.A- 1364).
Table 6: Compounds of the formula I.F, in which R1, R2 and R4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.F.A-1 to I.F.A- 1364).
Table 7: Compounds of the formula I.G, in which R1, R2 and R4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.G.A-1 to I.G.A- 1364).
Table 8: Compounds of the formula I.H, in which R1, R2 and R4 for each individual compound corresponds in each case to one line A-1 to A-1364 of Table A (compounds I.H.A-1 to I.H.A- 1364).
Table A:
Figure imgf000017_0001
Figure imgf000017_0002
Figure imgf000018_0001
Figure imgf000018_0002
Figure imgf000019_0001
Figure imgf000019_0002
Figure imgf000020_0002
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000021_0002
Figure imgf000022_0002
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000024_0002
Figure imgf000024_0001
Figure imgf000025_0002
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000027_0002
Figure imgf000028_0001
Figure imgf000028_0002
Figure imgf000029_0001
Figure imgf000029_0002
Figure imgf000030_0001
Figure imgf000030_0002
Figure imgf000031_0001
Figure imgf000031_0002
Figure imgf000032_0001
Figure imgf000032_0002
Figure imgf000033_0001
Figure imgf000033_0002
Figure imgf000034_0002
Figure imgf000034_0001
Figure imgf000035_0002
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000036_0002
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000039_0003
Figure imgf000039_0004
It is understood that, when in aqueous media, the compounds of the formula I according to the invention may be present in a reversible equilibrium with the corresponding covalently hydrated forms at the CF3-oxadiazole motif (for example, the compounds of formula l-l and formula l-ll as shown below, wherein A is phenyl). This dynamic equilibrium may be important for the biological activity of the compounds of the formula I. The designations of the variables in compounds of the formula I of the present invention apply generally to the compounds of Formula l-l and Formula l-ll.
Figure imgf000039_0001
Compounds of the present invention can be made as shown in the following schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula I. The compounds of the formula I can be prepared according to methods or in analogy to methods that are described in the prior art. The synthesis takes advantage of starting materials that are commercially available or may be prepared according to conventional procedures starting from readily available compounds.
For example, compounds of the formula I can be prepared by reacting amidines of type II with trifluoroacetic anhydride in an organic solvent, for example dichloromethane, or an ethereal solvent at temperatures between 0°C and 100°C, preferably at room temperature, as previously described in WO 2013/008162.
Figure imgf000039_0002
Compounds of type II can be accessed by treating nitriles of type III with hydroxylamine or its hydrochloride salt in an organic solvent, preferably an alcoholic solvent such as methanol, at a temperature between 0°C and 100°C and in the presence of a base, preferably an inorganic base, most preferably potassium carbonate (for precedents see for example WO 2009/074950, WO 2006/013104, EP 1932843). If appropriate, water may be added to enhance solubility of the reactants. The reaction is best performed at elevated temperatures, most preferably in the range between
Figure imgf000040_0001
X base, solvent
h4
Figure imgf000040_0002
Compounds of the formula III can be prepared by reacting a compound of the formula IV, for example with a carboxylic acid chloride or anhydride, with compounds of type V, wherein LG in compounds V is chlorine or a carboxylate, in an organic solvent and in the presence of a base as described in J. Org. Chem. 2015, 80, 511 1 -5124. Alternatively, compound III can be obtained by reacting compound V with the carboxylic acid IV (LG is OH) using peptide coupling reaction conditions such as 1-ethyl-3-(3-dimethylamino-propyl)carbodiimid (EDC) or its salts and hydroxybenzotriazole as described in Bioorganic & Medicinal Chemistry Letters 2010, 20(15), 4550-4554.
Figure imgf000040_0003
Compounds of the formula IV, wherein LG is chlorine can be prepared following standard procedures starting from esters of the formula Iva, which are converted to the corresponding carboxylic acid in a first step followed by treatment of this intermediate with a halogen source
(e.g. SOCI2) to give the corresponding carboxylic acid chloride.
Figure imgf000040_0004
Compounds of the formula IVa, wherein X is O, can be prepared from the alcohol V by alkylation under silver(l)oxide catalysis (WO 2016068287).
Figure imgf000040_0005
V
Compounds of the formula V can be prepared from compounds of type VI by Grignard reaction with the corresponding magnesium bromide in an anhydrous ethereal solvent (e.g. THF).
Br M9.r4
V
solvent
Figure imgf000040_0006
Compounds of the formula VI can be prepared from compounds of the formula VII by lithiation using butyl lithium in a solvent such as hexane at room temperature. The solution containing the lithiated species of compound VII may then be added at -78°C to a suitable electrophile, for example ethyl chloro(oxo)acetate. Preferably the chloro(oxo)acetate is prediluted, for example in THF.
Nº— A— H VI
VII
Alternatively, compounds VI can be prepared by oxidation of the hydroxy-ester VIII with an oxidizing agent such as oxalyl chloride and dimethylsulfoxide or by heating with manganese dioxide in a solvent such as toluene or dichloromethane as described in WO 9950257. oxidation
VII
Figure imgf000041_0001
Compounds of formula VIII can be prepared according to European Journal of Organic
Chemistry 2W&, (34), 5692-5695.
Compounds of the formula I, wherein X is S, can be prepared by reacting amidines of type XI with trifluoroacetic anhydride in an organic solvent, for example dichloromethane, or an ethereal solvent at temperatures between 0°C and 100°C, preferably at room temperature, as previously described i
Figure imgf000041_0003
Compounds of type XI can be accessed by treating nitriles of type XII with hydroxylamine or its hydrochloride salt in an organic solvent, preferably an alcoholic solvent such as methanol, at a temperature between 0°C and 100°C and in the presence of a base, preferably an inorganic base, most preferably potassium carbonate (for precedents see for example WO 2009/074950, WO 2006/013104, EP 1932843). If appropriate, water may be added to enhance solubility of the reactants. The reaction is best performed at elevated temperatures, most preferably in the range between
Figure imgf000041_0004
Compounds of formula XII can be prepared by treating from Compounds of type XIII with the respective amine in an organic solvent (e.g. toluene) as described in Journal of the chem.
society Perkin Transactions, 9, 1995, p. 11 15.
Figure imgf000041_0002
Compounds of formula XIII can be prepared by treating compounds of type V with triethylamine, methansulphonylchloride, the respective thiole in an organic solvent, for example in dichloromethane, as described in WO 2003/055482.
Figure imgf000042_0001
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, cucumber 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.
potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
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 mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect. Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, wich differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
Herbicide tolerance has been created by using mutagenesis as well as using genetic
engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield®.
Herbicide tolerance has been created via the use of transgenes to glyphosate, glufosinate, 2,4- D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitors and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.
Transgenes wich have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601 , gat4621 , goxv247; for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 , aad-12; for tolerance to dicamba: dmo; for tolerance to oxynil herbicies: bxn; for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA; for tolerance to ALS inhibitors: csr1-2; and for tolerance to HPPD inhibitors: hppdPF, W336, avhppd-03.
Transgenic corn events comprising herbicide tolerance genes include, but are not limited to, DAS40278, MON801 , MON802, MON809, MON810, MON832, MON8741 1 , MON87419, MON87427, MON88017, MON89034, NK603, GA21 , MZHGOJG, HCEM485, VCO-01981-5, 676, 678, 680, 33121 , 4114, 59122, 98140, Bt10, Bt176, CBH-351 , DBT418, DLL25, MS3,
MS6, MZIR098, T25, TC1507 and TC6275.
Transgenic soybean events comprising herbicide tolerance genes include, but are not limited to, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704- 21 , A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
Transgenic cotton events comprising herbicide tolerance genes include, but are not limited to, 19-51 a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN1021 1 , BXN10215, BXN10222, BXN 10224, MON1445, MON1698, MON88701 , MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1 , HCN10, HCN28, HCN92, MS1 , MS8, PHY14, PHY23, PHY35, PHY36, RF1 , RF2 and RF3.
Insect resistance has mainly been created by transferring bacterial genes for insecticidal proteins to plants: Transgenes which have most frequently been used are toxin genes of Bacillus spp. and synthetic variants thereof, like cry1A, crylAb, cry1Ab-Ac, crylAc, cry1A.105, cry1 F, cry1 Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1 , cry34Ab1 , cry35Ab1 , cry9C, vip3A(a), vip3Aa20. However, also genes of plant origin, such as genes coding for protease inhibitors, like CpTI and pinll, have been transferred to other plants. A further approach uses transgenes such as dvsnf7 to produce double-stranded RNA in plants.
Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA include, but are not limited to, Bt10, Bt1 1 , Bt176, MON801 , MON802, MON809, MON810, MON863, MON87411 , MON88017, MON89034, 33121 , 41 14, 5307, 59122, TC1507, TC6275, CBH-351 , MIR162, DBT418 and MZIR098. Transgenic soybean events comprising genes for insecticidal proteins include, but are not limited to, MON87701 , MON87751 and DAS-81419. Transgenic cotton events comprising genes for insecticidal proteins include, but are not limited to, SGK321 , MON531 , MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BN LA-601 , Eventl , COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281- 24-236, 3006-210-23, GHB119 and SGK321.
Increased yield has been created by using the transgene athb17, being present for example in corn event MON87403, or by using the transgene bbx32, being present for example in the soybean event MON87712.
Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1 , Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
Tolerance to abiotic conditions, such as drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb-4, comprised by soybean event IND-00410-5.
Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process resulting in a cultivated plant with stacked traits. Preferred combinations of traits are combinations of herbicide tolerance traits to different groups of herbicides, combinations of insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, combinations of herbicide tolerance with one or several types of insect resistance, combinations of herbicide tolerance with increased yield as well as combinations of herbicide tolerance and tolerance to abiotic conditions.
Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art. For example, detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations “International Service for the Acquisition of Agri-biotech Applications (ISAAA)”
(https://www.isaaa.org/gmapprovaldatabase) and the“Center for Environmental Risk
Assessment (CERA)” (https://cera-gmc.org/GMCropDatabase). Further information on specific events and methods to detect them can be found for canola events MS1 , MS8, RF3, GT73, MON88302, KK179 in W001/031042, W001/041558, W001/041558, W002/036831 ,
W01 1/153186, W013/003558, for cotton events MON 1445, MON 15985, MON531
(MON 15985), LLCotton25, MON88913, COT102, 281-24-236, 3006-210-23, COT67B,
GHB614, T304-40, GHB119, MON88701 , 81910 in WO02/034946, W002/100163,
W002/100163, WO03/013224, WO04/072235, WO04/039986, WO05/103266, WO05/103266, WO06/128573, W007/017186, WO08/122406, W008/151780, W012/134808, W013/1 12527; for corn events GA21 , MON810, DLL25, TC1507, MON863, MIR604, LY038, MON88017, 3272, 59122, NK603, MIR162, MON89034, 98140, 32138, MON87460, 5307, 41 14, MON87427, DAS40278, MON87411 , 33121 , MON87403, MON87419 in W098/044140, US02/102582, US03/126634, WO04/099447, WO04/01 1601 , WO05/103301 , W005/061720, W005/059103, WO06/098952, WO06/039376, US2007/292854, WO07/142840, WO07/140256, WO08/112019, WO09/103049, WO09/111263, W010/077816, W011/084621 , W011/062904, W01 1/022469, W013/169923, W014/1 16854, W015/053998, W015/142571 ; for potato events E12, F10, J3, J55, V1 1 , X17, Y9 in WO14/178910, W014/178913, W014/178941 ,
W014/179276, W016/183445, W017/062831 , W017/062825; for rice events LLRICE06, LLRICE601 , LLRICE62 in WO00/026345, WO00/026356, WO00/026345; and for soybean events H7-1 , MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701 ,
MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712, SYHT0H2,
DAS81419, DAS81419 x DAS44406-6, MON87751 in WO04/074492, W006/130436,
WO06/108674, WO06/108675, WO08/054747, W008/002872, WO09/064652, WO09/102873, W010/080829, W010/037016, W01 1/066384, W01 1/034704, WO12/051 199, WO12/082548, W013/016527, WO13/016516, W014/201235.
The use of compounds I and compositions according to the invention, respectively, on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
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), A Hern aria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauciox A. porri), oilseed rape {A. brass icicoia or brassicae ), sugar beets {A. tenuis ), fruits (e.g. A. grandis ), rice, soybeans, potatoes and tomatoes (e. g. A. soiani, A. grandis or A. alternate), tomatoes (e. g. A. soiani ox A. aiternata) and wheat (e.g. A. triticina), Aphanomyces spp. on sugar beets and vegetables; Ascochyta s . on cereals and vegetables, e. g. A. / 7fay (anthracnose) on wheat and A. hordeiox\ barley; Aureobasidium zeae (syn. Kapatieiia zeae) on corn; Bipoiaris and Drechsiera spp. (teleomorph: Cochiioboius spp.), e. g. Southern leaf blight (D. maydis) ox Northern leaf blight (B. zeicoia) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g.
B. oryzae ox\ rice and turfs; Biumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeiianar. grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages); B. squamosa ox B. aiiii on onion family), oilseed rape, ornamentals (e.g. B eiiptica), vines, forestry plants and wheat; Bremia iactucae (downy mildew) on lettuce; Ceratocystis { syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. uimi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticoia), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina ox
C. kikuchii) and rice; Ciadobotryum (syn. Dactyiium) spp. (e.g. C. mycophilum
(formerly Dactyiium dendroides, teleomorph: Nectria aibertinii, Nectria roseiia syn. Hypomyces roseiius) on mushrooms; Ciadosporium spp. on tomatoes (e. g. C. fuivum. leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Ciaviceps purpurea (ergot) on cereals;
Cochiioboius (anamorph: Heiminthosporium of Bipoiaris) spp. (leaf spots) on corn (C.
carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae) Coiietotrichum (teleomorph: Giomereiia) spp. (anthracnose) on cotton (e. g. C. gossypii), com (e. g. C. graminicoia: Anthracnose stalk rot), soft fruits, potatoes (e. g.
C. coccodes. black dot), beans (e. g. C. Hndemuthianum ), soybeans (e. g. C. truncatumox C. gloeosporioides ), vegetables (e.g. C. lagenariumox C. capsid), fruits (e.g. C. acutatum ), coffee (e.g. C. coffeanumox C. kahawae) and C. gloeosporioides on various crops; Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicoia (leaf spots) on soybeans, cotton and ornamentals; Cycioconium spp., e. g. C. oieaginumox\ olive trees; Cyiindrocarpon spp.
(e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. iiriodendri, teleomorph: Neonectria iiriodendri. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Roseiiinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseoiorum (damping off) on soybeans; Drechsiera (syn.
Heiminthosporium, 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. Pheiiinus) punctata, F. mediterranea,
Phaeomonieiia chiamydospora (formerly Phaeoacremonium chiamydosporum),
Phaeoacremonium aieophiium and/or Botryosphaeria obtusa, E/sinoe spp. on pome fruits (E. pyri), soft fruits ( E . veneta. anthracnose) and vines ( E . ampeiina anthracnose); Entyioma oryzae { leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets {E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E.
cichoracearum), cabbages, oilseed rape (e. g. E. cruciferarum) Eutypa iata (Eutypa canker or dieback, anamorph: Cytosporina iata, syn. Liberteiia biepharis) on fruit trees, vines and ornamental woods; Exserohiium (syn. Heiminthosporium ) spp. on corn (e. g. E. turcicum) Fusarium (teleomorph: Gibbereiia ) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. cuimorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. soiani{ . sp. glycines now syn. F. virguiiforme ) and F. tucumaniae and F. brasiiiense each causing sudden death syndrome on soybeans, and F. verticiiiioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn;
Gibbereiia s . on cereals (e. g. G. zeae) and rice (e. g. G. fujikuror. Bakanae disease);
Giomereiia cinguiata on vines, pome fruits and other plants and G. gossypiiox\ cotton; Grain- staining complex on rice; Guignardia bidweiiii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Heiminthosporium spp. (syn. Drechsiera, teleomorph: Cochiioboius) on corn, cereals, potatoes and rice; Hemiieia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; isariopsis ciavispora (syn. Ciadosporium vitis) on vines; Macrophomina phaseoiina (syn. phased Ί) (root and stem rot) on soybeans and cotton;
Microdochium (syn. Fusarium) nivaie (pink snow mold) on cereals (e. g. wheat or barley);
Microsphaera diffusa (powdery mildew) on soybeans; Moniiinia spp., e. g. M. iaxa, M. fructicoia and M. fructigena (syn. Moniiia spp:. bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaereiia spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicda (anamorph: Zymoseptoria M/c/formerly Septoria triticr. Septoria blotch) on wheat or M. fijiensis (syn. Pseudocercospora fijiensis. black Sigatoka disease) and M.
musicoia on bananas, M. arachidicoia (syn. M. arachidisox Cercospora arachid is), M. berkeieyi on peanuts, M. pisi on peas and M. brassicioia on brassicas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), oilseed 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; Phiaiophora spp. e. g. on vines (e. g. P. tracheiphiia and P. tetraspora ) and soybeans (e. g. P. gregata. stem rot); Phoma Hngam (syn. Leptosphaeria biglobosa and L macula ns. root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp. on sunflowers, vines (e. g. P. viticola. can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseoiorum) Physoderma 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, oilseed rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P.
haistedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits (e. g. P. ieucotricha on apples) and curcurbits ( P xanthii)·, Poiymyxa spp., e. g. on cereals, such as barley and wheat ( P graminis ) and sugar beets ( P betae) and thereby transmitted viral diseases; Pseudocercosporeiia herpotrichoides { syn. Ocuiimacuia yaiiundae,
O. acuformis. eyespot, teleomorph: Tapesia yaiiundae) on cereals, e. g. wheat or barley;
Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. hum Hi on hop; Pseudopezicuia tracheiphiia (red fire disease or .rotbrenner’, anamorph:
Phiaiophora) 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. recondite (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. a spa rag ion asparagus; Pyrenopeziza spp., e.g. P.
brassicae on oilseed rape; Pyrenophora (anamorph: Drechsiera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricuiaria 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, oilseed rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. uitimum o'c P. aphanidermatum) and P. oiigandrum on mushrooms; Ramuiaria s ., e. g. R. coiio-cygni Ramularia leaf spots, Physiological leaf spots) on barley, R. areoia (teleomorph: Mycosphaereiia areoia) on cotton and R. beticoia on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. soiani(roo\ and stem rot) on soybeans, R. soiani (sheath blight) on rice or R. cereaiis (Rhizoctonia spring blight) on wheat or barley;
Rhizopus stoionifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secaiis and R. commune (scald) on barley, rye and triticale; Sarociadium oryzae and S. attenuatum (sheath rot) on rice; Scierotinia spp. (stem rot or white mold) on vegetables (S. minorand S. scierotiorum) and field crops, such as oilseed rape, sunflowers (e. g. S. scierotiorum) and soybeans, S. roifsii{ syn. Atheiia roifsii) on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici{ syn. Zymoseptoria tritici, Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinuia (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tucker!) on vines; Setosphaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Heiminthosporium turcicum) and turf; Sphaceiotheca spp. (smut) on corn, (e. g. S. reiiiana, syn. Ustiiago reiiiana. head smut), sorghum und sugar cane;
Sphaerotheca fuiiginea (syn. Podosphaera xanthii. 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: Leptosphaeria [syn.
Phaeosphaeria] nodorum, syn. Septoria nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina ., e. g. T. deformans (leaf curl disease) on peaches and T. pruni{ \um pocket) on plums; Thielaviopsis s . (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn . Chalara e/egans), TMetia 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; Trichoderma harzianum on mushrooms, Typhu/a incarnate ( rey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta { stem smut) on rye; Uromyces ^ . (rust) on vegetables, such as beans (e. g. U. appendicuiatus, syn. U.
phased!), sugar beets (e. g. U. betae or U. beticoia) and on pulses (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae ), Ustiiago spp. (loose smut) on cereals (e. g. U. nuda and U.
avaenae), corn (e. g. U. maydis corn smut) and sugar cane; Venturis s . (scab) on apples (e. g. V. inaequaiis) and pears; and Verticiiiium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. iongisporum on oilseed rape, V. dahiiae on strawberries, oilseed rape, potatoes and tomatoes, and V. fungicoia on
mushrooms; Zymoseptoria tritici on cereals.
In a preferred embodiment the compounds I, their mixtures with other active compounds as defined herein and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases: Puccinia spp. (rusts) on various plants, for example, but not limited to P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondite (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. sorghi (common rust) on maize, P. poiysora (southern rust) on maize; P.
cor on at a e.g. on oats, P. sorghi und P. poiysora on corn; Puccinia spp. on other crops, e.g. P. heiiathi on sunflower, P. arachidis on peanuts; Uromyces spp. on pulses and other crops crops, e.g. Uromyces viciae-fabae, Uromyces vigniae, Uromyces pisi, U. ciceris-arietini, U. betae syn U. beticoia; an Phakopsoraceae spp. on various plants, in particular Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans.
Additionally, to date, no cross-resistance has been observed between the compounds I and the current fungicidal solutions used to control phytopathogenic fungi including but not limited to Zymoseptoria tritici, Phakopsora pachyrhizi, Botrytis cinerea, Biumeria graminis, Pyrenophora tritici-repentis, Pyrenophora teres, A item aria spp., Piasmopara viticoia, preferably selected from Zymospeptoria tritici and Phakopsora pachyrhizi.
Fungicide-resistant strains of the above-mentioned phytopathgenic fungi have been reported, with strains resistant to one or more fungicides from various fungicidal mode of action classes being observed including but not limited to beta-tubulin assembly inhibitors, sterol
demethylation-inhibitors (DMI), quinone-outside-inhibitors (Qol) and succinate dehydrogenase inhibitors (SDHI). Thus, compounds I are useful to control phytopathogenic fungi comprising at least one of the following mutations: E198A/G/K or F200Y in the beta-tubulin gene conferring resistance to beta-tubulin assembly inhibitors (Phytopathol (2008) 98: 397-404), I365N/S, V368F, Q369H/P, N373S, T447S in the histidine kinase gene Os1 conferring resistance to MAP / histidin kinase inhibitors (dicarboximides; ibida); G143A, G137R or F129L in the mitochondrial cytochrome B Gene (Phytopathol (2003) 93: 891-900; Pest Manag Sci (2016) 72: 121 1-1215) resulting in resistance to Qol; V136A, Y137F (homologous to Y144F/H e.g. in
Parastagonospora nodorum or Y136F e.g. in Erysiphe necator), K147Q, A379G, 1381V, G461S or S509T in the Cyp51 gene resulting in resistance to DMI (Phytopathol (2016) 106: 1278- 1284); P225T/L/F, N225I/T, R265P, T268I/A, H272R/Y/L, H277Y or N230I in the succinate dehydrogenase iron-sulfur subunit gene SdhB, K49E, R64K, N75S, G79R, T79N/I, W80S, P80H/L, N86S/A, G91 R, H134R, S135R, H146R/LK, R151S/T/M, H152R, H153R, I161 S, V166M, T168R and G171 D in the subunit C gene SdhC, and I50F, D124E, M114V, H134R, D145G in the subunit D gene SdhD conferring resistance to SDHI
Figure imgf000049_0001
; Pest Manag Sci (2014) 70: 378-388; Environ Microbiol (2014) 16: 2253-66; Pest Manag Sci (2018) 74: 672-681 ; https://www.frac.info/working-group/sdhi-fungicides), and I86F in the subunit C gene SdhC {Journal of Plant Diseases and Protection 125, 21-26).
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 s p p . , Aureobasidium pullulans, Sderophoma spp., Chaetomium spp., Humico/a spp., Petrie I la spp., Trichurus spp. Basidiomycetes such as Coniophora spp., Corioius spp., Gioeophyiium spp., Lentinus spp., P/eurotus spp., Poria spp., Serpuia spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., PeniciHium spp., Trichoderma spp., Alternaria spp., PaecHomyces spp. and Zygomycetes such as Mucorspp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida s . 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 processed 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 application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting. The invention also relates to 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
Grubemann, 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 esters, gamma-butyrolactone; fatty acids; phosphonates;
amines; amides, e. g. N-methyl pyrrolidone, 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 colloid, 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 sulfonates, 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 alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinyl pyrrolidone, 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 themselves, 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
hexacyanoferrate) 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 hydrocarbon) 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, fluidized 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 arylphenol 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 microcapsules. 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 isocyanate 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.
hexamethylenediamine) 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%, more preferably between 1 and 70%, and in particular between 10 and 60%, 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“pesticide” 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 e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant. 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.
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 optionally 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: azoxystrobin (A.1.1 ), coumethoxystrobin (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), kresoxim-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), trifloxy- strobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)- 2-methoxyimino-/V-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/chloro- dincarb (A.1.20), famoxadone (A.1.21 ), fenamidone (A.1.21 a), methyl-/V-[2-[(1 ,4-dimethyl- 5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-/V-methoxy-carbamate (A.1.22), metyltetrapole (A.1.25), (2(2£)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-/V,3-dirriethyl- pent-3-enamide (A.1.34), (^2£)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-A/,3- dimethyl-pent-3-enamide (A.1.35), pyriminostrobin (A.1.36), bifujunzhi (A.1.37), 2-(ortho- ((2,5-dimethylphenyl-oxymethylen)phenyl)-3-methoxy-acrylic acid methylester (A.1.38);
- inhibitors of complex III at Q, site: cyazofamid (A.2.1), amisulbrom (A.2.2),
[(6<S,7/?,8/t)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dl· oxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4), florylpicoxamid (A.2.5);
- inhibitors of complex II: 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.3.15), penthiopyrad (A.3.16), pydiflumetofen (A.3.17), pyraziflumid (A.3.18), sedaxane (A.3.19), tecloftalam (A.3.20), thifluzamide (A.3.21), inpyrfluxam (A.3.22), pyrapropoyne (A.3.23), fluindapyr (A.3.28), N-[2-[2-chloro-4- (trifluoro^methy phenoxylphenyll-S-idifluoromethy^-S-fluoro-l-methyl-pyrazole^- carboxamide (A.3.29), methyl (£)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3- methoxy-prop-2-enoate (A.3.30), isoflucypram (A.3.31), 2-(difluoromethyl)-/V-(1 ,1 ,3-trimethyl- indan-4-yl)pyridine-3-carboxamide (A.3.32), 2-(difluoromethyl)-/V-[(3/\ -1 ,1 ,3-trimethylindan- 4-yl]pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-/V-(3-ethyl-1 ,1-dimethyl-indan-4-yl)- pyridine-3-carboxamide (A.3.34), 2-(difluoromethyl)-/V-[(3/\ -3-ethyl-1 ,1-dimethyl-indan-4-yl]- pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-/V-(1 ,1-dimethyl-3-propyl-indan-4-yl)py- ridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-/V-[(3/\ -1 ,1-dimethyl-3-propyl-indan-4-yl]- pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-/V-(3-isobutyl-1 ,1-dimethyl-indan-4-yl)- pyridine-3-carboxamide (A.3.38), 2-(difluoromethyl)-/V-[(3/\ -3-isobutyl-1 ,1-dimethyl-indan- 4-yl]pyridine-3-carboxamide (A.3.39);
- other respiration inhibitors: diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone (A.4.7); organometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1); silthiofam (A.4.12);
B) Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors: triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromu- conazole (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.1.11 ), 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), prothio- conazole (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), 2-(2,4-difluorophenyl)-1 ,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]- 2-pyridyl]propan-2-ol (B.1.31), 2-(2,4-difluorophenyl)-1 ,1-difluoro-3-(tetrazol-1-yl)-
1-[5-[4-(trifluoromethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1.32), 4-[[6-[2-(2,4-difluorophenyl)- 1 ,1-difluoro-2-hydroxy-3-(5-sulfanyl-1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (B.1.33), ipfentrifluconazole (B.1.37), mefentrifluconazole (B.1.38), 2-(chloromethyl)-2- methyl-5-(p-tolylmethyl)-1-(1 ,2,4-triazol-1-ylmethyl)cyclopentanol (B.1.43); imidazoles:
imazalil (B.1.44), pefurazoate (B.1.45), prochloraz (B.1.46), triflumizol (B.1.47); pyrimidines, pyridines, piperazines: fenarimol (B.1.49), pyrifenox (B.1.50), triforine (B.1.51 ), [3-(4-chloro-
2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1.52);
- Deltal 4-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), spiroxamine (B.2.8);
- Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );
- Other Sterol biosynthesis inhibitors: chlorphenomizole (B.4.1 );
C) Nucleic acid synthesis inhibitors
- phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1 ), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);
- other nucleic acid synthesis inhibitors: 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), 5-fluoro- 2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8);
D) Inhibitors of cell division and cytoskeleton
- tubulin inhibitors: benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D1.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), pyridachlometyl (D.1.6), /V-ethyl-2-[(3-ethynyl-8-methyl- 6-quinolyl)oxy]butanamide (D.1.8), /V-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2- methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/V-(2- fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/V-(2-fluoroethyl)-2- methoxy-acetamide (D.1.1 1), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/V-propyl-butanamide (D.1.12), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-/V-propyl-acetamide (D.1.13), 2- [(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-/V-propyl-acetamide (D.1.14),
2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/V-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1.15), 4-(2-bromo-4-fluoro-phenyl)-/V-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine (D.1.16);
- other cell division inhibitors: diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7),
phenamacril (D.2.8);
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors: 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 hydro- chloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6);
F) Signal transduction inhibitors
- MAP / histidine kinase inhibitors: fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5);
- 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), zinc thiazole (G.2.8);
- 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);
- compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1 );
- inhibitors of oxysterol binding protein: oxathiapiprolin (G.5.1 ), fluoxapiprolin (G.5.3), 4-[1-[2- [3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-/V-tetralin-1-yl-pyridine-2- carboxamide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/V- tetralin-1-yl-pyridine-2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(tri- fluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/V-tetralin-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/V-tetralin-1-yl-pyri- dine-2-carboxamide (G.5.7), 4-[1-[2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperi- dyl]-/V-tetralin-1-yl-pyridine-2-carboxamide (G.5.8), 4-[1-[2-[5-(difluoromethyl)-3-(trifluoro- methyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/V-tetralin-1-yl-pyridine-2-carboxamide (G.5.9),
4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/V-tetralin-1-yl-pyridine-2-car- boxamide (G.5.10), (4-[1-[2-[5-cyclopropyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]- /V-tetralin-1-yl-pyridine-2-carboxamide (G.5.11 );
H) Inhibitors with Multi Site Action
- inorganic active substances: Bordeaux mixture (H.1.1 ), copper (H.1.2), copper acetate
(H.1.3), copper hydroxide (H.1.4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1.7);
- 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: 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.3.11 );
- 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 A/,5AL[1 ,4]di- thiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2A/,6A)-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 (I.2.2), carpropamid (1.2.3),
dicyclomet (I.2.4), fenoxanil (1.2.5);
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), calcium phosphonate (J.1.1 1), potassium phosphonate (J.1.12), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-/V-(2,4-dimethoxyphenyl)thiadiazole-
5-carboxamide (J.1.10);
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), diclocymet (K.1.7), diclomezine (K.1.8), difenzoquat (K.1.9), di- fenzoquat-methylsulfate (K.1.10), diphenylamin (K.1.11 ), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), metha- sulfocarb (K.1.18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21 ), oxin- copper (K.1.22), proquinazid (K.1.23), tebufloquin (K.1.24), tecloftalam (K.1.25), triazoxide (K.1.26), /Vi(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-/V-ethyl-/V-methyl formamidine (K.1.27), /Vi(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-/V-eth- yl-/V-methyl formamidine (K.1.28), /Vi[4-[[3-[(4-chlorophenyl)methyl]-1 ,2,4-thiadiazol-5-yl]- oxy]-2,5-dimethyl-phenyl]-/V-ethyl-/V-methyl-formamidine (K.1.29), /V^S-bromo-e-indan^- yloxy-2-methyl-3-pyridyl)-/V-ethyl-/V-methyl-formamidine (K.1.30), /V^S-bromo-e-ld-^S-diflu- orophenyl)ethoxy]-2-methyl-3-pyridyl]-/V-ethyl-/V-methyl-formamidine (K.1.31), /V^S-bromo-
6-(4-isopropylcyclohexoxy)-2-methyl-3-pyridyl]-/V-ethyl-/V-methyl-formamidine (K.1.32), /Vi[5-bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-/V-ethyl-/V-methyl-formamidine (K.1.33), /Vi(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-/V-ethyl-/V-methyl forma- midine (K.1.34), /Vi(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-/V-ethyl- /V-methyl formamidine (K.1.35), 2-(4-chloro-phenyl)-/V-[4-(3,4-dimethoxy-phenyl)-isoxazol- 5-yl]-2-prop-2-ynyloxy-acetamide (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine (pyrisoxazole) (K.1.37), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3 yl]- pyridine (K.1.38), 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 TT-benzoimidazole (K.1.39), ethyl (2)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41), pentyl /V-[6-[[(2)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carba- mate (K.1.42), but-3-ynyl /V-[6-[[(2)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxy- methyl]-2-pyridyl]carbamate (K.1.43), ipflufenoquin (K.1.44), quinofumelin (K.1.47), benziothiazolinone (K.1.48), bromothalonil (K.1.49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.50), 2-[6-(3-fluoro-4-methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51 ), dichlobentiazox (K.1.52), /Vi(2,5-dimethyl-4-phenoxy-phenyl)-/V-ethyl-/V-methyl-formamidine (K.1.53), pyrifenamine (K.1.54), fluopimomide (K.1.55), N'-[5-bromo-2-methyl-6-(1 -methyl-2 propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.56);
M) Growth regulators
abscisic acid (M.1.1 ), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, /V-6-benzyl adenine, paclobutrazol, prohexadione, prohexadione-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl, uniconazole;
N) Herbicides from classes N.1 to N.15
N.1 Lipid biosynthesis inhibitors: alloxydim, alloxydim-sodium, butroxydim, clethodim,
clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop- methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop- butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P- methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim, 4-(4'-chloro-4-cyclo~,propyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-5-hy- droxy-2,2,6,6-tetramethyl-2 /7-pyran-3(6A7)-one (1312337-72-6); 4-(2',4'-dichloro-4-cyclo- propyl[1 ,1 '-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2/7-pyran-3(6A7)-one (1312337-45- 3); 4-(4'-chloro-4-ethyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2ATLpyran- 3(67:)-one (1033757-93-5); 4-(2',4'-dichloro-4-ethyl[1 ,1'-biphenyl]-3-yl)-2,2,6,6-tetramethyl- 2/7-pyran-3,5(4A/,6AT)-dione (1312340-84-3); 5-(acetyloxy)-4-(4'-chloro-4-cyclopropyl-2'- fluoro[1 ,1 '-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2/7-pyran-3-one (1312337-48-6); 5-(acetyloxy)-4-(2',4'-dichloro-4-cyclopropyl- [1 ,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetra- methyl-277-pyran-3-one; 5-(acetyloxy)-4-(4'-chloro-4-ethyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)- 3,6-dihydro-2,2,6,6-tetramethyl-277-pyran-3-one (1312340-82-1); 5-(acetyloxy)-4-(2',4'-di- chloro-4-ethyl[1 ,1 '-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2/7-pyran-3-one (1033760- 55-2); 4-(4'-chloro-4-cyclopropyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl- S-oxo^/T-pyran-S-yl carbonic acid methyl ester (1312337-51-1); 4-(2',4'-dichloro -4-cyclo- propyl- [1 ,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-277-pyran-3-yl carbonic acid methyl ester; 4-(4'-chloro-4-ethyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetra- methyl-S-oxo^A pyran-S-yl carbonic acid methyl ester (1312340-83-2); 4-(2',4'-dichloro- 4-ethyh[1 ,1 '-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2A7Lpyran-3-yl carbonic acid methyl ester (1033760-58-5); benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate, vernolate;
N.2 ALS inhibitors: amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethamet- sulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron- methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfu- ron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, meta- zosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazo- sulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusul- furon, triflusulfuron-methyl, tritosulfuron, imazamethabenz, imazamethabenz-methyl, imaza- mox, imazapic, imazapyr, imazaquin, imazethapyr; cloransulam, cloransulam-methyl, diclo- sulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan, pyroxsulam; bispyri- bac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithio- bac, pyrithiobac-sodium, 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]- benzoic acid-1 -methyhethyl ester (420138-41-6), 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]- phenylj-'methyllaminol-benzoic acid propyl ester (420138-40-5), /V-(4-bromophenyl)- 2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (420138-01-8); flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone, thiencarbazone-methyl; triafamone;
N.3 Photosynthesis inhibitors: amicarbazone; chlorotriazine; ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, pro- pazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn, trietazin; chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, sidu- ron, tebuthiuron, thiadiazuron, desmedipham, karbutilat, phenmedipham, phenmedipham- ethyl, bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, bromacil, lenacil, terbacil, bentazon, bentazon-sodium, pyridate, pyridafol, pentanochlor, propanil; diquat, diquat-dibromide, paraquat, paraquat-dichloride, paraquat-dimetilsulfate, 1- (e-tert-butylpyrimidin^-yl^-hydroxy^-methnoxy-S-methyl^H-pynOl-S-one (1654744-66-7), 1 -(5-tert-butylisoxazol-3-yl)-2-hydroxy-4 methoxy-3-methyl-2H-pyrrol-5-one (1637455-12-9),
1-(5-tert-butylisoxazol-3-yl)-4-chloro-2 hydroxy-3-methyl-2H-pyrrol-5-one (1637453-94-1), 1- (5-tert-butyl-1 -methyl-pyrazol-3-yl)-4 chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one (1654057- 29-0), 1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-3-chloro-2-hydroxy-4-methyl-2H-pyrrol-5-one
(1654747-80-4), 4-hydroxy-1 methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-
2-one; (2023785-78-4), 4 hydroxy-1 ,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2- one (2023785-79-5), 5 ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2- pyridyl]imidazolidin-2-one (1701416-69-4), 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2- pyridyl]imidazolidin-2-one (1708087-22-2), 4 hydroxy-1 ,5-dimethyl-3-[1 -methyl-5- (trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one (2023785-80-8), 1-(5-tert-butylisoxazol-3-yl)-
4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one (1844836-64-1 );
N.4 protoporphyrinogen-IX oxidase inhibitors: acifluorfen, acifluorfen-sodium, azafenidin, ben- carbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlor- methoxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pen- tyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimi- din-3-yl)phenoxy]-2-pyridyloxy]acetate (353292-31-6), /V-ethyl-3-(2,6-dichloro-4-trifluoro- methylphenoxy)-5-methyl-1 //-pyrazole-1 -carboxamide (452098-92-9), /V-tetrahydrofurfuryl- 3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1 //-pyrazole-1 -carboxamide (915396-43- 9), /V-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethyhphenoxy)-5-methyl-1 //-pyrazole-1 -carbox- amide (452099-05-7), /V-tetrahydro-,furfuryl-3-(2-chloro-6-fluoro-4-trifluoro-,methylphenoxy)-
5-methyl-1 //-pyrazole-1 -carboxamide (452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-
3.4-dihydro-2//-benzo[1 ,4]oxazin-6-yl]-1 ,5-dimethyl-6-thioxo-[1 ,3,5]triazinan-2,4-dione (451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2//-benzo[1 ,4]oxazin-6-yl)- 4,5,6,7-tetrahydro-isoindole-1 ,3-dione (1300118-96-0), l-methyl-e-trifluorcnmethyl- 3-(2,2,7-tri-fluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2//-benzo[1 ,4]oxazin-6-yl)-1 //-pyrimidine-
2.4-dione (1304113-05-0), methyl (£)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1 //-methyl- pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-enoate (948893-00-3), 3-[7-chloro-5-fluoro- 2-(trifluoromethyl)-1 //-benzimidazol-4-yl]-1 -methyl-6-(trifluoromethyl)-1 //-pyrimidine-2, 4-di- one (212754-02-4);
N.5 Bleacher herbicides: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone,
norflurazon, picolinafen, 4-(3-trifluoromethyhphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (180608-33-7); benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquintrione, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone; aclonifen, amitrole, flumeturon;
N.6 EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium, glyposate- potassium, glyphosate-trimesium (sulfosate);
N.7 Glutamine synthase inhibitors: bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P, glufosinate-ammonium;
N.8 DHP synthase inhibitors: asulam;
N.9 Mitosis inhibitors: benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pen- dimethalin, prodiamine, trifluralin; amiprophos, amiprophos-methyl, butamiphos; chlorthal, chlorthal-dimethyl, dithiopyr, thiazopyr, propyzamide, tebutam; carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, propham;
N.10 VLCFA inhibitors: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethen- amid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, prop- isochlor, thenylchlor, flufenacet, mefenacet, diphenamid, naproanilide, napropamide, napro- pamide-M, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, isoxazoline compounds of the formulae 11.1 , II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9
Figure imgf000062_0001
N.1 1 Cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam, 1 -cyclohexyl-5-pentafluorphenyloxy-14-[1 ,2,4,6]thiatriazin-3-ylamine (175899-01 - 1 );
N.12 Decoupler herbicides: dinoseb, dinoterb, DNOC and its salts;
N.13 Auxinic herbicides: 2,4-D and its salts and esters, clacyfos, 2,4-DB and its salts and
esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-dimethylammonium, aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopy- ralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, fluroxypyr, fluroxypyr-butometyl, fluroxypyr- meptyl, halauxifen and its salts and esters (943832-60-8); MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, meco- prop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, 4-amino-3-chloro- 6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylic acid, florpyrauxifen- benzyl, florpyrauxifen;
N.14 Auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam, naptalam- sodium;
N.15 Other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate (499223-49-3) and its salts and esters, dalapon, dazomet, difenzoquat, di- fenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flu- renol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydra- zide, mefluidide, metam, methiozolin (403640-27-7), methyl azide, methyl bromide, methyl- dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, tridiphane;
O) Insecticides from classes 0.1 to 0.29
0.1 Acetylcholine esterase (AChE) inhibitors: aldicarb (0.1 .1 ), alanycarb (0.1.2), bendiocarb (0.1.3), benfuracarb (0.1 .4), butocarboxim (0.1.5), butoxycarboxim (0.1.6), carbaryl (0.1.7), carbofuran (0.1.8), carbosulfan (0.1.9), ethiofencarb (0.1 .10), fenobucarb (0.1 .1 1 ), formetanate (0.1 .12), furathiocarb (0.1.13), isoprocarb (0.1.14), methiocarb (0.1.15), methomyl (0.1 .16), metolcarb (0.1.17), oxamyl (0.1 .18), pirimicarb (0.1 .19), propoxur (0.1.20), thiodicarb (0.1.21 ), thiofanox (0.1 .22), trimethacarb (0.1 .23), XMC (0.1.24), xylylcarb (0.1.25), triazamate (0.1.26), acephate (0.1.27), azamethiphos (0.1.28), azinphos-ethyl (0.1 .29), azinphosmethyl (0.1 .30), cadusafos (0.1.31 ), chlorethoxyfos (0.1.32), chlorfenvinphos (0.1 .33), chlormephos (0.1 .34), chlorpyrifos (0.1.35), chlorpyrifos- methyl (0.1 .36), coumaphos (0.1.37), cyanophos (0.1 .38), demeton-S-methyl (0.1 .39), diazinon (0.1 .40), dichlorvos/ DDVP (0.1.41 ), dicrotophos (0.1.42), dimethoate (0.1.43), dimethylvinphos (0.1 .44), disulfoton (0.1.45), EPN (0.1 .46), ethion (0.1 .47), ethoprophos (0.1.48), famphur (0.1 .49), fenamiphos (0.1.50), fenitrothion (0.1.51 ), fenthion (0.1.52), fosthiazate (0.1 .53), heptenophos (0.1 .54), imicyafos (0.1.55), isofenphos (0.1 .56), isopropyl O-(methoxyaminothio-phosphoryl) salicylate (0.1.57), isoxathion (0.1.58), malathion (0.1 .59), mecarbam (0.1.60), methamidophos (0.1 .61 ), methidathion (0.1.62), mevinphos (0.1 .63), monocrotophos (0.1 .64), naled (0.1.65), omethoate (0.1.66), oxydemeton-methyl (0.1 .67), parathion (0.1.68), parathion-methyl (0.1 .69), phenthoate (0.1.70), phorate (0.1.71 ), phosalone (0.1.72), phosmet (0.1.73), phosphamidon (0.1.74), phoxim (0.1.75), pirimiphos- methyl (0.1 .76), profenofos (0.1.77), propetamphos (0.1.78), prothiofos (0.1 .79), pyraclofos (0.1 .80), pyridaphenthion (0.1 .81 ), quinalphos (0.1.82), sulfotep (0.1.83), tebupirimfos (0.1.84), temephos (0.1.85), terbufos (0.1.86),
tetrachlorvinphos (0.1 .87), thiometon (0.1 .88), triazophos (0.1 .89), trichlorfon (0.1.90), vamidothion (0.1 .91 );
0.2 GABA-gated chloride channel antagonists: endosulfan (0.2.1 ), chlordane (0.2.2), ethiprole (0.2.3), fipronil (0.2.4), flufiprole (0.2.5), pyrafluprole (0.2.6), pyriprole (0.2.7);
0.3 Sodium channel modulators: acrinathrin (0.3.1 ), allethrin (0.3.2), d-cis-trans allethrin
(0.3.3), d-trans allethrin (0.3.4), bifenthrin (0.3.5), kappa-bifenthrin (0.3.6), bioallethrin (0.3.7), bioallethrin S-cylclopentenyl (0.3.8), bioresmethrin (0.3.9), cycloprothrin (0.3.10), cyfluthrin (0.3.1 1 ), beta-cyfluthrin (0.3.12), cyhalothrin (0.3.13), lambda-cyhalothrin
(0.3.14), gamma-cyhalothrin (0.3.15), cypermethrin (0.3.16), alpha-cypermethrin (0.3.17), beta-cypermethrin (0.3.18), theta-cypermethrin (0.3.19), zeta-cypermethrin (0.3.20), cyphenothrin (0.3.21 ), deltamethrin (0.3.22), empenthrin (0.3.23), esfenvalerate (0.3.24), etofenprox (0.3.25), fenpropathrin (0.3.26), fenvalerate (0.3.27), flucythrinate (0.3.28), flumethrin (0.3.29), tau-fluvalinate (0.3.30), halfenprox (0.3.31 ), heptafluthrin (0.3.32), imiprothrin (0.3.33), meperfluthrin (0.3.34), metofluthrin (0.3.35), momfluorothrin (0.3.36), epsilon-momfluorothrin (0.3.37), permethrin (0.3.38), phenothrin (0.3.39), prallethrin (0.3.40), profluthrin (0.3.41 ), pyrethrin (pyrethrum) (0.3.42), resmethrin (0.3.43), silafluofen (0.3.44), tefluthrin (0.3.45), kappa-tefluthrin (0.3.46), tetramethylfluthrin (0.3.47), tetramethrin (0.3.48), tralomethrin (0.3.49), transfluthrin (0.3.50), DDT (0.3.51),
methoxychlor (0.3.52);
Nicotinic acetylcholine receptor agonists (nAChR): acetamiprid (0.4.1), clothianidin (0.4.2), cycloxaprid (0.4.3), dinotefuran (0.4.4), imidacloprid (0.4.5), nitenpyram (0.4.6), thiacloprid (0.4.7), thiamethoxam (0.4.8), 4,5-dihydro-/V-nitro-1-(2-oxiranylmethyl)-1 TT-imidazol^-amine (0.4.9), (2£)-1-[(6-chloropyridin-3-yl)methyl]-/V:-nitro-2-pentylidene- hydrazinecarboximidamide (0.4.10), 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5- propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridine (0.4.1 1), nicotine (0.4.12), sulfoxaflor (0.4.13), flupyradifurone (0.4.14), triflumezopyrim (0.4.15), (3/\ -3-(2-chlorothiazol-5-yl)-8- methyl-5-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-olate (0.4.16), (3S)-3-(6- chloro-3-pyridyl)-8-methyl-5-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-olate (0.4.17), (3S)-8-methyl-5-oxo-6-phenyl-3-pyrimidin-5-yl-2,3-dihydrothiazolo[3,2-a]pyrimidin- 8-ium-7-olate (0.4.18), (3/\ -3-(2-chlorothiazol-5-yl)-8-methyl-5-oxo-6-[3- (trifluoromethyl)phenyl]-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-olate (0.4.19), ( 3R)-3-{2 - chlorothiazol-5-yl)-6-(3,5-dichlorophenyl)-8-methyl-5-oxo-2,3-dihydrothiazolo[3,2-a]pyrimidin- 8-ium-7-olate (0.4.20), (3/\ -3-(2-chlorothiazol-5-yl)-8-ethyl-5-oxo-6-phenyl-2,3-di- hydrothiazolo[3,2-a]pyrimidin-8-ium-7-olate (0.4.21);
Nicotinic acetylcholine receptor allosteric activators: spinosad (0.5.1 ), spinetoram (0.5.2); Chloride channel activators: abamectin (0.6.1), emamectin benzoate (0.6.2), ivermectin (0.6.3), lepimectin (0.6.4), milbemectin (0.6.5);
Juvenile hormone mimics: hydroprene (0.7.1 ), kinoprene (0.7.2), methoprene (0.7.3), fenoxycarb (0.7.4), pyriproxyfen (0.7.5);
miscellaneous non-specific (multi-site) inhibitors: methyl bromide (0.8.1 ) and other alkyl halides, chloropicrin (0.8.2), sulfuryl fluoride (0.8.3), borax (0.8.4), tartar emetic (0.8.5); Chordotonal organ TRPV channel modulators: pymetrozine (0.9.1), pyrifluquinazon (0.9.2), flonicamid (0.9.3);
0 Mite growth inhibitors: clofentezine (0.10.1 ), hexythiazox (0.10.2), diflovidazin (0.10.3), etoxazole (0.10.4);
1 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, Bacillus sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp.
Israe/ensis (0.1 1.1), Bacillus sphaericus (0.1 1.2), Bacillus thuringiensis subsp. aizawai (0.1 1.3), Bacillus thuringiensis subsp. kurstaki (0L 1.4), Bacillus thuringiensis subsp.
tenebrionis (0.11.5), the Bt crop proteins: Cry1 Ab (0.1 1.6), Cry1 Ac (0.11.7), Cry1 Fa (0.11.8), Cry2Ab (0.11.9), mCry3A (0.11.10), Cry3Ab (0.11.1 1), Cry3Bb (0.1 1.12), Cry34/35Ab1 (0.11.13);
2 Inhibitors of mitochondrial ATP synthase: diafenthiuron (0.12.1), azocyclotin (0.12.2), cyhexatin (0.12.3), fenbutatin oxide (0.12.4), propargite (0.12.5), tetradifon (0.12.6);
3 Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr (0.13.1 ), DNOC (0.13.2), sulfluramid (0.13.3);
4 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap (0.14.1 ), cartap hydrochloride (0.14.2), thiocyclam (0.14.3), thiosultap sodium (0.14.4);
5 Inhibitors of the chitin biosynthesis type 0: bistrifluron (0.15.1 ), chlorfluazuron (0.15.2), diflubenzuron (0.15.3), flucycloxuron (0.15.4), flufenoxuron (0.15.5), hexaflumuron
(0.15.6), lufenuron (0.15.7), novaluron (0.15.8), noviflumuron (0.15.9), teflubenzuron (0.15.10), triflumuron (0.15.11 );
6 Inhibitors of the chitin biosynthesis type 1 : buprofezin (0.16.1);
7 Moulting disruptors: cyromazine (0.17.1 );
8 Ecdyson receptor agonists: methoxyfenozide (0.18.1 ), tebufenozide (0.18.2),
halofenozide (0.18.3), fufenozide (0.18.4), chromafenozide (0.18.5);
9 Octopamin receptor agonists: amitraz (0.19.1 );
0 Mitochondrial complex III electron transport inhibitors: hydramethylnon (0.20.1), acequinocyl (0.20.2), fluacrypyrim (0.20.3), bifenazate (0.20.4);
1 Mitochondrial complex I electron transport inhibitors: fenazaquin (0.21.1 ), fenpyroximate (0.21.2), pyrimidifen (0.21.3), pyridaben (0.21.4), tebufenpyrad (0.21.5), tolfenpyrad (0.21.6), rotenone (0.21.7);
2 Voltage-dependent sodium channel blockers: indoxacarb (0.22.1 ), metaflumizonev (0.22.2), 2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-/V-[4- (difluoromethoxy)phenyl]-hydrazinecarboxamide (0.22.3), /V-(3-chloro-2-methylphenyl)-2-[(4- chlorophenyl)-[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide (0.22.4);
3 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen (0.23.1 ), spiromesifen (0.23.2), spirotetramat (0.23.3), spiropidion (0.23.4);
4 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide (0.24.1), calcium phosphide (0.24.2), phosphine (0.24.3), zinc phosphide (0.24.4), cyanide (0.24.5);5 Mitochondrial complex II electron transport inhibitors: cyenopyrafen (0.25.1), cyflumetofen (0.25.2);
6 Ryanodine receptor-modulators: flubendiamide (0.26.1), chlorantraniliprole (0.26.2), cyantraniliprole (0.26.3), cyclaniliprole (0.26.4), tetraniliprole (0.26.5), (/7)-3-chloro-/V-{2- methyl-4-[1 ,2,2,2 -tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl}-Ae-(1 -methyl-2 - methylsulfonylethyl)phthalamide (0.26.6), (S)-3-chloro-/V-{2-methyl-4-[1 ,2,2,2-tetrafluoro-1- (trifluoromethyl)ethyl]phenyl}-Ae-(1-methyl-2-methylsulfonylethyl)phthalamide (0.26.7), methyl-2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1 /7-pyrazol-5-yl]carbonyl}- amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate (0.26.8), /V-[4,6-dichloro-2-[(diethyl- lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole- 3-carboxamide (0.26.9), /V-[4-chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6- methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (0.26.10), /V-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro- 2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (0.26.1 1), /V-[4,6-dichloro-2-[(di-2- propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide (0.26.12), /V-[4,6-dibromo-2-[(diethyl-lambda-4- sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide (0.26.13), /V-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3- bromo-1-(3-chloro-2-pyridinyl)-1 /7-pyrazole-5-carboxamide (0.26.14), 3-chloro-1-(3-chloro-2- pyridinyl)-/V-[2,4-dichloro-6-[[(1 -cyano-1 -methylethyl)amino]carbonyl]phenyl]-1 TT-pyrazole- 5-carboxamide (0.26.15), tetrachlorantraniliprole (0.26.16), /V-[4-chloro-2-[[(1 ,1- dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)- 1 TT-pyrazole-S-carboxamide (0.26.17), cyhalodiamide (0.26.18);
7: Chordotonal organ Modulators - undefined target site: flonicamid (0.27.1 );
8. insecticidal active compounds of unknown or uncertain mode of action: afidopyropen (0.28.1), afoxolaner (0.28.2), azadirachtin (0.28.3), amidoflumet (0.28.4), benzoximate (0.28.5), broflanilide (0.28.6), bromopropylate (0.28.7), chinomethionat (0.28.8), cryolite (0.28.9), dicloromezotiaz (0.28.10), dicofol (0.28.1 1), flufenerim (0.28.12), flometoquin (0.28.13), fluensulfone (0.28.14), fluhexafon (0.28.15), fluopyram (0.28.16), fluralaner (0.28.17), metoxadiazone (0.28.18), piperonyl butoxide (0.28.19), pyflubumide (0.28.20), pyridalyl (0.28.21 ), tioxazafen (0.28.22), 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4- dioxa-9-azadispiro[4.2.4.2]-tetradec-11 -en-10-one, 3-(4’-fluoro-2,4-dimethylbiphenyl-3-yl)-4- hydroxy-8-oxa-1 -azaspiro[4.5]dec-3-en-2-one, 1 -[2-fluoro-4-methyl-5-[(2,2,2- trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H- 1 ,2,4-triazole-5-amine (0.28.23), Bacillus firmus 1-1582 (0.28.24), flupyrimin (0.28.25), fluazaindolizine (0.28.26), 4-[5-(3,5-di- chlorophenyl)-5-(trifluoromethyl)-4A7Lisoxazol-3-yl]-2-methyl-/V-(1-oxothietan-3-yl)benzamide (0.28.27), fluxametamide (0.28.28), 5-[3-[2,6-dichloro-4-(3,3- dichloroallyloxy)phenoxy]propoxy]-1 TT-pyrazole (0.28.1), 4-cyano-/V-[2-cyano-5-[[2,6- dibromo-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2- methyl-benzamide (0.28.29), 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-/V-[2,6-dichloro- 4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide (0.28.30), /V-[5-[[2-chloro-6-cyano-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carba- moyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide (0.28.31 ), /V-[5-[[2-bromo-6-chloro-
4-[2, 2, 2-trifluoro-1 -hydroxy-1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cy- ano-2-methyl-benzamide (0.28.32), /V-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1 - (trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide (0.28.33), 4-cyano-/V-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)- propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide (0.28.34), 4-cyano-/V-[2-cyano-
5-[[2,6-dichloro-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2- methyl-benzamide (0.28.35), /V-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide (0.28.36); 2-(1 ,3-dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine (0.28.37), 2-[6-[2-(5- fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine (0.28.38), 2-[6-[2-(3-pyridinyl)-5-thi- azolyl]-2-pyridinyl]-pyrimidine (0.28.39), /V-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyri- dine-2-carboxamide (0.28.40), /V-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2- carboxamide (0.28.41), 1-[(6-chloro-3-pyridinyl)methyl]-1 ,2,3,5,6,7-hexahydro-5-methoxy-7- methyl-8-nitro-imidazo[1 ,2-a]pyridine (0.28.42), 1-[(6-chloropyridin-3-yl)methyl]-7-methyl- 8-nitro-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol (0.28.43), 1-isopropyl-/V,5-dimethyl- /V-pyridazin-4-yl-pyrazole-4-carboxamide (0.28.44), 1-(1 ,2-dimethylpropyl)-/V-ethyl-5-methyl- /V-pyridazin-4-yl-pyrazole-4-carboxamide (0.28.45), /V,5-dimethyl-/V-pyridazin-4-yl-1 -(2,2,2- trifluoro-1 -methyl-ethyl)pyrazole-4-carboxamide (0.28.46), 1 -[1 -(1 -cyanocyclopropyl)ethyl]- /V-ethyl-5-methyl-/V-pyridazin-4-yl-pyrazole-4-carboxamide (0.28.47), /V-ethyl-1 -(2-fluoro-1 - methyl-propyl)-5-meth-yl-/V-pyridazin-4-yl-pyrazole-4-carboxamide (0.28.48), 1-(1 ,2- dimethylpropyl)-/V,5-dimethyl-/V-pyridazin-4-yl-pyrazole-4-carboxamide (0.28.49),
1 -[1 -(1 -cyanocyclopropyl)ethyl]-/V,5-dimethyl-/V-pyridazin-4-yl-pyrazole-4-carboxamide (0.28.50), /V-methyl-1 -(2-fluoro-1 -methyl-propyl]-5-methyl-/V-pyridazin-4-yl-pyrazole-4- carboxamide (0.28.51), 1-(4,4-difluorocyclohexyl)-/V-ethyl-5-methyl-/V-pyridazin-4-yl-pyr- azole-4-carboxamide (0.28.52), 1-(4,4-difluorocyclohexyl)-/V,5-dimethyl-/V-pyridazin-4-yl- pyrazole-4-carboxamide (0.28.53), LA( 1 -methylethyl)-2-(3-pyridinyl)-2 TT-indazole-
4-carboxamide (0.28.54), /V-cyclopropyl-2-(3-pyridinyl)-2A7Lindazole-4-carboxamide
(0.28.55), /V-cyclohexyl-2-(3-pyridinyl)-2/7-indazole-4-carboxamide (0.28.56), 2-(3-pyridinyl)- /V-(2,2,2-trifluoroethyl)-2 TLindazole-4-carboxamide (0.28.57), 2-(3-pyridinyl)-/V-[(tetrahydro- 2-furanyl)methyl]-2/TLindazole-5-carboxamide (0.28.58), methyl 2-[[2-(3-pyridinyl)-2/TL indazol-5-yl]carbonyl]hydrazinecarboxylate (0.28.59), /V-[(2,2-difluorocyclopropyl)methyl]-2- (3-pyridinyl)-2/7-indazole-5-carboxamide (0.28.60), /V-(2,2-difluoropropyl)-2-(3-pyridinyl)-2/7- indazole-5-carboxamide (0.28.61), 2-(3-pyridinyl )-/V-(2-pyrimidinylmethyl )-2/7-indazole-5- carboxamide (0.28.62), /V-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2/7Lindazole-5-car- boxamide (0.28.63), tyclopyrazoflor (0.28.64), sarolaner (0.28.65), lotilaner (0.28.66), /V-[4-chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1 ,1 ,2,2,2-penta- fluoroethyl)-4-(trifluoromethyl)-1 /7-pyrazole-5-carboxamide (0.28.67), M.UN.22a 2-(3- ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (0.28.68), 2-[3- ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (0.28.69), iscocycloseram(O.28.70), /V-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-
5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide (0.28.72), LA[ 4- chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4- (trifluoromethyl)pyrazole-3-carboxamide (0.28.73), acynonapyr (0.28.74), benzpyrimoxan (0.28.75), chloro-/V-(1-cyanocyclopropyl)-5-[1-[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)- 4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide (0.28.76), oxazosulfyl (0.28.77), [(25,3/?,4/?,55,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl]-/V-[4-[1-[4-(tri- fluoromethoxy)phenyl]-1 ,2,4-triazol-3-yl]phenyl]carbamate (0.28.78),
[(25,3/?,4/?,55,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl] N-[4-[1-[4-(trifluoro- methoxy)phenyl]-1 ,2,4-triazol-3-yl]phenyl]carbamate (0.28.79), [(2S,3/?,4/?,5S,6S)-3,5- dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl]-/V-[4-[1-[4-(1 ,1 ,2,2,2- pentafluoroethoxy)phenyl]-1 ,2,4-triazol-3-yl]phenyl]carbamate (0.28.80), [(25, 3/?, 4/?, 55, 6S)- 3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl]-/V-[4-[1-[4-(1 ,1 ,2,2,2-penta- fluoroethoxy)phenyl]-1 ,2,4-triazol-3-yl]phenyl]carbamate (0.28.81), (22)-3-(2- isopropylphenyl)-2-[(£)-[4-[1-[4-(1 ,1 ,2,2,2-pentafluoroethoxy)phenyl]-1 ,2,4-triazol-3- yl]phenyl]methylenehydrazono]thiazolidin-4-one (0.28.82), 2-(6-chloro-3-ethylsulfonyl- imidazo[1 ,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (0.28.83), 2-(6- bromo-3-ethylsulfonyl-imidazo[1 ,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridine (0.28.84), 2-(3-ethylsulfonyl-6-iodo-imidazo[1 ,2-a]pyridin-2-yl)-3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridine (0.28.85), 2-[3-ethylsulfonyl-6- (trifluoromethyl)imidazo[1 ,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (0.28.86), 2-(7-chloro-3-ethylsulfonyl-imidazo[1 ,2-a]pyridin-2-yl)-3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridine (0.28.87), 2-(3-ethylsulfonyl-7-iodo-imidazo[1 ,2-a]py- ridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (0.28.88), 3-ethylsulfonyl-6- iodo-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]imidazo[1 ,2-a]pyridine-8- carbonitrile (0.28.89), 2-[3-ethylsulfonyl-8-fluoro-6-(trifluoromethyl)imidazo[1 ,2-a]pyridin-2- yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (0.28.90), 2-[3-ethylsulfonyl-7- (trifluoromethyl)imidazo[1 ,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethylsulfinyl)imidazo- [4,5-b]pyridine (0.28.91), 2-[3-ethylsulfonyl-7-(trifluoromethyl)imidazo[1 ,2-a]pyridin-2-yl]-3- methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (0.28.92), 2-(6-bromo-3-ethylsulfonyl- imidazo[1 ,2-a]pyridin-2-yl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine (0.28.93).
The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: https://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC 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 03/11853; 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 10/139271 , WO 1 1/028657, WO 12/168188, WO 07/006670, WO 11/77514; WO 13/047749, 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 13/24010, WO 13/047441 , WO 13/162072, WO 13/092224, WO 1 1/135833, CN 1907024, CN 1456054,
CN 103387541 , CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177,
WO 13/116251 , WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/16551 1 , WO 11/081174, WO 13/47441 , JP2015089883, JP2015120675,
WO2015119246, WO201 1135827, WO2012084812).
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 than 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 applied 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 compounds 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 day.
In 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 :10,000 to 10,000:1 , often 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 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.
Accordingly, the present invention furthermore relates to mixtures comprising one compound of the formula I (component 1 , a group represented by the expression“(I)”) and one pesticide II (component 2), wherein pesticide II is an active ingredient selected from the groups A) to O) defined above.
Further embodiments B-1 to B-705 listed in Table B below relate to mixtures comprising as active components one of the in the present specification individualized compounds of the formula I, which is selected from the group of compounds I.A.A-1 to I.A.A-1364, I.B.A-1 to I.B.A- 1364, I.C.A-1 to I.C.A-1364, I.D.A-1 to I.D.A-1364, I.E.A-1 to I.E.A-1364, I.F.A-1 to I.F.A-1364, I.G.A-1 to I.G.A-1364 and I.H.A-1 to I.H.A-1364 as defined in tables 1 to 8 (component 1 , a group represented by the expression“(I)”), and one pesticide II selected from the groups A) to O) as defined herein (component 2, for example, (A.1.1 ) or azoxystrobin, in embodiment B-1 ). Further embodiments B-1 to B-705 listed in Table B below relate to the mixtures comprising as active components one of the in the present specification individualized compounds of the formula I, which is selected from the group of compounds Ex-1 to Ex-4 as defined in Table I below (component 1 , a group represented by the expression“(I)”) and one pesticide II selected from the groups A) to O) as defined herein (component 2, for example, (A.1.1 ) or azoxystrobin, in embodiment B-1 ).
Preferably, the compositions described in Table B comprise the active components in synergistically effective amounts.
Table B:
B-1 : (I) + (A.1 .1 ), B-2: (I) + (A.1.2), B-3: (I) + (A.1 .3), B-4: (I) + (A.1.4), B-5: (I) + (A.1.5), B-6: (I)
+ (A.1 .6), B-7: (I) + (A.1.7), B-8: (I) + (A.1 .8), B-9: (I) + (A.1 .9), B-10: (I) + (A.1 .10), B-1 1 : (I) + (A.1.1 1), B-12: (I) + (A.1 .12), B-13: (I) + (A.1.13), B-14: (I) + (A.1.14), B-15: (I) + (A.1 .15), B-16: (I) + (A.1.16), B-17: (I) + (A.1.17), B-18: (I) + (A.1.18), B-19: (I) + (A.1 .19), B-20: (I) + (A.1.20), B-21 : (I) + (A.1.21 ), B-22: (I) + (A.1.21 a), B-23: (I) + (A.1.22), B-24: (I) + (A.1.25), B-25: (I) + (A.1.34), B-26: (I) + (A.1 .35), B-27: (I) + (A.1 .36), B-28: (I) + (A.1.37), B-29: (I) + (A.1 .38), B-30: (I) + (A.2.1 ), B-31 : (I) + (A.2.2), B-32: (I) + (A.2.3), B-33: (I) + (A.2.4), B-34: (I) + (A.2.5), B-35: (I) + (A.3.1 ), B-36: (I) + (A.3.2), B-37: (I) + (A.3.3), B-38: (I) + (A.3.4), B-39: (I) + (A.3.5), B-40: (I) + (A.3.6), B-41 : (I) + (A.3.7), B-42: (I) + (A.3.8), B-43: (I) + (A.3.9), B-44: (I) + (A.3.10), B-45: (I) + (A.3.1 1 ), B-46: (I) + (A.3.12), B-47: (I) + (A.3.13), B-48: (I) + (A.3.14), B-49: (I) + (A.3.15), B-50: (I) + (A.3.16), B-51 : (I) + (A.3.17), B-52: (I) + (A.3.18), B-53: (I) + (A.3.19), B-54: (I) + (A.3.20), B-55: (I) + (A.3.21 ), B-56: (I) + (A.3.22), B-57: (I) + (A.3.23), B-58: (I) + (A.3.24), B-59: (I) + (A.3.25), B-60: (I) + (A.3.26), B-61 : (I) + (A.3.27), B-62: (I) + (A.3.28), B-63: (I) + (A.3.30), B-64: (I) + (A.3.31 ), B-65: (I) + (A.3.32), B-66: (I) + (A.3.33), B-67: (I) + (A.3.34), B-68: (I) + (A.3.35), B-69: (I) + (A.3.36), B-70: (I) + (A.3.37), B-71 : (I) + (A.3.38), B-72: (I) + (A.3.39), B-73: (I) + (A.4.1 ), B-74: (I) + (A.4.2), B-75: (I) + (A.4.3), B-76: (I) + (A.4.4), B-77: (I) + (A.4.5), B-78: (I) + (A.4.6), B-79: (I) + (A.4.7), B-80: (I) + (A.4.8), B-81 : (I) + (A.4.9), B-82: (I) + (A.4.10), B-83: (I) + (A.4.1 1 ), B-84: (I) + (A.4.12), B-85: (I) + (B.1.1 ), B-86: (I) + (B.1.2), B-87: (I) + (B.1.3), B-88: (I) + (B.1 .4), B-89: (I) + (B.1.5), B-90: (I) + (B.1.6), B-91 : (I) + (B.1.7), B-92: (I) + (B.1.8), B-93: (I) + (B.1 .9), B-94: (I) + (B.1.10), B-95: (I) + (B.1 .1 1 ), B-96: (I) + (B.1 .12), B-97: (I) + (B.1 .13), B-98:
(I) + (B.1.14), B-99: (I) + (B.1.15), B-100: (I) + (B.1 .16), B-101 : (I) + (B.1 .17), B-102: (I) +
(B.1.18), B-103: (I) + (B.1 .19), B-104: (I) + (B.1 .20), B-105: (I) + (B.1 .21 ), B-106: (I) + (B.1.22), B-107: (I) + (B.1 .23), B-108: (I) + (B.1 .24), B-109: (I) + (B.1 .25), B-1 10: (I) + (B.1 .26), B-1 1 1 : (I)
+ (B.1 .27), B-1 12: (I) + (B.1 .28), B-1 13: (I) + (B.1 .29), B-1 14: (I) + (B.1 .30), B-1 15: (I) + (B.1.31 ), B-1 16: (I) + (B.1 .32), B-1 17: (I) + (B.1 .37), B-1 18: (I) + (B.1.38), B-1 19: (I) + (B.1 .39), B-120: (I)
+ (B.1 .40), B-121 : (I) + (B.1 .41 ), B-122: (I) + (B.1 .42), B-123: (I) + (B.1 .43), B-124: (I) + (B.1.44), B-125: (I) + (B.1 .45), B-126: (I) + (B.1 .46), B-127: (I) + (B.1 .47), B-128: (I) + (B.1 .48), B-129: (I)
+ (B.1 .49), B-130: (I) + (B.1 .50), B-131 : (I) + (B.1 .51 ), B-132: (I) + (B.1 .52), B-133: (I) + (B.2.1 ), B-134: (I) + (B.2.2), B-135: (I) + (B.2.3), B-136: (I) + (B.2.4), B-137: (I) + (B.2.5), B-138: (I) + (B.2.6), B-139: (I) + (B.2.7), B-140: (I) + (B.2.8), B-141 : (I) + (B.3.1 ), B-142: (I) + (B.4.1 ), B-143: (I) + (C.1 .1 ), B-144: (I) + (C.1.2), B-145: (I) + (C.1.3), B-146: (I) + (C.1.4), B-147: (I) + (C.1.5), B- 148: (I) + (C.1.6), B-149: (I) + (C.1.7), B-150: (I) + (C.2.1 ), B-151 : (I) + (C.2.2), B-152: (I) + (C.2.3), B-153: (I) + (C.2.4), B-154: (I) + (C.2.5), B-155: (I) + (C.2.6), B-156: (I) + (C.2.7), B-157: (I) + (C.2.8), B-158: (I) + (D.1.1 ), B-159: (I) + (D.1.2), B-160: (I) + (D.1.3), B-161 : (I) + (D.1.4), B- 162: (I) + (D.1.5), B-163: (I) + (D.1.6), B-164: (I) + (D.1 .7), B-165: (I) + (D.1.8), B-166: (I) + (D.1 .9), B-167: (I) + (D.1 .10), B-168: (I) + (D.1.1 1), B-169: (I) + (D.1.12), B-170: (I) + (D.1.13), B- 171: (I) + (D.1.14), B-172: (I) + (D.1.15), B-173: (I) + (D.1.16), B-174: (I) + (D.2.1), B-175: (I) + (D.2.2), B-176: (I) + (D.2.3), B-177: (I) + (D.2.4), B-178: (I) + (D.2.5), B-179: (I) + (D.2.6), B-180: (I) + (D.2.7), B-181 : (I) + (E.1.1), B-182: (I) + (E.1.2), B-183: (I) + (E.1.3), B-184: (I) + (E.2.1), B- 185: (I) + (E.2.2), B-186: (I) + (E.2.3), B-187: (I) + (E.2.4), B-188: (I) + (E.2.5), B-189: (I) + (E.2.6), B-190: (I) + (F.1.1), B-191 : (I) + (F.1.2), B-192: (I) + (F.1.3), B-193: (I) + (F.1.4), B-194: (I) + (F.1.5), B-195: (I) + (F.2.1), B-196: (I) + (G.1.1), B-197: (I) + (G.1.2), B-198: (I) + (G.1.3), B- 199: (I) + (G.1.4), B-200: (I) + (G.2.1), B-201 : (I) + (G.2.2), B-202: (I) + (G.2.3), B-203: (I) + (G.2.4), B-204: (I) + (G.2.5), B-205: (I) + (G.2.6), B-206: (I) + (G.2.7), B-207: (I) + (G.3.1), B-208: (I) + (G.3.2), B-209: (I) + (G.3.3), B-210: (I) + (G.3.4), B-211: (I) + (G.3.5), B-212: (I) + (G.3.6), B-213: (I) + (G.3.7), B-214: (I) + (G.4.1), B-215: (I) + (G.5.1), B-216: (I) + (G.5.2), B-217: (I) + (G.5.3), B-218: (I) + (G.5.4), B-219: (I) + (G.5.5), B-220: (I) + (G.5.6), B-221 : (I) + (G.5.7), B-222: (I) + (G.5.8), B-223: (I) + (G.5.9), B-224: (I) + (G.5.10), B-225: (I) + (G.5.11), B-226: (I) + (H.1.1), B-227: (I) + (H.1.2), B-228: (I) + (H.1.3), B-229: (I) + (H.1.4), B-230: (I) + (H.1.5), B-231 : (I) + (H.1.6), B-232: (I) + (H.1.7), B-233: (I) + (H.2.1), B-234: (I) + (H.2.2), B-235: (I) + (H.2.3), B-236: (I) + (H.2.4), B-237: (I) + (H.2.5), B-238: (I) + (H.2.6), B-239: (I) + (H.2.7), B-240: (I) + (H.2.8), B- 241: (I) + (H.2.9), B-242: (I) + (H.3.1), B-243: (I) + (H.3.2), B-244: (I) + (H.3.3), B-245: (I) + (H.3.4), B-246: (I) + (H.3.5), B-247: (I) + (H.3.6), B-248: (I) + (H.3.7), B-249: (I) + (H.3.8), B-250: (I) + (H.3.9), B-251 : (I) + (H.3.10), B-252: (I) + (H.3.11), B-253: (I) + (H.4.1), B-254: (I) + (H.4.2), B-255: (I) + (H.4.3), B-256: (I) + (H.4.4), B-257: (I) + (H.4.5), B-258: (I) + (H.4.6), B-259: (I) + (H.4.7), B-260: (I) + (H.4.8), B-261 : (I) + (H.4.9), B-262: (I) + (H.4.10), B-263: (I) + (1.1.1), B-264: (I) + (1.1.2), B-265: (I) + (1.2.1), B-266: (I) + (I.2.2), B-267: (I) + (I.2.3), B-268: (I) + (I.2.4), B-269: (I) + (I.2.5), B-270: (I) + (J.1.1), B-271: (I) + (J.1.2), B-272: (I) + (J.1.3), B-273: (I) + (J.1.4), B- 274: (I) + (J.1.5), B-275: (I) + (J.1.6), B-276: (I) + (J.1.7), B-277: (I) + (J.1.8), B-278: (I) + (J.1.9), B-279: (I) + (J.1.10), B-280: (I) + (K.1.1), B-281: (I) + (K.1.2), B-282: (I) + (K.1.3), B-283: (I) + (K.1.4), B-284: (I) + (K.1.5), B-285: (I) + (K.1.6), B-286: (I) + (K.1.7), B-287: (I) + (K.1.8), B-288: (I) + (K.1.9), B-289: (I) + (K.1.10), B-290: (I) + (K.1.11), B-291: (I) + (K.1.12), B-292: (I) +
(K.1.13), B-293: (I) + (K.1.14), B-294: (I) + (K.1.15), B-295: (I) + (K.1.16), B-296: (I) + (K.1.17), B-297: (I) + (K.1.18), B-298: (I) + (K.1.19), B-299: (I) + (K.1.20), B-300: (I) + (K.1.21), B-301: (I)
+ (K.1.22), B-302: (I) + (K.1.23), B-303: (I) + (K.1.24), B-304: (I) + (K.1.25), B-305: (I) + (K.1.26), B-306: (I) + (K.1.27), B-307: (I) + (K.1.28), B-308: (I) + (K.1.29), B-309: (I) + (K.1.30), B-310: (I)
+ (K.1.31), B-311: (I) + (K.1.32), B-312: (I) + (K.1.33), B-313: (I) + (K.1.34), B-314: (I) + (K.1.35), B-315: (I) + (K.1.36), B-316: (I) + (K.1.37), B-317: (I) + (K.1.38), B-318: (I) + (K.1.39), B-319: (I)
+ (K.1.40), B-320: (I) + (K.1.41), B-321 : (I) + (K.1.42), B-322: (I) + (K.1.43), B-323: (I) + (K.1.44), B-324: (I) + (K.1.45), B-325: (I) + (K.1.46), B-326: (I) + (K.1.47), B-327: (I) + (K.1.48), B-328: (I)
+ (K.1.49), B-329: (I) + (K.1.50), B-330: (I) + (K.1.51), B-331 : (I) + (K.1.52), B-332: (I) + (K.1.53), B-333: (I) + (K.1.54), B-334: (I) + (0.1.1), B-335: (I) + (0.1.2), B-336: (I) + (0.1.3), B-337: (I) + (0.1.4), B-338: (I) + (0.1.5), B-339: (I) + (0.1.6), B-340: (I) + (0.1.7), B-341 : (I) + (0.1.8), B-342: (I) + (0.1.9), B-343: (I) + (0.1.10), B-344: (I) + (0.1.11), B-345: (I) + (0.1.12), B-346: (I) + (0.1.13), B-347: (I) + (0.1.14), B-348: (I) + (0.1.15), B-349: (I) + (0.1.16), B-350: (I) + (0.1.17), B-351 : (I) + (0.1.18), B-352: (I) + (0.1.19), B-353: (I) + (0.1.20), B-354: (I) + (0.1.21), B-355: (I) + (0.1.22), B-356: (I) + (0.1.23), B-357: (I) + (0.1.24), B-358: (I) + (0.1.25), B-359: (I) +
(0.1.26), B-360: (I) + (0.1.27), B-361 : (I) + (0.1.28), B-362: (I) + (0.1.29), B-363: (I) + (0.1.30), B-364: (I) + (0.1.31), B-365: (I) + (0.1.32), B-366: (I) + (0.1.33), B-367: (I) + (0.1.34), B-368: (I) + (0.1.35), B-369: (I) + (0.1.36), B-370: (I) + (0.1.37), B-371 : (I) + (0.1.38), B-372: (I) + (0.1.39), B-373: (I) + (0.1.40), B-374: (I) + (0.1.41), B-375: (I) + (0.1.42), B-376: (I) + (0.1.43), B-377: (I) + (0.1.44), B-378: (I) + (0.1.45), B-379: (I) + (0.1.46), B-380: (I) + (0.1.47), B-381: (I) + (0.1.48), B-382: (I) + (0.1.49), B-383: (I) + (0.1.50), B-384: (I) + (0.1.51), B-385: (I) +
(0.1.52), B-386: (I) + (0.1.53), B-387: (I) + (0.1.54), B-388: (I) + (0.1.55), B-389: (I) + (0.1.56), B-390: (I) + (0.1.57), B-391 : (I) + (0.1.58), B-392: (I) + (0.1.59), B-393: (I) + (0.1.60), B-394: (I) + (0.1.61), B-395: (I) + (0.1.62), B-396: (I) + (0.1.63), B-397: (I) + (0.1.64), B-398: (I) +
(0.1.65), B-399: (I) + (0.1.66), B-400: (I) + (0.1.67), B-401 : (I) + (0.1.68), B-402: (I) + (0.1.69), B-403: (I) + (0.1.70), B-404: (I) + (0.1.71), B-405: (I) + (0.1.72), B-406: (I) + (0.1.73), B-407: (I) + (0.1.74), B-408: (I) + (0.1.75), B-409: (I) + (0.1.76), B-410: (I) + (0.1.77), B-411: (I) +
(0.1.78), B-412: (I) + (0.1.79), B-413: (I) + (0.1.80), B-414: (I) + (0.1.81), B-415: (I) + (0.1.82), B-416: (I) + (0.1.83), B-417: (I) + (0.1.84), B-418: (I) + (0.1.85), B-419: (I) + (0.1.86), B-420: (I) + (0.1.87), B-421 : (I) + (0.1.88), B-422: (I) + (0.1.89), B-423: (I) + (0.1.90), B-424: (I) +
(0.1.91), B-425: (I) + (0.2.1), B-426: (I) + (0.2.2), B-427: (I) + (0.2.3), B-428: (I) + (0.2.4), B- 429: (I) + (0.2.5), B-430: (I) + (0.2.6), B-431 : (I) + (0.2.7), B-432: (I) + (0.3.1), B-433: (I) + (0.3.2), B-434: (I) + (0.3.3), B-435: (I) + (0.3.4), B-436: (I) + (0.3.5), B-437: (I) + (0.3.6), B-438: (I) + (0.3.7), B-439: (I) + (0.3.8), B-440: (I) + (0.3.9), B-441 : (I) + (0.3.10), B-442: (I) + (0.3.11), B-443: (I) + (0.3.12), B-444: (I) + (0.3.13), B-445: (I) + (0.3.14), B-446: (I) + (0.3.15), B-447: (I) + (0.3.16), B-448: (I) + (0.3.17), B-449: (I) + (0.3.18), B-450: (I) + (0.3.19), B-451 : (I) +
(0.3.20), B-452: (I) + (0.3.21), B-453: (I) + (0.3.22), B-454: (I) + (0.3.23), B-455: (I) + (0.3.24), B-456: (I) + (0.3.25), B-457: (I) + (0.3.26), B-458: (I) + (0.3.27), B-459: (I) + (0.3.28), B-460: (I) + (0.3.29), B-461 : (I) + (0.3.30), B-462: (I) + (0.3.31), B-463: (I) + (0.3.32), B-464: (I) +
(0.3.33), B-465: (I) + (0.3.34), B-466: (I) + (0.3.35), B-467: (I) + (0.3.36), B-468: (I) + (0.3.37), B-469: (I) + (0.3.38), B-470: (I) + (0.3.39), B-471 : (I) + (0.3.40), B-472: (I) + (0.3.41), B-473: (I) + (0.3.42), B-474: (I) + (0.3.43), B-475: (I) + (0.3.44), B-476: (I) + (0.3.45), B-477: (I) +
(0.3.46), B-478: (I) + (0.3.47), B-479: (I) + (0.3.48), B-480: (I) + (0.3.49), B-481 : (I) + (0.3.50), B-482: (I) + (0.3.51), B-483: (I) + (0.3.52), B-484: (I) + (0.4.1), B-485: (I) + (0.4.2), B-486: (I) + (0.4.3), B-487: (I) + (0.4.4), B-488: (I) + (0.4.5), B-489: (I) + (0.4.6), B-490: (I) + (0.4.7), B-491: (I) + (0.4.8), B-492: (I) + (0.4.9), B-493: (I) + (0.4.10), B-494: (I) + (0.4.11), B-495: (I) +
(0.4.12), B-496: (I) + (0.4.13), B-497: (I) + (0.4.14), B-498: (I) + (0.4.15), B-499: (I) + (0.5.1), B-500: (I) + (0.5.2), B-501: (I) + (0.6.1), B-502: (I) + (0.6.2), B-503: (I) + (0.6.3), B-504: (I) + (0.6.4), B-505: (I) + (0.6.5), B-506: (I) + (0.7.1), B-507: (I) + (0.7.2), B-508: (I) + (0.7.3), B-509: (I) + (0.7.4), B-510: (I) + (0.7.5), B-511: (I) + (0.8.1), B-512: (I) + (0.8.2), B-513: (I) + (0.8.3), B-514: (I) + (0.8.4), B-515: (I) + (0.8.5), B-516: (I) + (0.9.1), B-517: (I) + (0.9.2), B-518: (I) + (0.9.3), B-519: (I) + (0.10.1), B-520: (I) + (0.10.2), B-521 : (I) + (0.10.3), B-522: (I) + (0.10.4), B-523: (I) + (0.11.1), B-524: (I) + (0.11.2), B-525: (I) + (0.11.3), B-526: (I) + (0.11.4), B-527: (I) + (0.11.5), B-528: (I) + (0.11.6), B-529: (I) + (0.11.7), B-530: (I) + (0.11.8), B-531 : (I) +
(0.11.9), B-532: (I) + (0.11.10), B-533: (I) + (0.11.11), B-534: (I) + (0.11.12), B-535: (I) + (0.11.13), B-536: (I) + (0.12.1), B-537: (I) + (0.12.2), B-538: (I) + (0.12.3), B-539: (I) +
(0.12.4), B-540: (I) + (0.12.5), B-541 : (I) + (0.12.6), B-542: (I) + (0.13.1), B-543: (I) + (0.13.2), B-544: (I) + (0.13.3), B-545: (I) + (0.14.1), B-546: (I) + (0.14.2), B-547: (I) + (0.14.3), B-548: (I) + (0.14.4), B-549: (I) + (0.15.1), B-550: (I) + (0.15.2), B-551 : (I) + (0.15.3), B-552: (I) +
(0.15.4), B-553: (I) + (0.15.5), B-554: (I) + (0.15.6), B-555: (I) + (0.15.7), B-556: (I) + (0.15.8), B-557: (I) + (0.15.9), B-558: (I) + (0.15.10), B-559: (I) + (0.15.11), B-560: (I) + (0.16.1), B-561: (I) + (0.17.1), B-562: (I) + (0.18.1), B-563: (I) + (0.18.2), B-564: (I) + (0.18.3), B-565: (I) + (0.18.4), B-566: (I) + (0.18.5), B-567: (I) + (0.19.1 ), B-568: (I) + (0.20.1 ), B-569: (I) + (0.20.2), B-570: (I) + (0.20.3), B-571 : (I) + (0.20.4), B-572: (I) + (0.21 .1 ), B-573: (I) + (0.21.2), B-574: (I) + (0.21 .3), B-575: (I) + (0.21.4), B-576: (I) + (0.21.5), B-577: (I) + (0.21.6), B-578: (I) + (0.21 .7), B-579: (I) + (0.22.1 ), B-580: (I) + (0.22.2), B-581 : (I) + (0.22.3), B-582: (I) + (0.22.4), B-583: (I) + (0.23.1 ), B-584: (I) + (0.23.2), B-585: (I) + (0.23.3), B-586: (I) + (0.23.4), B-587: (I) + (0.24.1 ), B-588: (I) + (0.24.2), B-589: (I) + (0.24.3), B-590: (I) + (0.24.4), B-591 : (I) + (0.24.5), B-592: (I) + (0.25.1 ), B-593: (I) + (0.25.2), B-594: (I) + (0.26.1 ), B-595: (I) + (0.26.2), B-596: (I) + (0.26.3), B-597: (I) + (0.26.4), B-598: (I) + (0.26.5), B-599: (I) + (0.26.6), B-600: (I) + (0.26.7), B-601 : (I) + (0.26.8), B-602: (I) + (0.26.9), B-603: (I) + (0.26.10), B-604: (I) + (0.26.1 1 ), B-605: (I) + (0.26.12), B-606: (I) + (0.26.13), B-607: (I) + (0.26.14), B-608: (I) + (0.26.15), B-609: (I) + (0.26.16), B-610: (I) + (0.26.17), B-61 1 : (I) + (0.26.18), B-612: (I) + (0.27.1 ), B-613: (I) + (0.28.1 ), B-614: (I) + (0.28.2), B-615: (I) + (0.28.3), B-616: (I) + (0.28.4), B-617: (I) + (0.28.5), B-618: (I) + (0.28.7), B-619: (I) + (0.28.8), B-620: (I) + (0.28.9), B-621 : (I) + (0.28.10), B-622: (I) + (0.28.1 1 ), B-623: (I) + (0.28.12), B-624: (I) + (0.28.13), B-625: (I) +
(0.28.14), B-626 (I) + (0.28.15), B-627 (I) + (0.28.16), B-628 (I) + (0.28.17), B-629 (l) + (0.28.18), B-630 (I) + (0.28.19), B-631 (I) + (0.28.20), B-632 (I) + (0.28.21 ), B-633 (l) + (0.28.22), B-634 (I) + (0.28.23), B-635 (I) + (0.28.24), B-636 (I) + (0.28.25), B-637 (l) + (0.28.26), B-638 (I) + (0.28.27), B-639 (I) + (0.28.28), B-640 (I) + (0.28.29), B-641 (l) + (0.28.30), B-642 (I) + (0.28.31 ), B-643 (I) + (0.28.42), B-644 (I) + (0.28.43), B-645 (l) + (0.28.44), B-646 (I) + (0.28.45), B-647 (I) + (0.28.46), B-648 (I) + (0.28.47), B-649 (l) + (0.28.48), B-650 (I) + (0.28.49), B-651 (I) + (0.28.50), B-652 (I) + (0.28.51 ), B-653 (l) + (0.28.52), B-654 (I) + (0.28.53), B-655 (I) + (0.28.54), B-656 (I) + (0.28.55), B-657 (l) + (0.28.56), B-658 (I) + (0.28.57), B-659 (I) + (0.28.58), B-660 (I) + (0.28.59), B-661 (i) + (0.28.60), B-662 (I) + (0.28.61 ), B-663 (I) + (0.28.62), B-664 (I) + (0.28.63), B-665 (i) + (0.28.64), B-666 (I) + (0.28.65), B-667 (I) + (0.28.66), B-668 (I) + (0.28.67), B-669 (i) + (0.28.68), B-670 (I) + (0.28.69), B-671 (I) + (0.28.70), B-672 (I) + (0.28.71 ), B-673 (i) + (0.28.72), B-674 (I) + (0.28.73), B-675 (I) + (0.28.74), B-676 (I) + (0.28.75), B-677 (i) + (0.28.76), B-678 (I) + (0.28.77), B-679 (I) + (0.28.78), B-680 (I) + (0.28.79), B-681 (i) + (0.28.80), B-682 (I) + (0.28.81 ), B-683 (I) + (0.28.82), B-684: (I) + (A.3.29), B-685: (I) +
(B.1.33), B-686: (I) + (D.2.8), B-687: (I) + (G.2.8), B-688: (I) + (K.1 .56), B-689: (I) + (0.4.16), B-690: (I) + (0.4.17), B-691 : (I) + (0.4.18), B-692: (I) + (0.4.19), B-693: (I) + (0.4.20), B-694: (I) + (0.4.21 ), B-695: (I) + (0.28.83), B-696: (I) + (0.28.84), B-697: (I) + (0.28.85), B-698: (I) + (0.28.86), B-699: (I) + (0.28.87), B-700: (I) + (0.28.88), B-701 : (I) + (0.28.89), B-702: (I) +
(0.28.90), B-703: (I) + (0.28.91 ), B-704: (I) + (0.28.92), B-705: (I) + (0.28.93).
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
Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is referred to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I, respectively.
I. Synthesis examples
The compounds of the formula I can be prepared according to the methods outlined below.
1.1 ) Synthesis of /V-ethyl-2-hydroxy-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]acetamide (Ex-2)
To a solution of ethyl 2-(4-cyanophenyl)-2-hydroxy-acetate (0.50 g), which can be prepared as described in European Journal of Organic Chemistry 2008, (34), 5692-5695, in tetrahydrofuran (5 ml.) was added ethylamine (0.79 mg, 70% in water, 5 eq.). The mixture was stirred overnight. Hydroxylamine hydrochloride (0.34 g, 2 eq.) in L/,/V-dimethylformamide (0.5 ml.) was added and the mixture was stirred at 70°C for 3 hours. Trifluoroacetic anhydride (2.0 g, 4 eq.) was then added dropwise to the mixture. Stirring was continued at room temperature overnight. The mixture was poured into a saturated aqueous solution of sodium bicarbonate and extracted with ethyl acetate. Then the organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated. The crude product was purified by flash chromatography to afford the title compound (136 mg, 15%).
The compounds listed in Table I were prepared in an analogous manner.
Table I: Compounds Ex-1 to Ex-4 of formula l-Ex, wherein L, R1 and R2 are as defined in each line.
Figure imgf000074_0001
Figure imgf000074_0002
* HPLC: High Performance Liquid Chromatography; HPLC-column Kinetex XB C18 1 ,7m (50 x 2,1 mm); eluent: acetonitrile / water + 0.1 % trifluoroacetic acid (gradient from 5:95 to 100 : 0 in 1 .5 min at 60°C, flow gradient from 0.8 to 1.0 ml/min in 1 .5 min). MS:
Quadrupol Electrospray Ionisation, 80 V (positive mode). Rt: retention time in minutes. Biological examples for fungicidal activity
The fungicidal action of the compounds of formula I was demonstrated by the following experiments:
Glass house trials
The spray solutions were prepared in several steps: The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml. This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.
11.1) Curative control of soybean rust on soybeans caused by Phakopsora pachyrhizi
Leaves of pot-grown soybean seedlings were inoculated with spores of Phakopsora pachyrhizi. To ensure the success of the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 20 to 24°C for 24 hours. The next day the plants were cultivated for 3 days in a greenhouse chamber at 23 to 27°C and a relative humidity between 60 and 80%. Then the plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. Then the trial plants were cultivated for 14 days in a greenhouse chamber at 23 to 27°C and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the plants which had been treated with 63 ppm of the active compounds Ex-1 , Ex-2, Ex-3, and Ex-4showed a diseased leaf area of 0%, whereas the untreated plants showed 90% diseased leaf area.
11.2) Protective control of soybean rust on soybeans caused by Phakopsora pachyrhizi
Leaves of pot-grown soybean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 2 days in a greenhouse chamber at
23 to 27°C and a relative humidity between 60 and 80%. Then the plants were inoculated with spores of Phakopsora pachyrhizi. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24°C for
24 hours. The trial plants were cultivated for fourteen days in a greenhouse chamber at 23 to 27°C and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the plants which had been treated with 63 ppm of the active compounds Ex-1 , Ex-2, Ex-3, and Ex-4showed a diseased leaf area of 0%, whereas the untreated plants showed 90% diseased leaf area. 11.3) Curative control of brown rust on wheat caused by Puccinia recondita
The first two developed leaves of pot-grown wheat seedling were dusted with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to 24°C for 24 hours. The next day the plants were cultivated for 3 days in a greenhouse chamber at 20 to 24°C and a relative humidity between 65 and 70%. Then the plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants could air-dry. Then the trial plants were cultivated for 8 days in a greenhouse chamber at 20 to 24°C and a relative humidity between 65 and 70%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the plants which had been treated with 63 ppm of the active compounds Ex-1 , Ex-2, Ex-3, and Ex-4 showed a diseased leaf area of at most 16%, whereas the untreated plants showed 90% diseased leaf area.
11.4) Preventative control of brown rust on wheat caused by Puccinia recondita
The first two developed leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The next day the plants were inoculated with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to 24°C for 24 hours. Then the trial plants were cultivated for 6 days in a greenhouse chamber at 20 to 24°C and a relative humidity between 65 and 70%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the plants which had been treated with 63 ppm of the active compounds Ex-1 , Ex-2, Ex-3, and Ex-4 showed a diseased leaf area of at most 9%, whereas the untreated plants showed 90% diseased leaf area.

Claims

Claims
1. Compounds of the formula I, or the N-oxides, or the agriculturally acceptable salts thereof,
Figure imgf000077_0001
wherein:
A is phenyl or a 6-membered aromatic heterocycle; wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 or 2 nitrogen atoms as ring member atoms; and wherein the phenyl ring or the aromatic heterocycle is unsubstituted or substituted with 1 , 2, 3 or 4 identical or different groups RA; wherein RA is halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy or
Ci-C6-haloalkoxy;
X is O or S;
Y is O or S;
R1 is hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl, Ci-C6-alkoxyimino-Ci-C4- alkyl, C2-C6-alkenyloxyimino-Ci-C4-alkyl, C2-C6-alkynyloxyimino-Ci-C4-alkyl, C3-C11- cycloalkyl, C3-Cn-cycloalkenyl, C3-Cn-cycloalkyl-Ci-C4-alkyl, phenyl-Ci-C4-alkyl, heterocyclyl-Ci-C4-alkyl, heteroaryl-Ci-C4-alkyl, phenyl, naphthyl or a 3- to 10- membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle, wherein the ring member atoms of said mono- or bicyclic heterocycle include besides carbon atoms further 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein 1 or 2 carbon ring member atoms of the heterocycle may be replaced by 1 or 2 groups independently selected from C(=0) and C(=S); and wherein the heterocyclyl group in heterocyclyl-Ci-C4- alkyl is a 3- to 10-membered saturated, partially unsaturated, mono- or bicyclic heterocycle, wherein the ring member atoms of said mono- or bicyclic heterocycle include besides carbon atoms further 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein 1 or 2 carbon ring member atoms of the heterocycle may be replaced by 1 or 2 groups independently selected from C(=0) and C(=S); and wherein the heteroaryl group in heteroaryl-Ci-C4-alkyl is a 5- or 6-membered aromatic heterocycle, wherein the ring member atoms of the aromatic heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring member atoms with the provision that the heterocycle cannot contain 2 contiguous atoms selected from O and S; and wherein any of the aliphatic or cyclic groups R1 are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different groups R1a; wherein
R1a is halogen, cyano, Ci-C6-alkyl, Ci-C6-alkoxy or Ci-C6-haloalkoxy; R2 is hydrogen, formyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy,
C3-C8-cycloalkyl, Cs-Cs-cycloalkenyl, C3-C8-cycloalkyl-Ci-C4-alkyl, phenyl- Ci-C4-alkyl, phenyl, pyridinyl, C(=0)-(Ci-C6-alkyl), C(=0)-(C3-C8-cycloalkyl), C(=0)-(Ci-C6-alkoxy) or -N(R2a)2; wherein
R2a is independently selected from the group consisting of hydrogen, OH,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkenyl, Ci-C6-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl and Ci-C6-alkylthio;
and wherein any of the aliphatic or cyclic groups in R2 are unsubstituted or substituted with 1 , 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, hydroxy, oxo, cyano, Ci-C6-alkyl, Ci-C6-alkoxy and Cs-Cs-cycloalkyl;
R3, R4 independently of each other are selected from the group consisting of hydrogen and Ci-C4-alkyl.
2. Compounds according to claim 1 , wherein A is phenyl.
3. Compounds according to claim 1 , which are of the formula 1.1 , or the N-oxides, or the
agriculturally acceptable salts thereof,
Figure imgf000078_0001
wherein n is 0, 1 or 2, and wherein the meaning of the variables are as defined in claim 1 for compounds of the formula I.
4. Compounds according to any one of claims 1 to 3, wherein R3 is hydrogen, methyl or ethyl.
5. Compounds according to any one of claims 1 to 4, wherein R4 is hydrogen, methyl or ethyl.
6. Compounds according to any one of claims 1 to 5, wherein X is O.
7. Compounds according to any one of claims 1 to 6, wherein Y is O.
8. Compounds according to any one of claims 1 to 7, wherein X is O and R4 is hydrogen.
9. Compounds according to any one of claims 1 to 8, wherein n is 0.
10 Compounds according to any one of claims 1 to 9, wherein R1 and R2 are independently selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl and C3-Cii-cycloalkyl.
1 1 . Compounds according to any one of claims 1 to 9, wherein R1 is hydrogen, Ci-C6-alkyl, C2- C6-alkenyl, C3-C6-alkynyl, or C3-Cn-cycloalkyl and R2 is hydrogen.
12. Compounds according to any one of claims 1 to 9, wherein R1 is hydrogen, methyl, ethyl, ri-propyl, /so-propyl, /7-butyl, /so-butyl, sec-butyl, tert- butyl, cyclopropyl, or
bicyclo[1.1 1]pentan-1-yl and R2 is hydrogen.
13. An agrochemical composition, which comprises an auxiliary and at least one compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof, as defined in any one of claims 1 to 12.
14. An agrochemical composition according to claim 13, further comprising seed, wherein the amount of the compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof, is from 0.1 g to 10 kg per 100 kg of seed.
15. The use of compounds according to any one of claims 1 to 12 for combating
phytopathogenic harmful fungi.
16. A method for combating phytopathogenic harmful fungi, which process comprises treating the fungi or the plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of formula I, or an N-oxide, or an agriculturally acceptable salt thereof, as defined in any one of claims 1 to 12.
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