WO2014198557A1 - Substituted [1,2,4]triazole and imidazole compounds - Google Patents

Substituted [1,2,4]triazole and imidazole compounds Download PDF

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WO2014198557A1
WO2014198557A1 PCT/EP2014/061226 EP2014061226W WO2014198557A1 WO 2014198557 A1 WO2014198557 A1 WO 2014198557A1 EP 2014061226 W EP2014061226 W EP 2014061226W WO 2014198557 A1 WO2014198557 A1 WO 2014198557A1
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alkyl
chf2
och3
individualized compound
compounds
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PCT/EP2014/061226
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French (fr)
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Wassilios Grammenos
Ian Robert CRAIG
Nadege Boudet
Bernd Müller
Erica May Wilson LAUTERWASSER
Jan Klaas Lohmann
Egon Haden
Ana Escribano Cuesta
Thomas Grote
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to substituted [1 ,2,4]triazole and imidazole compounds and the N- oxides and the salts thereof for combating phytopathogenic fungi, and to the use and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound.
  • the invention also relates to processes for preparing these compounds, intermediates, processes for preparing such intermediates, and to compositions comprising at least one inventive compound.
  • J. of Computer-Aided Molecular Design, 7 (1993), 349-362 describes certain bistriazole- substituted para-biphenyl compounds.
  • EP 0 044 605 relates to fungicidal bisazolyls, in particular bis triazolyl compounds.
  • CN 1923819 relates to bistriazoles. J. Agric. Food Chem. 2009, 57, 4854-4860 describes certain bistriazoles and triazole-imidazoles with para phenoxyphenyl unit and their use as fungicide.
  • CN 1923819 relates to certain para-phenoxyphenyl-bistriazoles.
  • the present invention relates to com ounds of the formula I
  • X is CH or N
  • Y is CH or N
  • R 2 is d-Ce-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-Ci-C 6 -alkyl, phenyl, phenyl-Ci-C4-alkyl, phenyl-C2-C4-alkenyl or phenyl-C2-C4-alkynyl;
  • R 2 wherein the aliphatic moieties of R 2 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 2a which independently of one another are selected from:
  • R 2a halogen, OH, CN, nitro, Ci-C 4 -alkoxy, C 3 -C 8 -cycloalkyl, C 3 -C 8 -halocycloalkyl and Ci-C 4 - halogenalkoxy;
  • R 2b which independently of one another are selected from: R 2b halogen, OH, CN, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C 3 -C8-cycloalkyl, C3-C8-halocycloalkyl and Ci-C4-halogenalkoxy;
  • n 0, 1 , 2, 3 or 4;
  • R 3 is independently selected from halogen, CN, NO2, OH, SH, Ci-C6-alkyl, Ci-C6-alkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyloxy, NH 2 , NH(Ci-C 4 -alkyl), N(Ci-C 4 -alkyl) 2 , NH(C 3 -C 6 -cycloalkyl), N(C 3 -C 6 -cycloalkyl) 2 , S(0) P (Ci-C 4 -alkyl),
  • R 3a is independently selected from halogen, CN, N0 2 , OH, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cs- cycloalkyl, C3-Cs-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
  • n 0, 1 , 2, 3, 4 or 5;
  • R 4 is in each case independently selected from halogen, CN, N0 2 , OH, SH, Ci-C6-alkyl, Ci- Ce-alkoxy, C 2 -Ce-alkenyl, C 2 -Ce-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyloxy, NH 2 , NH(Ci-C4- alkyl), N(Ci-C 4 -alkyl) 2 , NH(C 3 -C 6 -cycloalkyl), N(C 3 -C 6 -cycloalkyl) 2 , S(0) P (Ci-C 4 -alkyl),
  • R 4a is independently selected from halogen, CN, N0 2 , OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C 3 -Cs- cycloalkyl, C 3 -C8-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
  • p 0, 1 or 2;
  • a further aspect of the present invention are processes for the synthesis of compounds I and intermediates, in particular intermediates of formula II and the N-oxides and the salts thereof.
  • the invention also relates to methods for combating phytopathogenic fungi, and to the use and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound.
  • the compounds I and II can be obtained for example in analogy to prior art processes known (see above) and (cf. J.Agric. Food Chem. (2009) 57, 4854-4860; EP 0 126 430 A2), EP 0 044 605, CN 1923819 and by the synthesis routes shown in the following schemes.
  • a catalyst e.g. Pd
  • X 2 is CI, F, I or Br.
  • the resulting compounds VII, in particular Vila are then transformed into Grignard reagents by the reaction with transmetallation reagents such as iso- propylmagnesium halides and subsequently reacted with acetyl chloride preferably under anhydrous conditions and preferably in the presence of a catalyst such as CuC , AlC , LiCI and mixtures thereof, to obtain acetophenones VI.
  • transmetallation reagents such as iso- propylmagnesium halides
  • acetyl chloride preferably under anhydrous conditions and preferably in the presence of a catalyst such as CuC , AlC , LiCI and mixtures thereof, to obtain acetophenones VI.
  • These compounds VI can be halogenated e.g. with bromine preferably in an organic solvent such as diethyl ether, methyl tert. -butyl ether (MTBE), methanol or acetic acid.
  • organic solvent such as diethyl ether, methyl tert. -butyl ether (MTBE), methanol or acetic acid.
  • halo en such as e.g. Br or CI.
  • Compounds V can subsequently be reacted with 1 H-1 ,2,4-triazole or imidazole preferably in the presence of a solvent such as tetrahydrofuran (THF), dimethylformamide (DMF), toluene, and in the presence of a base such as potassium carbonate, sodium hydroxide or sodium hydride to obtain com ounds IV.
  • a solvent such as tetrahydrofuran (THF), dimethylformamide (DMF), toluene
  • a base such as potassium carbonate, sodium hydroxide or sodium hydride
  • intermediates IV may be reacted with trimethylsulf(ox)onium halides, preferably iodide, referably in the presence of a base such as sodium h droxide, to result in epoxides III.
  • trimethylsulf(ox)onium halides preferably iodide
  • a base such as sodium h droxide
  • the epoxides III may then be reacted with 1 H-1 ,2,4-triazole or imidazole, respectively, prefera- bly in the presence of a base such as potassium carbonate and preferably in the presence of an or anic solvent such as DMF to obtain alcohol com ounds II.
  • a base such as potassium carbonate
  • an or anic solvent such as DMF
  • Compounds I can be obtained from compounds II by reacting the alcohol compound of formula II with R 2 -LG, wherein LG represents a nucleophilically replaceable leaving group, such as halogen, alkylsulfonyl, alkylsulfonyloxy and arylsulfonyloxy, preferably chloro, bromo or iodo, particularly preferably bromo, preferably in the presence of a base.
  • X, Y, R 2 , R 3 , R 4 , n and m are as defined and preferably defined herein.
  • a further object of the present invention are compounds of formula II and the N- oxides and the agriculturally acceptable salts thereof, wherein the variables R 3 , R 4 , X, Y, n and m are as defined and preferably defined for formula I herein.
  • the substituents are specific embodiments independently of each other or in any combination.
  • n+m is 1 , 2 or 3.
  • Compounds II are also suitable as fungicides as described herein for compounds of formula I.
  • X is N and Y is N, corresponding to compounds II.A:
  • X is N and Y is CH, corresponding to compounds II.
  • Table 1 d Compounds of the formula II.A in which the meaning for the combination of (R 3 ) n and (R 4 )m for each individual compound corresponds in each case to one line of Table A (com- pounds II.A.A1 to II.A.A21 12).
  • Table 1 e Compounds of the formula II. B in which the meaning for the combination of (R 3 ) n and (R 4 )m for each individual compound corresponds in each case to one line of Table A (compounds II.B.A1 to II.B.A21 12).
  • Table 1f Compounds of the formula II.C in which the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds II.C.A1 to II.C.A21 12).
  • inventive compounds cannot be directly obtained by the routes described above, they may be prepared by derivatization of other inventive compounds.
  • the N-oxides may be prepared from the inventive compounds according to conventional oxida- tion methods, e. g. by treating compounds I with an organic peracid such as metachloroper- benzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(1 1 ), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981 ) or oxone (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001 ).
  • the oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
  • C n -C m indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • Ci-C6-alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2- methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl,
  • C2-C4-alkyl refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1 -methylethyl (iso-propoyl), butyl, 1 -methylpropyl (sec. -butyl), 2-methylpropyl (iso-butyl), 1 ,1 -dimethylethyl (tert.
  • Ci-C6-haloalkyl refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • Ci-C2-haloalkyl such as chloromethyl, bro- momethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 - fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl.
  • C2-C6-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in a n position.
  • Examples are “C2-C4-alkenyl” groups, 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.
  • C2-C6-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond.
  • Examples are "C2-C4- alkynyl” groups, such as ethynyl, prop-1 -ynyl, prop-2-ynyl (propargyl), but-1 -ynyl, but-2-ynyl, but-3-ynyl, 1 -methyl-prop-2-ynyl.
  • Cs-Cs-cycloalkyl refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • C3-C8-cycloalkyl-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical hav- ing 3 to 8 carbon atoms (as defined above).
  • Ci-C6-alkoxy refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group.
  • Examples are “C1-C4- alkoxy” groups, such as methoxy, ethoxy, n-propoxy, 1 -methylethoxy, butoxy, 1 - methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
  • Ci-C6-haloalkoxy refers to a Ci-C6-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • Examples are "Ci-C4-haloalkoxy” groups, such as OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoro- ethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-tri- chloro-"ethoxy, OC2F5, 2-fluoro
  • Agriculturally acceptable salts of the inventive compounds encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of said compounds.
  • Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manga- nese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammoni- um, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phos- phonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and
  • Anions of useful acid addition salts are primarily chloride, bro- mide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting such inventive compound with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
  • the compounds of formula I and II, respectively, and their N-oxides may have one or more centers of chirality, in which case they are present as pure en- antiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.
  • the embodiments of the compounds I also apply to the intermediates, in particular to compounds II.
  • X according to the invention is N or CH. According to one embodiment X is N. According to a further embodiment X is CH.
  • Y according to the invention is N or CH. According to one embodiment Y is N. According to a further embodiment Y is CH.
  • X and Y are N.
  • X is N and Y is CH.
  • R 2 is Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3- C8-cycloalkyl-Ci-C6-alkyl, phenyl, phenyl-Ci-C4-alkyl, phenyl-C2-C4-alkenyl or phenyl-C2-C 4 - alkynyl, wherein the aliphatic moieties of R 2 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 2a which independently of one another are selected from halogen, OH, CN, nitro, Ci-C 4 -alkoxy, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl and Ci-C 4 -halogenalkoxy; and wherein the aliphatic moieties of R 2 are not further substituted or carry one, two,
  • R 2 is selected from Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the R 2 are in each case unsubstituted or are substituted by R 2a as defined and preferably defined herein, in particular wherein each R 2a is independently selected from halogen, OH, CN , Ci-C 4 -alkoxy and Ci-C 4 -halogenalkoxy, more specifically selected from OH, CN, Ci-C 4 -alkoxy and Ci-C 4 -halogenalkoxy. Specific embodiments thereof can be found in the below Table P2.
  • R 2 is selected from Ci-C6-alkyl, C2-C6-alkenyl and C2- C6-alkynyl, wherein the R 2 are in each case unsubstituted or are substituted by R 2a as defined and preferably defined herein.
  • the substituents may also have the preferred meanings for the respective substituent as defined herein. Specific embodiments thereof can be found in the below Table P2.
  • R 2 is Ci-C6-alkyl, in particular Ci-C 4 -alkyl, such as CHs, C 2 H 5 , CH(CHs) 2 , CH2CH2CH3, CH2CH2CH2CH3, CH 2 CH(CH 3 ) 2 .
  • a further embodiment relates to compounds, wherein R 2 is Ci-C6-alkyl, in particular Ci-C 4 -alkyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 2a , as defined and preferably defined herein.
  • R 2 is C1-C6- haloalkyl, in particular Ci-C 4 -haloalkyl, more particularly Ci-C2-haloalkyl.
  • R 2 is Ci-C 4 -alkoxy-Ci-C6-alkyl, in particular Ci-C 4 -alkoxy-Ci-C 4 - alkyl, such as CH2OCH3 or CH2CH2OCH3.
  • R 2 is hydroxy-Ci-C6-alkyl, in particular hydroxyl-Ci-C 4 -alkyl, such as CH2CH2OH.
  • R 2 is cyano-Ci-C6-alkyl, in particular C1-C4- cyano-Ci-C 4 -alkyl, such as CH2CN or CH2CH2CN. Further specific embodiments thereof can be found in the below Table P2.
  • R 2 is C3-C8-cycloalkyl-Ci-C6-alkyl, in particular C3-C6- cycloalkyl-Ci-C 4 -alkyl.
  • a further embodiment relates to compounds, wherein R 2 is C3-C8- cycloalkyl-Ci-C6-alkyl, in particular C3-C6-cycloalkyl-Ci-C 4 -alkyl, more particularly C3-C6- cycloalkyl-Ci-C2-alkyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 2a in the alkyl moiety and/or substituted by one, two, three four or five or up to the maximum possible number of identical or different groups R 2b in the cycloalkyl moiety.
  • R 2a and R 2b are in each case as defined and preferably defined herein. Specific embodiments thereof can be found in the below Table P2.
  • a further embodiment relates to compounds, wherein R 2 is C2-C6-alkenyl, in particular C2-C4-alkenyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 2a as defined and pref- erably defined herein.
  • R 2 is C3-C8-cycloalkyl-C2-C6-alkenyl or C3-C8-halocycloalkyl-C2-C6- alkenyl, in particular C3-C6-cycloalkyl-C2-C4-alkenyl or C3-C6-halocycloalkyl-C2-C4-alkenyl. Further specific embodiments thereof can be found in the below Table P2.
  • R 2 is C2-C6-alkynyl, in particular C2-C4-alkynyl, such as CH2C ⁇ CH or CH2C ⁇ CCH3.
  • a further embodiment relates to compounds, wherein R 2 is C2-C6- alkynyl, in particular C2-C4-alkynyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 2a , as defined and preferably defined herein.
  • R 2 is C2-C6-haloalkynyl, in particular C2-C4- haloalkynyl.
  • R 2 is C3-C8-cycloalkyl-C2-C6- alkynyl or C3-C8-halocycloalkyl-C2-C6-alkynyl, in particular C3-C6-cycloalkyl-C2-C4-alkynyl or C3- C6-halocycloalkyl-C2-C4-alkynyl. Specific embodiments thereof can be found in the below Table P2.
  • R 2 is phenyl-Ci-C4-alkyl, in particular phenyl-Ci-C2-alkyl, such as benzyl, wherein the alkyl moiety in each case is unsubstituted or carries one, two or three R 2a as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C4-alkoxy, in particular OCH3, and CN, and wherein the phenyl in each case is unsubstituted or carries one, two or three R 2b as as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH3, C1-C4- alkyl, in particular CH3 or C2H5, and CN. Specific embodiments thereof can be found in the below Table P2.
  • R 2 is phenyl-C2-C4-alkenyl, in particular phenyl-C2-C3- alkenyl, such as phenylethenyl, wherein the alkenyl moiety in each case is unsubstituted or carries one, two or three R 2a as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C4-alkoxy, in particular OCH3, and CN, and wherein the phenyl in each case is unsubstituted or carries one, two or three R 2b as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH3, Ci-C4-alkyl, in particular CH3 or C2H5, and CN.
  • R 2a as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C4-alkoxy, in particular OCH3, Ci-C4-
  • R 2 is phenyl-C2-C4-alkynyl, in particular phenyl-C2-C3- alkynyl, such as phenylethinyl, wherein the alkynyl moiety in each case is unsubstituted or carries one, two or three R 2a , as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C4-alkoxy, in particular OCH3, and CN, and wherein the phenyl in each case is unsubstituted or carries one, two or three R 2b as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH 3 , Ci-C 4 -alkyl, in particular CH 3 or C 2 H 5 , and CN.
  • R 2a as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C4-alkoxy,
  • R 2 is Cs-Cs-cycloalkyl, in particular C3-C6-cycloalkyl, such as C3H5 (cyclopropyl), C4H7 (cyclobutyl), cyclopentyl or cyclohexyl.
  • a further embodiment relates to compounds, wherein R 2 is Cs-Cs-cycloalkyl, in particular C3-C6-cycloalkyl, such as C3H5 (cyclopropyl) or C4H7 (cyclobutyl), that is substituted by one, two, three four or five or up to the maximum possible number of identical or different groups R 2b as defined and preferably defined herein.
  • R 2 is Cs-Cs-halocycloalkyl, in particular C3- C6-halocycloalkyl, such as halocyclopropyl, in particular 1 -F-cyclopropyl or 1 -CI-cyclopropyl.
  • R 2 is Cs-Cs-cycloalkyl-Cs-Cs-cycloalkyl, in particular C3-C6-cycloalkyl-C3-C6-cycloalkyl, wherein each of said cycloalkyl-cycloalkyl moieties is unsubstituted or carries one, two or three R 2b as defined and preferably defined herein.
  • R 2 is phenyl, wherein the phenyl is unsubstituted or carries one, two, three, four or five independently selected R 2b as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH3, Ci-C 4 -alkyl, in particular CH 3 or C 2 H 5 , and CN.
  • R 2 Particularly preferred embodiments of R 2 according to the invention are in Table P2 below, wherein each line of lines P2-1 to P2-87 corresponds to one particular embodiment of the invention, wherein P2-1 to P2-87 are also in any combination a preferred embodiment of the present invention.
  • R 2 More specific embodiments of R 2 according to the invention are in Table B below, wherein each line of lines B-1 to B-13 corresponds to one particular embodiment of the invention, wherein B-1 to B-13 are also in any combination preferred embodiments of the present invention.
  • n 0, 1 , 2, 3 or 4.
  • n 0.
  • n is 1 .
  • n is 2 or 3. According to one specific embodiment thereof, n is 2, according to a further specific embodiment, n is 3.
  • one R 3 is attached to the 2-position in relation to the position of the attachment of the tertiary ether group(R 31 ). According to one specific embodiment thereof, n is 1 , according to a further specific embodiment, n is 2. According to one embodiment of the invention, one R 3 is attached to the 4-position in relation to the position of the attachment of the tertiary ether group (R 32 ). According to one specific embodiment thereof, n is 1 , according to a further specific embodiment, n is 2.
  • one R 3 is attached to the 5-position in relation to the position of the attachment of the tertiary ether group (R 33 ).
  • n is 1 , according to a further specific embodiment, n is 2.
  • one R 3 is attached to the 6-position in relation to the position of the attachment of the tertiary ether group (R 34 ).
  • n is 1 , according to a further specific embodiment, n is 2.
  • n is 1 , 2 or 3 and one R 3 is in 2-position in relation to the position of the attachment of the tertiary ether group.
  • n 2
  • n 3
  • n 2
  • n 3
  • n 2
  • n 3
  • n 2
  • n 3
  • n 2
  • n 3
  • R 3 (or R 31 , R 32 , R 33 , R 34 , respectively) that is present in the inventive compounds
  • the following embodiments and preferences apply independently of the meaning of any other R 3 (or R 31 , R 32 , R 33 , R 34 , respectively) that may be present in the phenyl ring.
  • R 3 is independently selected from F, CI, Br, CN, C1-C4- alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, S(Ci-C 4 -alkyl), S(0)(Ci-C 4 -alkyl) and S(0) 2 (Ci-C 4 -alkyl).
  • R 3 is halogen, in particular Br, F or CI, more specifically F or CI.
  • R 3 is CN
  • R 3 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH 3 .
  • R 3 is Ci-C6-haloalkyl, in particular Ci-C4-haloalkyl, such as CF 3 , CHF 2 , CH 2 F, CCI 3 , CHCI2 or CH 2 CI.
  • R 3 is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH 3 or OCH2CH 3 .
  • R 3 is Ci-C6-haloalkoxy, in particular C1-C4- haloalkoxy, more specifically Ci-C 2 -haloalkoxy such as OCF 3 , OCHF 2 , OCH 2 F, OCCI 3 , OCHC or OCH2CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHCb.
  • R 3 is C2-C6-alkynyl or C2-C6-haloalkynyl, in particular C2-C4-alkynyl or C2-C4-haloalkynyl, such as C CH.
  • R 3 is selected from S(Ci-C2-alkyl), S(0)(Ci-C2-alkyl) and S(0) 2 (Ci-C 2 -alkyl), in particular SCH 3 , S(0)(CH 3 ) and S(0) 2 (CH 3 ).
  • R 3 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R 3a , as defined herein.
  • R 3 is unsubstituted phenoxy or phenoxy that is substituted by one, two, three or four R 3a , as defined herein. According to still a further embodiment, R 3 is unsubstituted 5- or 6-membered heteroaryl.
  • R 3 is 5- or 6-membered heteroaryl that is substituted by one, two or three R 3a , as defined herein.
  • the heteroaryl in each case is 5-membered such as .
  • the heteroaryl in each case is 6-membered such as .
  • R 3 is unsubstituted 5- or 6-membered heteroaryloxy.
  • R 3 is 5- or 6-membered heteroaryloxy that is substituted by one, two or three R 3a , as defined herein.
  • the heteroaryloxy in each case is 5-membered.
  • the heteroaryloxy in each case is 6-membered.
  • R 3a is independently selected from halogen, CN, NO2, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C8- cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy, in particular selected from halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C2- alkoxy and Ci-C2-halogenalkoxy.
  • R 3a is independently selected from F, CI, CN, OH, CH3, halomethyl, cyclopropyl, halocyclopropyl, OCH3 and halogenmethoxy.
  • R 3 Particularly preferred embodiments of R 3 according to the invention are in Table P3 below, wherein each line of lines P3-1 to P3-16 corresponds to one particular embodiment of the invention, wherein P3-1 to P3-16 are also in any combination with one another a preferred embodiment of the present invention.
  • these specific embodiments and preferences apply independently of the meaning of any other R 3 that may be present in the phenyl ring:
  • R 4 there can be zero, one, two, three, four or five R 4 present, namely for m is 0, 1 , 2, 3, 4 or 5.
  • m is 0, 1 , 2, 3 or 4.
  • m is 0.
  • m is 1 , 2, 3 or 4, in particular 1 , 2 or 3, more specifically 1 or 2. According to one specific embodiment thereof, m is 1 , according to a further specific embodiment, m is 2.
  • m is 2, 3 or 4.
  • m is 3.
  • one R 4 is attached to the para-position (4- position).
  • one R 4 is attached to the meta-position (3- position). According to a further embodiment of the invention, one R 4 is attached to the ortho-position (2- position).
  • two R 4 are attached in 2,4-position.
  • two R 4 are attached in 2,3-position.
  • two R 4 are attached in 2,5-position.
  • two R 4 are attached in 2,6-position.
  • two R 4 are attached in 3,4-position.
  • two R 4 are attached in 3,5-position.
  • R 4 are attached in 2,4,6-position.
  • the following embodiments and preferences apply independently of the meaning of any other R 4 that may be present in the phenyl ring.
  • R 4a independently selected R 4a , wherein R 4a is as defined and preferably defined herein.
  • each of R 4 is unsubstituted or further substituted by one, two, three or four independently selected R 4a , wherein R 4a is as defined and preferably defined herein.
  • R 4 is independently selected from F, CI, Br, CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, S(Ci-C 4 -alkyl), S(0)(Ci-C 4 -alkyl) and S(0) 2 (Ci- C 4 -alkyl).
  • R 4 is independently selected from halogen, in particular from Br, F and CI, more specifically from F and CI. According to a further specific embodiment, R 4 is CN.
  • R 4 is NO2.
  • R 4 is OH.
  • R 4 is SH.
  • R 4 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH3. Further appropriate alkyls are ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl.
  • R 4 is Ci-C6-haloalkyl, in particular Ci-C4-haloalkyl, such as CF 3 , CHF 2 , CH 2 F, CCI 3 , CHC or CH 2 CI.
  • R 4 is Ci-C6-alkyl, preferably Ci-C4-alkyl, substituted by OH, more preferably CH 2 OH, CH 2 CH 2 OH, CH 2 CH 2 CH 2 OH, CH(CH 3 )CH 2 OH,
  • R 4 is CH 2 CH(CH 3 )OH, CH2CH2CH2CH2OH.
  • R 4 is CH 2 OH.
  • R 4 is Ci-C6-alkyl, preferably Ci-C4-alkyl substituted by CN, more preferably CH 2 CN, CH 2 CH 2 CN, CH 2 CH 2 CH 2 CN, CH(CH 3 )CH 2 CN, CH 2 CH(CH 3 )CN, CH 2 CH- 2CH2CH2CN.
  • R 4 is CH2CH2CN.
  • R 4 is CH(CH 3 )CN.
  • R 4 is Ci-C4-alkoxy-Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl.
  • R 4 is CH20CH 3 .
  • R 4 is CH 2 CH 2 OCH 3 .
  • R 4 is CH(CH 3 )OCH 3 .
  • R 4 is CH(CH 3 )OCH2CH 3 .
  • R 4 is CH2CH20CH2CH 3 .
  • R 4 is Ci-C4-haloalkoxy-Ci-C6- alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl.
  • R 4 is CH20CF 3 .
  • R 4 is CH2CH20CF 3 .
  • R 4 is
  • R 4 is CH 2 CH 2 OCCI 3 .
  • R 4 is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH 3 or OCH2CH 3 .
  • R 4 is Ci-C6-haloalkoxy, in particular C1-C4- haloalkoxy, more specifically Ci-C 2 -haloalkoxy such as OCF 3 , OCHF 2 , OCH 2 F, OCCI 3 , OCHC or OCH2CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHCb.
  • R 4 is Ci-C4-alkoxy-C2-C6-alkenyl, more preferably Ci-C4-alkoxy-C2-C4-alkenyl.
  • R 4 is C1-C4- haloalkoxy-C2-C6-alkenyl, more preferably Ci-C4-haloalkoxy-C2-C4-alkenyl.
  • R 4 is
  • R 4 is C 3 -C8-cycloalkyl-C2-Ce- alkenyl, preferably C3-C6-cycloalkyl-C2-C4-alkenyl.
  • R 4 is C3-C6-halocycloalkyl-C2-C4-alkenyl, preferably C3-C8-halocycloalkyl-C2-C6-alkenyl.
  • R 4 is C2-C6-alkynyl or C2-C6-haloalkynyl, in particular C 2 -C 4 -alkynyl or C 2 -C 4 -haloalkynyl, such as C ⁇ CH, CH 2 CCH or CH2CCCH3.
  • R 4 is C2-C6-alkynyl, preferably C2-C 4 -alkynyl, substituted by OH, more preferably, CCOH, CH 2 CCOH. In a special embodiment R 4 is CCOH. In a further special embodiment R 4 is CH2CCOH. According to a further specific embodiment R 4 is Ci-C 4 -alkoxy-C2-C6-alkynyl, more preferably Ci-C 4 -alkoxy-C2-C 4 -alkynyl. In a special embodiment R 4 is CCOCH3. In a further special embodiment R 4 is CH2CCOCH3.
  • R 4 is Ci-C 4 -haloalkoxy-C2-C6-alkynyl, more preferably Ci-C 4 -haloalkoxy- C2-C 4 -alkynyl.
  • R 4 is CCOCF3.
  • R 4 is CH2CCOCF3.
  • R 4 is CCOCCI3.
  • R 4 is CH2CCOCCI3.
  • R 4 is C3-C8-cycloalkyl-C2-C6- alkynyl, preferably C3-C6-cycloalkyl-C2-C 4 -alkynyl.
  • R 4 is C3-C6-halocycloalkyl-C2-C 4 -alkynyl, preferably C3-C8-halocycloalkyl-C2-C6-alkynyl.
  • R 4 is Cs-Cs-cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl.
  • R 4 is cyclopropyl.
  • R 4 is cyclobutyl.
  • R 4 is cyclopentyl.
  • R 4 is cyclohexyl.
  • R 4 is Cs-Cs-cycloalkoxy, preferably C3-C6-cycloalkoxy.
  • R 4 is O-cyclopropyl.
  • R 4 is Cs-Cs-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl.
  • R 4 is fully or partially halogenated cyclopropyl.
  • R 4 is 1-CI-cyclopropyl.
  • R 4 is 2-CI-cyclopropyl.
  • R 4 is 1-F-cyclopropyl.
  • R 4 is 2-F-cyclopropyl.
  • R 4 is fully or partially halogenated cyclobutyl.
  • R 4 is 1-CI-cyclobutyl.
  • R 4 is 1-F-cyclobutyl. In a further special embodiment R 4 is 3,3-Cl2-cyclobutyl. In a further special embodiment R 4 is 3,3-F2-cyclobutyl. According to a specific embodiment R 4 is C3- Cs-cycloalkyl substituted by Ci-C 4 -alkyl, more preferably is C3-C6-cycloalkyl substituted by Ci- C 4 -alkyl. In a special embodiment R 4 is 1-CH3-cyclopropyl. According to a specific embodiment R 4 is Cs-Cs-cycloalkyl substituted by CN, more preferably is C3-C6-cycloalkyl substituted by CN.
  • R 4 is 1-CN-cyclopropyl.
  • R 4 is C3-C8-cycloalkyl-C3-C8-cycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-cycloalkyl.
  • R 4 is cyclopropyl-cyclopropyl.
  • R 4 is 2-cyclopropyl- cyclopropyl.
  • R 4 is C3-Cs-cycloalkyl-C3-Cs- halocycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-halocycloalkyl.
  • R 4 is C3-C8-cycloalkyl-Ci-C 4 -alkyl, preferably C3-C6- cycloalkyl-Ci-C 4 -alkyl.
  • R 4 is CH(CH3)(cyclopropyl).
  • R 4 is CH2-(cyclopropyl).
  • R 4 is C3-C8-cycloalkyl-Ci-C4-alkyl wherein the alkyl moiety can be substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein and the cycloalkyi moiety can be substituted by one, two, three or up to the maximum possible number of identical or different groups R b as defined and preferably herein.
  • R 4 is C3-C8-cycloalkyl-Ci-C4-haloalkyl, C3-C6-cycloalkyl-Ci- C4-haloalkyl. According to a specific embodiment R 4 is C3-C8-halocycloalkyl-Ci-C4-alkyl, C3-C6- halocycloalkyl-Ci-C4-alkyl. In a special embodiment R 4 is fully or partially halogenated cyclopro- pyl-Ci-C4-alkyl. In a further special embodiment R 4 is 1 -CI-cyclopropyl-Ci-C4-alkyl. In a further special embodiment R 4 is 1 -F-cyclopropyl-Ci-C4-alkyl.
  • R 4 is NH2.
  • R 4 is NH(Ci-C4-alkyl). According to a specific embodiment R 4 is NH(CH3). According to a specific embodiment R 4 is NH(CH2CH3). According to a specific embodiment R 4 is NH(CH2CH2CH3). According to a specific embodiment R 4 is
  • R 4 is NH(CH2CH2CH 2 CH 3 ). According to a specific embodiment R 4 is NH(C(CH 3 ) 3 ).
  • R 4 is N(Ci-C4-alkyl)2. According to a specific embodiment R 4 is N(CH3)2. According to a specific embodiment R 4 is N(CH2CH3)2. According to a specific embodiment R 4 is N(CH2CH 2 CI-l3)2. According to a specific embodiment R 4 is N(CH(CH 3 )2)2.
  • R 4 is N(CH2CH2CH2CH3)2. According to a specific embodiment R 4 is NH(C(CH 3 ) 3 )2.
  • R 4 is NH(C3-C8-cycloalkyl) preferably NH(C3-C6- cycloalkyl). According to a specific embodiment R 4 is NH(cyclopropyl). According to a specific embodiment R 4 is NH(cyclobutyl). According to a specific embodiment R 4 is NH(cyclopentyl). According to a specific embodiment R 4 is NH(cyclohexyl).
  • R 4 is N(C3-C8-cycloalkyl)2 preferably N(C3-C6- cycloalkyl)2. According to a specific embodiment R 4 is N(cyclopropyl)2. According to a specific embodiment R 4 is N(cyclobutyl)2. According to a specific embodiment R 4 is N(cyclopentyl)2.
  • R 4 is N(cyclohexyl)2.
  • R 4 is selected from S(Ci-C2-alkyl), S(0)(Ci-C2-alkyl) and S(0) 2 (Ci-C 2 -alkyl), in particular SCH 3 , S(0)(CH 3 ) and S(0) 2 (CH 3 ).
  • R 4 is selected from S(Ci-C 2 -haloalkyl), S(0)(Ci-C 2 -haloalkyl) and S(0) 2 (Ci-C 2 - haloalkyl), such as SO2CF3.
  • R 4 Particularly preferred embodiments of R 4 according to the invention are in Table P4 below, wherein each line of lines P4-1 to P4-16 corresponds to one particular embodiment of the invention, wherein P4-1 to P4-16 are also in any combination with one another preferred embodiments of the present invention. Thereby, for every R 4 that is present in the inventive
  • R 4 m Particularly preferred embodiments of (R 4 ) m according to the invention are in Table P41 below, wherein each line of lines P41 -1 to P41 -156 corresponds to one particular embodiment of the invention, wherein P41-1 to P41-156 are also in any combination preferred embodiments of the present invention.
  • R 4 m More particularly preferred embodiments of (R 4 ) m according to the invention are in Table P42 below, wherein each line of lines P42-1 to P42-64 corresponds to one particular embodiment of the invention, wherein P42-1 to P42-64 are also in any combination preferred embodiments of the present invention.
  • P42-10 4-CN P42-21 3-S0 2 CH 3 P42-32 2-CHF 2
  • n+m is 1 or > 1 , namely, 1 , 2, 3, 4, 5, 6, 7, 8 or 9, more specifically 1 , 2, 3, 4 or 5.
  • n+m is 1 , 2 or 3.
  • X is N and Y is N, corresponding to compounds I.
  • X is N and Y is CH, corresponding to compounds I.B:
  • X is CH and Y is CH, corresponding to compounds I.C:
  • Table 1 a Compounds of the formula I .A in which R 2 corresponds to line B-1 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-1 .A1 to I.A.B-1 .A21 12).
  • Table 2a Compounds of the formula I. A in which R 2 corresponds to line B-2 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-2.A1 to I.A.B-2.A21 12).
  • Table 3a Compounds of the formula I. A in which R 2 corresponds to line B-3 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-3.A1 to I.A.B-3.A21 12).
  • Table 4a Compounds of the formula I .A in which R 2 corresponds to line B-4 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-4.A1 to I.A.B-4.A21 12).
  • Table 5a Compounds of the formula I. A in which R 2 corresponds to line B-5 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-5.A1 to I.A.B-5.A21 12).
  • Table 6a Compounds of the formula I. A in which R 2 corresponds to line B-6 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-6.A1 to I.A.B-6.A21 12).
  • Table 7a Compounds of the formula I. A in which R 2 corresponds to line B-7 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-7.A1 to I.A.B-7.A21 12).
  • Table 8a Compounds of the formula I. A in which R 2 corresponds to line B-8 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-8.A1 to I.A.B-8.A21 12).
  • Table 9a Compounds of the formula I. A in which R 2 corresponds to line B-9 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-9.A1 to I.A.B-9.A21 12).
  • Table 10a Compounds of the formula I .A in which R 2 corresponds to line B-10 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corre- sponds in each case to one line of Table A (compounds I.A.B-10.A1 to I.A.B-10.A21 12).
  • Table 1 1 a Compounds of the formula I .A in which R 2 corresponds to line B-1 1 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-1 1 .A1 to I.A.B-1 1 .A21 12).
  • Table 12a Compounds of the formula I .A in which R 2 corresponds to line B-12 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-12.A1 to I.A.B-12.A21 12).
  • Table 13a Compounds of the formula I .A in which R 2 corresponds to line B-13 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-13.A1 to I.A.B-13.A21 12).
  • Table 1 b Compounds of the formula I.B in which R 2 corresponds to line B-1 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B. B-1 .A1 to I.B. B-1 .A21 12).
  • Table 2b Compounds of the formula I.B in which R 2 corresponds to line B-2 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-2.A1 to I.B.B-2.A21 12).
  • Table 3b Compounds of the formula I.B in which R 2 corresponds to line B-3 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-3.A1 to I.B.B-3.A21 12).
  • Table 4b Compounds of the formula I.B in which R 2 corresponds to line B-4 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-4.A1 to I.B.B-4.A21 12).
  • Table 5b Compounds of the formula I.B in which R 2 corresponds to line B-5 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-5.A1 to I.B.B-5.A21 12).
  • Table 6b Compounds of the formula I.B in which R 2 corresponds to line B-6 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-6.A1 to I.B.B-6.A21 12).
  • Table 7b Compounds of the formula I.B in which R 2 corresponds to line B-7 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-7.A1 to I.B.B-7.A21 12).
  • Table 8b Compounds of the formula I.B in which R 2 corresponds to line B-8 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-8.A1 to I.B.B-8.A21 12).
  • Table 9b Compounds of the formula I.B in which R 2 corresponds to line B-9 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-9.A1 to I.B.B-9.A21 12).
  • Table 10b Compounds of the formula I.B in which R 2 corresponds to line B-10 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-10.A1 to I.B.B-10.A21 12).
  • Table 1 1 b Compounds of the formula I.B in which R 2 corresponds to line B-1 1 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corre- sponds in each case to one line of Table A (compounds I.B. B-1 1 .A1 to I.B. B-1 1 .A21 12).
  • Table 12b Compounds of the formula I.B in which R 2 corresponds to line B-12 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-12.A1 to I.B.B-12.A21 12).
  • Table 13b Compounds of the formula I.B in which R 2 corresponds to line B-13 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-13.A1 to I.B.B-13.A21 12).
  • Table 1 c Compounds of the formula I .C in which R 2 corresponds to line B-1 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-1 .A1 to I.C.B-1 .A21 12).
  • Table 2c Compounds of the formula I.C in which R 2 corresponds to line B-2 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-2.A1 to I.C.B-2.A21 12).
  • Table 3c Compounds of the formula I.C in which R 2 corresponds to line B-3 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-3.A1 to I.C.B-3.A21 12).
  • Table 4c Compounds of the formula I.C in which R 2 corresponds to line B-4 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-4.A1 to I.C.B-4.A21 12).
  • Table 5c Compounds of the formula I.C in which R 2 corresponds to line B-5 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-5.A1 to I.C.B-5.A21 12).
  • Table 6c Compounds of the formula I.C in which R 2 corresponds to line B-6 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-6.A1 to I.C.B-6.A21 12).
  • Table 7c Compounds of the formula I.C in which R 2 corresponds to line B-7 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-7.A1 to I.C.B-7.A21 12).
  • Table 8c Compounds of the formula I.C in which R 2 corresponds to line B-8 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-8.A1 to I.C.B-8.A21 12).
  • Table 9c Compounds of the formula I.C in which R 2 corresponds to line B-9 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-9.A1 to I.C.B-9.A21 12).
  • Table 10c Compounds of the formula I .C in which R 2 corresponds to line B-10 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-10.A1 to I.C.B-10.A21 12).
  • Table 1 1 c Compounds of the formula I .C in which R 2 corresponds to line B-1 1 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C. B-1 1.A1 to I.C. B-1 1 .A21 12).
  • Table 12c Compounds of the formula I .C in which R 2 corresponds to line B-12 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-12.A1 to I.C.B-12.A21 12).
  • Table 13c Compounds of the formula I .C in which R 2 corresponds to line B-13 of Table B and the meaning for the combination of (R 3 ) n and (R 4 ) m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-13.A1 to I.C.B-13.A21 12).
  • A-429 4-F 2,3-CI 2 A-468 5-F 2-SO2CH3 line (R 3 )n (R 4 )m line (R 3 )n (R 4 )m
  • A-645 4-CN 2-F
  • A-684 4-CN 2,4,6-(CH 3 ) 3
  • A-651 4-CN 2-N0 2
  • A-690 4-CN 2,6-CI 2
  • A-652 4-CN 3-N0 2
  • A-691 4-CN 2,3-F 2
  • A-1 171 4-CH3 4-SOCH3 A-1210 4-CH3 2-CF3-4-F
  • A-1 172 4-CH3 2-SO2CH3 A-121 1 4-CH3 2-CI-4-CF3
  • A-1 173 4-CH3 3-SO2CH3 A-1212 4-CH3 2-F-4-CF3
  • A-1 180 4-CH3 4-CH3 A-1219 5-CH3 3-CI
  • A-1 182 4-CH3 3-CF3 A-1221 5-CH3 2-F
  • A-1 191 4-CH3 3-OCF3 A-1230 5-CH3 2-SCH3
  • A-141 1 4-CF3 3-CI
  • A-1450 4-CF3 3-OCHF2
  • A-1429 4-CF3 3-SO2CH3
  • A-1468 4-CF3 2-F-4-CF3

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Abstract

The present invention relates to compoundsof the formula (I) wherein the substituents are described in the specification and claims; to the use of said compounds, to processes for the preparation of the compounds and to intermediates and their use and preparation.

Description

Substituted [1 ,2,4]triazole and imidazole compounds
Description
The present invention relates to substituted [1 ,2,4]triazole and imidazole compounds and the N- oxides and the salts thereof for combating phytopathogenic fungi, and to the use and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound. The invention also relates to processes for preparing these compounds, intermediates, processes for preparing such intermediates, and to compositions comprising at least one inventive compound.
J. of Computer-Aided Molecular Design, 7 (1993), 349-362 describes certain bistriazole- substituted para-biphenyl compounds. EP 0 044 605 relates to fungicidal bisazolyls, in particular bis triazolyl compounds. CN 1923819 relates to bistriazoles. J. Agric. Food Chem. 2009, 57, 4854-4860 describes certain bistriazoles and triazole-imidazoles with para phenoxyphenyl unit and their use as fungicide. CN 1923819 relates to certain para-phenoxyphenyl-bistriazoles.
Using known pesticidal compounds, in many cases, in particular at low application rates, the fungicidal activity of the known fungicidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic fungi.
Surprisingly, this object is achieved by the use of the inventive substituted [1 ,2,4]triazole and imidazole compounds having favorable fungicidal activity against phytopathogenic fungi.
Accordingly, the present invention relates to com ounds of the formula I
Figure imgf000002_0001
wherein
X is CH or N;
Y is CH or N;
R2 is d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci-C6-alkyl, phenyl, phenyl-Ci-C4-alkyl, phenyl-C2-C4-alkenyl or phenyl-C2-C4-alkynyl;
wherein the aliphatic moieties of R2 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R2a which independently of one another are selected from:
R2a halogen, OH, CN, nitro, Ci-C4-alkoxy, C3-C8-cycloalkyl, C3-C8-halocycloalkyl and Ci-C4- halogenalkoxy;
wherein the cycloalkyl and/or phenyl moieties of R2 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R2b which independently of one another are selected from: R2b halogen, OH, CN, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl and Ci-C4-halogenalkoxy;
n is 0, 1 , 2, 3 or 4;
R3 is independently selected from halogen, CN, NO2, OH, SH, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyloxy, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl),
Figure imgf000003_0001
alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4-alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)-(N(C3-C6-cycloalkyl)2; wherein each of R3 is unsubsti- tuted or further substituted by one, two, three or four R3a; wherein
R3a is independently selected from halogen, CN, N02, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cs- cycloalkyl, C3-Cs-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
m is 0, 1 , 2, 3, 4 or 5; and
R4 is in each case independently selected from halogen, CN, N02, OH, SH, Ci-C6-alkyl, Ci- Ce-alkoxy, C2-Ce-alkenyl, C2-Ce-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyloxy, NH2, NH(Ci-C4- alkyl), N(Ci-C4-alkyl)2, NH(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl),
Figure imgf000003_0002
C4-alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4-alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)-(N(C3-C6-cycloalkyl)2); wherein each of R4 is unsubstituted or further substituted by one, two, three or four R4a wherein
R4a is independently selected from halogen, CN, N02, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-Cs- cycloalkyl, C3-C8-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
p is 0, 1 or 2;
and the N-oxides and the agriculturally acceptable salts thereof.
A further aspect of the present invention are processes for the synthesis of compounds I and intermediates, in particular intermediates of formula II and the N-oxides and the salts thereof. The invention also relates to methods for combating phytopathogenic fungi, and to the use and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound.
The compounds I and II can be obtained for example in analogy to prior art processes known (see above) and (cf. J.Agric. Food Chem. (2009) 57, 4854-4860; EP 0 126 430 A2), EP 0 044 605, CN 1923819 and by the synthesis routes shown in the following schemes.
For example, Di-halo compounds VIII are reacted in a crosscoupling reaction using a catalyst (e.g. Pd) and an organometallic species (e.g. M= MgX, SnR3, BOR3, wherein R is for example Ci-C6-alkyl) in presence or absence of an appropriate additive known to the skilled person to obtain compounds VII. X1 stands for I or Br, in particular Br (=bromo derivatives Villa), X2 is CI, F, I or Br.
Figure imgf000004_0001
Thereafter, the resulting compounds VII, in particular Vila (wherein X1 is Br) are then transformed into Grignard reagents by the reaction with transmetallation reagents such as iso- propylmagnesium halides and subsequently reacted with acetyl chloride preferably under anhydrous conditions and preferably in the presence of a catalyst such as CuC , AlC , LiCI and mixtures thereof, to obtain acetophenones VI.
Figure imgf000004_0002
These compounds VI can be halogenated e.g. with bromine preferably in an organic solvent such as diethyl ether, methyl tert. -butyl ether (MTBE), methanol or acetic acid. In the resulting com ounds V, "Hal" stands for "halo en" such as e.g. Br or CI.
Figure imgf000004_0003
Compounds V can subsequently be reacted with 1 H-1 ,2,4-triazole or imidazole preferably in the presence of a solvent such as tetrahydrofuran (THF), dimethylformamide (DMF), toluene, and in the presence of a base such as potassium carbonate, sodium hydroxide or sodium hydride to obtain com ounds IV.
Figure imgf000004_0004
Thereafter, intermediates IV may be reacted with trimethylsulf(ox)onium halides, preferably iodide, referably in the presence of a base such as sodium h droxide, to result in epoxides III.
Figure imgf000004_0005
The epoxides III may then be reacted with 1 H-1 ,2,4-triazole or imidazole, respectively, prefera- bly in the presence of a base such as potassium carbonate and preferably in the presence of an or anic solvent such as DMF to obtain alcohol com ounds II.
Figure imgf000005_0001
Compounds I can be obtained from compounds II by reacting the alcohol compound of formula II with R2-LG, wherein LG represents a nucleophilically replaceable leaving group, such as halogen, alkylsulfonyl, alkylsulfonyloxy and arylsulfonyloxy, preferably chloro, bromo or iodo, particularly preferably bromo, preferably in the presence of a base. X, Y, R2, R3, R4, n and m are as defined and preferably defined herein.
A skilled person will readily understand that the preferences for the substituents given herein in connection with compounds I apply for the intermediates accordingly, in particular for compounds II. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein. Some of the intermediates occurring in the synthesis of the inventive compounds are novel and therefore are also an object of the present invention.
In particular, a further object of the present invention are compounds of formula II and the N- oxides and the agriculturally acceptable salts thereof, wherein the variables R3, R4, X, Y, n and m are as defined and preferably defined for formula I herein. The substituents are specific embodiments independently of each other or in any combination. One particular embodiment relates to compounds II, wherein n+m is >= 1 , namely, 1 , 2, 3, 4, 5, 6, 7, 8 or 9, more specifically 1 , 2, 3, 4 or 5. In specific embodiment thereof, n+m is 1 , 2 or 3. Compounds II are also suitable as fungicides as described herein for compounds of formula I.
According to one embodiment of the intermediate II, X is N and Y is N, corresponding to compounds II.A:
Figure imgf000005_0002
According to a further embodiment of the intermediate II, X is N and Y is CH, corresponding to compounds II. B:
Figure imgf000005_0003
According to still a further embodiment of the intermediate II, X is CH and Y is CH, correspondin to compounds II. C:
Figure imgf000006_0001
In particular with a view to their use, preference is given to the compounds of the formula II, in particular 11. A, II. B and II. C, compiled in the Tables 1 d, 1 e and 1f below. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Table 1 d Compounds of the formula II.A in which the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (com- pounds II.A.A1 to II.A.A21 12).
Table 1 e Compounds of the formula II. B in which the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds II.B.A1 to II.B.A21 12).
Table 1f Compounds of the formula II.C in which the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds II.C.A1 to II.C.A21 12).
If individual inventive compounds cannot be directly obtained by the routes described above, they may be prepared by derivatization of other inventive compounds.
The N-oxides may be prepared from the inventive compounds according to conventional oxida- tion methods, e. g. by treating compounds I with an organic peracid such as metachloroper- benzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(1 1 ), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981 ) or oxone (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001 ). The oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
In the 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 "Ci-C6-alkyl" refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2- methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl,
2,2-dimethylpropyl, 1 -ethylpropyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl,
1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl,
2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl and 1 -ethyl-2- methylpropyl. Likewise, the term "C2-C4-alkyl" refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1 -methylethyl (iso-propoyl), butyl, 1 -methylpropyl (sec. -butyl), 2-methylpropyl (iso-butyl), 1 ,1 -dimethylethyl (tert. -butyl). The term "Ci-C6-haloalkyl" refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. Examples are "Ci-C2-haloalkyl" groups such as chloromethyl, bro- momethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 - fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl.
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 an position. Examples are "C2-C4-alkenyl" groups, 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. Examples are "C2-C4- alkynyl" groups, such as ethynyl, prop-1 -ynyl, prop-2-ynyl (propargyl), but-1 -ynyl, but-2-ynyl, but-3-ynyl, 1 -methyl-prop-2-ynyl.
The term "Cs-Cs-cycloalkyl" refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
The term "C3-C8-cycloalkyl-Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical hav- ing 3 to 8 carbon atoms (as defined above).
The term "Ci-C6-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group. Examples are "C1-C4- alkoxy" groups, such as methoxy, ethoxy, n-propoxy, 1 -methylethoxy, butoxy, 1 - methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
The term "Ci-C6-haloalkoxy" refers to a Ci-C6-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. Examples are "Ci-C4-haloalkoxy" groups, such as OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoro- ethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-tri- chloro-"ethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoro-,propoxy, 2 chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bro- mo-'propoxy, 3 bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1 -fluoromethyl-2-fluoroethoxy, 1 -chloromethyl-2-chloroethoxy, 1 -bromomethyl-2- bromo-Othoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
Agriculturally acceptable salts of the inventive compounds encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of said compounds. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manga- nese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammoni- um, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phos- phonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bro- mide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting such inventive compound with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
Depending on the substitution pattern, the compounds of formula I and II, respectively, and their N-oxides may have one or more centers of chirality, in which case they are present as pure en- antiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.
In the following, particular embodiments of the inventive compounds are described. Therein, specific meanings of the respective substituents are further detained, wherein the meanings are in each case on their own but also in any combination with one another, particular embodiments of the present invention.
Furthermore, in respect of the variables, generally, the embodiments of the compounds I also apply to the intermediates, in particular to compounds II.
X according to the invention is N or CH. According to one embodiment X is N. According to a further embodiment X is CH.
Y according to the invention is N or CH. According to one embodiment Y is N. According to a further embodiment Y is CH.
According to one particular embodiment, X and Y are N.
According to a further particular embodiment, X is N and Y is CH.
According to still a further embodiment, X and Y are CH. According to the invention, R2 is Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3- C8-cycloalkyl-Ci-C6-alkyl, phenyl, phenyl-Ci-C4-alkyl, phenyl-C2-C4-alkenyl or phenyl-C2-C4- alkynyl, wherein the aliphatic moieties of R2 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R2a which independently of one another are selected from halogen, OH, CN, nitro, Ci-C4-alkoxy, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl and Ci-C4-halogenalkoxy; and wherein the cycloalkyl and/or phenyl moieties of R2 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R2b which independently of one another are selected from halogen, OH, CN, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl and Ci-C4-halogenalkoxy.
According to one embodiment of the invention, R2 is selected from Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the R2 are in each case unsubstituted or are substituted by R2a as defined and preferably defined herein, in particular wherein each R2a is independently selected from halogen, OH, CN , Ci-C4-alkoxy and Ci-C4-halogenalkoxy, more specifically selected from OH, CN, Ci-C4-alkoxy and Ci-C4-halogenalkoxy. Specific embodiments thereof can be found in the below Table P2.
In a further embodiment of the invention, R2 is selected from Ci-C6-alkyl, C2-C6-alkenyl and C2- C6-alkynyl, wherein the R2 are in each case unsubstituted or are substituted by R2a as defined and preferably defined herein. In each case, the substituents may also have the preferred meanings for the respective substituent as defined herein. Specific embodiments thereof can be found in the below Table P2.
According to one particular embodiment, R2 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CHs, C2H5, CH(CHs)2, CH2CH2CH3, CH2CH2CH2CH3, CH2CH(CH3)2. A further embodiment relates to compounds, wherein R2 is Ci-C6-alkyl, in particular Ci-C4-alkyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R2a, as defined and preferably defined herein. According to a specific embodiment thereof, R2 is C1-C6- haloalkyl, in particular Ci-C4-haloalkyl, more particularly Ci-C2-haloalkyl. According to a further specific embodiment thereof, R2 is Ci-C4-alkoxy-Ci-C6-alkyl, in particular Ci-C4-alkoxy-Ci-C4- alkyl, such as CH2OCH3 or CH2CH2OCH3. According to still a further specific embodiment thereof, R2 is hydroxy-Ci-C6-alkyl, in particular hydroxyl-Ci-C4-alkyl, such as CH2CH2OH. According to a further specific embodiment thereof, R2 is cyano-Ci-C6-alkyl, in particular C1-C4- cyano-Ci-C4-alkyl, such as CH2CN or CH2CH2CN. Further specific embodiments thereof can be found in the below Table P2.
According to still another embodiment, R2 is C3-C8-cycloalkyl-Ci-C6-alkyl, in particular C3-C6- cycloalkyl-Ci-C4-alkyl. A further embodiment relates to compounds, wherein R2 is C3-C8- cycloalkyl-Ci-C6-alkyl, in particular C3-C6-cycloalkyl-Ci-C4-alkyl, more particularly C3-C6- cycloalkyl-Ci-C2-alkyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R2a in the alkyl moiety and/or substituted by one, two, three four or five or up to the maximum possible number of identical or different groups R2b in the cycloalkyl moiety. R2a and R2b are in each case as defined and preferably defined herein. Specific embodiments thereof can be found in the below Table P2. According to another embodiment, R2 is C2-C6-alkenyl, in particular C2-C4-alkenyl, such as CH2CH=CH2, CH2C(CH3)=CI-l2 or CH2CH=CHCH3. A further embodiment relates to compounds, wherein R2 is C2-C6-alkenyl, in particular C2-C4-alkenyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R2a as defined and pref- erably defined herein. According to a specific embodiment thereof, R2 is C2-C6-haloalkenyl, in particular C2-C4-haloalkenyl, such as CH2C(CI)=CH2 and CH2C(H)=CHCI . According to a further specific embodiment thereof, R2 is C3-C8-cycloalkyl-C2-C6-alkenyl or C3-C8-halocycloalkyl-C2-C6- alkenyl, in particular C3-C6-cycloalkyl-C2-C4-alkenyl or C3-C6-halocycloalkyl-C2-C4-alkenyl. Further specific embodiments thereof can be found in the below Table P2.
According to still another embodiment, R2 is C2-C6-alkynyl, in particular C2-C4-alkynyl, such as CH2C≡CH or CH2C≡CCH3. A further embodiment relates to compounds, wherein R2 is C2-C6- alkynyl, in particular C2-C4-alkynyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R2a, as defined and preferably defined herein. According to a specific embodiment thereof, R2 is C2-C6-haloalkynyl, in particular C2-C4- haloalkynyl. According to a further specific embodiment thereof, R2 is C3-C8-cycloalkyl-C2-C6- alkynyl or C3-C8-halocycloalkyl-C2-C6-alkynyl, in particular C3-C6-cycloalkyl-C2-C4-alkynyl or C3- C6-halocycloalkyl-C2-C4-alkynyl. Specific embodiments thereof can be found in the below Table P2.
According to still another embodiment, R2 is phenyl-Ci-C4-alkyl, in particular phenyl-Ci-C2-alkyl, such as benzyl, wherein the alkyl moiety in each case is unsubstituted or carries one, two or three R2a as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C4-alkoxy, in particular OCH3, and CN, and wherein the phenyl in each case is unsubstituted or carries one, two or three R2b as as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH3, C1-C4- alkyl, in particular CH3 or C2H5, and CN. Specific embodiments thereof can be found in the below Table P2.
According to still another embodiment, R2 is phenyl-C2-C4-alkenyl, in particular phenyl-C2-C3- alkenyl, such as phenylethenyl, wherein the alkenyl moiety in each case is unsubstituted or carries one, two or three R2a as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C4-alkoxy, in particular OCH3, and CN, and wherein the phenyl in each case is unsubstituted or carries one, two or three R2b as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH3, Ci-C4-alkyl, in particular CH3 or C2H5, and CN.
According to still another embodiment, R2 is phenyl-C2-C4-alkynyl, in particular phenyl-C2-C3- alkynyl, such as phenylethinyl, wherein the alkynyl moiety in each case is unsubstituted or carries one, two or three R2a, as defined and preferably defined herein, in particular selected from halogen, in particular F and CI, Ci-C4-alkoxy, in particular OCH3, and CN, and wherein the phenyl in each case is unsubstituted or carries one, two or three R2b as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH3, Ci-C4-alkyl, in particular CH3 or C2H5, and CN.
According to still another embodiment, R2 is Cs-Cs-cycloalkyl, in particular C3-C6-cycloalkyl, such as C3H5 (cyclopropyl), C4H7 (cyclobutyl), cyclopentyl or cyclohexyl. A further embodiment relates to compounds, wherein R2 is Cs-Cs-cycloalkyl, in particular C3-C6-cycloalkyl, such as C3H5 (cyclopropyl) or C4H7 (cyclobutyl), that is substituted by one, two, three four or five or up to the maximum possible number of identical or different groups R2b as defined and preferably defined herein. According to a specific embodiment thereof, R2 is Cs-Cs-halocycloalkyl, in particular C3- C6-halocycloalkyl, such as halocyclopropyl, in particular 1 -F-cyclopropyl or 1 -CI-cyclopropyl. According to a further specific embodiment thereof, R2 is Cs-Cs-cycloalkyl-Cs-Cs-cycloalkyl, in particular C3-C6-cycloalkyl-C3-C6-cycloalkyl, wherein each of said cycloalkyl-cycloalkyl moieties is unsubstituted or carries one, two or three R2b as defined and preferably defined herein.
According to still another embodiment, R2 is phenyl, wherein the phenyl is unsubstituted or carries one, two, three, four or five independently selected R2b as defined and preferably defined herein, in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH3, Ci-C4-alkyl, in particular CH3 or C2H5, and CN.
Particularly preferred embodiments of R2 according to the invention are in Table P2 below, wherein each line of lines P2-1 to P2-87 corresponds to one particular embodiment of the invention, wherein P2-1 to P2-87 are also in any combination a preferred embodiment of the present invention.
Figure imgf000011_0001
Figure imgf000012_0001
More specific embodiments of R2 according to the invention are in Table B below, wherein each line of lines B-1 to B-13 corresponds to one particular embodiment of the invention, wherein B-1 to B-13 are also in any combination preferred embodiments of the present invention.
Each R3 according to the present invention is independently selected from halogen, CN, N02, OH, SH, d-Ce-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8- cycloalkyloxy, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl), C(=0)(Ci-C4-alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4- alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)-(N(C3-C6-cycloalkyl)2); wherein each of R3 is unsubstituted or further substituted by one, two, three or four R3a; wherein R3a is independently selected from halogen, CN, N02, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C3- cycloalkyl, C3-C8-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
According to the invention, there can be zero, one, two, three or four R3 present, namely for n is 0, 1 , 2, 3 or 4.
According to one embodiment, n is 0.
According to a further embodiment, n is 1 .
According to a further embodiment, n is 2 or 3. According to one specific embodiment thereof, n is 2, according to a further specific embodiment, n is 3.
According to one embodiment of the invention, one R3 is attached to the 2-position in relation to the position of the attachment of the tertiary ether group(R31). According to one specific embodiment thereof, n is 1 , according to a further specific embodiment, n is 2. According to one embodiment of the invention, one R3 is attached to the 4-position in relation to the position of the attachment of the tertiary ether group (R32). According to one specific embodiment thereof, n is 1 , according to a further specific embodiment, n is 2.
According to one embodiment of the invention, one R3 is attached to the 5-position in relation to the position of the attachment of the tertiary ether group (R33). According to one specific embodiment thereof, n is 1 , according to a further specific embodiment, n is 2.
According to one embodiment of the invention, one R3 is attached to the 6-position in relation to the position of the attachment of the tertiary ether group (R34). According to one specific embodiment thereof, n is 1 , according to a further specific embodiment, n is 2.
According to still a further embodiment, n is 1 , 2 or 3 and one R3 is in 2-position in relation to the position of the attachment of the tertiary ether group.
According to a further embodiment of the invention, two R3 are attached in 2, 4-position in relation to the position of the attachment of the tertiary ether group. According to one specific embodiment thereof, n is 2, according to a further specific embodiment, n is 3.
According to a further embodiment of the invention, two R3 are attached in 2, 5-position in relation to the position of the attachment of the tertiary ether group. According to one specific embodiment thereof, n is 2, according to a further specific embodiment, n is 3.
According to a further embodiment of the invention, two R3 are attached in 2, 6-position in relation to the position of the attachment of the tertiary ether group. According to one specific embodiment thereof, n is 2, according to a further specific embodiment, n is 3.
According to a further embodiment of the invention, two R3 are attached in 4, 5-position in relation to the position of the attachment of the tertiary ether group. According to one specific embodiment thereof, n is 2, according to a further specific embodiment, n is 3.
According to a further embodiment of the invention, two R3 are attached in 4, 6-position in relation to the position of the attachment of the tertiary ether group. According to one specific embodiment thereof, n is 2, according to a further specific embodiment, n is 3.
For every R3 (or R31, R32, R33, R34, respectively) that is present in the inventive compounds, the following embodiments and preferences apply independently of the meaning of any other R3 (or R31, R32, R33, R34, respectively) that may be present in the phenyl ring. Furthermore, the particular embodiments and preferences given herein for R3 (or R31, R32, R33, R34, respectively) apply independently for each of n=1 , n=2, n=3 and n=4.
According to one embodiment, R3 is independently selected from halogen, CN, NO2, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4- alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, S(Ci-C2-alkyl), S(0)(Ci-C2- alkyl), S(0)2(Ci-C2-alkyl), C(=0)(Ci-C2-alkyl), C(=0)(OH) and C(=0)(0-Ci-C2-alkyl).
According to a further embodiment, R3 is independently selected from halogen, CN, NO2, OH, SH, d-Ce-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8- cycloalkyloxy, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, N H(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl) (p=0, 1 or 2), C(=0)(Ci-C4-alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4-alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)- (N(C3-C6-cycloalkyl)2); wherein each of R3 is unsubstituted or further substituted by one, two, three or four R3a, wherein R3a is as defined and preferably defined herein.
According to still a further embodiment, R3 is independently selected from halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, S(Ci-C2-alkyl), S(0)(Ci- C2-alkyl), S(0)2(Ci-C2-alkyl), C(=0)(Ci-C2-alkyl), C(=0)(OH) and C(=0)(0-Ci-C2-alkyl).
According to still a further embodiment, R3 is independently selected from F, CI, Br, CN, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, S(Ci-C4-alkyl), S(0)(Ci-C4-alkyl) and S(0)2(Ci-C4-alkyl).
According to one specific embodiment, R3 is halogen, in particular Br, F or CI, more specifically F or CI.
According to a further specific embodiment, R3 is CN.
According to a further specific embodiment, R3 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH3.
According to a further specific embodiment, R3 is Ci-C6-haloalkyl, in particular Ci-C4-haloalkyl, such as CF3, CHF2, CH2F, CCI3, CHCI2 or CH2CI.
According to a further specific embodiment, R3 is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH3 or OCH2CH3.
According to a further specific embodiment, R3 is Ci-C6-haloalkoxy, in particular C1-C4- haloalkoxy, more specifically Ci-C2-haloalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHC or OCH2CI, in particular OCF3, OCHF2, OCCI3 or OCHCb.
According to still a further embodiment, R3 is C2-C6-alkenyl or C2-C6-haloalkenyl, in particular C2-C4-alkenyl or C2-C4-haloalkenyl, such as CH=CH2.
According to still a further embodiment, R3 is C2-C6-alkynyl or C2-C6-haloalkynyl, in particular C2-C4-alkynyl or C2-C4-haloalkynyl, such as C CH.
According to still a further embodiment, R3 is selected from C(=0)(Ci-C4-alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4-alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6- cycloalkyl)) and C(=0)(N(C3-C6-cycloalkyl)2), in particular selected from C(=0)(Ci-C2-alkyl), C(=0)(OH), C(=0)(0-Ci-C2-alkyl), C(=0)(NH(Ci-C2-alkyl)), C(=0)(N(Ci-C2-alkyl)2),
C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)(N(C3-C6-cycloalkyl)2). According to one specific embodiment thereof, R3 is C(=0)(OH) or C(=0)(0-Ci-C4-alkyl), in particular C(=0)(OCH3).
According to still a further embodiment, R3 is selected from S(Ci-C2-alkyl), S(0)(Ci-C2-alkyl) and S(0)2(Ci-C2-alkyl), in particular SCH3, S(0)(CH3) and S(0)2(CH3).
According to still a further embodiment, R3 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R3a, as defined herein.
According to still a further embodiment, R3 is unsubstituted phenoxy or phenoxy that is substituted by one, two, three or four R3a, as defined herein. According to still a further embodiment, R3 is unsubstituted 5- or 6-membered heteroaryl.
According to still a further embodiment, R3 is 5- or 6-membered heteroaryl that is substituted by one, two or three R3a, as defined herein. According to one specific embodiment, the heteroaryl in each case is 5-membered such as . According to a further specific embodiment, the heteroaryl in each case is 6-membered such as .
According to still a further embodiment, R3 is unsubstituted 5- or 6-membered heteroaryloxy. According to still a further embodiment, R3 is 5- or 6-membered heteroaryloxy that is substituted by one, two or three R3a, as defined herein. According to one specific embodiment, the heteroaryloxy in each case is 5-membered. According to a further specific embodiment, the heteroaryloxy in each case is 6-membered.
R3a is independently selected from halogen, CN, NO2, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C8- cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy, in particular selected from halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C2- alkoxy and Ci-C2-halogenalkoxy. Specifically, R3a is independently selected from F, CI, CN, OH, CH3, halomethyl, cyclopropyl, halocyclopropyl, OCH3 and halogenmethoxy.
Particularly preferred embodiments of R3 according to the invention are in Table P3 below, wherein each line of lines P3-1 to P3-16 corresponds to one particular embodiment of the invention, wherein P3-1 to P3-16 are also in any combination with one another a preferred embodiment of the present invention. Thereby, for every R3 that is present in the inventive compounds, these specific embodiments and preferences apply independently of the meaning of any other R3 that may be present in the phenyl ring:
Table P3:
Figure imgf000015_0004
Figure imgf000015_0002
Figure imgf000015_0001
Figure imgf000015_0003
Particularly preferred embodiments of (R3)n according to the invention are in Table P31 below, wherein each line of lines P31 -1 to P31 -103 corresponds to one particular embodiment of the invention, wherein P31 -1 to P31 -103 are also in any combination preferred embodiments of the present invention. The positions of the R3 are given in relation to the position of the attachment of the tertiary ether group.
Table P31 :
No. I (R3)n I I No. I (R3)n 1 I No. I (R3)n
P31 -1 -* P31 -4 5-CI P31 -7 4-F
P31 -2 2-CI P31 -5 6-CI P31 -8 5-F
P31 -3 4-CI P31 -6 2-F P31 -9 6-F No. (R3)n No. (R3)n No. (R3)n
P31-10 2-CN P31-42 2-F-5-CI P31-74 6-OCF3
P31-11 4-CN P31-43 2-F-6-CI P31-75 2-OCHF2
P31-12 5-CN P31-44 4-CI-6-F P31-76 4-OCHF2
P31-13 6-CN P31-45 4-F-6-CI P31-77 5-OCHF2
P31-14 2-NO2 P31-46 2-CI-5-F P31-78 6-OCHF2
P31-15 4-NO2 P31-47 2-CH3 P31-79 4,6-(CH3)2
P31-16 5-NO2 P31-48 4-CH3 P31-80 2,6-(CH3)2
P31-17 6-NO2 P31-49 5-CH3 P31-81 4,6-(CH2CH3)2
P31-18 2-SCHs P31-50 6-CH3 P31-82 2,6-(CH2CH3)2
P31-19 4-SCHs P31-51 2-CH2CH3 P31-83 4,6-(CF3)2
P31-20 5-SCHs P31-52 4-CH2CH3 P31-84 2,5-(CF3)2
P31-21 6-SCH3 P31-53 5-CH2CH3 P31-85 2,6-(CF3)2
P31-22 2-SOCH3 P31-54 6-CH2CH3 P31-86 4,6-(CHF2)2
P31-23 4-SOCH3 P31-55 2-CF3 P31-87 2,6-(CHF2)2
P31-24 5-SOCH3 P31-56 4-CF3 P31-88 4,6-(OCH3)2
P31-25 6-SOCH3 P31-57 5-CF3 P31-89 2,6-(OCH3)2
P31-26 2-SO2CH3 P31-58 6-CF3 P31-90 4,6-(OCH2CH3)2
P31-27 4-SO2CH3 P31-59 2-CHF2 P31-91 2,6-(OCH2CH3)2
P31-28 5-SO2CH3 P31-60 4-CHF2 P31-92 4,6-(OCF3)2
P31-29 6-SO2CH3 P31-61 5-CHF2 P31-93 2,6-(OCF3)2
P31-30 2-CO2CH3 P31-62 6-CHF2 P31-94 4,6-(OCHF2)2
P31-31 4-CO2CH3 P31-63 2-OCH3 P31-95 2,6-(OCHF2)2
P31-32 5-CO2CH3 P31-64 4-OCH3 P31-96 2-CF3-5-CI
P31-33 6-CO2CH3 P31-65 5-OCH3 P31-97 2-CF3-5-F
P31-34 4,6-CI2 P31-66 6-OCH3 P31-98 2-CF3-4-CI-
P31-35 2,5-CI2 P31-67 2-OCH2CH3 P31-99 2-CF3-4-F
P31-36 2,6-CI2 P31-68 4-OCH2CH3 P31-100 4-CF3-6-CI
P31-37 4,6-F2 P31-69 5-OCH2CH3 P31-101 4-CF3-6-F
P31-38 2,5-F2 P31-70 6-OCH2CH3 P31-102 6-CF3-4-F
P31-39 2,6-F2 P31-71 2-OCF3 P31-103 6-CF3-4-CI
P31-40 4-F-6-CI P31-72 4-OCF3
P31-41 4-CI-6-F P31-73 5-OCF3
-* means that n=0
More specific embodiments of (R3)n according to the invention are in Table P32 below, wherein each line of lines P32-1 to P32-47 corresponds to one particular embodiment of the invention, wherein P32-1 to P32-47 are also in any combination preferred embodiments of the present invention. The positions of the R3 are given in relation to the position of the attachment of the tertiary ether group. Table P32:
Figure imgf000017_0003
Figure imgf000017_0002
-* means that n=0
Each R4 according to the present invention is independently selected from halogen, CN, N02, OH, SH, d-Ce-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8- cycloalkyloxy, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl), C(=0)(Ci-C4-alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4- alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)-(N(C3-C6-cycloalkyl)2); wherein each of R4 is unsubstituted or further substituted by one, two, three or four R4a independently selected from halogen, CN, N02, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C3- cycloalkyl, C3-C8-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy and p is 0, 1 or 2.
According to the invention, there can be zero, one, two, three, four or five R4 present, namely for m is 0, 1 , 2, 3, 4 or 5. In particular, m is 0, 1 , 2, 3 or 4.
According to one embodiment, m is 0.
According to a further embodiment, m is 1 , 2, 3 or 4, in particular 1 , 2 or 3, more specifically 1 or 2. According to one specific embodiment thereof, m is 1 , according to a further specific embodiment, m is 2.
According to still a further embodiment, m is 2, 3 or 4.
According to still a further embodiment, m is 3.
According to one embodiment of the invention, one R4 is attached to the para-position (4- position).
According to a further embodiment of the invention, one R4 is attached to the meta-position (3- position). According to a further embodiment of the invention, one R4 is attached to the ortho-position (2- position).
According to a further embodiment of the invention, two R4 are attached in 2,4-position.
According to a further embodiment of the invention, two R4 are attached in 2,3-position.
According to a further embodiment of the invention, two R4 are attached in 2,5-position.
According to a further embodiment of the invention, two R4 are attached in 2,6-position.
According to a further embodiment of the invention, two R4 are attached in 3,4-position.
According to a further embodiment of the invention, two R4 are attached in 3,5-position.
According to a further embodiment of the invention, three R4 are attached in 2,4,6-position. For every R4 that is present in the inventive compounds, the following embodiments and preferences apply independently of the meaning of any other R4 that may be present in the phenyl ring. Furthermore, the particular embodiments and preferences given herein for R4 apply independently for each of m=1 , m=2, m=3, m= 4 and m=5.
According to one embodiment, R4 is independently selected from halogen, CN, NO2, OH, SH, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyloxy, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, N H(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4- alkyl) (p=0, 1 or 2), C(=0)(Ci-C4-alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4- alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)-(N(C3-C6-cycloalkyl)2); wherein each of R4 is unsubstituted or further substituted by one, two, three or four
independently selected R4a, wherein R4a is as defined and preferably defined herein.
According to a further embodiment, R4 is independently selected from halogen, CN, NO2, C1-C4- alkyl, Ci-C4-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, NH2, NH(Ci-C42-alkyl), N(Ci-C2-alkyl)2, S(0)P(Ci-C2-alkyl) (p=0, 1 or 2), C(=0)(Ci-C2-alkyl),
C(=0)(OH) and C(=0)(0-Ci-C2-alkyl), wherein each of R4 is unsubstituted or further substituted by one, two, three or four independently selected R4a, wherein R4a is as defined and preferably defined herein.
According to a further embodiment, R4 is independently selected from halogen, CN, NO2, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4- alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, S(Ci-C2-alkyl), S(0)(Ci-C2- alkyl), S(0)2(Ci-C2-alkyl), C(=0)(Ci-C2-alkyl), C(=0)(OH) and C(=0)(0-Ci-C2-alkyl).
According to a further embodiment, R4 is independently selected from halogen, CN, NO2, C1-C2- alkyl, Ci-C2-haloalkyl, Ci-C2-alkoxy, Ci-C2-haloalkoxy, S(Ci-C2-alkyl), S(0)(Ci-C2-alkyl), S(0)2(Ci-C2-alkyl), C(=0)(OH) and C(=0)(0-Ci-C2-alkyl).
According to a further embodiment, R4 is independently selected from F, CI, Br, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, S(Ci-C4-alkyl), S(0)(Ci-C4-alkyl) and S(0)2(Ci- C4-alkyl).
According to still a further specific embodiment, R4 is independently selected from halogen, in particular from Br, F and CI, more specifically from F and CI. According to a further specific embodiment, R4 is CN.
According to one further embodiment R4 is NO2.
According to one further embodiment R4 is OH.
According to one further embodiment R4 is SH.
According to a further specific embodiment, R4 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH3. Further appropriate alkyls are ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl.
According to a further specific embodiment, R4 is Ci-C6-haloalkyl, in particular Ci-C4-haloalkyl, such as CF3, CHF2, CH2F, CCI3, CHC or CH2CI.
According to a further specific embodiment R4 is Ci-C6-alkyl, preferably Ci-C4-alkyl, substituted by OH, more preferably CH2OH, CH2CH2OH, CH2CH2CH2OH, CH(CH3)CH2OH,
CH2CH(CH3)OH, CH2CH2CH2CH2OH. In a special embodiment R4 is CH2OH. According to a further specific embodiment R4 is Ci-C6-alkyl, preferably Ci-C4-alkyl substituted by CN, more preferably CH2CN, CH2CH2CN, CH2CH2CH2CN, CH(CH3)CH2CN, CH2CH(CH3)CN, CH2CH- 2CH2CH2CN. In a special embodiment R4 is CH2CH2CN. In a further special embodiment R4 is CH(CH3)CN. According to a further specific embodiment R4 is Ci-C4-alkoxy-Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl. In a special embodiment R4 is CH20CH3. In a further special embodiment R4 is CH2CH2OCH3. In a further special embodiment R4 is CH(CH3)OCH3. In a further special embodiment R4 is CH(CH3)OCH2CH3. In a further special embodiment R4 is CH2CH20CH2CH3. According to a further specific embodiment R4 is Ci-C4-haloalkoxy-Ci-C6- alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl. In a special embodiment R4 is CH20CF3. In a further special embodiment R4 is CH2CH20CF3. In a further special embodiment R4 is
CH2OCCI3. In a further special embodiment R4 is CH2CH2OCCI3.
According to a further specific embodiment, R4 is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH3 or OCH2CH3.
According to a further specific embodiment, R4 is Ci-C6-haloalkoxy, in particular C1-C4- haloalkoxy, more specifically Ci-C2-haloalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHC or OCH2CI, in particular OCF3, OCHF2, OCCI3 or OCHCb.
According to still a further embodiment, R4 is C2-C6-alkenyl or C2-C6-haloalkenyl, in particular C2-C4-alkenyl or C2-C4-haloalkenyl, such as CH=CH2, CH2CH=CH2, CH=CHCH3 or
C(CH3)=CH2.
According to a further specific embodiment R4 is C2-C6-alkenyl, preferably C2-C4-alkenyl, substituted by OH, more preferably, CH=CHOH, CH=CHCH2OH, C(CH3)=CHOH, CH=C(CH3)OH. In a special embodiment R4 is CH=CHOH. In a further special embodiment R4 is CH=CHCH2OH. According to a further specific embodiment R4 is Ci-C4-alkoxy-C2-C6-alkenyl, more preferably Ci-C4-alkoxy-C2-C4-alkenyl. In a special embodiment R4 is CH=CHOCH3. In a further special embodiment R4 is CH=CHCH20CH3. According to a further specific embodiment R4 is C1-C4- haloalkoxy-C2-C6-alkenyl, more preferably Ci-C4-haloalkoxy-C2-C4-alkenyl. In a special embodiment R4 is CH=CHOCF3. In a further special embodiment R4 is CH=CHCH2OCF3. In a further special embodiment R4 is CH=CHOCCI3. In a further special embodiment R4 is
CH=CHCH2OCCI3. According to a further specific embodiment R4 is C3-C8-cycloalkyl-C2-Ce- alkenyl, preferably C3-C6-cycloalkyl-C2-C4-alkenyl. According to a further specific embodiment R4 is C3-C6-halocycloalkyl-C2-C4-alkenyl, preferably C3-C8-halocycloalkyl-C2-C6-alkenyl.
According to still a further embodiment, R4 is C2-C6-alkynyl or C2-C6-haloalkynyl, in particular C2-C4-alkynyl or C2-C4-haloalkynyl, such as C≡CH, CH2CCH or CH2CCCH3.
According to a further specific embodiment R4 is C2-C6-alkynyl, preferably C2-C4-alkynyl, substituted by OH, more preferably, CCOH, CH2CCOH. In a special embodiment R4 is CCOH. In a further special embodiment R4 is CH2CCOH. According to a further specific embodiment R4 is Ci-C4-alkoxy-C2-C6-alkynyl, more preferably Ci-C4-alkoxy-C2-C4-alkynyl. In a special embodiment R4 is CCOCH3. In a further special embodiment R4 is CH2CCOCH3. According to a further specific embodiment R4 is Ci-C4-haloalkoxy-C2-C6-alkynyl, more preferably Ci-C4-haloalkoxy- C2-C4-alkynyl. In a special embodiment R4 is CCOCF3. In a further special embodiment R4 is CH2CCOCF3. In a further special embodiment R4 is CCOCCI3. In a further special embodiment R4 is CH2CCOCCI3. According to a further specific embodiment R4 is C3-C8-cycloalkyl-C2-C6- alkynyl, preferably C3-C6-cycloalkyl-C2-C4-alkynyl. According to a further specific embodiment R4 is C3-C6-halocycloalkyl-C2-C4-alkynyl, preferably C3-C8-halocycloalkyl-C2-C6-alkynyl.
According to one another embodiment R4 is Cs-Cs-cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl. In a special embodiment R4 is cyclopropyl. In a further special embodiment R4 is cyclobutyl. In a further special embodiment R4 is cyclopentyl. In a further special embodiment R4 is cyclohexyl.
According to one another embodiment R4 is Cs-Cs-cycloalkoxy, preferably C3-C6-cycloalkoxy. In a special embodiment R4 is O-cyclopropyl.
According to a specific embodiment R4 is Cs-Cs-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl. In a special embodiment R4 is fully or partially halogenated cyclopropyl. In a further special embodiment R4 is 1-CI-cyclopropyl. In a further special embodiment R4 is 2-CI-cyclopropyl. In a further special embodiment R4 is 1-F-cyclopropyl. In a further special embodiment R4 is 2-F-cyclopropyl. In a further special embodiment R4 is fully or partially halogenated cyclobutyl. In a further special embodiment R4 is 1-CI-cyclobutyl. In a further special embodiment R4 is 1-F-cyclobutyl. In a further special embodiment R4 is 3,3-Cl2-cyclobutyl. In a further special embodiment R4 is 3,3-F2-cyclobutyl. According to a specific embodiment R4 is C3- Cs-cycloalkyl substituted by Ci-C4-alkyl, more preferably is C3-C6-cycloalkyl substituted by Ci- C4-alkyl. In a special embodiment R4 is 1-CH3-cyclopropyl. According to a specific embodiment R4 is Cs-Cs-cycloalkyl substituted by CN, more preferably is C3-C6-cycloalkyl substituted by CN. In a special embodiment R4 is 1-CN-cyclopropyl.According to a further specific embodiment R4 is C3-C8-cycloalkyl-C3-C8-cycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-cycloalkyl. In a special embodiment R4 is cyclopropyl-cyclopropyl. In a special embodiment R4 is 2-cyclopropyl- cyclopropyl. According to a further specific embodiment R4 is C3-Cs-cycloalkyl-C3-Cs- halocycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-halocycloalkyl.
According to one another embodiment R4 is C3-C8-cycloalkyl-Ci-C4-alkyl, preferably C3-C6- cycloalkyl-Ci-C4-alkyl. In a special embodiment R4 is CH(CH3)(cyclopropyl). In a further special embodiment R4 is CH2-(cyclopropyl). According to a further preferred embodiment R4 is C3-C8-cycloalkyl-Ci-C4-alkyl wherein the alkyl moiety can be substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein and the cycloalkyi moiety can be substituted by one, two, three or up to the maximum possible number of identical or different groups Rb as defined and preferably herein.
According to a specific embodiment R4 is C3-C8-cycloalkyl-Ci-C4-haloalkyl, C3-C6-cycloalkyl-Ci- C4-haloalkyl. According to a specific embodiment R4 is C3-C8-halocycloalkyl-Ci-C4-alkyl, C3-C6- halocycloalkyl-Ci-C4-alkyl. In a special embodiment R4 is fully or partially halogenated cyclopro- pyl-Ci-C4-alkyl. In a further special embodiment R4 is 1 -CI-cyclopropyl-Ci-C4-alkyl. In a further special embodiment R4 is 1 -F-cyclopropyl-Ci-C4-alkyl.
According to one another embodiment R4 is NH2.
According to one another embodiment R4 is NH(Ci-C4-alkyl). According to a specific embodiment R4 is NH(CH3). According to a specific embodiment R4 is NH(CH2CH3). According to a specific embodiment R4 is NH(CH2CH2CH3). According to a specific embodiment R4 is
NH(CH(CH3)2). According to a specific embodiment R4 is NH(CH2CH2CH2CH3). According to a specific embodiment R4 is NH(C(CH3)3).
According to one another embodiment R4 is N(Ci-C4-alkyl)2. According to a specific embodiment R4 is N(CH3)2. According to a specific embodiment R4 is N(CH2CH3)2. According to a specific embodiment R4 is N(CH2CH2CI-l3)2. According to a specific embodiment R4 is N(CH(CH3)2)2.
According to a specific embodiment R4 is N(CH2CH2CH2CH3)2. According to a specific embodiment R4 is NH(C(CH3)3)2.
According to one another embodiment R4 is NH(C3-C8-cycloalkyl) preferably NH(C3-C6- cycloalkyl). According to a specific embodiment R4 is NH(cyclopropyl). According to a specific embodiment R4 is NH(cyclobutyl). According to a specific embodiment R4 is NH(cyclopentyl). According to a specific embodiment R4 is NH(cyclohexyl).
According to one another embodiment R4 is N(C3-C8-cycloalkyl)2 preferably N(C3-C6- cycloalkyl)2. According to a specific embodiment R4 is N(cyclopropyl)2. According to a specific embodiment R4 is N(cyclobutyl)2. According to a specific embodiment R4 is N(cyclopentyl)2.
According to a specific embodiment R4 is N(cyclohexyl)2.
According to still a further embodiment, R4 is selected from C(=0)(Ci-C4-alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4-alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6- cycloalkyl)) and C(=0)(N(C3-C6-cycloalkyl)2), in particular selected from C(=0)(Ci-C2-alkyl), C(=0)(OH), C(=0)(0-Ci-C2-alkyl), C(=0)(NH(Ci-C2-alkyl)), C(=0)(N(Ci-C2-alkyl)2),
C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)(N(C3-C6-cycloalkyl)2). According to one specific embod- iment thereof, R4 is C(=0)(OH) or C(=0)(0-Ci-C4-alkyl), in particular C(=0)(OCH3).
According to one another embodiment R4 is C(=0)(-Ci-C4-alkyl). According to a specific embodiment R4 is C(=0)CH3.. According to a further specific embodiment R4 is C(=0)CH2CH3. According to a further specific embodiment R4 is C(=0)CH2CH2CH3. According to a further specific embodiment R4 is C(=0)CH(CH3)2. According to a further specific embodiment R4 is C(=0)C(CH3)3. According to one another embodiment R4 is C(=0)OH.
According to one another embodiment R4 is C(=0)(-0-Ci-C4-alkyl). According to a specific embodiment R4 is C(=0)OCH3, According to a further specific embodiment R4 is C(=0)OCH2CH3. According to a further specific embodiment R4 is C(=0)OCH2CH2CH3. According to a further spe- cific embodiment R4 is C(=0)OCH(CH3)2. According to a further specific embodiment R4 is C(=0)OC(CH3)3.
According to one another embodiment R4 is C(=0)-NH(Ci-C4-alkyl). According to a specific embodiment R4 is C(=0)NHCH3, According to a further specific embodiment R4 is C(=0)NHCH2CH3. According to a further specific embodiment R4 is C(=0)NHCH2CH2CH3. According to a further specific embodiment R4 is C(=0)NHCH(CH3)2. According to a further specific embodiment R4 is C(=0)NHC(CH3)3.
According to one another embodiment R4 is C(=0)-N(Ci-C4-alkyl)2. According to a specific embodiment R4 is C(=0)N(CH3)2. According to a further specific embodiment R4 is
C(=0)N(CH2CH3)2. According to a further specific embodiment R4 is C(=0)N(CH2CH2CH3)2. Ac- cording to a further specific embodiment R4 is C(=0)N(CH(CH3)2)2. According to a further specific embodiment R4 is C(=0)N(C(CH3)3)2.
According to one another embodiment R4 is C(=0)-NH(C3-C6-cycloalkyl). According to a specific embodiment R4 is C(=0)NH(cyclopropyl).. According to a further specific embodiment R4 is C(=0)NH(cyclobutyl). According to a further specific embodiment R4 is C(=0)NH(cyclopentyl). Ac- cording to a further specific embodiment R4 is C(=0)NH(cyclohexyl).
According to one another embodiment R4 is C(=0)-N(C3-C6-cycloalkyl)2. According to a specific embodiment R4 is C(=0)N(cyclopropyl)2. According to a further specific embodiment R4 is C(=0)N(cyclobutyl)2. According to a further specific embodiment R4 is C(=0)N(cyclopentyl)2. According to a further specific embodiment R4 is C(=0)N(cyclohexyl)2.
According to still a further embodiment, R4 is selected from S(Ci-C2-alkyl), S(0)(Ci-C2-alkyl) and S(0)2(Ci-C2-alkyl), in particular SCH3, S(0)(CH3) and S(0)2(CH3). According to a specific embodiment R4 is selected from S(Ci-C2-haloalkyl), S(0)(Ci-C2-haloalkyl) and S(0)2(Ci-C2- haloalkyl), such as SO2CF3.
Particularly preferred embodiments of R4 according to the invention are in Table P4 below, wherein each line of lines P4-1 to P4-16 corresponds to one particular embodiment of the invention, wherein P4-1 to P4-16 are also in any combination with one another preferred embodiments of the present invention. Thereby, for every R4 that is present in the inventive
compounds, these specific embodiments and preferences apply independently of the meaning of any other R4 that may be present in the phenyl ring:
Table P4:
No. R4 No. R4 No. R4
P4-1 CI P4-5 CH3 P4-9 OCH3
P4-2 F P4-6 CH2CH3 P4-10 OCH2CH3
P4-3 CN P4-7 CF3 P4-1 1 OCF3
P4-4 N02 P4-8 CHF2 P4-12 OCHF2
Figure imgf000023_0001
Particularly preferred embodiments of (R4)m according to the invention are in Table P41 below, wherein each line of lines P41 -1 to P41 -156 corresponds to one particular embodiment of the invention, wherein P41-1 to P41-156 are also in any combination preferred embodiments of the present invention. The positions of the R4 are given in relation to the position of the attachment of the phenoxy-moiety (= in 1 -position).
Table P41:
No. (R4)m No. (R4)m No. (R4)m
P41-1 * P41-31 2,6-CI2 P41-61 3-CH3
P41-2 2-CI P41-32 2,3-F2 P41-62 4-CH3
P41-3 3-CI P41-33 2,4-F2 P41-63 2-CH2CH3
P41-4 4-CI P41-34 2,5-F2 P41-64 3-CH2CH3
P41-5 2-F P41-35 3,4-F2 P41-65 4-CH2CH3
P41-6 3-F P41-36 3,5-F2 P41-66 2-CF3
P41-7 4-F P41-37 2,6-F2 P41-67 3-CF3
P41-8 2-CN P41-38 2-F-3-CI P41-68 4-CF3
P41-9 3-CN P41-39 2-F-5-CI P41-69 2-CHF2
P41-10 4-CN P41-40 3-F-4-CI P41-70 3-CHF2
P41-11 2-NO2 P41-41 2-F-6-CI P41-71 4-CHF2
P41-12 3-NO2 P41-42 2-CI-3-F P41-72 2-OCH3
P41-13 4-NO2 P41-43 2-CI-5-F P41-73 3-OCH3
P41-14 2-SCHs P41-44 3-CI-4-F P41-74 4-OCH3
P41-15 3-SCH3 P41-45 2,3,4-C P41-75 2-OCH2CH3
P41-16 4-SCH3 P41-46 2,4,5-CI3 P41-76 3-OCH2CH3
P41-17 2-SOCH3 P41-47 3,4,5-CI3 P41-77 4-OCH2CH3
P41-18 3-SOCH3 P41-48 2,4,6-CI3 P41-78 2-OCF3
P41-19 4-SOCH3 P41-49 2,3,4-F3 P41-79 3-OCF3
P41-20 2-SO2CH3 P41-50 2,4,5-F3 P41-80 4-OCF3
P41-21 3-SO2CH3 P41-51 3,4,5-F3 P41-81 2-OCHF2
P41-22 4-SO2CH3 P41-52 2,4,6-F3 P41-82 3-OCHF2
P41-23 2-CO2CH3 P41-53 2,3-4-F3 P41-83 4-OCHF2
P41-24 3-CO2CH3 P41-54 2,4-F2-3-CI P41-84 2,3-(CH3)2
P41-25 4-CO2CH3 P41-55 2,6-F2-4-CI P41-85 2,4-(CH3)2
P41-26 2,3-CI2 P41-56 2,5-F2-4-CI P41-86 3,4-(CH3)2
P41-27 2,4-CI2 P41-57 2,4-CI2-3-F P41-87 2,6-(CH3)2
P41-28 2,5-CI2 P41-58 2,6-CI2-4-F P41-88 2,3-(CH2CH3)2
P41-29 3,4-CI2 P41-59 2,5-CI2-4-F P41-89 2,4-(CH2CH3)2
P41-30 3,5-CI2 P41-60 2-CH3 P41-90 3,4-(CH2CH3)2 No. (R4)m No. (R4)m No. (R4)m
P41-91 2,6-(CH2CH3)2 P41-113 2,4-(OCHF2)2 P41-135 2,4,6-(OCH3)3
P41-92 2,3-(CF3)2 P41-114 3,4-(OCHF2)2 P41-136 2,3,4-(OCH2CH3)3
P41-93 2,5-(CF3)2 P41-115 2,6-(OCHF2)2 P41-137 2,4,5-(OCH2CH3)3
P41-94 3,5-(CF3)2 P41-116 2,3,4-(CH3)3 P41-138 3,4,5-(OCH2CH3)3
P41-95 2,6-(CF3)2 P41-117 2,4,5-(CH3)3 P41-139 2,4,6-(OCH2CH3)3
P41-96 2,3-(CHF2)2 P41-118 3,4,5-(CH3)3 P41-140 2,3,4-(OCF3)3
P41-97 2,4-(CHF2)2 P41-119 2,4,6-(CH3)3 P41-141 2,4,5-(OCF3)3
P41-98 3,4-(CHF2)2 P41-120 2,3,4-(CH2CH3)3 P41-142 3,4,5-(OCF3)3
P41-99 2,6-(CHF2)2 P41-121 2,4,5-(CH2CH3)3 P41-143 2,4,6-(OCF3)3
P41-100 2,3-(OCH3)2 P41-122 3,4,5-(CH2CH3)3 P41-144 2,3,4-(OCHF2)3
P41-101 2,4-(OCH3)2 P41-123 2,4,6-(CH2CH3)3 P41-145 2,4,5-(OCHF2)3
P41-102 3,4-(OCH3)2 P41-124 2,3,4-(CF3)3 P41-146 3,4,5-(OCHF2)3
P41-103 2,6-(OCH3)2 P41-125 2,4,5-(CF3)3 P41-147 2,4,6-(OCHF2)3
P41-104 2,3-(OCH2CH3)2 P41-126 3,4,5-(CF3)3 P41-148 2-CF3-5-CI
P41-105 2,4-(OCH2CH3)2 P41-127 2,4,6-(CF3)3 P41-149 2-CF3-5-F
P41-106 3,4-(OCH2CH3)2 P41-128 2,3,4-(CHF2)3 P41-150 2-CF3-3-CI-
P41-107 2,6-(OCH2CH3)2 P41-129 2,4,5-(CHF2)3 P41-151 2-CF3-3-F
P41-108 2,3-(OCF3)2 P41-130 3,4,5-(CHF2)3 P41-152 3-CF3-5-CI
P41-109 2,4-(OCF3)2 P41-131 2,4,6-(CHF2)3 P41-153 3-CF3-5-F
P41-110 3,4-(OCF3)2 P41-132 2,3,4-(OCH3)3 P41-154 3-CF3-5-CI-
P41-111 2,6-(OCF3)2 P41-133 2,4,5-(OCH3)3 P41-155 3-CF3-6-F
P41-112 2,3-(OCHF2)2 P41-134 3,4,5-(OCH3)3 P41-156 3-CF3-6-CI
-* means that m=0
More particularly preferred embodiments of (R4)m according to the invention are in Table P42 below, wherein each line of lines P42-1 to P42-64 corresponds to one particular embodiment of the invention, wherein P42-1 to P42-64 are also in any combination preferred embodiments of the present invention. The positions of the R4 are given in relation to the position of the attachment of the phenoxy-moiety (= in 1 -position).
Table P42:
line (R4)m line (R4)m line (R4)m
P42-1 * P42-12 3-N02 P42-23 2-C02CH3
P42-2 2-CI P42-13 4-N02 P42-24 3-C02CH3
P42-3 3-CI P42-14 2-SCH3 P42-25 4-C02CH3
P42-4 4-CI P42-15 3-SCH3 P42-26 2-CH3
P42-5 2-F P42-16 4-SCH3 P42-27 3-CH3
P42-6 3-F P42-17 2-SOCH3 P42-28 4-CH3
P42-7 4-F P42-18 3-SOCH3 P42-29 2-CF3
P42-8 2-CN P42-19 4-SOCH3 P42-30 3-CF3
P42-9 3-CN P42-20 2-S02CH3 P42-31 4-CF3
P42-10 4-CN P42-21 3-S02CH3 P42-32 2-CHF2
P42-11 2-N02 P42-22 4-S02CH3 P42-33 3-CHF2 line (R4)m line (R4)m line (R4)m
P42-34 4-CHF2 P42-45 2,3-C P42-56 2,6-F2
P42-35 2-OCHs P42-46 2,4-Cfe P42-57 2-CF3-4-CI
P42-36 3-OCHs P42-47 2,5-CI2 P42-58 2-CF3-4-F
P42-37 4-OCHs P42-48 3,4-C P42-59 2-CI-4-CF3
P42-38 2-OCFs P42-49 3,5-CI2 P42-60 2-F-4-CF3
P42-39 3-OCF3 P42-50 2,6-CI2 P42-61 2-CN-4-CI
P42-40 4-OCF3 P42-51 2,3-F2 P42-62 2-CN-4-F
P42-41 2-OCHF2 P42-52 2,4-F2 P42-63 2-CI-4-CN
P42-42 3-OCHF2 P42-53 2,5-F2 P42-64 2-F-4-CN
P42-43 4-OCHF2 P42-54 3,4-F2
P42-44 2,4,6-(CH3)3 P42-55 3,5-F2
-* means that m=0
One particular embodiment relates to compounds I, wherein n+m is 1 or > 1 , namely, 1 , 2, 3, 4, 5, 6, 7, 8 or 9, more specifically 1 , 2, 3, 4 or 5. In specific embodiment thereof, n+m is 1 , 2 or 3.
Accordin to one embodiment, X is N and Y is N, corresponding to compounds I. A:
Figure imgf000025_0001
According to a further embodiment, X is N and Y is CH, corresponding to compounds I.B:
Figure imgf000025_0002
According to still a further embodiment, X is CH and Y is CH, corresponding to compounds I.C:
Figure imgf000025_0003
In particular with a view to their use, preference is given to the compounds of the formula I, in particular I.A, I.B and I.C, compiled in the Tables 1 a to 13a, Tables 1 b to 13b and Tables 1 c to 13c below. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question. Table 1 a Compounds of the formula I .A in which R2 corresponds to line B-1 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-1 .A1 to I.A.B-1 .A21 12).
Table 2a Compounds of the formula I. A in which R2 corresponds to line B-2 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-2.A1 to I.A.B-2.A21 12).
Table 3a Compounds of the formula I. A in which R2 corresponds to line B-3 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-3.A1 to I.A.B-3.A21 12).
Table 4a Compounds of the formula I .A in which R2 corresponds to line B-4 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-4.A1 to I.A.B-4.A21 12).
Table 5a Compounds of the formula I. A in which R2 corresponds to line B-5 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-5.A1 to I.A.B-5.A21 12).
Table 6a Compounds of the formula I. A in which R2 corresponds to line B-6 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-6.A1 to I.A.B-6.A21 12).
Table 7a Compounds of the formula I. A in which R2 corresponds to line B-7 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-7.A1 to I.A.B-7.A21 12).
Table 8a Compounds of the formula I. A in which R2 corresponds to line B-8 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-8.A1 to I.A.B-8.A21 12).
Table 9a Compounds of the formula I. A in which R2 corresponds to line B-9 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-9.A1 to I.A.B-9.A21 12).
Table 10a Compounds of the formula I .A in which R2 corresponds to line B-10 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corre- sponds in each case to one line of Table A (compounds I.A.B-10.A1 to I.A.B-10.A21 12).
Table 1 1 a Compounds of the formula I .A in which R2 corresponds to line B-1 1 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-1 1 .A1 to I.A.B-1 1 .A21 12).
Table 12a Compounds of the formula I .A in which R2 corresponds to line B-12 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-12.A1 to I.A.B-12.A21 12).
Table 13a Compounds of the formula I .A in which R2 corresponds to line B-13 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.A.B-13.A1 to I.A.B-13.A21 12).
Table 1 b Compounds of the formula I.B in which R2 corresponds to line B-1 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B. B-1 .A1 to I.B. B-1 .A21 12). Table 2b Compounds of the formula I.B in which R2 corresponds to line B-2 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-2.A1 to I.B.B-2.A21 12).
Table 3b Compounds of the formula I.B in which R2 corresponds to line B-3 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-3.A1 to I.B.B-3.A21 12).
Table 4b Compounds of the formula I.B in which R2 corresponds to line B-4 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-4.A1 to I.B.B-4.A21 12).
Table 5b Compounds of the formula I.B in which R2 corresponds to line B-5 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-5.A1 to I.B.B-5.A21 12).
Table 6b Compounds of the formula I.B in which R2 corresponds to line B-6 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-6.A1 to I.B.B-6.A21 12).
Table 7b Compounds of the formula I.B in which R2 corresponds to line B-7 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-7.A1 to I.B.B-7.A21 12).
Table 8b Compounds of the formula I.B in which R2 corresponds to line B-8 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-8.A1 to I.B.B-8.A21 12).
Table 9b Compounds of the formula I.B in which R2 corresponds to line B-9 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-9.A1 to I.B.B-9.A21 12).
Table 10b Compounds of the formula I.B in which R2 corresponds to line B-10 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-10.A1 to I.B.B-10.A21 12).
Table 1 1 b Compounds of the formula I.B in which R2 corresponds to line B-1 1 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corre- sponds in each case to one line of Table A (compounds I.B. B-1 1 .A1 to I.B. B-1 1 .A21 12).
Table 12b Compounds of the formula I.B in which R2 corresponds to line B-12 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-12.A1 to I.B.B-12.A21 12).
Table 13b Compounds of the formula I.B in which R2 corresponds to line B-13 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.B.B-13.A1 to I.B.B-13.A21 12).
Table 1 c Compounds of the formula I .C in which R2 corresponds to line B-1 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-1 .A1 to I.C.B-1 .A21 12).
Table 2c Compounds of the formula I.C in which R2 corresponds to line B-2 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-2.A1 to I.C.B-2.A21 12). Table 3c Compounds of the formula I.C in which R2 corresponds to line B-3 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-3.A1 to I.C.B-3.A21 12).
Table 4c Compounds of the formula I.C in which R2 corresponds to line B-4 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-4.A1 to I.C.B-4.A21 12).
Table 5c Compounds of the formula I.C in which R2 corresponds to line B-5 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-5.A1 to I.C.B-5.A21 12).
Table 6c Compounds of the formula I.C in which R2 corresponds to line B-6 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-6.A1 to I.C.B-6.A21 12).
Table 7c Compounds of the formula I.C in which R2 corresponds to line B-7 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-7.A1 to I.C.B-7.A21 12).
Table 8c Compounds of the formula I.C in which R2 corresponds to line B-8 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-8.A1 to I.C.B-8.A21 12).
Table 9c Compounds of the formula I.C in which R2 corresponds to line B-9 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-9.A1 to I.C.B-9.A21 12).
Table 10c Compounds of the formula I .C in which R2 corresponds to line B-10 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-10.A1 to I.C.B-10.A21 12).
Table 1 1 c Compounds of the formula I .C in which R2 corresponds to line B-1 1 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C. B-1 1.A1 to I.C. B-1 1 .A21 12).
Table 12c Compounds of the formula I .C in which R2 corresponds to line B-12 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-12.A1 to I.C.B-12.A21 12).
Table 13c Compounds of the formula I .C in which R2 corresponds to line B-13 of Table B and the meaning for the combination of (R3)n and (R4)m for each individual compound corresponds in each case to one line of Table A (compounds I.C.B-13.A1 to I.C.B-13.A21 12).
Table B
Figure imgf000028_0001
Figure imgf000028_0003
Figure imgf000028_0002
Table A
Figure imgf000029_0001
line (R3)n (R4)m line (R3)n (R4)m
A-79 2-CI 3-SCHs A-1 18 2-CI 3,4-F2
A-80 2-CI 4-SCHs A-1 19 2-CI 3,5-F2
A-81 2-CI 2-SOCH3 A-120 2-CI 2,6-F2
A-82 2-CI 3-SOCH3 A-121 2-CI 2-CF3-4-CI
A-83 2-CI 4-SOCH3 A-122 2-CI 2-CF3-4-F
A-84 2-CI 2-SO2CH3 A-123 2-CI 2-CI-4-CF3
A-85 2-CI 3-SO2CH3 A-124 2-CI 2-F-4-CF3
A-86 2-CI 4-SO2CH3 A-125 2-CI 2-CN-4-CI
A-87 2-CI 2-CO2CH3 A-126 2-CI 2-CN-4-F
A-88 2-CI 3-CO2CH3 A-127 2-CI 2-CI-4-CN
A-89 2-CI 4-CO2CH3 A-128 2-CI 2-F-4-CN
A-90 2-CI 2-CH3 A-129 4-CI *
A-91 2-CI 3-CH3 A-130 4-CI 2-CI
A-92 2-CI 4-CH3 A-131 4-CI 3-CI
A-93 2-CI 2-CF3 A-132 4-CI 4-CI
A-94 2-CI 3-CF3 A-133 4-CI 2-F
A-95 2-CI 4-CF3 A-134 4-CI 3-F
A-96 2-CI 2-CHF2 A-135 4-CI 4-F
A-97 2-CI 3-CHF2 A-136 4-CI 2-CN
A-98 2-CI 4-CHF2 A-137 4-CI 3-CN
A-99 2-CI 2-OCH3 A-138 4-CI 4-CN
A-100 2-CI 3-OCH3 A-139 4-CI 2-NO2
A-101 2-CI 4-OCH3 A-140 4-CI 3-NO2
A-102 2-CI 2-OCF3 A-141 4-CI 4-NO2
A-103 2-CI 3-OCF3 A-142 4-CI 2-SCH3
A-104 2-CI 4-OCF3 A-143 4-CI 3-SCH3
A-105 2-CI 2-OCHF2 A-144 4-CI 4-SCH3
A-106 2-CI 3-OCHF2 A-145 4-CI 2-SOCH3
A-107 2-CI 4-OCHF2 A-146 4-CI 3-SOCH3
A-108 2-CI 2,4,6-(CH3)3 A-147 4-CI 4-SOCH3
A-109 2-CI 2,3-CI2 A-148 4-CI 2-SO2CH3
A-1 10 2-CI 2,4-CI2 A-149 4-CI 3-SO2CH3
A-1 1 1 2-CI 2,5-CI2 A-150 4-CI 4-SO2CH3
A-1 12 2-CI 3,4-CI2 A-151 4-CI 2-CO2CH3
A-1 13 2-CI 3,5-CI2 A-152 4-CI 3-CO2CH3
A-1 14 2-CI 2,6-CI2 A-153 4-CI 4-CO2CH3
A-1 15 2-CI 2,3-F2 A-154 4-CI 2-CH3
A-1 16 2-CI 2,4-F2 A-155 4-CI 3-CH3
A-1 17 2-CI 2,5-F2 A-156 4-CI 4-CH3 line (R3)n (R4)m line (R3)n (R4)m
A-157 4-CI 2-CFs A-196 5-CI 4-CI
A-158 4-CI 3-CFs A-197 5-CI 2-F
A-159 4-CI 4-CF3 A-198 5-CI 3-F
A-160 4-CI 2-CHF2 A-199 5-CI 4-F
A-161 4-CI 3-CHF2 A-200 5-CI 2-CN
A-162 4-CI 4-CHF2 A-201 5-CI 3-CN
A-163 4-CI 2-OCH3 A-202 5-CI 4-CN
A-164 4-CI 3-OCH3 A-203 5-CI 2-NO2
A-165 4-CI 4-OCH3 A-204 5-CI 3-NO2
A-166 4-CI 2-OCF3 A-205 5-CI 4-NO2
A-167 4-CI 3-OCF3 A-206 5-CI 2-SCH3
A-168 4-CI 4-OCF3 A-207 5-CI 3-SCH3
A-169 4-CI 2-OCHF2 A-208 5-CI 4-SCH3
A-170 4-CI 3-OCHF2 A-209 5-CI 2-SOCH3
A-171 4-CI 4-OCHF2 A-210 5-CI 3-SOCH3
A-172 4-CI 2,4,6-(CH3)3 A-21 1 5-CI 4-SOCH3
A-173 4-CI 2,3-CI2 A-212 5-CI 2-SO2CH3
A-174 4-CI 2,4-CI2 A-213 5-CI 3-SO2CH3
A-175 4-CI 2,5-CI2 A-214 5-CI 4-SO2CH3
A-176 4-CI 3,4-CI2 A-215 5-CI 2-CO2CH3
A-177 4-CI 3,5-CI2 A-216 5-CI 3-CO2CH3
A-178 4-CI 2,6-CI2 A-217 5-CI 4-CO2CH3
A-179 4-CI 2,3-F2 A-218 5-CI 2-CH3
A-180 4-CI 2,4-F2 A-219 5-CI 3-CH3
A-181 4-CI 2,5-F2 A-220 5-CI 4-CH3
A-182 4-CI 3,4-F2 A-221 5-CI 2-CFs
A-183 4-CI 3,5-F2 A-222 5-CI 3-CFs
A-184 4-CI 2,6-F2 A-223 5-CI 4-CF3
A-185 4-CI 2-CF3-4-CI A-224 5-CI 2-CHF2
A-186 4-CI 2-CF3-4-F A-225 5-CI 3-CHF2
A-187 4-CI 2-CI-4-CF3 A-226 5-CI 4-CHF2
A-188 4-CI 2-F-4-CF3 A-227 5-CI 2-OCH3
A-189 4-CI 2-CN-4-CI A-228 5-CI 3-OCH3
A-190 4-CI 2-CN-4-F A-229 5-CI 4-OCH3
A-191 4-CI 2-CI-4-CN A-230 5-CI 2-OCF3
A-192 4-CI 2-F-4-CN A-231 5-CI 3-OCF3
A-193 5-CI * A-232 5-CI 4-OCF3
A-194 5-CI 2-CI A-233 5-CI 2-OCHF2
A-195 5-CI 3-CI A-234 5-CI 3-OCHF2 line (R3)n (R4)m line (R3)n (R4)m
A-235 5-CI 4-OCHF2 A-274 6-CI 3-SOCH3
A-236 5-CI 2,4,6-(CH3)3 A-275 6-CI 4-SOCH3
A-237 5-CI 2,3-CI2 A-276 6-CI 2-S02CH3
A-238 5-CI 2,4-CI2 A-277 6-CI 3-S02CH3
A-239 5-CI 2,5-CI2 A-278 6-CI 4-S02CH3
A-240 5-CI 3,4-CI2 A-279 6-CI 2-C02CH3
A-241 5-CI 3,5-CI2 A-280 6-CI 3-C02CH3
A-242 5-CI 2,6-CI2 A-281 6-CI 4-C02CH3
A-243 5-CI 2,3-F2 A-282 6-CI 2-CH3
A-244 5-CI 2,4-F2 A-283 6-CI 3-CH3
A-245 5-CI 2,5-F2 A-284 6-CI 4-CH3
A-246 5-CI 3,4-F2 A-285 6-CI 2-CF3
A-247 5-CI 3,5-F2 A-286 6-CI 3-CF3
A-248 5-CI 2,6-F2 A-287 6-CI 4-CF3
A-249 5-CI 2-CF3-4-CI A-288 6-CI 2-CHF2
A-250 5-CI 2-CF3-4-F A-289 6-CI 3-CHF2
A-251 5-CI 2-CI-4-CF3 A-290 6-CI 4-CHF2
A-252 5-CI 2-F-4-CF3 A-291 6-CI 2-OCH3
A-253 5-CI 2-CN-4-CI A-292 6-CI 3-OCH3
A-254 5-CI 2-CN-4-F A-293 6-CI 4-OCH3
A-255 5-CI 2-CI-4-CN A-294 6-CI 2-OCF3
A-256 5-CI 2-F-4-CN A-295 6-CI 3-OCF3
A-257 6-CI * A-296 6-CI 4-OCF3
A-258 6-CI 2-CI A-297 6-CI 2-OCHF2
A-259 6-CI 3-CI A-298 6-CI 3-OCHF2
A-260 6-CI 4-CI A-299 6-CI 4-OCHF2
A-261 6-CI 2-F A-300 6-CI 2,4,6-(CH3)3
A-262 6-CI 3-F A-301 6-CI 2,3-CI2
A-263 6-CI 4-F A-302 6-CI 2,4-CI2
A-264 6-CI 2-CN A-303 6-CI 2,5-CI2
A-265 6-CI 3-CN A-304 6-CI 3,4-CI2
A-266 6-CI 4-CN A-305 6-CI 3,5-CI2
A-267 6-CI 2-N02 A-306 6-CI 2,6-CI2
A-268 6-CI 3-N02 A-307 6-CI 2,3-F2
A-269 6-CI 4-N02 A-308 6-CI 2,4-F2
A-270 6-CI 2-SCH3 A-309 6-CI 2,5-F2
A-271 6-CI 3-SCH3 A-310 6-CI 3,4-F2
A-272 6-CI 4-SCH3 A-31 1 6-CI 3,5-F2
A-273 6-CI 2-SOCH3 A-312 6-CI 2,6-F2
Figure imgf000033_0001
line (R3)n (R4)m line (R3)n (R4)m
A-391 4-F 4-F A-430 4-F 2,4-CI2
A-392 4-F 2-CN A-431 4-F 2,5-CI2
A-393 4-F 3-CN A-432 4-F 3,4-CI2
A-394 4-F 4-CN A-433 4-F 3,5-CI2
A-395 4-F 2-NO2 A-434 4-F 2,6-CI2
A-396 4-F 3-NO2 A-435 4-F 2,3-F2
A-397 4-F 4-NO2 A-436 4-F 2,4-F2
A-398 4-F 2-SCHs A-437 4-F 2,5-F2
A-399 4-F 3-SCHs A-438 4-F 3,4-F2
A-400 4-F 4-SCH3 A-439 4-F 3,5-F2
A-401 4-F 2-SOCH3 A-440 4-F 2,6-F2
A-402 4-F 3-SOCH3 A-441 4-F 2-CF3-4-CI
A-403 4-F 4-SOCH3 A-442 4-F 2-CF3-4-F
A-404 4-F 2-SO2CH3 A-443 4-F 2-CI-4-CF3
A-405 4-F 3-SO2CH3 A-444 4-F 2-F-4-CF3
A-406 4-F 4-SO2CH3 A-445 4-F 2-CN-4-CI
A-407 4-F 2-CO2CH3 A-446 4-F 2-CN-4-F
A-408 4-F 3-CO2CH3 A-447 4-F 2-CI-4-CN
A-409 4-F 4-CO2CH3 A-448 4-F 2-F-4-CN
A-410 4-F 2-CH3 A-449 5-F *
A-41 1 4-F 3-CH3 A-450 5-F 2-CI
A-412 4-F 4-CH3 A-451 5-F 3-CI
A-413 4-F 2-CF3 A-452 5-F 4-CI
A-414 4-F 3-CF3 A-453 5-F 2-F
A-415 4-F 4-CF3 A-454 5-F 3-F
A-416 4-F 2-CHF2 A-455 5-F 4-F
A-417 4-F 3-CHF2 A-456 5-F 2-CN
A-418 4-F 4-CHF2 A-457 5-F 3-CN
A-419 4-F 2-OCH3 A-458 5-F 4-CN
A-420 4-F 3-OCH3 A-459 5-F 2-NO2
A-421 4-F 4-OCH3 A-460 5-F 3-NO2
A-422 4-F 2-OCF3 A-461 5-F 4-NO2
A-423 4-F 3-OCF3 A-462 5-F 2-SCHs
A-424 4-F 4-OCF3 A-463 5-F 3-SCH3
A-425 4-F 2-OCHF2 A-464 5-F 4-SCH3
A-426 4-F 3-OCHF2 A-465 5-F 2-SOCH3
A-427 4-F 4-OCHF2 A-466 5-F 3-SOCH3
A-428 4-F 2,4,6-(CH3)3 A-467 5-F 4-SOCH3
A-429 4-F 2,3-CI2 A-468 5-F 2-SO2CH3 line (R3)n (R4)m line (R3)n (R4)m
A-469 5-F 3-SO2CH3 A-508 5-F 2-F-4-CF3
A-470 5-F 4-SO2CH3 A-509 5-F 2-CN-4-CI
A-471 5-F 2-CO2CH3 A-510 5-F 2-CN-4-F
A-472 5-F 3-CO2CH3 A-51 1 5-F 2-CI-4-CN
A-473 5-F 4-CO2CH3 A-512 5-F 2-F-4-CN
A-474 5-F 2-CH3 A-513 6-F *
A-475 5-F 3-CH3 A-514 6-F 2-CI
A-476 5-F 4-CH3 A-515 6-F 3-CI
A-477 5-F 2-CF3 A-516 6-F 4-CI
A-478 5-F 3-CF3 A-517 6-F 2-F
A-479 5-F 4-CF3 A-518 6-F 3-F
A-480 5-F 2-CHF2 A-519 6-F 4-F
A-481 5-F 3-CHF2 A-520 6-F 2-CN
A-482 5-F 4-CHF2 A-521 6-F 3-CN
A-483 5-F 2-OCH3 A-522 6-F 4-CN
A-484 5-F 3-OCH3 A-523 6-F 2-NO2
A-485 5-F 4-OCH3 A-524 6-F 3-NO2
A-486 5-F 2-OCF3 A-525 6-F 4-NO2
A-487 5-F 3-OCF3 A-526 6-F 2-SCH3
A-488 5-F 4-OCF3 A-527 6-F 3-SCH3
A-489 5-F 2-OCHF2 A-528 6-F 4-SCH3
A-490 5-F 3-OCHF2 A-529 6-F 2-SOCH3
A-491 5-F 4-OCHF2 A-530 6-F 3-SOCH3
A-492 5-F 2,4,6-(CH3)3 A-531 6-F 4-SOCH3
A-493 5-F 2,3-CI2 A-532 6-F 2-SO2CH3
A-494 5-F 2,4-CI2 A-533 6-F 3-SO2CH3
A-495 5-F 2,5-CI2 A-534 6-F 4-SO2CH3
A-496 5-F 3,4-CI2 A-535 6-F 2-CO2CH3
A-497 5-F 3,5-CI2 A-536 6-F 3-CO2CH3
A-498 5-F 2,6-CI2 A-537 6-F 4-CO2CH3
A-499 5-F 2,3-F2 A-538 6-F 2-CH3
A-500 5-F 2,4-F2 A-539 6-F 3-CH3
A-501 5-F 2,5-F2 A-540 6-F 4-CH3
A-502 5-F 3,4-F2 A-541 6-F 2-CF3
A-503 5-F 3,5-F2 A-542 6-F 3-CF3
A-504 5-F 2,6-F2 A-543 6-F 4-CF3
A-505 5-F 2-CF3-4-CI A-544 6-F 2-CHF2
A-506 5-F 2-CF3-4-F A-545 6-F 3-CHF2
A-507 5-F 2-CI-4-CF3 A-546 6-F 4-CHF2 line (R3)n (R4)m line (R3)n (R4)m
A-547 6-F 2-OCHs A-586 2-CN 4-CN
A-548 6-F 3-OCHs A-587 2-CN 2-N02
A-549 6-F 4-OCH3 A-588 2-CN 3-N02
A-550 6-F 2-OCF3 A-589 2-CN 4-N02
A-551 6-F 3-OCF3 A-590 2-CN 2-SCH3
A-552 6-F 4-OCF3 A-591 2-CN 3-SCH3
A-553 6-F 2-OCHF2 A-592 2-CN 4-SCH3
A-554 6-F 3-OCHF2 A-593 2-CN 2-SOCH3
A-555 6-F 4-OCHF2 A-594 2-CN 3-SOCH3
A-556 6-F 2,4,6-(CH3)3 A-595 2-CN 4-SOCH3
A-557 6-F 2,3-CI2 A-596 2-CN 2-S02CH3
A-558 6-F 2,4-CI2 A-597 2-CN 3-S02CH3
A-559 6-F 2,5-CI2 A-598 2-CN 4-S02CH3
A-560 6-F 3,4-CI2 A-599 2-CN 2-C02CH3
A-561 6-F 3,5-CI2 A-600 2-CN 3-C02CH3
A-562 6-F 2,6-CI2 A-601 2-CN 4-C02CH3
A-563 6-F 2,3-F2 A-602 2-CN 2-CH3
A-564 6-F 2,4-F2 A-603 2-CN 3-CH3
A-565 6-F 2,5-F2 A-604 2-CN 4-CH3
A-566 6-F 3,4-F2 A-605 2-CN 2-CF3
A-567 6-F 3,5-F2 A-606 2-CN 3-CF3
A-568 6-F 2,6-F2 A-607 2-CN 4-CF3
A-569 6-F 2-CF3-4-CI A-608 2-CN 2-CHF2
A-570 6-F 2-CF3-4-F A-609 2-CN 3-CHF2
A-571 6-F 2-CI-4-CF3 A-610 2-CN 4-CHF2
A-572 6-F 2-F-4-CF3 A-61 1 2-CN 2-OCH3
A-573 6-F 2-CN-4-CI A-612 2-CN 3-OCH3
A-574 6-F 2-CN-4-F A-613 2-CN 4-OCH3
A-575 6-F 2-CI-4-CN A-614 2-CN 2-OCF3
A-576 6-F 2-F-4-CN A-615 2-CN 3-OCF3
A-577 2-CN * A-616 2-CN 4-OCF3
A-578 2-CN 2-CI A-617 2-CN 2-OCHF2
A-579 2-CN 3-CI A-618 2-CN 3-OCHF2
A-580 2-CN 4-CI A-619 2-CN 4-OCHF2
A-581 2-CN 2-F A-620 2-CN 2,4,6-(CH3)3
A-582 2-CN 3-F A-621 2-CN 2,3-CI2
A-583 2-CN 4-F A-622 2-CN 2,4-CI2
A-584 2-CN 2-CN A-623 2-CN 2,5-CI2
A-585 2-CN 3-CN A-624 2-CN 3,4-CI2 line (R3)n (R4)m line (R3)n (R4)m
A-625 2-CN 3,5-CI2 A-664 4-CN 3-C02CH3
A-626 2-CN 2,6-CI2 A-665 4-CN 4-C02CH3
A-627 2-CN 2,3-F2 A-666 4-CN 2-CH3
A-628 2-CN 2,4-F2 A-667 4-CN 3-CH3
A-629 2-CN 2,5-F2 A-668 4-CN 4-CH3
A-630 2-CN 3,4-F2 A-669 4-CN 2-CF3
A-631 2-CN 3,5-F2 A-670 4-CN 3-CF3
A-632 2-CN 2,6-F2 A-671 4-CN 4-CF3
A-633 2-CN 2-CF3-4-CI A-672 4-CN 2-CHF2
A-634 2-CN 2-CF3-4-F A-673 4-CN 3-CHF2
A-635 2-CN 2-CI-4-CF3 A-674 4-CN 4-CHF2
A-636 2-CN 2-F-4-CF3 A-675 4-CN 2-OCH3
A-637 2-CN 2-CN-4-CI A-676 4-CN 3-OCH3
A-638 2-CN 2-CN-4-F A-677 4-CN 4-OCH3
A-639 2-CN 2-CI-4-CN A-678 4-CN 2-OCF3
A-640 2-CN 2-F-4-CN A-679 4-CN 3-OCF3
A-641 4-CN * A-680 4-CN 4-OCF3
A-642 4-CN 2-CI A-681 4-CN 2-OCHF2
A-643 4-CN 3-CI A-682 4-CN 3-OCHF2
A-644 4-CN 4-CI A-683 4-CN 4-OCHF2
A-645 4-CN 2-F A-684 4-CN 2,4,6-(CH3)3
A-646 4-CN 3-F A-685 4-CN 2,3-CI2
A-647 4-CN 4-F A-686 4-CN 2,4-CI2
A-648 4-CN 2-CN A-687 4-CN 2,5-CI2
A-649 4-CN 3-CN A-688 4-CN 3,4-CI2
A-650 4-CN 4-CN A-689 4-CN 3,5-CI2
A-651 4-CN 2-N02 A-690 4-CN 2,6-CI2
A-652 4-CN 3-N02 A-691 4-CN 2,3-F2
A-653 4-CN 4-N02 A-692 4-CN 2,4-F2
A-654 4-CN 2-SCH3 A-693 4-CN 2,5-F2
A-655 4-CN 3-SCH3 A-694 4-CN 3,4-F2
A-656 4-CN 4-SCH3 A-695 4-CN 3,5-F2
A-657 4-CN 2-SOCH3 A-696 4-CN 2,6-F2
A-658 4-CN 3-SOCH3 A-697 4-CN 2-CF3-4-CI
A-659 4-CN 4-SOCH3 A-698 4-CN 2-CF3-4-F
A-660 4-CN 2-S02CH3 A-699 4-CN 2-CI-4-CF3
A-661 4-CN 3-S02CH3 A-700 4-CN 2-F-4-CF3
A-662 4-CN 4-S02CH3 A-701 4-CN 2-CN-4-CI
A-663 4-CN 2-C02CH3 A-702 4-CN 2-CN-4-F line (R3)n (R4)m line (R3)n (R4)m
A-703 4-CN 2-CI-4-CN A-742 5-CN 2-OCF3
A-704 4-CN 2-F-4-CN A-743 5-CN 3-OCF3
A-705 5-CN * A-744 5-CN 4-OCF3
A-706 5-CN 2-CI A-745 5-CN 2-OCHF2
A-707 5-CN 3-CI A-746 5-CN 3-OCHF2
A-708 5-CN 4-CI A-747 5-CN 4-OCHF2
A-709 5-CN 2-F A-748 5-CN 2,4,6-(CH3)3
A-710 5-CN 3-F A-749 5-CN 2,3-CI2
A-71 1 5-CN 4-F A-750 5-CN 2,4-CI2
A-712 5-CN 2-CN A-751 5-CN 2,5-CI2
A-713 5-CN 3-CN A-752 5-CN 3,4-CI2
A-714 5-CN 4-CN A-753 5-CN 3,5-CI2
A-715 5-CN 2-NO2 A-754 5-CN 2,6-CI2
A-716 5-CN 3-NO2 A-755 5-CN 2,3-F2
A-717 5-CN 4-NO2 A-756 5-CN 2,4-F2
A-718 5-CN 2-SCHs A-757 5-CN 2,5-F2
A-719 5-CN 3-SCHs A-758 5-CN 3,4-F2
A-720 5-CN 4-SCH3 A-759 5-CN 3,5-F2
A-721 5-CN 2-SOCH3 A-760 5-CN 2,6-F2
A-722 5-CN 3-SOCH3 A-761 5-CN 2-CF3-4-CI
A-723 5-CN 4-SOCH3 A-762 5-CN 2-CF3-4-F
A-724 5-CN 2-SO2CH3 A-763 5-CN 2-CI-4-CF3
A-725 5-CN 3-SO2CH3 A-764 5-CN 2-F-4-CF3
A-726 5-CN 4-SO2CH3 A-765 5-CN 2-CN-4-CI
A-727 5-CN 2-CO2CH3 A-766 5-CN 2-CN-4-F
A-728 5-CN 3-CO2CH3 A-767 5-CN 2-CI-4-CN
A-729 5-CN 4-CO2CH3 A-768 5-CN 2-F-4-CN
A-730 5-CN 2-CH3 A-769 6-CN *
A-731 5-CN 3-CH3 A-770 6-CN 2-CI
A-732 5-CN 4-CH3 A-771 6-CN 3-CI
A-733 5-CN 2-CF3 A-772 6-CN 4-CI
A-734 5-CN 3-CF3 A-773 6-CN 2-F
A-735 5-CN 4-CF3 A-774 6-CN 3-F
A-736 5-CN 2-CHF2 A-775 6-CN 4-F
A-737 5-CN 3-CHF2 A-776 6-CN 2-CN
A-738 5-CN 4-CHF2 A-777 6-CN 3-CN
A-739 5-CN 2-OCH3 A-778 6-CN 4-CN
A-740 5-CN 3-OCH3 A-779 6-CN 2-NO2
A-741 5-CN 4-OCH3 A-780 6-CN 3-NO2
Figure imgf000039_0001
line (R3)n (R4)m line (R3)n (R4)m
A-859 4,6-CI2 3-CHs A-898 4,6-F2 2-CI
A-860 4,6-CI2 4-CHs A-899 4,6-F2 3-CI
A-861 4,6-CI2 2-CF3 A-900 4,6-F2 4-CI
A-862 4,6-CI2 3-CF3 A-901 4,6-F2 2-F
A-863 4,6-CI2 4-CF3 A-902 4,6-F2 3-F
A-864 4,6-CI2 2-CHF2 A-903 4,6-F2 4-F
A-865 4,6-CI2 3-CHF2 A-904 4,6-F2 2-CN
A-866 4,6-CI2 4-CHF2 A-905 4,6-F2 3-CN
A-867 4,6-CI2 2-OCH3 A-906 4,6-F2 4-CN
A-868 4,6-CI2 3-OCH3 A-907 4,6-F2 2-NO2
A-869 4,6-CI2 4-OCH3 A-908 4,6-F2 3-NO2
A-870 4,6-CI2 2-OCF3 A-909 4,6-F2 4-NO2
A-871 4,6-CI2 3-OCF3 A-910 4,6-F2 2-SCH3
A-872 4,6-CI2 4-OCF3 A-91 1 4,6-F2 3-SCH3
A-873 4,6-CI2 2-OCHF2 A-912 4,6-F2 4-SCH3
A-874 4,6-CI2 3-OCHF2 A-913 4,6-F2 2-SOCH3
A-875 4,6-CI2 4-OCHF2 A-914 4,6-F2 3-SOCH3
A-876 4,6-CI2 2,4,6-(CH3)3 A-915 4,6-F2 4-SOCH3
A-877 4,6-CI2 2,3-C A-916 4,6-F2 2-SO2CH3
A-878 4,6-CI2 2,4-C A-917 4,6-F2 3-SO2CH3
A-879 4,6-CI2 2,5-CI2 A-918 4,6-F2 4-SO2CH3
A-880 4,6-CI2 3,4-C A-919 4,6-F2 2-CO2CH3
A-881 4,6-CI2 3,5-CI2 A-920 4,6-F2 3-CO2CH3
A-882 4,6-CI2 2,6-CI2 A-921 4,6-F2 4-CO2CH3
A-883 4,6-CI2 2,3-F2 A-922 4,6-F2 2-CH3
A-884 4,6-CI2 2,4-F2 A-923 4,6-F2 3-CHs
A-885 4,6-CI2 2,5-F2 A-924 4,6-F2 4-CHs
A-886 4,6-CI2 3,4-F2 A-925 4,6-F2 2-CF3
A-887 4,6-CI2 3,5-F2 A-926 4,6-F2 3-CF3
A-888 4,6-CI2 2,6-F2 A-927 4,6-F2 4-CF3
A-889 4,6-CI2 2-CF3-4-CI A-928 4,6-F2 2-CHF2
A-890 4,6-CI2 2-CF3-4-F A-929 4,6-F2 3-CHF2
A-891 4,6-CI2 2-CI-4-CF3 A-930 4,6-F2 4-CHF2
A-892 4,6-CI2 2-F-4-CF3 A-931 4,6-F2 2-OCH3
A-893 4,6-CI2 2-CN-4-CI A-932 4,6-F2 3-OCH3
A-894 4,6-CI2 2-CN-4-F A-933 4,6-F2 4-OCH3
A-895 4,6-CI2 2-CI-4-CN A-934 4,6-F2 2-OCF3
A-896 4,6-CI2 2-F-4-CN A-935 4,6-F2 3-OCF3
A-897 *
4,6-F2 A-936 4,6-F2 4-OCF3 line (R3)n (R4)m line (R3)n (R4)m
A-937 4,6-F2 2-OCHF2 A-976 4-CI-6-F 4-SCH3
A-938 4,6-F2 3-OCHF2 A-977 4-CI-6-F 2-SOCH3
A-939 4,6-F2 4-OCHF2 A-978 4-CI-6-F 3-SOCH3
A-940 4,6-F2 2,4,6-(CH3)3 A-979 4-CI-6-F 4-SOCH3
A-941 4,6-F2 2,3-C A-980 4-CI-6-F 2-S02CH3
A-942 4,6-F2 2,4-Cfe A-981 4-CI-6-F 3-S02CH3
A-943 4,6-F2 2,5-CI2 A-982 4-CI-6-F 4-S02CH3
A-944 4,6-F2 3,4-C A-983 4-CI-6-F 2-C02CH3
A-945 4,6-F2 3,5-CI2 A-984 4-CI-6-F 3-C02CH3
A-946 4,6-F2 2,6-CI2 A-985 4-CI-6-F 4-C02CH3
A-947 4,6-F2 2,3-F2 A-986 4-CI-6-F 2-CH3
A-948 4,6-F2 2,4-F2 A-987 4-CI-6-F 3-CH3
A-949 4,6-F2 2,5-F2 A-988 4-CI-6-F 4-CH3
A-950 4,6-F2 3,4-F2 A-989 4-CI-6-F 2-CF3
A-951 4,6-F2 3,5-F2 A-990 4-CI-6-F 3-CF3
A-952 4,6-F2 2,6-F2 A-991 4-CI-6-F 4-CF3
A-953 4,6-F2 2-CF3-4-CI A-992 4-CI-6-F 2-CHF2
A-954 4,6-F2 2-CF3-4-F A-993 4-CI-6-F 3-CHF2
A-955 4,6-F2 2-CI-4-CF3 A-994 4-CI-6-F 4-CHF2
A-956 4,6-F2 2-F-4-CF3 A-995 4-CI-6-F 2-OCH3
A-957 4,6-F2 2-CN-4-CI A-996 4-CI-6-F 3-OCH3
A-958 4,6-F2 2-CN-4-F A-997 4-CI-6-F 4-OCH3
A-959 4,6-F2 2-CI-4-CN A-998 4-CI-6-F 2-OCF3
A-960 4,6-F2 2-F-4-CN A-999 4-CI-6-F 3-OCF3
A-961 4-CI-6-F * A-1000 4-CI-6-F 4-OCF3
A-962 4-CI-6-F 2-CI A-1001 4-CI-6-F 2-OCHF2
A-963 4-CI-6-F 3-CI A-1002 4-CI-6-F 3-OCHF2
A-964 4-CI-6-F 4-CI A-1003 4-CI-6-F 4-OCHF2
A-965 4-CI-6-F 2-F A-1004 4-CI-6-F 2,4,6-(CH3)3
A-966 4-CI-6-F 3-F A-1005 4-CI-6-F 2,3-CI2
A-967 4-CI-6-F 4-F A-1006 4-CI-6-F 2.4-CI2
A-968 4-CI-6-F 2-CN A-1007 4-CI-6-F 2,5-CI2
A-969 4-CI-6-F 3-CN A-1008 4-CI-6-F 3,4-C
A-970 4-CI-6-F 4-CN A-1009 4-CI-6-F 3,5-CI2
A-971 4-CI-6-F 2-N02 A-1010 4-CI-6-F 2,6-CI2
A-972 4-CI-6-F 3-N02 A-101 1 4-CI-6-F 2,3-F2
A-973 4-CI-6-F 4-N02 A-1012 4-CI-6-F 2,4-F2
A-974 4-CI-6-F 2-SCH3 A-1013 4-CI-6-F 2,5-F2
A-975 4-CI-6-F 3-SCH3 A-1014 4-CI-6-F 3,4-F2 line (R3)n (R4)m line (R3)n (R4)m
A-1015 4-CI-6-F 3,5-F2 A-1054 6-CI-4-F 3-CF3
A-1016 4-CI-6-F 2,6-F2 A-1055 6-CI-4-F 4-CF3
A-1017 4-CI-6-F 2-CF3-4-CI A-1056 6-CI-4-F 2-CHF2
A-1018 4-CI-6-F 2-CF3-4-F A-1057 6-CI-4-F 3-CHF2
A-1019 4-CI-6-F 2-CI-4-CF3 A-1058 6-CI-4-F 4-CHF2
A-1020 4-CI-6-F 2-F-4-CF3 A-1059 6-CI-4-F 2-OCH3
A-1021 4-CI-6-F 2-CN-4-CI A-1060 6-CI-4-F 3-OCH3
A-1022 4-CI-6-F 2-CN-4-F A-1061 6-CI-4-F 4-OCH3
A-1023 4-CI-6-F 2-CI-4-CN A-1062 6-CI-4-F 2-OCF3
A-1024 4-CI-6-F 2-F-4-CN A-1063 6-CI-4-F 3-OCF3
A-1025 6-CI-4-F * A-1064 6-CI-4-F 4-OCF3
A-1026 6-CI-4-F 2-CI A-1065 6-CI-4-F 2-OCHF2
A-1027 6-CI-4-F 3-CI A-1066 6-CI-4-F 3-OCHF2
A-1028 6-CI-4-F 4-CI A-1067 6-CI-4-F 4-OCHF2
A-1029 6-CI-4-F 2-F A-1068 6-CI-4-F 2,4,6-(CH3)3
A-1030 6-CI-4-F 3-F A-1069 6-CI-4-F 2,3-CI2
A-1031 6-CI-4-F 4-F A-1070 6-CI-4-F 2,4-CI2
A-1032 6-CI-4-F 2-CN A-1071 6-CI-4-F 2,5-CI2
A-1033 6-CI-4-F 3-CN A-1072 6-CI-4-F 3,4-CI2
A-1034 6-CI-4-F 4-CN A-1073 6-CI-4-F 3,5-CI2
A-1035 6-CI-4-F 2-NO2 A-1074 6-CI-4-F 2,6-CI2
A-1036 6-CI-4-F 3-NO2 A-1075 6-CI-4-F 2,3-F2
A-1037 6-CI-4-F 4-NO2 A-1076 6-CI-4-F 2,4-F2
A-1038 6-CI-4-F 2-SCH3 A-1077 6-CI-4-F 2,5-F2
A-1039 6-CI-4-F 3-SCH3 A-1078 6-CI-4-F 3,4-F2
A-1040 6-CI-4-F 4-SCH3 A-1079 6-CI-4-F 3,5-F2
A-1041 6-CI-4-F 2-SOCH3 A-1080 6-CI-4-F 2,6-F2
A-1042 6-CI-4-F 3-SOCH3 A-1081 6-CI-4-F 2-CF3-4-CI
A-1043 6-CI-4-F 4-SOCH3 A-1082 6-CI-4-F 2-CF3-4-F
A-1044 6-CI-4-F 2-SO2CH3 A-1083 6-CI-4-F 2-CI-4-CF3
A-1045 6-CI-4-F 3-SO2CH3 A-1084 6-CI-4-F 2-F-4-CF3
A-1046 6-CI-4-F 4-SO2CH3 A-1085 6-CI-4-F 2-CN-4-CI
A-1047 6-CI-4-F 2-CO2CH3 A-1086 6-CI-4-F 2-CN-4-F
A-1048 6-CI-4-F 3-CO2CH3 A-1087 6-CI-4-F 2-CI-4-CN
A-1049 6-CI-4-F 4-CO2CH3 A-1088 6-CI-4-F 2-F-4-CN
A-1050 6-CI-4-F 2-CH3 A-1089 *
Figure imgf000042_0001
A-1051 6-CI-4-F 3-CH3 A-1090 2-CH3 2-CI
A-1052 6-CI-4-F 4-CH3 A-1091 2-CH3 3-CI
A-1053 6-CI-4-F 2-CF3 A-1092 2-CH3 4-CI line (R3)n (R4)m line (R3)n (R4)m
A-1093 2-CHs 2-F A-1 132 2-CHs 2,4,6-(CH3)s
A-1094 2-CHs 3-F A-1 133 2-CHs 2,3-CI2
A-1095 2-CHs 4-F A-1 134 2-CHs 2,4-CI2
A-1096 2-CHs 2-CN A-1 135 2-CHs 2,5-CI2
A-1097 2-CHs 3-CN A-1 136 2-CHs 3,4-CI2
A-1098 2-CHs 4-CN A-1 137 2-CHs 3,5-CI2
A-1099 2-CHs 2-NO2 A-1 138 2-CHs 2,6-CI2
A-1 100 2-CHs 3-NO2 A-1 139 2-CHs 2,3-F2
A-1 101 2-CHs 4-NO2 A-1 140 2-CHs 2,4-F2
A-1 102 2-CHs 2-SCHs A-1 141 2-CHs 2,5-F2
A-1 103 2-CHs 3-SCHs A-1 142 2-CHs 3,4-F2
A-1 104 2-CHs 4-SCHs A-1 143 2-CHs 3,5-F2
A-1 105 2-CHs 2-SOCHs A-1 144 2-CHs 2,6-F2
A-1 106 2-CHs 3-SOCHs A-1 145 2-CHs 2-CF3-4-CI
A-1 107 2-CHs 4-SOCHs A-1 146 2-CHs 2-CF3-4-F
A-1 108 2-CHs 2-SO2CH3 A-1 147 2-CHs 2-CI-4-CF3
A-1 109 2-CHs 3-SO2CH3 A-1 148 2-CHs 2-F-4-CF3
A-1 1 10 2-CHs 4-SO2CH3 A-1 149 2-CHs 2-CN-4-CI
A-1 1 1 1 2-CHs 2-CO2CH3 A-1 150 2-CHs 2-CN-4-F
A-1 1 12 2-CHs 3-CO2CH3 A-1 151 2-CHs 2-CI-4-CN
A-1 1 13 2-CHs 4-CO2CH3 A-1 152 2-CHs 2-F-4-CN
A-1 1 14 2-CHs 2-CHs A-1 153 *
4-CHs
A-1 1 15 2-CHs 3-CHs A-1 154 4-CHs 2-CI
A-1 1 16 2-CHs 4-CHs A-1 155 4-CHs 3-CI
A-1 1 17 2-CHs 2-CFs A-1 156 4-CHs 4-CI
A-1 1 18 2-CHs 3-CFs A-1 157 4-CHs 2-F
A-1 1 19 2-CHs 4-CFs A-1 158 4-CHs 3-F
A-1 120 2-CHs 2-CHF2 A-1 159 4-CHs 4-F
A-1 121 2-CHs 3-CHF2 A-1 160 4-CHs 2-CN
A-1 122 2-CHs 4-CHF2 A-1 161 4-CHs 3-CN
A-1 123 2-CHs 2-OCHs A-1 162 4-CHs 4-CN
A-1 124 2-CHs 3-OCHs A-1 163 4-CHs 2-NO2
A-1 125 2-CHs 4-OCHs A-1 164 4-CHs 3-NO2
A-1 126 2-CHs 2-OCFs A-1 165 4-CHs 4-NO2
A-1 127 2-CHs 3-OCFs A-1 166 4-CHs 2-SCHs
A-1 128 2-CHs 4-OCFs A-1 167 4-CHs 3-SCHs
A-1 129 2-CHs 2-OCHF2 A-1 168 4-CHs 4-SCHs
A-1 130 2-CHs 3-OCHF2 A-1 169 4-CHs 2-SOCHs
A-1 131 2-CHs 4-OCHF2 A-1 170 4-CHs 3-SOCHs line (R3)n (R4)m line (R3)n (R4)m
A-1 171 4-CH3 4-SOCH3 A-1210 4-CH3 2-CF3-4-F
A-1 172 4-CH3 2-SO2CH3 A-121 1 4-CH3 2-CI-4-CF3
A-1 173 4-CH3 3-SO2CH3 A-1212 4-CH3 2-F-4-CF3
A-1 174 4-CH3 4-SO2CH3 A-1213 4-CH3 2-CN-4-CI
A-1 175 4-CH3 2-CO2CH3 A-1214 4-CH3 2-CN-4-F
A-1 176 4-CH3 3-CO2CH3 A-1215 4-CH3 2-CI-4-CN
A-1 177 4-CH3 4-CO2CH3 A-1216 4-CH3 2-F-4-CN
A-1 178 4-CH3 2-CH3 A-1217 *
Figure imgf000044_0001
A-1 179 4-CH3 3-CH3 A-1218 5-CH3 2-CI
A-1 180 4-CH3 4-CH3 A-1219 5-CH3 3-CI
A-1 181 4-CH3 2-CF3 A-1220 5-CH3 4-CI
A-1 182 4-CH3 3-CF3 A-1221 5-CH3 2-F
A-1 183 4-CH3 4-CF3 A-1222 5-CH3 3-F
A-1 184 4-CH3 2-CHF2 A-1223 5-CH3 4-F
A-1 185 4-CH3 3-CHF2 A-1224 5-CH3 2-CN
A-1 186 4-CH3 4-CHF2 A-1225 5-CH3 3-CN
A-1 187 4-CH3 2-OCH3 A-1226 5-CH3 4-CN
A-1 188 4-CH3 3-OCH3 A-1227 5-CH3 2-NO2
A-1 189 4-CH3 4-OCH3 A-1228 5-CH3 3-NO2
A-1 190 4-CH3 2-OCF3 A-1229 5-CH3 4-NO2
A-1 191 4-CH3 3-OCF3 A-1230 5-CH3 2-SCH3
A-1 192 4-CH3 4-OCF3 A-1231 5-CH3 3-SCH3
A-1 193 4-CH3 2-OCHF2 A-1232 5-CH3 4-SCH3
A-1 194 4-CH3 3-OCHF2 A-1233 5-CH3 2-SOCH3
A-1 195 4-CH3 4-OCHF2 A-1234 5-CH3 3-SOCH3
A-1 196 4-CH3 2,4,6-(CH3)3 A-1235 5-CH3 4-SOCH3
A-1 197 4-CH3 2,3-CI2 A-1236 5-CH3 2-SO2CH3
A-1 198 4-CH3 2,4-CI2 A-1237 5-CH3 3-SO2CH3
A-1 199 4-CH3 2,5-CI2 A-1238 5-CH3 4-SO2CH3
A-1200 4-CH3 3,4-CI2 A-1239 5-CH3 2-CO2CH3
A-1201 4-CH3 3,5-CI2 A-1240 5-CH3 3-CO2CH3
A-1202 4-CH3 2,6-CI2 A-1241 5-CH3 4-CO2CH3
A-1203 4-CH3 2,3-F2 A-1242 5-CH3 2-CH3
A-1204 4-CH3 2,4-F2 A-1243 5-CH3 3-CH3
A-1205 4-CH3 2,5-F2 A-1244 5-CH3 4-CH3
A-1206 4-CH3 3,4-F2 A-1245 5-CH3 2-CF3
A-1207 4-CH3 3,5-F2 A-1246 5-CH3 3-CF3
A-1208 4-CH3 2,6-F2 A-1247 5-CH3 4-CF3
A-1209 4-CH3 2-CF3-4-CI A-1248 5-CH3 2-CHF2 line (R3)n (R4)m line (R3)n (R4)m
A-1249 5-CHs 3-CHF2 A-1288 6-CH3 2-CN
A-1250 5-CHs 4-CHF2 A-1289 6-CH3 3-CN
A-1251 5-CHs 2-OCH3 A-1290 6-CH3 4-CN
A-1252 5-CHs 3-OCH3 A-1291 6-CH3 2-NO2
A-1253 5-CHs 4-OCH3 A-1292 6-CH3 3-NO2
A-1254 5-CHs 2-OCF3 A-1293 6-CH3 4-NO2
A-1255 5-CHs 3-OCF3 A-1294 6-CH3 2-SCH3
A-1256 5-CHs 4-OCF3 A-1295 6-CH3 3-SCH3
A-1257 5-CHs 2-OCHF2 A-1296 6-CH3 4-SCH3
A-1258 5-CHs 3-OCHF2 A-1297 6-CH3 2-SOCH3
A-1259 5-CHs 4-OCHF2 A-1298 6-CH3 3-SOCH3
A-1260 5-CHs 2,4,6-(CH3)3 A-1299 6-CH3 4-SOCH3
A-1261 5-CHs 2,3-CI2 A-1300 6-CH3 2-SO2CH3
A-1262 5-CHs 2,4-CI2 A-1301 6-CH3 3-SO2CH3
A-1263 5-CHs 2,5-CI2 A-1302 6-CH3 4-SO2CH3
A-1264 5-CHs 3,4-CI2 A-1303 6-CH3 2-CO2CH3
A-1265 5-CHs 3,5-CI2 A-1304 6-CH3 3-CO2CH3
A-1266 5-CHs 2,6-CI2 A-1305 6-CH3 4-CO2CH3
A-1267 5-CHs 2,3-F2 A-1306 6-CH3 2-CH3
A-1268 5-CHs 2,4-F2 A-1307 6-CH3 3-CH3
A-1269 5-CHs 2,5-F2 A-1308 6-CH3 4-CH3
A-1270 5-CHs 3,4-F2 A-1309 6-CH3 2-CF3
A-1271 5-CHs 3,5-F2 A-1310 6-CH3 3-CF3
A-1272 5-CHs 2,6-F2 A-131 1 6-CH3 4-CF3
A-1273 5-CHs 2-CF3-4-CI A-1312 6-CH3 2-CHF2
A-1274 5-CHs 2-CF3-4-F A-1313 6-CH3 3-CHF2
A-1275 5-CHs 2-CI-4-CF3 A-1314 6-CH3 4-CHF2
A-1276 5-CHs 2-F-4-CF3 A-1315 6-CH3 2-OCH3
A-1277 5-CHs 2-CN-4-CI A-1316 6-CH3 3-OCH3
A-1278 5-CHs 2-CN-4-F A-1317 6-CH3 4-OCH3
A-1279 5-CHs 2-CI-4-CN A-1318 6-CH3 2-OCF3
A-1280 5-CHs 2-F-4-CN A-1319 6-CH3 3-OCF3
A-1281 *
6-CH3 A-1320 6-CH3 4-OCF3
A-1282 6-CH3 2-CI A-1321 6-CH3 2-OCHF2
A-1283 6-CH3 3-CI A-1322 6-CH3 3-OCHF2
A-1284 6-CH3 4-CI A-1323 6-CH3 4-OCHF2
A-1285 6-CH3 2-F A-1324 6-CH3 2,4,6-(CH3)3
A-1286 6-CH3 3-F A-1325 6-CH3 2,3-CI2
A-1287 6-CH3 4-F A-1326 6-CH3 2,4-CI2 line (R3)n (R4)m line (R3)n (R4)m
A-1327 6-CH3 2,5-CI2 A-1366 2-CF3 4-S02CH3
A-1328 6-CH3 3,4-CI2 A-1367 2-CF3 2-C02CH3
A-1329 6-CH3 3,5-CI2 A-1368 2-CF3 3-C02CH3
A-1330 6-CH3 2,6-CI2 A-1369 2-CF3 4-C02CH3
A-1331 6-CH3 2,3-F2 A-1370 2-CF3 2-CH3
A-1332 6-CH3 2,4-F2 A-1371 2-CF3 3-CH3
A-1333 6-CH3 2,5-F2 A-1372 2-CF3 4-CH3
A-1334 6-CH3 3,4-F2 A-1373 2-CF3 2-CF3
A-1335 6-CH3 3,5-F2 A-1374 2-CF3 3-CF3
A-1336 6-CH3 2,6-F2 A-1375 2-CF3 4-CF3
A-1337 6-CH3 2-CF3-4-CI A-1376 2-CF3 2-CHF2
A-1338 6-CH3 2-CF3-4-F A-1377 2-CF3 3-CHF2
A-1339 6-CH3 2-CI-4-CF3 A-1378 2-CF3 4-CHF2
A-1340 6-CH3 2-F-4-CF3 A-1379 2-CF3 2-OCH3
A-1341 6-CH3 2-CN-4-CI A-1380 2-CF3 3-OCH3
A-1342 6-CH3 2-CN-4-F A-1381 2-CF3 4-OCH3
A-1343 6-CH3 2-CI-4-CN A-1382 2-CF3 2-OCF3
A-1344 6-CH3 2-F-4-CN A-1383 2-CF3 3-OCF3
A-1345 *
2-CF3 A-1384 2-CF3 4-OCF3
A-1346 2-CF3 2-CI A-1385 2-CF3 2-OCHF2
A-1347 2-CF3 3-CI A-1386 2-CF3 3-OCHF2
A-1348 2-CF3 4-CI A-1387 2-CF3 4-OCHF2
A-1349 2-CF3 2-F A-1388 2-CF3 2,4,6-(CH3)3
A-1350 2-CF3 3-F A-1389 2-CF3 2,3-CI2
A-1351 2-CF3 4-F A-1390 2-CF3 2,4-CI2
A-1352 2-CF3 2-CN A-1391 2-CF3 2,5-CI2
A-1353 2-CF3 3-CN A-1392 2-CF3 3,4-CI2
A-1354 2-CF3 4-CN A-1393 2-CF3 3,5-CI2
A-1355 2-CF3 2-N02 A-1394 2-CF3 2,6-CI2
A-1356 2-CF3 3-N02 A-1395 2-CF3 2,3-F2
A-1357 2-CF3 4-N02 A-1396 2-CF3 2,4-F2
A-1358 2-CF3 2-SCH3 A-1397 2-CF3 2,5-F2
A-1359 2-CF3 3-SCH3 A-1398 2-CF3 3,4-F2
A-1360 2-CF3 4-SCH3 A-1399 2-CF3 3,5-F2
A-1361 2-CF3 2-SOCH3 A-1400 2-CF3 2,6-F2
A-1362 2-CF3 3-SOCH3 A-1401 2-CF3 2-CF3-4-CI
A-1363 2-CF3 4-SOCH3 A-1402 2-CF3 2-CF3-4-F
A-1364 2-CF3 2-S02CH3 A-1403 2-CF3 2-CI-4-CF3
A-1365 2-CF3 3-S02CH3 A-1404 2-CF3 2-F-4-CF3 line (R3)n (R4)m line (R3)n (R4)m
A-1405 2-CF3 2-CN-4-CI A-1444 4-CF3 3-OCH3
A-1406 2-CF3 2-CN-4-F A-1445 4-CF3 4-OCH3
A-1407 2-CF3 2-CI-4-CN A-1446 4-CF3 2-OCF3
A-1408 2-CF3 2-F-4-CN A-1447 4-CF3 3-OCF3
A-1409 *
4-CF3 A-1448 4-CF3 4-OCF3
A-1410 4-CF3 2-CI A-1449 4-CF3 2-OCHF2
A-141 1 4-CF3 3-CI A-1450 4-CF3 3-OCHF2
A-1412 4-CF3 4-CI A-1451 4-CF3 4-OCHF2
A-1413 4-CF3 2-F A-1452 4-CF3 2,4,6-(CH3)3
A-1414 4-CF3 3-F A-1453 4-CF3 2,3-CI2
A-1415 4-CF3 4-F A-1454 4-CF3 2,4-CI2
A-1416 4-CF3 2-CN A- 1455 4-CF3 2,5-CI2
A-1417 4-CF3 3-CN A-1456 4-CF3 3,4-CI2
A-1418 4-CF3 4-CN A-1457 4-CF3 3,5-CI2
A-1419 4-CF3 2-NO2 A-1458 4-CF3 2,6-CI2
A-1420 4-CF3 3-NO2 A-1459 4-CF3 2,3-F2
A-1421 4-CF3 4-NO2 A-1460 4-CF3 2,4-F2
A-1422 4-CF3 2-SCH3 A-1461 4-CF3 2,5-F2
A-1423 4-CF3 3-SCH3 A-1462 4-CF3 3,4-F2
A-1424 4-CF3 4-SCH3 A-1463 4-CF3 3,5-F2
A-1425 4-CF3 2-SOCH3 A-1464 4-CF3 2,6-F2
A-1426 4-CF3 3-SOCH3 A-1465 4-CF3 2-CF3-4-CI
A-1427 4-CF3 4-SOCH3 A-1466 4-CF3 2-CF3-4-F
A-1428 4-CF3 2-SO2CH3 A-1467 4-CF3 2-CI-4-CF3
A-1429 4-CF3 3-SO2CH3 A-1468 4-CF3 2-F-4-CF3
A-1430 4-CF3 4-SO2CH3 A-1469 4-CF3 2-CN-4-CI
A-1431 4-CF3 2-CO2CH3 A-1470 4-CF3 2-CN-4-F
A-1432 4-CF3 3-CO2CH3 A-1471 4-CF3 2-CI-4-CN
A-1433 4-CF3 4-CO2CH3 A-1472 4-CF3 2-F-4-CN
A-1434 4-CF3 2-CH3 A-1473 *
Figure imgf000047_0001
A-1435 4-CF3 3-CH3 A-1474 5-CF3 2-CI
A-1436 4-CF3 4-CH3 A-1475 5-CF3 3-CI
A-1437 4-CF3 2-CF3 A-1476 5-CF3 4-CI
A-1438 4-CF3 3-CF3 A-1477 5-CF3 2-F
A-1439 4-CF3 4-CF3 A-1478 5-CF3 3-F
A-1440 4-CF3 2-CHF2 A-1479 5-CF3 4-F
A-1441 4-CF3 3-CHF2 A-1480 5-CF3 2-CN
A-1442 4-CF3 4-CHF2 A-1481 5-CF3 3-CN
A-1443 4-CF3 2-OCH3 A-1482 5-CF3 4-CN line (R3)n (R4)m line (R3)n (R4)m
A-1483 5-CFs 2-N02 A-1522 5-CF3 2,6-CI2
A-1484 5-CFs 3-N02 A-1523 5-CF3 2,3-F2
A-1485 5-CFs 4-N02 A-1524 5-CF3 2,4-F2
A-1486 5-CFs 2-SCH3 A-1525 5-CF3 2,5-F2
A-1487 5-CFs 3-SCH3 A-1526 5-CF3 3,4-F2
A-1488 5-CFs 4-SCH3 A-1527 5-CF3 3,5-F2
A-1489 5-CFs 2-SOCH3 A-1528 5-CF3 2,6-F2
A-1490 5-CFs 3-SOCH3 A-1529 5-CF3 2-CF3-4-CI
A-1491 5-CFs 4-SOCH3 A-1530 5-CF3 2-CF3-4-F
A-1492 5-CFs 2-SO2CH3 A-1531 5-CF3 2-CI-4-CF3
A-1493 5-CFs 3-SO2CH3 A-1532 5-CF3 2-F-4-CF3
A-1494 5-CFs 4-SO2CH3 A-1533 5-CF3 2-CN-4-CI
A-1495 5-CFs 2-CO2CH3 A-1534 5-CF3 2-CN-4-F
A-1496 5-CFs 3-CO2CH3 A-1535 5-CF3 2-CI-4-CN
A-1497 5-CFs 4-CO2CH3 A-1536 5-CF3 2-F-4-CN
A-1498 5-CFs 2-CH3 A-1537 *
Figure imgf000048_0001
A-1499 5-CFs 3-CH3 A-1538 6-CF3 2-CI
A-1500 5-CFs 4-CH3 A-1539 6-CF3 3-CI
A-1501 5-CFs 2-CF3 A-1540 6-CF3 4-CI
A-1502 5-CFs 3-CF3 A-1541 6-CF3 2-F
A-1503 5-CFs 4-CF3 A-1542 6-CF3 3-F
A-1504 5-CFs 2-CHF2 A-1543 6-CF3 4-F
A-1505 5-CFs 3-CHF2 A-1544 6-CF3 2-CN
A-1506 5-CFs 4-CHF2 A-1545 6-CF3 3-CN
A-1507 5-CFs 2-OCH3 A-1546 6-CF3 4-CN
A-1508 5-CFs 3-OCH3 A-1547 6-CF3 2-NO2
A-1509 5-CFs 4-OCH3 A-1548 6-CF3 3-NO2
A-1510 5-CFs 2-OCF3 A-1549 6-CF3 4-NO2
A-151 1 5-CFs 3-OCF3 A-1550 6-CF3 2-SCH3
A-1512 5-CFs 4-OCF3 A-1551 6-CF3 3-SCH3
A-1513 5-CFs 2-OCHF2 A-1552 6-CF3 4-SCH3
A-1514 5-CFs 3-OCHF2 A-1553 6-CF3 2-SOCH3
A-1515 5-CFs 4-OCHF2 A- 1554 6-CF3 3-SOCH3
A-1516 5-CFs 2,4,6-(CH3)3 A-1555 6-CF3 4-SOCH3
A-1517 5-CFs 2,3-CI2 A-1556 6-CF3 2-SO2CH3
A-1518 5-CFs 2,4-CI2 A- 1557 6-CF3 3-SO2CH3
A-1519 5-CFs 2,5-CI2 A-1558 6-CF3 4-SO2CH3
A-1520 5-CFs 3,4-CI2 A-1559 6-CF3 2-CO2CH3
A-1521 5-CFs 3,5-CI2 A-1560 6-CF3 3-CO2CH3 line (R3)n (R4)m line (R3)n (R4)m
A-1561 6-CFs 4-CO2CH3 A-1600 6-CF3 2-F-4-CN
A-1562 *
6-CFs 2-CHs A-1601 2-CHF2
A-1563 6-CFs 3-CHs A-1602 2-CHF2 2-CI
A-1564 6-CFs 4-CHs A-1603 2-CHF2 3-CI
A-1565 6-CFs 2-CFs A-1604 2-CHF2 4-CI
A-1566 6-CFs 3-CFs A-1605 2-CHF2 2-F
A-1567 6-CFs 4-CFs A-1606 2-CHF2 3-F
A-1568 6-CFs 2-CHF2 A-1607 2-CHF2 4-F
A-1569 6-CFs 3-CHF2 A-1608 2-CHF2 2-CN
A-1570 6-CFs 4-CHF2 A-1609 2-CHF2 3-CN
A-1571 6-CFs 2-OCHs A-1610 2-CHF2 4-CN
A-1572 6-CFs 3-OCHs A-161 1 2-CHF2 2-NO2
A-1573 6-CFs 4-OCHs A-1612 2-CHF2 3-NO2
A-1574 6-CFs 2-OCFs A-1613 2-CHF2 4-NO2
A- 1575 6-CFs 3-OCFs A-1614 2-CHF2 2-SCHs
A-1576 6-CFs 4-OCFs A-1615 2-CHF2 3-SCHs
A- 1577 6-CFs 2-OCHF2 A-1616 2-CHF2 4-SCHs
A-1578 6-CFs 3-OCHF2 A-1617 2-CHF2 2-SOCHs
A-1579 6-CFs 4-OCHF2 A-1618 2-CHF2 3-SOCHs
A-1580 6-CFs 2,4,6-(CHs)s A-1619 2-CHF2 4-SOCHs
A-1581 6-CFs 2,3-C A-1620 2-CHF2 2-SO2CH3
A-1582 6-CFs 2,4-C A-1621 2-CHF2 3-SO2CH3
A-1583 6-CFs 2,5-CI2 A-1622 2-CHF2 4-SO2CH3
A-1584 6-CFs 3,4-C A-1623 2-CHF2 2-CO2CH3
A-1585 6-CFs 3,5-CI2 A-1624 2-CHF2 3-CO2CH3
A-1586 6-CFs 2,6-CI2 A-1625 2-CHF2 4-CO2CH3
A-1587 6-CFs 2,3-F2 A-1626 2-CHF2 2-CHs
A-1588 6-CFs 2,4-F2 A-1627 2-CHF2 3-CHs
A-1589 6-CFs 2,5-F2 A-1628 2-CHF2 4-CHs
A-1590 6-CFs 3,4-F2 A-1629 2-CHF2 2-CFs
A-1591 6-CFs 3,5-F2 A-1630 2-CHF2 3-CFs
A-1592 6-CFs 2,6-F2 A-1631 2-CHF2 4-CFs
A-1593 6-CFs 2-CF3-4-CI A-1632 2-CHF2 2-CHF2
A-1594 6-CFs 2-CF3-4-F A-1633 2-CHF2 3-CHF2
A-1595 6-CFs 2-CI-4-CF3 A-1634 2-CHF2 4-CHF2
A-1596 6-CFs 2-F-4-CF3 A-1635 2-CHF2 2-OCHs
A-1597 6-CFs 2-CN-4-CI A-1636 2-CHF2 3-OCHs
A-1598 6-CFs 2-CN-4-F A-1637 2-CHF2 4-OCHs
A-1599 6-CFs 2-CI-4-CN A-1638 2-CHF2 2-OCFs line (R3)n (R4)m line (R3)n (R4)m
A-1639 2-CHF2 3-OCFs A-1678 4-CHF2 2-SCH3
A-1640 2-CHF2 4-OCFs A-1679 4-CHF2 3-SCH3
A-1641 2-CHF2 2-OCHF2 A-1680 4-CHF2 4-SCH3
A-1642 2-CHF2 3-OCHF2 A-1681 4-CHF2 2-SOCH3
A-1643 2-CHF2 4-OCHF2 A-1682 4-CHF2 3-SOCH3
A-1644 2-CHF2 2,4,6-(CH3)3 A-1683 4-CHF2 4-SOCH3
A-1645 2-CHF2 2,3-CI2 A-1684 4-CHF2 2-SO2CH3
A-1646 2-CHF2 2,4-CI2 A-1685 4-CHF2 3-SO2CH3
A-1647 2-CHF2 2,5-CI2 A-1686 4-CHF2 4-SO2CH3
A-1648 2-CHF2 3,4-CI2 A-1687 4-CHF2 2-CO2CH3
A-1649 2-CHF2 3,5-CI2 A-1688 4-CHF2 3-CO2CH3
A-1650 2-CHF2 2,6-CI2 A-1689 4-CHF2 4-CO2CH3
A-1651 2-CHF2 2,3-F2 A-1690 4-CHF2 2-CH3
A-1652 2-CHF2 2,4-F2 A-1691 4-CHF2 3-CH3
A-1653 2-CHF2 2,5-F2 A-1692 4-CHF2 4-CH3
A-1654 2-CHF2 3,4-F2 A-1693 4-CHF2 2-CF3
A-1655 2-CHF2 3,5-F2 A-1694 4-CHF2 3-CF3
A-1656 2-CHF2 2,6-F2 A-1695 4-CHF2 4-CF3
A-1657 2-CHF2 2-CF3-4-CI A-1696 4-CHF2 2-CHF2
A-1658 2-CHF2 2-CF3-4-F A-1697 4-CHF2 3-CHF2
A-1659 2-CHF2 2-CI-4-CF3 A-1698 4-CHF2 4-CHF2
A-1660 2-CHF2 2-F-4-CF3 A-1699 4-CHF2 2-OCH3
A-1661 2-CHF2 2-CN-4-CI A-1700 4-CHF2 3-OCH3
A-1662 2-CHF2 2-CN-4-F A-1701 4-CHF2 4-OCH3
A-1663 2-CHF2 2-CI-4-CN A-1702 4-CHF2 2-OCF3
A-1664 2-CHF2 2-F-4-CN A-1703 4-CHF2 3-OCFs
A-1665 *
4-CHF2 A-1704 4-CHF2 4-OCFs
A-1666 4-CHF2 2-CI A-1705 4-CHF2 2-OCHF2
A-1667 4-CHF2 3-CI A-1706 4-CHF2 3-OCHF2
A-1668 4-CHF2 4-CI A-1707 4-CHF2 4-OCHF2
A-1669 4-CHF2 2-F A-1708 4-CHF2 2,4,6-(CH3)3
A-1670 4-CHF2 3-F A-1709 4-CHF2 2,3-CI2
A-1671 4-CHF2 4-F A-1710 4-CHF2 2,4-CI2
A-1672 4-CHF2 2-CN A-171 1 4-CHF2 2,5-CI2
A-1673 4-CHF2 3-CN A-1712 4-CHF2 3,4-CI2
A-1674 4-CHF2 4-CN A-1713 4-CHF2 3,5-CI2
A-1675 4-CHF2 2-NO2 A-1714 4-CHF2 2,6-CI2
A-1676 4-CHF2 3-NO2 A-1715 4-CHF2 2,3-F2
A-1677 4-CHF2 4-NO2 A-1716 4-CHF2 2,4-F2 line (R3)n (R4)m line (R3)n (R4)m
A-1717 4-CHF2 2,5-F2 A-1756 5-CHF2 4-CH3
A-1718 4-CHF2 3,4-F2 A- 1757 5-CHF2 2-CF3
A-1719 4-CHF2 3,5-F2 A-1758 5-CHF2 3-CF3
A-1720 4-CHF2 2,6-F2 A-1759 5-CHF2 4-CF3
A-1721 4-CHF2 2-CF3-4-CI A-1760 5-CHF2 2-CHF2
A-1722 4-CHF2 2-CF3-4-F A-1761 5-CHF2 3-CHF2
A-1723 4-CHF2 2-CI-4-CF3 A-1762 5-CHF2 4-CHF2
A-1724 4-CHF2 2-F-4-CF3 A-1763 5-CHF2 2-OCH3
A-1725 4-CHF2 2-CN-4-CI A-1764 5-CHF2 3-OCH3
A-1726 4-CHF2 2-CN-4-F A-1765 5-CHF2 4-OCH3
A-1727 4-CHF2 2-CI-4-CN A-1766 5-CHF2 2-OCF3
A-1728 4-CHF2 2-F-4-CN A-1767 5-CHF2 3-OCF3
A-1729 *
5-CHF2 A-1768 5-CHF2 4-OCF3
A-1730 5-CHF2 2-CI A-1769 5-CHF2 2-OCHF2
A-1731 5-CHF2 3-CI A-1770 5-CHF2 3-OCHF2
A-1732 5-CHF2 4-CI A-1771 5-CHF2 4-OCHF2
A-1733 5-CHF2 2-F A-1772 5-CHF2 2,4,6-(CH3)3
A-1734 5-CHF2 3-F A-1773 5-CHF2 2,3-C
A-1735 5-CHF2 4-F A-1774 5-CHF2 2,4-Cfe
A-1736 5-CHF2 2-CN A- 1775 5-CHF2 2,5-CI2
A-1737 5-CHF2 3-CN A-1776 5-CHF2 3,4-C
A-1738 5-CHF2 4-CN A- 1777 5-CHF2 3,5-CI2
A-1739 5-CHF2 2-NO2 A-1778 5-CHF2 2,6-CI2
A-1740 5-CHF2 3-NO2 A-1779 5-CHF2 2,3-F2
A-1741 5-CHF2 4-NO2 A-1780 5-CHF2 2,4-F2
A-1742 5-CHF2 2-SCH3 A-1781 5-CHF2 2,5-F2
A-1743 5-CHF2 3-SCH3 A-1782 5-CHF2 3,4-F2
A-1744 5-CHF2 4-SCH3 A-1783 5-CHF2 3,5-F2
A-1745 5-CHF2 2-SOCH3 A-1784 5-CHF2 2,6-F2
A-1746 5-CHF2 3-SOCH3 A-1785 5-CHF2 2-CF3-4-CI
A-1747 5-CHF2 4-SOCH3 A-1786 5-CHF2 2-CF3-4-F
A-1748 5-CHF2 2-SO2CH3 A-1787 5-CHF2 2-CI-4-CF3
A-1749 5-CHF2 3-SO2CH3 A-1788 5-CHF2 2-F-4-CF3
A-1750 5-CHF2 4-SO2CH3 A-1789 5-CHF2 2-CN-4-CI
A-1751 5-CHF2 2-CO2CH3 A-1790 5-CHF2 2-CN-4-F
A-1752 5-CHF2 3-CO2CH3 A-1791 5-CHF2 2-CI-4-CN
A-1753 5-CHF2 4-CO2CH3 A-1792 5-CHF2 2-F-4-CN
A-1754 *
5-CHF2 2-CH3 A-1793
Figure imgf000051_0001
A- 1755 5-CHF2 3-CH3 A-1794 6-CHF2 2-CI line (R3)n (R4)m line (R3)n (R4)m
A-1795 6-CHF2 3-CI A-1834 6-CHF2 3-OCHF2
A-1796 6-CHF2 4-CI A-1835 6-CHF2 4-OCHF2
A-1797 6-CHF2 2-F A-1836 6-CHF2 2,4,6-(CH3)3
A-1798 6-CHF2 3-F A-1837 6-CHF2 2,3-CI2
A-1799 6-CHF2 4-F A-1838 6-CHF2 2,4-CI2
A-1800 6-CHF2 2-CN A-1839 6-CHF2 2,5-CI2
A-1801 6-CHF2 3-CN A-1840 6-CHF2 3,4-CI2
A-1802 6-CHF2 4-CN A-1841 6-CHF2 3,5-CI2
A-1803 6-CHF2 2-NO2 A-1842 6-CHF2 2,6-CI2
A-1804 6-CHF2 3-NO2 A-1843 6-CHF2 2,3-F2
A-1805 6-CHF2 4-NO2 A-1844 6-CHF2 2,4-F2
A-1806 6-CHF2 2-SCHs A-1845 6-CHF2 2,5-F2
A-1807 6-CHF2 3-SCHs A-1846 6-CHF2 3,4-F2
A-1808 6-CHF2 4-SCH3 A-1847 6-CHF2 3,5-F2
A-1809 6-CHF2 2-SOCH3 A-1848 6-CHF2 2,6-F2
A-1810 6-CHF2 3-SOCH3 A-1849 6-CHF2 2-CF3-4-CI
A-181 1 6-CHF2 4-SOCH3 A-1850 6-CHF2 2-CF3-4-F
A-1812 6-CHF2 2-SO2CH3 A-1851 6-CHF2 2-CI-4-CF3
A-1813 6-CHF2 3-SO2CH3 A-1852 6-CHF2 2-F-4-CF3
A-1814 6-CHF2 4-SO2CH3 A-1853 6-CHF2 2-CN-4-CI
A-1815 6-CHF2 2-CO2CH3 A-1854 6-CHF2 2-CN-4-F
A-1816 6-CHF2 3-CO2CH3 A-1855 6-CHF2 2-CI-4-CN
A-1817 6-CHF2 4-CO2CH3 A-1856 6-CHF2 2-F-4-CN
A-1818 6-CHF2 2-CH3 A-1857 *
Figure imgf000052_0001
A-1819 6-CHF2 3-CH3 A-1858 2-OCH3 2-CI
A-1820 6-CHF2 4-CH3 A-1859 2-OCH3 3-CI
A-1821 6-CHF2 2-CF3 A-1860 2-OCH3 4-CI
A-1822 6-CHF2 3-CF3 A-1861 2-OCH3 2-F
A-1823 6-CHF2 4-CF3 A-1862 2-OCH3 3-F
A-1824 6-CHF2 2-CHF2 A-1863 2-OCH3 4-F
A-1825 6-CHF2 3-CHF2 A-1864 2-OCH3 2-CN
A-1826 6-CHF2 4-CHF2 A-1865 2-OCH3 3-CN
A-1827 6-CHF2 2-OCH3 A-1866 2-OCH3 4-CN
A-1828 6-CHF2 3-OCH3 A-1867 2-OCH3 2-NO2
A-1829 6-CHF2 4-OCH3 A-1868 2-OCH3 3-NO2
A-1830 6-CHF2 2-OCF3 A-1869 2-OCH3 4-NO2
A-1831 6-CHF2 3-OCF3 A-1870 2-OCH3 2-SCH3
A-1832 6-CHF2 4-OCF3 A-1871 2-OCH3 3-SCH3
A-1833 6-CHF2 2-OCHF2 A-1872 2-OCH3 4-SCH3 line (R3)n (R4)m line (R3)n (R4)m
A-1873 2-OCHs 2-SOCH3 A-1912 2-OCHs 2,6-F2
A-1874 2-OCHs 3-SOCH3 A-1913 2-OCHs 2-CF3-4-CI
A-1875 2-OCHs 4-SOCH3 A-1914 2-OCHs 2-CF3-4-F
A-1876 2-OCHs 2-SO2CH3 A-1915 2-OCHs 2-CI-4-CF3
A-1877 2-OCHs 3-SO2CH3 A-1916 2-OCH3 2-F-4-CF3
A-1878 2-OCH3 4-SO2CH3 A-1917 2-OCH3 2-CN-4-CI
A-1879 2-OCH3 2-CO2CH3 A-1918 2-OCH3 2-CN-4-F
A-1880 2-OCH3 3-CO2CH3 A-1919 2-OCH3 2-CI-4-CN
A-1881 2-OCH3 4-CO2CH3 A-1920 2-OCH3 2-F-4-CN
A-1882 2-OCH3 2-CH3 A-1921 *
Figure imgf000053_0001
A-1883 2-OCH3 3-CH3 A-1922 4-OCH3 2-CI
A-1884 2-OCH3 4-CH3 A-1923 4-OCH3 3-CI
A-1885 2-OCH3 2-CF3 A-1924 4-OCH3 4-CI
A-1886 2-OCH3 3-CF3 A-1925 4-OCH3 2-F
A-1887 2-OCH3 4-CF3 A-1926 4-OCH3 3-F
A-1888 2-OCH3 2-CHF2 A-1927 4-OCH3 4-F
A-1889 2-OCH3 3-CHF2 A-1928 4-OCH3 2-CN
A-1890 2-OCH3 4-CHF2 A-1929 4-OCH3 3-CN
A-1891 2-OCH3 2-OCH3 A-1930 4-OCH3 4-CN
A-1892 2-OCH3 3-OCH3 A-1931 4-OCH3 2-NO2
A-1893 2-OCH3 4-OCH3 A-1932 4-OCH3 3-NO2
A-1894 2-OCH3 2-OCF3 A-1933 4-OCH3 4-NO2
A-1895 2-OCH3 3-OCF3 A-1934 4-OCH3 2-SCH3
A-1896 2-OCH3 4-OCF3 A-1935 4-OCH3 3-SCH3
A-1897 2-OCH3 2-OCHF2 A-1936 4-OCH3 4-SCH3
A-1898 2-OCH3 3-OCHF2 A-1937 4-OCH3 2-SOCH3
A-1899 2-OCH3 4-OCHF2 A-1938 4-OCH3 3-SOCH3
A-1900 2-OCH3 2,4,6-(CH3)3 A-1939 4-OCH3 4-SOCH3
A-1901 2-OCH3 2,3-CI2 A-1940 4-OCH3 2-SO2CH3
A-1902 2-OCH3 2,4-CI2 A-1941 4-OCH3 3-SO2CH3
A-1903 2-OCH3 2,5-CI2 A-1942 4-OCH3 4-SO2CH3
A-1904 2-OCH3 3,4-CI2 A-1943 4-OCH3 2-CO2CH3
A-1905 2-OCH3 3,5-CI2 A-1944 4-OCH3 3-CO2CH3
A-1906 2-OCH3 2,6-CI2 A-1945 4-OCH3 4-CO2CH3
A-1907 2-OCH3 2,3-F2 A-1946 4-OCH3 2-CH3
A-1908 2-OCH3 2,4-F2 A-1947 4-OCH3 3-CH3
A-1909 2-OCH3 2,5-F2 A-1948 4-OCH3 4-CH3
A-1910 2-OCH3 3,4-F2 A-1949 4-OCH3 2-CF3
A-191 1 2-OCH3 3,5-F2 A-1950 4-OCH3 3-CF3 line (R3)n (R4)m line (R3)n (R4)m
A-1951 4-OCH3 4-CF3 A-1990 5-OCH3 3-F
A-1952 4-OCH3 2-CHF2 A-1991 5-OCH3 4-F
A-1953 4-OCH3 3-CHF2 A-1992 5-OCH3 2-CN
A-1954 4-OCH3 4-CHF2 A-1993 5-OCH3 3-CN
A-1955 4-OCH3 2-OCH3 A-1994 5-OCH3 4-CN
A-1956 4-OCH3 3-OCH3 A-1995 5-OCH3 2-NO2
A-1957 4-OCH3 4-OCH3 A-1996 5-OCH3 3-NO2
A-1958 4-OCH3 2-OCF3 A-1997 5-OCH3 4-NO2
A-1959 4-OCH3 3-OCF3 A-1998 5-OCH3 2-SCH3
A-1960 4-OCH3 4-OCF3 A-1999 5-OCH3 3-SCH3
A-1961 4-OCH3 2-OCHF2 A-2000 5-OCH3 4-SCH3
A-1962 4-OCH3 3-OCHF2 A-2001 5-OCH3 2-SOCH3
A-1963 4-OCH3 4-OCHF2 A-2002 5-OCH3 3-SOCH3
A-1964 4-OCH3 2,4,6-(CH3)3 A-2003 5-OCH3 4-SOCH3
A-1965 4-OCH3 2,3-C A-2004 5-OCH3 2-SO2CH3
A-1966 4-OCH3 2,4-Cfe A-2005 5-OCH3 3-SO2CH3
A-1967 4-OCH3 2,5-CI2 A-2006 5-OCH3 4-SO2CH3
A-1968 4-OCH3 3,4-C A-2007 5-OCH3 2-CO2CH3
A-1969 4-OCH3 3,5-CI2 A-2008 5-OCH3 3-CO2CH3
A-1970 4-OCH3 2,6-CI2 A-2009 5-OCH3 4-CO2CH3
A-1971 4-OCH3 2,3-F2 A-2010 5-OCH3 2-CH3
A-1972 4-OCH3 2,4-F2 A-201 1 5-OCH3 3-CH3
A-1973 4-OCH3 2,5-F2 A-2012 5-OCH3 4-CH3
A-1974 4-OCH3 3,4-F2 A-2013 5-OCH3 2-CF3
A-1975 4-OCH3 3,5-F2 A-2014 5-OCH3 3-CF3
A-1976 4-OCH3 2,6-F2 A-2015 5-OCH3 4-CF3
A-1977 4-OCH3 2-CF3-4-CI A-2016 5-OCH3 2-CHF2
A-1978 4-OCH3 2-CF3-4-F A-2017 5-OCH3 3-CHF2
A-1979 4-OCH3 2-CI-4-CF3 A-2018 5-OCH3 4-CHF2
A-1980 4-OCH3 2-F-4-CF3 A-2019 5-OCH3 2-OCH3
A-1981 4-OCH3 2-CN-4-CI A-2020 5-OCH3 3-OCH3
A-1982 4-OCH3 2-CN-4-F A-2021 5-OCH3 4-OCH3
A-1983 4-OCH3 2-CI-4-CN A-2022 5-OCH3 2-OCF3
A-1984 4-OCH3 2-F-4-CN A-2023 5-OCH3 3-OCF3
A-1985 *
5-OCH3 A-2024 5-OCH3 4-OCF3
A-1986 5-OCH3 2-CI A-2025 5-OCH3 2-OCHF2
A-1987 5-OCH3 3-CI A-2026 5-OCH3 3-OCHF2
A-1988 5-OCH3 4-CI A-2027 5-OCH3 4-OCHF2
A-1989 5-OCH3 2-F A-2028 5-OCH3 2,4,6-(CH3)3 line (R3)n (R4)m line (R3)n (R4)m
A-2029 5-OCHs 2,3-C A-2068 6-OCH3 2-S02CH3
A-2030 5-OCHs 2,4-Cfe A-2069 6-OCH3 3-S02CH3
A-2031 5-OCHs 2,5-CI2 A-2070 6-OCH3 4-S02CH3
A-2032 5-OCHs 3,4-C A-2071 6-OCH3 2-C02CH3
A-2033 5-OCHs 3,5-CI2 A-2072 6-OCH3 3-C02CH3
A-2034 5-OCH3 2,6-CI2 A-2073 6-OCH3 4-C02CH3
A-2035 5-OCH3 2,3-F2 A-2074 6-OCH3 2-CH3
A-2036 5-OCH3 2,4-F2 A-2075 6-OCH3 3-CH3
A-2037 5-OCH3 2,5-F2 A-2076 6-OCH3 4-CH3
A-2038 5-OCH3 3,4-F2 A-2077 6-OCH3 2-CF3
A-2039 5-OCH3 3,5-F2 A-2078 6-OCH3 3-CF3
A-2040 5-OCH3 2,6-F2 A-2079 6-OCH3 4-CF3
A-2041 5-OCH3 2-CF3-4-CI A-2080 6-OCH3 2-CHF2
A-2042 5-OCH3 2-CF3-4-F A-2081 6-OCH3 3-CHF2
A-2043 5-OCH3 2-CI-4-CF3 A-2082 6-OCH3 4-CHF2
A-2044 5-OCH3 2-F-4-CF3 A-2083 6-OCH3 2-OCH3
A-2045 5-OCH3 2-CN-4-CI A-2084 6-OCH3 3-OCH3
A-2046 5-OCH3 2-CN-4-F A-2085 6-OCH3 4-OCH3
A-2047 5-OCH3 2-CI-4-CN A-2086 6-OCH3 2-OCF3
A-2048 5-OCH3 2-F-4-CN A-2087 6-OCH3 3-OCF3
A-2049 *
6-OCH3 A-2088 6-OCH3 4-OCF3
A-2050 6-OCH3 2-CI A-2089 6-OCH3 2-OCHF2
A-2051 6-OCH3 3-CI A-2090 6-OCH3 3-OCHF2
A-2052 6-OCH3 4-CI A-2091 6-OCH3 4-OCHF2
A-2053 6-OCH3 2-F A-2092 6-OCH3 2,4,6-(CH3)3
A-2054 6-OCH3 3-F A-2093 6-OCH3 2,3-CI2
A-2055 6-OCH3 4-F A-2094 6-OCH3 2.4-CI2
A-2056 6-OCH3 2-CN A-2095 6-OCH3 2,5-CI2
A-2057 6-OCH3 3-CN A-2096 6-OCH3 3,4-C
A-2058 6-OCH3 4-CN A-2097 6-OCH3 3,5-CI2
A-2059 6-OCH3 2-N02 A-2098 6-OCH3 2,6-CI2
A-2060 6-OCH3 3-N02 A-2099 6-OCH3 2,3-F2
A-2061 6-OCH3 4-N02 A-2100 6-OCH3 2,4-F2
A-2062 6-OCH3 2-SCH3 A-2101 6-OCH3 2,5-F2
A-2063 6-OCH3 3-SCH3 A-2102 6-OCH3 3,4-F2
A-2064 6-OCH3 4-SCH3 A-2103 6-OCH3 3,5-F2
A-2065 6-OCH3 2-SOCH3 A-2104 6-OCH3 2,6-F2
A-2066 6-OCH3 3-SOCH3 A-2105 6-OCH3 2-CF3-4-CI
A-2067 6-OCH3 4-SOCH3 A-2106 6-OCH3 2-CF3-4-F line (R3)n (R4)m line (R3)n (R4)m
A-2107 6-OCH3 2-CI-4-CF3 A-21 10 6-OCH3 2-CN-4-F
A-2108 6-OCH3 2-F-4-CF3 A-21 1 1 6-OCH3 2-CI-4-CN
A-2109 6-OCH3 2-CN-4-CI A-21 12 6-OCH3 2-F-4-CN
-* means that m or n=0
The compounds I and II, respectively, and the compositions according to the invention, respectively, are suitable as fungicides.
Consequently, according to a further aspect, the present invention relates to the use of com- pounds of formula I, the N-oxides and the agriculturally acceptable salts thereof or of the compositions of the invention for combating phytopathogenic fungi.
Accordingly, the present invention also encompasses a method for combating harmful fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I or with a composi- tion comprising according to the invention.
They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmo- diophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemi- cally effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
The compounds I and II, respectively, 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 II, respectively, and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. pota- toes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
Preferably, treatment of plant propagation materials with compounds I and II, respectively, and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prejated, acetylated or farnesylated moieties or PEG moieties.
Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbi- cides such as dicamba or 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxy- genase (HPPD) inhibitors or phytoene desaturase (PDS) inhibittors; acetolactate synthase (ALS) inhibitors such as sulfoj ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfo ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cul- tivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; aggluti- nins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdyster- oid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone ester- ase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ). Further examples of such toxins or genetically modified plants ca- pable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278,
WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins toler- ance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coelop- tera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the CrylAb toxin), YieldGard® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme Phosphinothri- cin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the CrylAc toxin), Bollgard® I (cotton cultivars producing the CrylAc toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (po- tato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Pro- tecta®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis- related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Er- winia a vora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral patho- gens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Cana- da).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
The compounds I and II, respectively, and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Altemaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassi- cae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. altemata), tomatoes (e. g. A. solani or A. altemata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e.g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) gram- inis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botry- otinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (down mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. soro- kiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: An- thracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemu- thianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sa- sakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. lirio- dendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D.
phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyr- enophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formiti- poria (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (£. pyri), soft fruits (£. veneta: anthracnose) and vines (£. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Ery- siphe spp. (powdery mildew) on sugar beets (£. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani ( sp. glycines now syn. F. virguliforme ) and F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans and F. verticillioides on corn; Gaeumannoynces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Ncosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (down mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopso- ra pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lin- gam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); 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, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine down mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (down mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner', an- amorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. feres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R. collo-cygni (Ram ularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vege- tables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soy- beans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tucker}) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterra- nea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeo- sphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendicula- tus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
The compounds I and II, respectively, and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials. The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, colling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomy- cetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilonces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
The compounds I and II, respectively, 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 or II, respectively, 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 and II, respectively, can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
The compounds I and II, respectively, 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 or II, respectively, as such or a composition comprising at least one compound I or II, respectively, prophylactically either at or before planting or transplanting.
The invention also relates to compositions comprising one compound I and II, respectively, according to the invention. In particular, such composition further comprises an auxiliary as defined below.
The term "effective amount" used denotes an amount of the composition or of the compounds I or II, respectively, 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 or II, respectively, used.
The compounds I and II, respectively, 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), in- secticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. ce- real 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 emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & De- tergents, 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 alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. 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-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, 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 or II, respectively, and 5-15 wt% wetting agent (e.g. alcohol alkox- ylates) 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 or II, respectively, and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) 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 or II, respectively, and 5-10 wt% emulsifiers (e.g. calcium do- decylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic sol- vent (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 or II, respectively, and 1 -10 wt% emulsifiers (e.g. calcium do- decylbenzenesulfonate 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 or II, respectively, are comminuted with ad- dition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1 -2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I or II, respectively, 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 or II, respectively, 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 or II, respectively, are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxy- methylcellulose) 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 or II, respectively, are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide 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 or II, respectively, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethac- rylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator re- suits 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 pol- yurea 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 or II, respectively, 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 or II, respectively, 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 or II, respectively, are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%.
The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble pow- ders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and II, respectively, and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compound I and II, respectively, 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 g to 10 kg, in particular 0.1 to 1000 g, more particularly from 1 to 1000 g, specificaly from 1 to 100 g and most specificaly 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) 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.
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 agrochemi- cal 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 in- vention such as parts of a kit or parts of a composition comprising two or three active ingredients, may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
Mixing the compounds I or II, respectively, or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spec- trum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.
The following list of active substances, in conjunction with which the compounds I and II, re- spectively,can be used, is intended to illustrate the possible combinations but does not limit them:
A) Respiration inhibitors
Inhibitors of complex III at Q0 site (e.g. strobilurins): azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3- methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxy- methyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone, (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]- 6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate;
inhibitors of complex III at Q, site: cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8-benzyl-3-[(3- acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-
2- carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)- 8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-
1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5- ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2- methylpropanoate; (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]- 6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate;
- inhibitors of complex II (e. g. carboxamides): benodanil, benzovindiflupyr, bixafen, bos- calid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, iso- pyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N- (2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide,
3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide,
3- (trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl- N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide, N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4- carboxamide, N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl- pyrazole-4-carboxamide;
other respiration inhibitors (e.g. complex I, uncouplers): diflumetorim, (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fen- tin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam;
B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, bro- muconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipcona- zole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticona- zole, uniconazole,
1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H- [1 ,2,4]triazole, 2-[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]- 2H-[1 ,2,4]triazole-3-thiol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2- ol, 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1 -yl)ethanol,
2- [4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[2-chloro-4- (4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1-yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-
3- methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -
(1 ,2,4-triazol-1 -yl)pentan-2-ol, 2-[4-(4-fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol- 1 -yl)propan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine, [3-(4-chloro-2-fluoro-phenyl)-5-(2,4- difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol;
- Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
- Inhibitors of 3-keto reductase: fenhexamid;
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
others: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p- tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
D) Inhibitors of cell division and cytoskeleton
tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl, carbendazim, fuber- idazole, thiabendazole, thiophanate-methyl; triazolopynmidines: 5-chloro-7-(4-methylpiperidin-1 - yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine
other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zox- amide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis
methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil, mepanipyrim, pyrimethan- il;
protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride- hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F) Signal transduction inhibitors
MAP / histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fen- piclonil, fludioxonil;
G protein inhibitors: quinoxyfen;
G) Lipid and membrane synthesis inhibitors
Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane; lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
phospholipid biosynthesis and cell wall deposition: dimethomorph, flumorph, mandipro- pamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1 -(4-cyano-phenyl)- ethanesulfomyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
compounds affecting cell membrane permeability and fatty acides: propamocarb, pro- pamocarb-hydrochlorid
fatty acid amide hydrolase inhibitors: 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro- 3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1 -yl]ethanone; 2-{3-[2-(1 -{[3,5-bis(difluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5- dihydro-1 ,2-oxazol-5-yl}phenyl methanesulfonate, 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate;
H) Inhibitors with Multi Site Action
- inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;
organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlo- rothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlor- phenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide;
guanidines and others: guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6- dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
I) Cell wall synthesis inhibitors
inhibitors of glucan synthesis: validancin, polyoxin B; melanin synthesis inhibitors: pyroqui- lon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
J) Plant defence inducers
- acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phospho- nates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
K) Unknown mode of action
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, dif- enzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxathiapiprolin, tolprocarb, 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2- oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]- 1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2- yl)piperidin-1 -yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6- (prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen- 4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N- methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3- dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole),
N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1 -(4,6-dimethoxy- pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)-
N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide, ethyl (Z)-3-amino-2- cyano-3-phenyl-prop-2-enoate, tert-butyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate, 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6- fluoro-phenyl]propan-2-ol, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, 3- (5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1 -yl)quinoline, 3-(4,4-difluoro-3,3-dimethyl- 3,4-dihydroisoquinolin-1 -yl)quinoline, 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 - yl)quinoline; 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1 ,4-benzoxazepine; picarbutrazox;
L) Biopesticides
L1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus amyloliquefaciens, B. mojavensis, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibacter michiga- nensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Crypto- coccus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f . catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter an- tibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Micro- sphaeropsis ochracea, Muscodor albus, Paenibacillus polymyxa, Pantoea vagans, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma floc- culosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomy- ces griseoviridis, S. lydicus, S. microflavus, S. violaceusniger, Talaromyces flavus,
Trichoderma asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum; mixture of T. harzianum and T. viride; mixture of T. polysporum and T. harzianum; T. stromaticum, T. virens (also named Gliocladium virens), T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense acti- vator activity: chitosan (hydrolysate), harpin protein, laminarin, Menhaden fish oil, na- tamycin, Plum pox virus coat protein, potassium or sodium bicarbonate, Reynoutria sachlinensis extract, salicylic acid, tea tree oil;
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity:
Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. fe- nebrionis, Beauveria bassiana, B. brongniartii, Burkholderia sp., Chromobacterium sub- tsugae, Cydia pomonella granulosis virus, Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium sp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Isaria fumosorosea, Heterorhabditis bacteriophora, Lecanicillium longisporum, L. mus- carium (formerly Verticillium lecanii), Metarhizium anisopliae, M. anisopliae var. acrid- urn, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria sp., P. nishizawae, P. penetrans, P. ramose, P. reneformis, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus
(SpliNPV), Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces microfla- vus;
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl bu- tyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1 -butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1 -ol, (E,Z)-2,13-octadeca- dien-1 -ol acetate, (E,Z)-3,13-octadecadien-1 -ol, R-1 -octen-3-ol, pentatermanone, potassium silicate, sorbitol actanoate, (E,Z,Z)-3,8,1 1-tetradecatrienyl acetate, (Z,E)-9,12- tetradecadien-1 -yl acetate, Z-7-tetradecen-2-one, Z-9-tetradecen-1 -yl acetate, Z-1 1 - tetradecenal, Z-1 1 -tetradecen-1 -ol, Acacia negra extract, extract of grapefruit seeds and pulp, extract of Chenopodium ambrosiodes, Catnip oil, Neem oil, Quillay extract, Tagetes oil;
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. elkanii, B. japonicum,
B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium sp., Paenibacillus alvei, Penici Ilium bilaiae, Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti;
L6) Biochemical pesticides with plant stress reducing, plant growth regulator and/or plant yield enhancing activity: abscisic acid, aluminium silicate (kaolin), 3-decen-2-one, formononetin, genistein, hesperetin, homobrassinlide, humates, jasmonic acid or salts or derivatives thereof, lysophosphatidyl ethanolamine, naringenin, polymeric polyhydroxy acid, Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract and Ecklonia maxima (kelp) extract;
M) Growth regulators
abscisic acid, 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, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione- calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate,
2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole;
N) Herbicides
acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
- amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
aryloxyphenoxypropionat.es: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
Bipyridyls: diquat, paraquat;
(thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thioben- carb, triallate;
cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepralox- ydim, tralkoxydim;
dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; - diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen;
hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;
imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, ima- zethapyr;
- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlor- prop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
- sulfonl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, met- sulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfu- ron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusul- furon, tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonl)-3-(4,6-dimethoxy- pyrimidin-2-yl)urea; triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam,
propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisul- fan, pyrithiobac, pyroxasulfone, pyroxsulam;
others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarba- zone,benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromobu- tide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlorthal, cinmethylin, clomazone, cu uron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoc- eras, endothal, ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraf I uf en-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinodamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, (3-[2-chloro-4-fluoro-5-(3- methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1 -yl)-phenoxy]-pyridin-2-yloxy)- acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro- phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy- phenyl)-pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3- dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester.
O) Insecticides
organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothi- ofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
carbamates: alancarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosul- fan, fenoxycarb, furathiocarb, methiocarb, methonl, oxaj, pirimicarb, propoxur, thiodicarb, triazamate;
- pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin; insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cy- ramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ec- dysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spi- romesifen, spirotetramat;
nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, flupyradi- furone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1 -2-chloro-thiazol-5- ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
- GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1 H-pyrazole-3-carbothioic acid amide;
macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spi- nosad, spinetoram;
- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon;
Uncouplers: chlorfenapyr;
oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; - moulting disruptor compounds: cryomazine;
mixed function oxidase inhibitors: piperomyl butoxide;
sodium channel blockers: indoxacarb, metaflumizone;
ryanodine receptor inhibitors: chlorantraniliprole, cyantraniliprole, flubendiamide, N-[4,6- dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(diethyl-lambda-4- sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4,6-dichloro-2-[(di-2-propyl- lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro- 2-pyridyl)-5-(difluoromethyl)pyrazole-3-carboxamide; N-[4,6-dibromo-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-cyano-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4,6-dibromo-2-[(diethyl- lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide;
others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocy- clam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, pyrifluquinazon and 1 ,1 '- [(3S,4R,4aR,6S,6aS, 12R, 12aS, 12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]- 1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-1 1 -oxo-9-(3-pyridinyl)- 21-1,1 1 H-naphtho[2,1 -b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester.
The present invention furthermore relates to compositions comprising a compound I or II, respectively, (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. fungicide from the groups A) to L), as described above, and if desired one suitable solvent or solid carrier. Those compositions 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 compristion comprising a compound I or II, respectively, and a fungicide from groups A) to L), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to L). By applying compounds I or II, re- spectively, together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic compositions).
This can be obtained by applying the compounds I or II, respectively,and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or seperately, or in succes- sion, 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.
In compositions according to the invention comprising one compound I or II, respectively, (com- ponent 1 ) and one further active substance (component 2), e. g. one active substance from groups A) to O), the weight ratio of component 1 and component 2 generally 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 :3 to 3:1 .
In compositions according to the invention comprising one compound I or II, respectively, (component 1 ) and a first further active substance (component 2) and a second further active substance (component 3), e. g. two active substances from groups A) to O), the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1 , and the weight ratio of component 1 and component 3 preferably is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1.
Preference is also given to compositions comprising a compound I or II, respectively, (component 1 ) and at least one active substance selected from group A) (component 2) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin; famoxadone, fenamidone; benzovindiflupyr, bixafen, boscalid, fluopyram, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid, fluazinam, fentin salts, such as fentin acetate.
Preference is given to compositions comprising a compound of formula I or II, respectively, (component 1 ) and at least one active substance selected from group B) (component 2) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusi- lazole, flutriafol, metconazole, nclobutanil, penconazole, propiconazole, prothioconazole, triadi- mefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, fenarimol, triforine; dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine; fenhexamid.
Preference is given to compositions comprising a compound of formula I or II, respectively, (component 1 ) and at least one active substance selected from group C) (component 2) and particularly selected from metalaxyl, (metalaxyl-M) mefenoxam, ofurace.
Preference is given to compositions comprising a compound of formula I or II, respectively, (component 1 ) and at least one active substance selected from group D) (component 2) and particularly selected from benomyl, carbendazim, thiophanate-methyl, ethaboxam, fluopicolide, zoxamide, metrafenone, pyriofenone.
Preference is also given to compositions comprising a compound I or II, respectively, (component 1 ) and at least one active substance selected from group E) (component 2) and particularly selected from cyprodinil, mepanipyrim, pyrimethanil.
Preference is also given to compositions comprising a compound I or II, respectively, (compo- nent 1 ) and at least one active substance selected from group F) (component 2) and particularly selected from iprodione, fludioxonil, vinclozolin, quinoxyfen.
Preference is also given to compositions comprising a compound I or II, respectively, (component 1 ) and at least one active substance selected from group G) (component 2) and particularly selected from dimethomorph, flumorph, iprovalicarb, benthiavalicarb, mandipropamid, pro- pamocarb.
Preference is also given to compositions comprising a compound I or II, respectively, (component 1 ) and at least one active substance selected from group H) (component 2) and particularly selected from copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, mancozeb, metiram, propineb, thiram, captafol, folpet, chlorothalonil, dichlofluanid, dithianon. Preference is also given to compositions comprising a compound I or II, respectively, (component 1 ) and at least one active substance selected from group I) (component 2) and particularly selected from carpropamid and fenoxanil.
Preference is also given to compositions comprising a compound I or II, respectively, (component 1 ) and at least one active substance selected from group J) (component 2) and particularly selected from acibenzolar-S-methyl, probenazole, tiadinil, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof.
Preference is also given to compositions comprising a compound I or II, respectively, (component 1 ) and at least one active substance selected from group K) (component 2) and particularly selected from cymoxanil, proquinazid and A/-methyl-2-{1 -[(5-methyl-3-trifluoromethyl-1 H- pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-A/-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]- 4-thiazolecarboxamide.
Preference is also given to compositions comprising a compound I or II, respectively, (compo- nent 1 ) and at least one active substance selected from group L) (component 2) and particularly selected from Bacillus subtilis strain NRRL No. B-21661 , Bacillus pumilus strain NRRL No. B- 30087 and Ulocladium oudemansii .
Accordingly, the present invention furthermore relates to compositions comprising one compound I (component 1 ) and one further active substance (component 2), which further active substance is selected from the column "Component 2" of the lines C-1 to C-402 of Table C.
A further embodiment relates to the compositions C-1 to C-402 listed in Table C, wherein one row of Table C corresponds in each case to a composition comprising one of the compounds I that are individualized compounds of formula I (component 1 ) and the respective further active substance from groups A) to O) (component 2) stated in the respective row. According to a pre- ferred embodiment, the "individualized compound I" is one of the compounds as individualized in Tables 1 a to 13a, Tables 1 b to 13b and Tables 1 c to 13c. Preferably, the compositions described comprise the active substances in synergistically effective amounts.
Table C: Composition comprising one individualized compound of the present invention and one further active substance from groups A) to O)
Mixture Component 1 Component 2
C-1 one individualized compound I Azoxystrobin
C-2 one individualized compound I Coumethoxystrobin
C-3 one individualized compound I Coumoxystrobin
C-4 one individualized compound I Dimoxystrobin
C-5 one individualized compound I Enestroburin
C-6 one individualized compound I Fenaminstrobin
C-7 one individualized compound I Fenoxystrobin/Flufenoxystrobin
C-8 one individualized compound I Fluoxastrobin
C-9 one individualized compound I Kresoxim-methyl
C-10 one individualized compound I Metominostrobin
C-1 1 one individualized compound I Orysastrobin
C-12 one individualized compound I Picoxystrobin
C-13 one individualized compound I Pyraclostrobin
C-14 one individualized compound I Pyrametostrobin
C-15 one individualized compound I Pyraoxystrobin
C-16 one individualized compound I Pyribencarb
C-17 one individualized compound I Trifloxystrobin
C-18 one individualized compound I Triclopyricarb/Chlorodincarb Mixture Component 1 Component 2
2-[2-(2,5-dimethyl-phenoxymethyl)-
C-19 one individualized compound I phenyl]-3-methoxy-acrylic acid methyl ester
2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-
C-20 one individualized compound I allylideneaminooxymethyl)-phenyl)-
2-methoxyimino-N-methyl-acetamide
C-21 one individualized compound I Cyazofamid
C-22 one individualized compound I Amisulbrom
C-23 one individualized compound I Benalaxyl
C-24 one individualized compound I Benalaxyl-M
C-25 one individualized compound I Benodanil
C-26 one individualized compound I Benzovindiflupyr
C-27 one individualized compound I Bixafen
C-28 one individualized compound I Boscalid
C-29 one individualized compound I Carboxin
C-30 one individualized compound I Fenfuram
C-31 one individualized compound I Fenhexamid
C-32 one individualized compound I Flutolanil
C-33 one individualized compound I Fluxapyroxad
C-34 one individualized compound I Furametpyr
C-35 one individualized compound I Isofetamid
C-36 one individualized compound I Isopyrazam
C-37 one individualized compound I Isotianil
C-38 one individualized compound I Kiralaxyl
C-39 one individualized compound I Mepronil
C-40 one individualized compound I Metalaxyl
C-41 one individualized compound I Metalaxyl-M
C-42 one individualized compound I Ofurace
C-43 one individualized compound I Oxadixyl
C-44 one individualized compound I Oxycarboxin
C-45 one individualized compound I Penflufen
C-46 one individualized compound I Penthiopyrad
C-47 one individualized compound I Sedaxane
C-48 one individualized compound I Tecloftalam
C-49 one individualized compound I Thifluzamide
C-50 one individualized compound I Tiadinil
2-Amino-4-methyl-thiazole-5-carboxylic
C-51 one individualized compound I
acid anilide Mixture Component 1 Component 2
N-(4'-trifluoromethylthiobiphenyl-2-yl)-
C-52 one individualized compound I 3- difluoromethyl-1 -methyl-1 H-pyrazole-
4- carboxamide
N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-
C-53 one individualized compound I 1 ,3-dimethyl-5-fluoro-1 H-pyrazole- 4-carboxamide
3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-tri-
C-54 one individualized compound I methylindan-4-yl)pyrazole-4-carbox- amide
3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-tri-
C-55 one individualized compound I methylindan-4-yl)pyrazole-4-carbox- amide
1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-
C-56 one individualized compound I
4-yl)pyrazole-4-carboxamide
3- (trifluoromethyl)-1 ,5-dimethyl-
C-57 one individualized compound I N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-
4- carboxamide
N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-
C-58 one individualized compound I
1 ,3-dimethyl-pyrazole-4-carboxamide
1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-
C-59 one individualized compound I
4-yl)pyrazole-4-carboxamide
N-[2-(2,4-dichlorophenyl)-2-methoxy-
C-60 one individualized compound I 1 -methyl-ethyl]-3-(difluoromethyl)- 1 -methyl-pyrazole-4-carboxamide
C-61 one individualized compound I Dimethomorph
C-62 one individualized compound I Flumorph
C-63 one individualized compound I Pyrimorph
C-64 one individualized compound I Flumetover
C-65 one individualized compound I Fluopicolide
C-66 one individualized compound I Fluopyram
C-67 one individualized compound I Zoxamide
C-68 one individualized compound I Carpropamid
C-69 one individualized compound I Diclocymet
C-70 one individualized compound I Mandipropamid
C-71 one individualized compound I Oxytetracyclin
C-72 one individualized compound I Silthiofam
N-(6-methoxy-pyridin-3-yl) cyclopro-
C-73 one individualized compound I
panecarboxylic acid amide
C-74 one individualized compound I Azaconazole
C-75 one individualized compound I Bitertanol Mixture Component 1 Component 2
C-76 one individualized compound I Bromuconazole
C-77 one individualized compound I Cyproconazole
C-78 one individualized compound I Difenoconazole
C-79 one individualized compound I Diniconazole
C-80 one individualized compound I Diniconazole-M
C-81 one individualized compound I Epoxiconazole
C-82 one individualized compound I Fenbuconazole
C-83 one individualized compound I Fluquinconazole
C-84 one individualized compound I Flusilazole
C-85 one individualized compound I Flutriafol
C-86 one individualized compound I Hexaconazol
C-87 one individualized compound I Imibenconazole
C-88 one individualized compound I Ipconazole
C-89 one individualized compound I Metconazole
C-90 one individualized compound I Myclobutanil
C-91 one individualized compound I Oxpoconazol
C-92 one individualized compound I Paclobutrazol
C-93 one individualized compound I Penconazole
C-94 one individualized compound I Propiconazole
C-95 one individualized compound I Prothioconazole
C-96 one individualized compound I Simeconazole
C-97 one individualized compound I Tebuconazole
C-98 one individualized compound I Tetraconazole
C-99 one individualized compound I Triadimefon
C-100 one individualized compound I Triadimenol
C-101 one individualized compound I Triticonazole
C-102 one individualized compound I Uniconazole
1 - [re/-(2S;3R)-3-(2-chlorophenyl)-
C-103 one individualized compound I 2- (2,4-difluorophenyl)-oxiranylmethyl]- 5-thiocyanato-1 H-[1 ,2,4]triazole,
2-[re/-(2S;3R)-3-(2-chlorophenyl)-
C-104 one individualized compound I 2-(2,4-difluorophenyl)-oxiranylmethyl]-
2H-[1 ,2,4]triazole-3-thiol
2-[2-chloro-4-(4-chlorophenoxy)phenyl]-
C-105 one individualized compound I
1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol
1 -[4-(4-chlorophenoxy)-2-(trifluorometh-
C-106 one individualized compound I yl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol- 1 -yl)ethanol Mixture Component 1 Component 2
2-[4-(4-chlorophenoxy)-2-(trifluorometh-
C-107 one individualized compound I yl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan- 2-ol
2-[2-chloro-4-(4-chlorophenoxy)phenyl]-
C-108 one individualized compound I
1 -(1 ,2,4-triazoM -yl)butan-2-ol
2-[4-(4-chlorophenoxy)-2-(trifluorometh-
C-109 one individualized compound I yl)phenyl]-3-methyl-1 -(1 ,2,4-triazol- 1 -yl)butan-2-ol
2-[4-(4-chlorophenoxy)-2-(trifluorometh-
C-1 10 one individualized compound I yl)phenyl]-1 -(1 ,2,4-triazoM -yl)propan- 2-ol
2- [2-chloro-4-(4-chlorophenoxy)phenyl]-
C-1 1 1 one individualized compound I
3- methyM -(1 ,2,4-triazoM -yl)butan-2-ol
2-[4-(4-chlorophenoxy)-2-
C-1 12 one individualized compound I (trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol- 1 -yl)pentan-2-ol;
2-[4-(4-fluorophenoxy)-2-(trifluorometh-
C-1 13 one individualized compound I yl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan- 2-ol
C-1 14 one individualized compound I Amisulbrom
C-1 15 one individualized compound I Imazalil
C-1 16 one individualized compound I Imazalil-sulfate
C-1 17 one individualized compound I Pefurazoate
C-1 18 one individualized compound I Prochloraz
C-1 19 one individualized compound I Triflumizole
C-120 one individualized compound I Benomyl
C-121 one individualized compound I Carbendazim
C-122 one individualized compound I Fuberidazole
C-123 one individualized compound I Thiabendazole
C-124 one individualized compound I Ethaboxam
C-125 one individualized compound I Etridiazole
C-126 one individualized compound I Hymexazole
2-(4-Chloro-phenyl)-N-[4-(3,4-dimeth-
C-127 one individualized compound I oxy-phenyl)-isoxazol-5-yl]-2-prop-2-yn- yloxy-acetamide
C-128 one individualized compound I Fluazinam
C-129 one individualized compound I Pyrifenox
3-[5-(4-Chloro-phenyl)-2,3-dimethyl-is-
C-130 one individualized compound I
oxazolidin-3-yl]-pyridine (Pyrisoxazole) Mixture Component 1 Component 2
3-[5-(4-Methyl-phenyl)-2,3-dimethyl-
C-131 one individualized compound I
isoxazolidin-3-yl]-pyridine
C-132 one individualized compound I Bupirimate
C-133 one individualized compound I Cyprodinil
C-134 one individualized compound I 5-Fluorocytosine
5-Fluoro-2-(p-tolylmethoxy)pyrimidin-
C-135 one individualized compound I
4-amine
5-Fluoro-2-(4-fluorophenylmethoxy)-
C-136 one individualized compound I
pyrimidin-4-amine
C-137 one individualized compound I Diflumetorim
(5,8-Difluoroquinazolin-4-yl)-{2-[2-fluo-
C-138 one individualized compound I ro-4-(4-trifluoromethylpyridin-2-yloxy)- phenyl]-ethyl}-amine
C-139 one individualized compound I Fenarimol
C-140 one individualized compound I Ferimzone
C-141 one individualized compound I Mepanipyrim
C-142 one individualized compound I Nitra pyrin
C-143 one individualized compound I Nuarimol
C-144 one individualized compound I Pyrimethanil
C-145 one individualized compound I Triforine
C-146 one individualized compound I Fenpiclonil
C-147 one individualized compound I Fludioxonil
C-148 one individualized compound I Aldimorph
C-149 one individualized compound I Dodemorph
C-150 one individualized compound I Dodemorph-acetate
C-151 one individualized compound I Fenpropimorph
C-152 one individualized compound I Tridemorph
C-153 one individualized compound I Fenpropidin
C-154 one individualized compound I Fluoroimid
C-155 one individualized compound I Iprodione
C-156 one individualized compound I Procymidone
C-157 one individualized compound I Vinclozolin
C-158 one individualized compound I Famoxadone
C-159 one individualized compound I Fenamidone
C-160 one individualized compound I Flutianil
C-161 one individualized compound I Octhilinone
C-162 one individualized compound I Probenazole
C-163 one individualized compound I Fenpyrazamine
C-164 one individualized compound I Acibenzolar-S-methyl Mixture Component 1 Component 2
C-165 one individualized compound I Ametoctradin
C-166 one individualized compound I Amisulbrom
[(3S,6S,7R,8R)-8-benzyl-3-[(3-isobuty- ryloxymethoxy-4-methoxypyridine-
C-167 one individualized compound I
2-carbonyl)amino]-6-methyl-4,9-dioxo- [1 ,5]dioxonan-7-yl] 2-methylpropanoate
[(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy- 4-methoxy-pyridine-2-carbonyl)amino]-
C-168 one individualized compound I
6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate
[(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet- oxymethoxy)-4-methoxy-pyridine-
C-169 one individualized compound I
2-carbonyl]amino]-6-methyl-4,9-dioxo- 1 ,5-dioxonan-7-yl] 2-methylpropanoate
[(3S,6S,7R,8R)-8-benzyl-3-[(3-isobut- oxycarbonyloxy-4-methoxy-pyridine-
C-170 one individualized compound I
2-carbonyl)amino]-6-methyl-4,9-dioxo- 1 ,5-dioxonan-7-yl] 2-methylpropanoate
[(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-ben- zodioxol-5-ylmethoxy)-4-methoxy-pyri-
C-171 one individualized compound I dine-2-carbonyl]amino]-6-methyl-4,9-di- oxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate
(3S,6S,7R,8R)-3-[[(3-hydroxy-4-meth- oxy-2-pyridinyl)carbonyl]amino]-
C-172 one individualized compound I
6-methyl-4,9-dioxo-8-(phenylmethyl)- 1 ,5-dioxonan-7-yl 2-methylpropanoate
C-173 one individualized compound I Anilazin
C-174 one individualized compound I Blasticidin-S
C-175 one individualized compound I Captafol
C-176 one individualized compound I Captan
C-177 one individualized compound I Chinomethionat
C-178 one individualized compound I Dazomet
C-179 one individualized compound I Debacarb
C-180 one individualized compound I Diclomezine
C-181 one individualized compound I Difenzoquat,
C-182 one individualized compound I Difenzoquat-methylsulfate
C-183 one individualized compound I Fenoxanil
C-184 one individualized compound I Folpet
C-185 one individualized compound I Oxolinsaure Mixture Component 1 Component 2
C-186 one individualized compound I Piperalin
C-187 one individualized compound I Proquinazid
C-188 one individualized compound I Pyroquilon
C-189 one individualized compound I Quinoxyfen
C-190 one individualized compound I Triazoxid
C-191 one individualized compound I Tricyclazole
2-Butoxy-6-iodo-3-propyl-chromen-4-
C-192 one individualized compound I
one
5-Chloro-1 -(4,6-dimethoxy-pyrimidin-2-
C-193 one individualized compound I
yl)-2-methyl-1 H-benzoimidazole
5- Chloro-7-(4-methyl-piperidin-1 -yl)-
C-194 one individualized compound I 6- (2,4,6-trifluoro-phenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine
C-195 one individualized compound I Ferbam
C-196 one individualized compound I Mancozeb
C-197 one individualized compound I Maneb
C-198 one individualized compound I Metam
C-199 one individualized compound I Methasulphocarb
C-200 one individualized compound I Metiram
C-201 one individualized compound I Propineb
C-202 one individualized compound I Thiram
C-203 one individualized compound I Zineb
C-204 one individualized compound I Ziram
C-205 one individualized compound I Diethofencarb
C-206 one individualized compound I Benthiavalicarb
C-207 one individualized compound I Iprovalicarb
C-208 one individualized compound I Propamocarb
C-209 one individualized compound I Propamocarb hydrochlorid
C-210 one individualized compound I Valifenalate
N-(1 -(1 -(4-cyanophenyl)ethanesulfon-
C-21 1 one individualized compound I yl)-but-2-yl) carbamic acid-(4-fluoro- phenyl) ester
C-212 one individualized compound I Dodine
C-213 one individualized compound I Dodine free base
C-214 one individualized compound I Guazatine
C-215 one individualized compound I Guazatine-acetate
C-216 one individualized compound I Iminoctadine
C-217 one individualized compound I Iminoctadine-triacetate
C-218 one individualized compound I Iminoctadine-tris(albesilate) Mixture Component 1 Component 2
C-219 one individualized compound I Kasugamycin
C-220 one individualized compound I Kasugamycin-hydrochloride-hydrate
C-221 one individualized compound I Polyoxine
C-222 one individualized compound I Streptomycin
C-223 one individualized compound I Validamycin A
C-224 one individualized compound I Binapacryl
C-225 one individualized compound I Dicloran
C-226 one individualized compound I Dinobuton
C-227 one individualized compound I Dinocap
C-228 one individualized compound I Nitrothal-isopropyl
C-229 one individualized compound I Tecnazen
C-230 one individualized compound I Fentin salts
C-231 one individualized compound I Dithianon
2,6-dimethyl-1 H,5H-[1 ,4]dithiino
C-232 one individualized compound I [2,3-c:5,6-c']dipyrrole-
1 ,3,5,7(2H,6H)-tetraone
C-233 one individualized compound I Isoprothiolane
C-234 one individualized compound I Edifenphos
C-235 one individualized compound I Fosetyl, Fosetyl-aluminium
C-236 one individualized compound I Iprobenfos
Phosphorous acid (H3PO3) and deriva¬
C-237 one individualized compound I
tives
C-238 one individualized compound I Pyrazophos
C-239 one individualized compound I Tolclofos-methyl
C-240 one individualized compound I Chlorothalonil
C-241 one individualized compound I Dichlofluanid
C-242 one individualized compound I Dichlorophen
C-243 one individualized compound I Flusulfamide
C-244 one individualized compound I Hexachlorbenzene
C-245 one individualized compound I Pencycuron
C-246 one individualized compound I Pentachlorophenol and salts
C-247 one individualized compound I Phthalide
C-248 one individualized compound I Quintozene
C-249 one individualized compound I Thiophanate Methyl
C-250 one individualized compound I Tolylfluanid
N-(4-chloro-2-nitro-phenyl)-N-ethyl-
C-251 one individualized compound I
4-methyl-benzenesulfonamide
C-252 one individualized compound I Bordeaux mixture
C-253 one individualized compound I Copper acetate Mixture Component 1 Component 2
C-254 one individualized compound Copper hydroxide
C-255 one individualized compound Copper oxychloride
C-256 one individualized compound basic Copper sulfate
C-257 one individualized compound Sulfur
C-258 one individualized compound Biphenyl
C-259 one individualized compound Bronopol
C-260 one individualized compound Cyflufenamid
C-261 one individualized compound Cymoxanil
C-262 one individualized compound Diphenylamin
C-263 one individualized compound Metrafenone
C-264 one individualized compound Pyriofenone
C-265 one individualized compound Mildiomycin
C-266 one individualized compound Oxin-copper
C-267 one individualized compound Oxathiapiprolin
C-268 one individualized compound Tolprocarb
2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 - y|]-1 -[4-(4-{5-[2-(prop-2-yn-1 -yloxy)phe-
C-269 one individualized compound I
nyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thi- azol-2-yl)piperidin-1 -yl]ethanone
2- [3,5-bis(difluoromethyl)-1 H-pyrazol- 1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-
C-270 one individualized compound I 1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-
3- yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]- ethanone
2- [3,5-bis(difluoromethyl)-1 H-pyrazol- 1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-
C-271 one individualized compound I 1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-
3- yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]- ethanone
ethyl (Z)-3-amino-2-cyano-3-phenyl-
C-272 one individualized compound I
prop-2-enoate
tert-butyl N-[6-[[(Z)-[(1 -methyltetrazol-
C-273 one individualized compound I 5-yl)-phenyl-methylene]amino]oxy- methyl]-2-pyridyl]carbamate
pentyl N-[6-[[(Z)-[(1 -methyltetrazol-
C-274 one individualized compound I 5-yl)-phenyl-methylene]amino]oxy- methyl]-2-pyridyl]carbamate
2-[2-[(7,8-difluoro-2-methyl-3-quinol-
C-275 one individualized compound I
yl)oxy]-6-fluoro-phenyl]propan-2-ol Mixture Component 1 Component 2
2- [2-fluoro-6-[(8-fluoro-2-methyl-
C-276 one individualized compound I
3- quinolyl)oxy]phenyl]propan-2-ol
3-(5-fluoro-3,3,4,4-tetramethyl-3,4-di-
C-277 one individualized compound I
hydroisoquinolin-1 -yl)quinoline
3-(4 ,4-d if I uoro-3 , 3-d i methyl-3 ,4-d i-
C-278 one individualized compound I
hydroisoquinolin-1 -yl)quinoline
3-(4,4,5-trifluoro-3,3-dimethyl-3,4-di-
C-279 one individualized compound I
hydroisoquinolin-1 -yl)quinoline
C-280 one individualized compound I Prohexadione calcium
C-281 one individualized compound I Spiroxamine
C-282 one individualized compound I Tebufloquin
C-283 one individualized compound I Tolylfluanid
N-(Cyclopropylmethoxyimino-(6-
C-284 one individualized compound I difluoromethoxy-2,3-difluoro-phenyl)- methyl)-2-phenyl acetamide
N'-(4-(4-chloro-3-trifluoromethyl-
C-285 one individualized compound I phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine
N'-(4-(4-fluoro-3-trifluoromethyl-
C-286 one individualized compound I phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine
N'-(2-methyl-5-trifluoromethyl-4-(3-tri-
C-287 one individualized compound I methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine
N'-(5-difluoromethyl-2-methyl-4-(3-tri-
C-288 one individualized compound I methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine
Methoxy-acetic acid 6-tert-butyl-8-
C-289 one individualized compound I fluoro-2,3-dimethyl-quinolin-4-yl ester
C-290 one individualized compound I Bacillus subtilis NRRL No. B-21661
C-291 one individualized compound I Bacillus pumilus NRRL No. B-30087
C-292 one individualized compound I Ulocladium oudemansii
C-293 one individualized compound I Carbaryl
C-294 one individualized compound I Carbofuran
C-295 one individualized compound I Carbosulfan
C-296 one individualized compound I Methomylthiodicarb
C-297 one individualized compound I Bifenthrin
C-298 one individualized compound I Cyfluthrin
C-299 one individualized compound I Cypermethrin
C-300 one individualized compound I alpha-Cypermethrin Mixture Component 1 Component 2
C-301 one individualized compound I zeta-Cypermethrin
C-302 one individualized compound I Deltamethrin
C-303 one individualized compound I Esfenvalerate
C-304 one individualized compound I Lambda-cyhalothrin
C-305 one individualized compound I Permethrin
C-306 one individualized compound I Tefluthrin
C-307 one individualized compound I Diflubenzuron
C-308 one individualized compound I Flufenoxuron
C-309 one individualized compound I Lufenuron
C-310 one individualized compound I Teflubenzuron
C-31 1 one individualized compound I Spirotetramate
C-312 one individualized compound I Clothianidin
C-313 one individualized compound I Dinotefuran
C-314 one individualized compound I Imidacloprid
C-315 one individualized compound I Thiamethoxam
C-316 one individualized compound I Flupyradifurone
C-317 one individualized compound I Acetamiprid
C-318 one individualized compound I Thiacloprid
C-319 one individualized compound I Endosulfan
C-320 one individualized compound I Fipronil
C-321 one individualized compound I Abamectin
C-322 one individualized compound I Emamectin
C-323 one individualized compound I Spinosad
C-324 one individualized compound I Spinetoram
C-325 one individualized compound I Hydramethylnon
C-326 one individualized compound I Chlorfenapyr
C-327 one individualized compound I Fenbutatin oxide
C-328 one individualized compound I Indoxacarb
C-329 one individualized compound I Metaflumizone
C-330 one individualized compound I Flonicamid
C-331 one individualized compound I Flubendiamide
C-332 one individualized compound I Chlorantraniliprole
C-333 one individualized compound I Cyantraniliprole
N-[4,6-dichloro-2-[(diethyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-
C-334 one individualized compound I
2-(3-chloro-2-pyridyl)-5-(trifluorometh- yl)pyrazole-3-carboxamide Mixture Component 1 Component 2
N-[4-chloro-2-[(diethyl-lambda-4-sul- fanylidene)carbamoyl]-6-methyl-phe-
C-335 one individualized compound I
nyl]-2-(3-chloro-2-pyridyl)-5-(trifluoro- methyl)pyrazole-3-carboxamide
N-[4-chloro-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-6-methyl-
C-336 one individualized compound I
phenyl]-2-(3-chloro-2-pyridyl)-5-(tri- fluoromethyl)pyrazole-3-carboxamide
N-[4,6-dichloro-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-
C-337 one individualized compound I
2-(3-chloro-2-pyridyl)-5-(trifluoro- methyl)pyrazole-3-carboxamide
N-[4,6-dichloro-2-[(diethyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-
C-338 one individualized compound I
2-(3-chloro-2-pyridyl)-5-(difluoro- methyl)pyrazole-3-carboxamide
N-[4,6-dibromo-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-2-
C-339 one individualized compound I
(3-chloro-2-pyridyl)-5-(trifluoromethyl)- pyrazole-3-carboxamide
N-[4-chloro-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-6-cyano-
C-340 one individualized compound I
phenyl]-2-(3-chloro-2-pyridyl)-5-(tri- fluoromethyl)pyrazole-3-carboxamide
N-[4,6-dibromo-2-[(diethyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-
C-341 one individualized compound I
2-(3-chloro-2-pyridyl)-5-(trifluorometh- yl)pyrazole-3-carboxamide
C-342 one individualized compound I Cyflumetofen
C-343 one individualized compound I Acetochlor
C-344 one individualized compound I Dimethenamid
C-345 one individualized compound I metolachlor
C-346 one individualized compound I Metazachlor
C-347 one individualized compound I Glyphosate
C-348 one individualized compound I Glufosinate
C-349 one individualized compound I Sulfosate
C-350 one individualized compound I Clodinafop
C-351 one individualized compound I Fenoxaprop
C-352 one individualized compound I Fluazifop
C-353 one individualized compound I Haloxyfop Mixture Component 1 Component 2
C-354 one individualized compound I Paraquat
C-355 one individualized compound I Phenmedipham
C-356 one individualized compound I Clethodim
C-357 one individualized compound I Cycloxydim
C-358 one individualized compound I Profoxydim
C-359 one individualized compound I Sethoxydim
C-360 one individualized compound I Tepraloxydim
C-361 one individualized compound I Pendimethalin
C-362 one individualized compound I Prodiamine
C-363 one individualized compound I Trifluralin
C-364 one individualized compound I Acifluorfen
C-365 one individualized compound I Bromoxynil
C-366 one individualized compound I Imazamethabenz
C-367 one individualized compound I Imazamox
C-368 one individualized compound I Imazapic
C-369 one individualized compound I Imazapyr
C-370 one individualized compound I Imazaquin
C-371 one individualized compound I Imazethapyr
2,4-Dichlorophenoxyacetic acid (2,4-
C-372 one individualized compound I
D)
C-373 one individualized compound I Chloridazon
C-374 one individualized compound I Clopyralid
C-375 one individualized compound I Fluroxypyr
C-376 one individualized compound I Picloram
C-377 one individualized compound I Picolinafen
C-378 one individualized compound I Bensulfuron
C-379 one individualized compound I Chlorimuron-ethyl
C-380 one individualized compound I Cyclosulfamuron
C-381 one individualized compound I lodosulfuron
C-382 one individualized compound I Mesosulfuron
C-383 one individualized compound I Metsulfuron-methyl
C-384 one individualized compound I Nicosulfuron
C-385 one individualized compound I Rimsulfuron
C-386 one individualized compound I Triflusulfuron
C-387 one individualized compound I Atrazine
C-388 one individualized compound I Hexazinone
C-389 one individualized compound I Diuron
C-390 one individualized compound I Florasulam
C-391 one individualized compound I Pyroxasulfone Mixture Component 1 Component 2
C-392 one individualized compound Bentazone
C-393 one individualized compound Cinidon-ethyl
C-394 one individualized compound Cinmethylin
C-395 one individualized compound Dicamba
C-396 one individualized compound Diflufenzopyr
C-397 one individualized compound Quinclorac
C-398 one individualized compound Quinmerac
C-399 one individualized compound Mesotrione
C-400 one individualized compound Saflufenacil
C-401 one individualized compound Topramezone
1 ,1 '-[(3S,4R,4aR,6S,6aS,12R,12aS,
12bS)-4-[[(2-cyclopropylacetyl)oxy]me- thyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-deca-
C-402 one individualized compound I hydro-12-hydroxy-4,6a,12b-trimethyl-
1 1 -oxo-9-(3-pyridinyl)-2H,1 1 H-naph- tho[2,1 -b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester
A further embodiment relates to compositions comprising one compound II (component 1 ) and one further active substance (component 2), which further active substance is selected from the column "Component 2" of the lines C2-1 to C2-402 of Table C2.
Specifically, a further embodiment relates to the compositions C2-1 to C2-402 listed in Table C2, wherein one row of Table C2 corresponds in each case to a composition comprising one of the compounds I that are individualized compounds of formula I (component 1 ) and the respective further active substance from groups A) to O) (component 2) stated in the respective row. According to a preferred embodiment, the "individualized compound II" is one of the compounds as individualized in Tables 1 d, 1 e and 1f. Preferably, the compositions described comprise the active substances in synergistically effective amounts.
Table C2: Composition comprising one individualized compound II and one further active substance from groups A) to O). This table corresponds to table C above, wherein in the first column the number/name of the individualized mixture is named "C2-..." instead of "C-..." and in the second column, it says in each line "one individualized compound II" instead of "one individ- ualized compound I".
The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by lUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP- A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244,
JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 1 1/028657, WO2012/168188, WO
2007/006670, WO 201 1/77514; WO13/047749, WO 10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009,
WO 13/024010 and WO 2013/047441 )..The composition of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient by usual means, e. g. by the means given for the compositions of compounds I or II, respectively.
Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I orll, respectively.
The compositions of active substances according to the present invention are suitable as fungi- cides, as are the compounds of formula I or II. 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 refered to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I or II, respectively.

Claims

Claims
1 . Compounds of the formula I
Figure imgf000095_0001
is CH or N;
is CH or N;
is Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-Cs- cycloalkyl-Ci-C6-alkyl, phenyl, phenyl-Ci-C4-alkyl, phenyl-C2-C4-alkenyl or phenyl-C2-C4-alkynyl;
wherein the aliphatic moieties of R2 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R2a which independently of one another are selected from:
R2a halogen, OH, CN, nitro, Ci-C4-alkoxy, C3-C8-cycloalkyl, C3-C8- halocycloalkyl and Ci-C4-halogenalkoxy;
wherein the cycloalkyl and/or phenyl moieties of R2 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R2b which independently of one another are selected from:
R2b halogen, OH, CN, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, C1-C4- halogenalkyl, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl and C1-C4- halogenalkoxy;
is 0, 1 , 2, 3 or 4;
is independently selected from halogen, CN, NO2, OH, SH, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C3- cycloalkyloxy, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C3-C6- cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl), C(=0)(Ci-C4-alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4-alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)-(N(C3-C6- cycloalkyl)2; wherein each of R3 is unsubstituted or further substituted by one, two, three or four R3a; wherein
R3a is independently selected from halogen, CN, NO2, OH, C1-C4- alkyl, Ci-C4-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, Ci- C4-alkoxy and Ci-C4-haloalkoxy;
m is 0, 1 , 2, 3, 4 or 5; and
R4 is in each case independently selected from halogen, CN, NO2, OH, SH, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkyloxy, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C3-C6- cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl), C(=0)(Ci-C4-alkyl), C(=0)(OH), C(=0)(0-Ci-C4-alkyl), C(=0)(NH(Ci-C4-alkyl)), C(=0)(N(Ci-C4-alkyl)2), C(=0)(NH(C3-C6-cycloalkyl)) and C(=0)- (N(C3-C6-cycloalkyl)2); wherein each of R4 is unsubstituted or further substituted by one, two, three or four R4a wherein
R4a is independently selected from halogen, CN, N02, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
p is 0, 1 or 2;
and the N-oxides and the agriculturally acceptable salts thereof.
2. The compounds of claim 1 , wherein X and Y are N.
3. The compounds of claim 1 , wherein X is N and Y is CH.
4. The compounds of claim 1 , wherein X and Y are CH.
5. The compounds of any one of claims 1 to 4, wherein n+m is 1 , 2, 3, 4, 5, 6, 7, 8 or 9.
6. The compounds of any one of claims 1 to 5, wherein m is 1 , 2 or 3.
7. The compounds of any one of claims 1 to 6, wherein one of the respective R4 is in para-(4-)position.
8. The compounds of any one of claims 1 to 7, wherein R2 is selected from C1-C6- alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the R2 are in each case unsubstituted or are substituted by R2a as defined and preferably defined in claim 1 .
9. An agricultural composition, comprising one compound of formula I, as defined in any of the claims 1 to 8, an N-oxide or an agriculturally acceptable salt thereof.
10. The composition according to claim 9, comprising additionally a further active substance.
1 1 . A use of a compound of the formula I, as defined in any of the claims 1 to 8, and/or of an agriculturally acceptable salt thereof or of the compositions, as defined in any of the claims 9 or 10, for combating phytopathogenic fungi.
12. A method for combating phytopathogenic fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I, as defined in any of the claims 1 to 8, or with a composition, as defined in any of the claims 8 or 9.
13. Seed, coated with at least one compound of the formula I, as defined in any of the claims 1 to 8, and/or an agriculturally acceptable salt thereof or with a composition, as defined in any of the claims 9 or 10, in an amount of from 0.1 to 10 kg per 100 kg of seed.
14. A process for the preparation of compounds I according to any of claims 1 to 8, comprising the following step
(a) reactin an alcohol compound of formula II
Figure imgf000097_0001
with R2-LG, wherein LG represents a nucleophilically replaceable leaving group, and wherein X, Y, R2, R3, R4, n and m are as defined in any one of claims 1 to 8.
15. The intermediate compounds II according to claim 14.
PCT/EP2014/061226 2013-06-12 2014-05-30 Substituted [1,2,4]triazole and imidazole compounds WO2014198557A1 (en)

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Cited By (4)

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

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2628420A1 (en) * 1976-06-24 1978-01-05 Bayer Ag (1)-Acyloxy-(1)-phenyl-(2)-triazolyl or imidazolyl-ethane derivs. - fungicides, nematocides and bacteriostats used as plant protection agents
EP0029542A2 (en) * 1979-11-21 1981-06-03 Bayer Ag Hydroxybutyl-imidazole derivatives, process for their preparation, intermediates necessary for the latter and their use as fungicides
EP0044605A1 (en) * 1980-06-02 1982-01-27 Imperial Chemical Industries Plc Fungicidal bis-azolyl compounds
US4400388A (en) * 1975-10-27 1983-08-23 Bayer Aktiengesellschaft Fungicidal 1-phenyl-2-(1,2,4-triazol-1-yl)-ethyl ethers
EP0126430A2 (en) * 1983-05-19 1984-11-28 Ciba-Geigy Ag Process for the preparation of 1-triazolylethylether-derivatives, and microbicidal compositions containing novel 1-triazolyl-phenoxyphenylethylether-derivatives as active ingredients and their use
WO2005006860A2 (en) * 2003-07-18 2005-01-27 The Board Of Governors For Higher Education State Of Rhode Island And Providence Plantations Azole derivatives and methods for making the same
CN1923819A (en) * 2006-10-12 2007-03-07 青岛科技大学 compound containing aromatic ether and ditriazole and use thereof
CN101824002A (en) * 2010-05-13 2010-09-08 南京华威医药科技开发有限公司 Water soluble triazole compound and synthesis method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400388A (en) * 1975-10-27 1983-08-23 Bayer Aktiengesellschaft Fungicidal 1-phenyl-2-(1,2,4-triazol-1-yl)-ethyl ethers
DE2628420A1 (en) * 1976-06-24 1978-01-05 Bayer Ag (1)-Acyloxy-(1)-phenyl-(2)-triazolyl or imidazolyl-ethane derivs. - fungicides, nematocides and bacteriostats used as plant protection agents
EP0029542A2 (en) * 1979-11-21 1981-06-03 Bayer Ag Hydroxybutyl-imidazole derivatives, process for their preparation, intermediates necessary for the latter and their use as fungicides
EP0044605A1 (en) * 1980-06-02 1982-01-27 Imperial Chemical Industries Plc Fungicidal bis-azolyl compounds
EP0126430A2 (en) * 1983-05-19 1984-11-28 Ciba-Geigy Ag Process for the preparation of 1-triazolylethylether-derivatives, and microbicidal compositions containing novel 1-triazolyl-phenoxyphenylethylether-derivatives as active ingredients and their use
WO2005006860A2 (en) * 2003-07-18 2005-01-27 The Board Of Governors For Higher Education State Of Rhode Island And Providence Plantations Azole derivatives and methods for making the same
CN1923819A (en) * 2006-10-12 2007-03-07 青岛科技大学 compound containing aromatic ether and ditriazole and use thereof
CN101824002A (en) * 2010-05-13 2010-09-08 南京华威医药科技开发有限公司 Water soluble triazole compound and synthesis method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200753, Derwent World Patents Index; AN 2007-535004, XP002727280 *
DATABASE WPI Week 201107, Derwent World Patents Index; AN 2010-M39954, XP002727281 *
TAJANA A ET AL: "Synthesis and antimycotic activity of alpha-aryl-beta,N-imidazolylalkyl benzyl ethers", ARZNEIMITTEL FORSCHUNG. DRUG RESEARCH, ECV EDITIO CANTOR VERLAG, AULENDORF, DE, vol. 31, no. 12, 1981, pages 2121 - 2123, XP001526279, ISSN: 0004-4172 *
YU GUAN-PING ET AL: "Synthesis and fungicidal evaluation of 2-arylphenyl ether-3-(1H-1,2,4-triazol-1-yl)propan-2-ol derivatives", JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 57, no. 11, 10 June 2009 (2009-06-10), pages 4854 - 4860, XP002659633, ISSN: 0021-8561, DOI: 10.1021/JF900222S *

Cited By (4)

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

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