WO2014095555A1 - New substituted triazoles and imidazoles and their use as fungicides - Google Patents

New substituted triazoles and imidazoles and their use as fungicides Download PDF

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Publication number
WO2014095555A1
WO2014095555A1 PCT/EP2013/076354 EP2013076354W WO2014095555A1 WO 2014095555 A1 WO2014095555 A1 WO 2014095555A1 EP 2013076354 W EP2013076354 W EP 2013076354W WO 2014095555 A1 WO2014095555 A1 WO 2014095555A1
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compounds
iii
alkyl
special embodiment
cycloalkyl
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PCT/EP2013/076354
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French (fr)
Inventor
Wassilios Grammenos
Ian Robert CRAIG
Nadege Boudet
Bernd Müller
Jochen Dietz
Erica May Wilson LAUTERWASSER
Jan Klaas Lohmann
Thomas Grote
Egon Haden
Ana Escribano Cuesta
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to new substituted triazoles and imidazoles of the formula I
  • the present invention relates to a process for preparing compounds of the formula
  • the present invention relates to agrochemical compositions, comprising an auxilia- ry and at least one compound of formula I an N-oxide or an agriculturally acceptable salt thereof.
  • the present invention relates to the use of a compound of the formula I and/or of an agriculturally acceptable salt thereof or of the compositions for combating phytopathogenic fungi.
  • the present invention relates to a method for combating harmful fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I or with a composition.
  • the present invention relates to seed, coated with at least one compound of the formula I and/or an agriculturally acceptable salt thereof or with a composition in an amount of from 0.1 to 10 kg per 100 kg of seed.
  • the compounds according to the present invention differ from those described in the above- mentioned publications inter alia by the substitution of the phenyl ring and the oxetane group. 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 harmful fungi.
  • R is O or CH 2 ;
  • Q is O or CH 2 ;
  • R or Q is O
  • A is CH or N ;
  • R D is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl , C2-C6-haloalkenyl, C2-C6- alkynyl, C 2 -C6-haloalkynyl or CN ;
  • R 3 is unsubstituted or further substituted by one, two, three or four R 3a ;
  • R 3a is independently selected from halogen, CN, NO2, OH, Ci-C 4 -alkyl, Ci-C4-haloalkyl, C 3 -C8-cycloalkyl, C 3 -C8-halocycloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -halogenalkoxy; n is 0, 1 , 2, 3 or 4;
  • Y is a direct bond or a divalent group selected from the group consisting of -0-, -S-, SO-,
  • R 8 , R 9 ,R 10 , R 11 , R 12 , R 13 , R 14 , R 15 are independently selected from hydrogen, halogen, CN, nitro, OH , Ci-C4-alkyl, Ci-C 4 -halogenalkyl, Ci-C 4 -alkoxy and Ci-C 4 -halogenalkoxy;
  • n 0, 1 , 2, 3, 4 or 5;
  • R 4a is independently selected from halogen, CN, NO2, OH, Ci-C4-alkyl, C1-C4- haloalkyl, C 3 -Cs-cycloalkyl, C 3 -C8-halocycloalkyl, Ci-C4-alkoxy and C1-C4- haloalkoxy;
  • p 0, 1 or 2;
  • x 0, 1 , 2, 3 or 4;
  • R 5 is H, halogen, CN, N0 2 , OH, SH, Ci-C 6 -alkyl, Ci-C 6 -alkoxy, Ci-C 6 -alkylthio, Ci-C 6 -alkylsul- finyl, Ci-C6-alkylsulfonyl, C2-C6-alkenyl, C2-C6-alkynyl, C 3 -Cs-cycloalkyl, C 3 -Ce- cycloalkyloxy, C 3 -C 8 -cycloalkyl-Ci-C 4 -alkyl, 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 ,
  • R 5a is independently selected from halogen, CN, N0 2 , OH, SH, NH 2 , Ci-C 6 -alkyl, Ci-C 6 - haloalkyl, C 3 -C8-cycloalkyl, C 3 -C8-halocycloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, d-Ce-alkylthio, Ci-C 6 -haloalkylthio and Ci-C 4 -alkoxy-Ci-C 4 -alkyl;
  • R 6 is H or is selected from the substituents defined for R 5 , wherein the aliphatic, alicyclic and aromatic moieties of R 6 are unsubstituted or substituted by one, two, three or four or up to the maximum possible number of R 6a , wherein R 6a is defined as R 5a ;
  • R 5 and R 6 together with the carbon atom to which they are bound form a saturated or partially unsaturated three-, four-, five-, six- or seven-membered carbocycle or a saturated or partially unsaturated three-, four-, five-, six- or seven-membered heterocycle, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the carbo- or heterocycle is unsubstituted or carries one, two, three or four substituents independently se- lected from halogen, CN, N0 2 , OH, SH, NH 2 , Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy,
  • R 55 , R 56 are independently selected from hydrogen, halogen, CN, NO2, OH, SH, NH2,
  • R 7 is independently selected from Ci-C6-alkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl, Ca-Ce-cycloalkyl, wherein each of R 7 is unsubstituted or further substituted by one, two, three or four R 7a ; wherein
  • R 7a is independently selected from halogen, OH and Ci-C6-alkoxy
  • R 7 R 71 and R 72 together with the carbon atom(s) to which they are bound form a saturated three-, four-, five-, six- or seven-membered carbocycle or heterocycle, wherein the heterocycle contains one, two, three or four O atoms.
  • o 0, 1 , 2, 3 or 4;
  • the present invention provides a process for preparing compounds of the formula I.
  • an agrochemical composition comprising an auxil- iary and at least one compound of formula I an N-oxide or an agriculturally acceptable salt thereof.
  • the present invention provides a method for combating harmful fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I or with a composition.
  • the present invention provides seed, coated with at least one compound of the formula I and/or an agriculturally acceptable salt thereof or with a composition in an amount of from 0.1 to 10 kg per 100 kg of seed.
  • halogen fluorine, bromine, chlorine or iodine, especially fluorine, chlorine or bromine;
  • alkyl and the alkyl moieties of composite groups such as, for example, alkoxy, alkylamino, alkoxycarbonyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 10 carbon atoms, for example Ci-Cio-akyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1- methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethyl butyl, 1 ,2-dimethylbutyl, 1
  • Ci-C4-alkyl refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl (n-propyl), 1 -methylethyl (iso-propoyl), butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (iso-butyl), 1 ,1-dimethylethyl (tert. -butyl).
  • haloalkyl straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above.
  • the alkyl groups are substituted at least once or completely by a particular halogen atom, preferably fluorine, chlorine or bromine.
  • the alkyl groups are partially or fully halogenated by different halogen atoms; in the case of mixed halogen substitutions, the combination of chlorine and fluorine is preferred.
  • (Ci-C3)-haloalkyl more preferably (Ci-C2)-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1 -bromoethyl, 1 - fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1 ,1 ,1 -trifluoroprop-
  • alkenyl and also the alkenyl moieties in composite groups such as alkenyloxy: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and one double bond in any position.
  • alkenyloxy unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and one double bond in any position.
  • small alkenyl groups such as (C2-C4)-alkenyl
  • larger alkenyl groups such as (C 5 -Ce)-alkenyl.
  • alkenyl groups are, for example, C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1 -methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1- methyl-1 -propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2- pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1-butenyl, 1 - methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 2-methyl-3-butenyl, 2-methyl-3-butenyl,
  • cycloalkyl and also the cycloalkyl moieties in composite groups mono- or bicyclic saturated hydrocarbon groups having 3 to 10, in particular 3 to 6, carbon ring members, for example C3-C6- cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1 .1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
  • optionally substituted C3-Ce-cycloalkyl means a cycloalkyl radical having from 3 to 8 carbon atoms, in which at least one hydrogen atom, for example 1 , 2, 3, 4 or 5 hydrogen atoms, is/are replaced by substituents which are inert under the conditions of the reaction.
  • substituents which are inert under the conditions of the reaction.
  • inert substituents are CN, Ci-C6-alkyl, Ci-C4-haloalkyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, and Ci-C4-alkoxy-Ci-C6-alkyl;
  • halocycloalkyl and the halocycloalkyl moieties in halocycloalkoxy, halocycloalkylcarbonyl and the like monocyclic saturated hydrocarbon groups having 3 to 10 carbon ring members (as mentioned above) in which some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
  • alkoxy an alkyl group as defined above which is attached via an oxygen, preferably having 1 to 10, more preferably 2 to 6, carbon atoms.
  • Examples are: methoxy, ethoxy, n-propoxy, 1 -methyl- ethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy, and also for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethyl- propoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2, 3-d i methyl butoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-
  • Ci-C4-alkoxy groups, such as methoxy, ethoxy, n-propoxy, 1 -methylethoxy, butoxy, 1- methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
  • Ci-C4-alkoxy refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms which is bonded via an oxygen, at any position in the alkyl group, examples are methoxy, ethoxy, n-propoxy, 1 - methylethoxy, butoxy, 1 -methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
  • halogenalkoxy alkoxy as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular by fluorine, chlorine or bromine.
  • Examples are OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHCI2, OCCI 3 , chloro- fluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2- bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2- chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2- fluoropropoxy, 3-fluoropropoxy, 2,2-di
  • the compounds according to the invention may have one or more centers of chirality, and are generally obtained in the form of racemates or as diastere- omer compositions of erythro and threo forms.
  • the erythro and threo diastereomers of the compounds according to the invention can be separated and isolated in pure form, for example, on the basis of their different solubilities or by column chromatography. Using known methods, such uniform pairs of diastereomers can be used to obtain uniform enantiomers.
  • Suitable for use as antimicrobial agents are both the uniform diastereomers or enantiomers and compositions thereof obtained in the synthesis. This applies correspondingly to the fungicidal compositions.
  • the invention provides both the pure enantiomers or diastereomers and compositions thereof.
  • the scope of the present invention includes in particular the (R) and (S) isomers and the racemates of the compounds according to the invention, in particular of the formula I, which have centers of chirality.
  • Suitable compounds of the formula I according to the invention also comprise all possible stereoisomers (cis/trans isomers) and compositions thereof.
  • the compounds according to the invention may be present in various crystal modifications which may differ in their biological activity. They are likewise provided by the present invention.
  • the compounds according to the invention are capable of forming salts or adducts with inorganic or organic acids or with metal ions.
  • Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds of the formula I.
  • suitable cations are in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium and sulfoxonium ions
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hex- afluorosilicate, hexafluorophosphate, benzoate, and also the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
  • the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer compositions. Both, the pure enantiomers or diastereomers and their compositions are subject matter of the present invention.
  • the compounds of the formula I according to the invention can be prepared by different routes analogously to processes known per se of the prior art (see, for example, the prior art cited at the outset).
  • Compounds of formula III can be prepared from ketone compounds II using sulfonium or sulfox- onium chemistry ( Fukuoka Daigaku Rigaku, Shuho (1990), 20(2), 83-7 ; Synthesis, (9), 1613-1624; 1999; Chemical & Pharmaceutical Bulletin, 51 (9), 1 113-1 1 16; 2003; Organic Letters, 9(13), 2541 -2544; 2007; Tetrahedron, 64(52), 11839-11845; 2008; Angewandte Chemie, International Edition, 48(9), 1677-1680; 2009; Angewandte Chemie, International Edition, 51 (30), 7532-7536, S7532/1 -S7532/48; 2012).
  • Compounds III can be optionally substituted using a strong base such as BuLi, LDA, LHMDS, KHMDS, BuLi, LTMP, Zn-TMP and an electro- phile E + (S8, l 2 , ICI, C 2 F 4 Br 2 ) (WO 2012025506 A1 , Synthesis, (1 ), 100-106; 1999).
  • a strong base such as BuLi, LDA, LHMDS, KHMDS, BuLi, LTMP, Zn-TMP and an electro- phile E + (S8, l 2 , ICI, C 2 F 4 Br 2 ) (WO 2012025506 A1 , Synthesis, (1 ), 100-106; 1999).
  • compounds I can be prepared by adding a C2 nucleophile G (Synthetic Communications, 19(1 1-12), 2167-73; 1989) to ketone compound II, or by the addition of allyl magnesium bromide, to obtain compound of formula IV.
  • G C2 nucleophile
  • ketone compound II or by the addition of allyl magnesium bromide, to obtain compound of formula IV.
  • a transformation of G into OH e.g. via reduction with LiAIH4, LiBH4, DiBAH leads to a compound of formula V, or e.g. in the case of the allyl alcohol via first a well known ozonolysis.
  • Compounds III can be optionally substituted using a strong base such as BuLi, LDA, LHMDS, KHMDS, BuLi, LTMP, Zn-TMP and an elec- trophile E + (S8, ⁇ 2 , ICI, C 2 F 4 Br 2 ) (WO 2012025506 A1 , Synthesis, (1 ), 100-106; 1999).
  • a strong base such as BuLi, LDA, LHMDS, KHMDS, BuLi, LTMP, Zn-TMP and an elec- trophile E + (S8, ⁇ 2 , ICI, C 2 F 4 Br 2 )
  • One aspect of the invention is also the synthesis process as follows:
  • A, Z, Y, R 3 , R 5 , R 6 , n are as defined herein and G is preferably C02Me,C02Et, CN, CHO;
  • A, Z, Y, R 3 , R 5 , R S ,R 7 , o, n are as defined herein;
  • the invention relates to a process for preparing compounds of formula I as defined herein, which comprises reacting a compound of formula which comprises following steps:
  • an aspect of the invention is the intermediate Compounds of formulae V, VI, VII, VIII, IX, wherein Z, Y, A, R 3 , R 5 , R 6 , R 7 , o, n, x if applicable, are as defined and preferably defined herein for compounds I.
  • inventive compounds cannot be directly obtained by the routes described above, they can be prepared by derivatization of other inventive compounds.
  • the N-oxides may be prepared from the inventive compounds according to conventional 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 composition of different N-oxides, which can be separated by conven- tional methods such as chromatography.
  • compositions of isomers If the synthesis yields compositions of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be intercon verted 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.
  • variables Z, Y, R 3 , R 5 , R 6 ,R 7 , o, n are as defined in tables 1a-l to 1a-18, 1 a-ll to 18a-ll, 1a-lll to 9a-lll, 1a-IV to 9a-IV for compounds I, wherein the substituents are specific embodiments independently of each other or in any combination.
  • a further embodiment of the present invention is compounds of formula VI (see above), wherein variables Z, Y, R 3 , R 5 , R 6 ,R 7 , o, n are as defined and preferably defined for formula I herein, and wherein G is an ester group or CH2OR.
  • the variables Z, Y, R 3 , R 5 , R 6 ,R 7 , o, n are as defined in tables 1 a-l to 1a- 18, 1 a-l I to 18a-l I, 1 a-l 11 to 9a-l 11 , 1 a-l V to 9a-IV for compounds I, wherein the substituents are specific embodiments independently of each other or in any combination.
  • a further embodiment of the present invention is compounds of formula VII (see above), wherein the variables variables Z, Y, R 3 , R 5 , R 6 ,R 7 , o, n are as defined and preferably defined for formula I herein and LG is a nucleophilically replaceable leaving group.
  • the variables Z, Y, R 3 , R 5 , R 5 ,R 7 , o, n are as defined in tables 1a-l to 1 a-18, 1a-ll to 18a-ll, 1 a-lll to 9a-lll, 1 a-IV to 9a-IV for compounds I, wherein the substituents are specific embodiments independently of each other or in any combination.
  • a further embodiment of the present invention is compounds of formula IX (see above), wherein the variables Z, Y, R 3 , R 5 , R 6 ,R 7 , o, n are as defined and preferably defined for formula I herein and X stands for halogen, in particular CI or Br. According to one preferred embodiment, Hal in compounds VI stands for Br.
  • variables Z, Y, R 3 , R 5 , R 6 ,R 7 , o, n are as defined in tables 1 a-l to 1 a-18, 1a-ll to 18a-ll, 1 a-lll to 9a-lll, 1a-IV to 9a-IV a for compounds I, wherein the substituents are specific embodiments independently of each other or in any combination.
  • a further embodiment of the present invention is compounds of formula X, wherein the variables Z, Y, R 3 , R 5 , R 6 ,R 7 , o, n are as defined and preferably defined for formula I herein.
  • the variables Z, Y, R 3 , R 5 , R 6 ,R 7 , o, n are as defined in tables in tables 1 a-l to 1a-18, 1a-ll to 18a-ll, 1a-lll to 9a-lll, 1 a-IV to 9a-IV for compounds I , wherein the substituents are specific embodiments independently of each other or in any combination.
  • a in the compounds according to the invention is, according to one embodiment, CH.
  • a in the compounds according to the invention is, according to one further embodiment, N.
  • R is O and Q is CH2.
  • R is CH2 and Q is O.
  • D in the compounds according to the invention is as defined in claim 1 .
  • D is selected from H, halogen, SH or S-C1- Ce-alkyl.
  • D is H. According to one further embodiment D is SH . According to one further embodiment D is S-CN.
  • D is halogen. In a special embodiment D is I. In a further special embodiment D is Br. In a further special embodiment D is CI.
  • D is S-Ci-C6-alkyl preferably S-methyl, S-ethyl, S-n-propyl, S-i-propyl, S-n-butyl, S-i-butyl or S-t-butyl.
  • D is S-methyl.
  • D is S-ethyl.
  • D is S-n-propyl.
  • D is S-t-butyl.
  • D is S-Ci-C6-haloalkyl wherein Ci-C6-haloalkyl is preferably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • D is S-CF3.
  • D is S-CHF2.
  • D is S-CFH2.
  • D is S-CCI3.
  • D is S-CHC .
  • D is S-CCIH2.
  • D is S-C 2 -C6-alkynyl, wherein C 2 -C6-alkynyl is preferably CCH, CH 2 CCH, CH2CCCH3.
  • D is S-CCH.
  • D is S-CCCH3.
  • D is S-CCCH(CH3)2.
  • D is S-CCC(CH3) 3 .
  • D is C2-C6- haloalkynyl, more preferably fully or partially halogenated C2-C4-alkynyl.
  • D is fully or partially halogenated C2-alkynyl.
  • R 3 in the compounds according to the invention is, according to one embodiment, as defined in claim 1.
  • n is 0. According to one further embodiment n is 1. According to one further embodiment n is 2. According to one further embodiment n is 3. According to one further embodiment n is 4.
  • R 3 in the compounds according to the invention is, according to a further embodiment, halogen, CN, NO2, d-Ce-alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, S(0) p (Ci-C 4 -alkyl), wherein R 3 is unsubsti- tuted or further substituted by one, two, three or four R 3a ; wherein R 3a is independently selected from halogen, CN, NO 2 , OH, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cs-cycloalkyl, C 3 -C8-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy; p is an integrer and is 0, 1 , 2.
  • R 3 is halogen. According to a specific embodiment R 3 is CI. According to a further specific embodiment R 3 is F. According to a further specific embodiment R 3 is Br. According to one further embodiment R 3 is CN. According to one further embodiment R 3 is NO 2 . According to one further embodiment R 3 is OH. According to one further embodiment R 3 is SH.
  • R 3 is Ci-C6-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • R 3 is methyl.
  • R 3 is ethyl.
  • R 3 is n-propyl.
  • R 3 is i- propyl.
  • R 3 is 1 -methylpropyl.
  • R 3 is n-butyl.
  • R 3 is i-butyl.
  • R 3 is t- butyl.
  • R 3 is Ci-C6-alkyl substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 3 is Ci-Cs-haloalkyl, more preferably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • R 3 is CF3.
  • R 3 is CHF2.
  • R 3 is CFH2.
  • R 3 is CCI3.
  • R 3 is CHCI2.
  • R 3 is CCIH2.
  • R 3 is Ci-C6-alkyl, preferably Ci-C 4 -alkyl substituted by OH, more preferably CH 2 OH, CH 2 CH 2 OH, CH 2 CH 2 CH 2 OH, CH(CH 3 )CH 2 OH, CH 2 CH(CH 3 )OH, CH 2 CH 2 CH 2 CH 2 OH.
  • R 3 is CH 2 OH.
  • R 3 is Ci-C6-alkyl, preferably d-Gralkyl substituted by CN, more preferably CH 2 CN, CH 2 CH 2 CN, CH 2 CH 2 CH 2 CN, CH(CH 3 )CH 2 CN, CH 2 CH(CH 3 )CN, CH 2 CH 2 CH 2 CH 2 CN.
  • R 3 is CH 2 CH 2 CN.
  • R 3 is CH(CH3)CN.
  • R 3 is Ci-C4-alkoxy-Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl.
  • R 3 is CH2OCH3.
  • R 3 is CH2CH2OCH3. In a further special embodiment R 3 is CH(CH3)OCH3. In a further special embodiment R 3 is CH(CH 3 )OCH 2 CH3. In a further special embodiment R 3 is CH 2 CH 2 OCH 2 CH3. According to a further specific embodiment R 3 is Ci-C4-haloalkoxy-C-i-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl. In a special embodiment R 3 is CH 2 OCF3. In a further special embodiment R 3 is CH2CH2OCF3. In a further special embodiment R 3 is CH2OCCI3. In a further special embodiment R 3 is CH2CH2OCCI3.
  • R 3 is Ci-C6-alkoxy, preferably Ci-C4-alkoxy.
  • R 3 is OCH3.
  • R 3 is OCH2CH3.
  • R 3 is OCH(CH3)2.
  • R 3 is OCH2CH2CH3.
  • R 3 is OC(CH 3 ) 3 .
  • R 3 is CH2CI- CH2.
  • R 3 is
  • C(CH 3 ) C(CH 3 )H.
  • R 3 is C 2 -C6-alkenyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 3 is C2-C6-alkynyl, preferably CCH, CH2CCH, CH2CCCH3.
  • R 3 is CCH.
  • R 3 is CCCH3.
  • R 3 is CH2CCH.
  • R 3 is CH2CCCH3.
  • R 3 is CH2CCH2CH3.
  • R 3 is C 2 -C6-alkynyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 3 is CC-CH3.
  • R 3 is C2-C6-haloalkynyl, more preferably fully or partially hal- ogenated C 2 -C6-alkynyl.
  • R 3 is CC-CI.
  • R 3 is CC- Br.
  • R 3 is CC-l.ln a special embodiment R 3 is fully or partially halogenated C2-alkynyl.
  • R 3 is fully or partially halogenated C3-alkynyl.
  • R 3 is C 2 -C6-alkynyl, preferably C 2 -C4-alkynyl, substituted by OH, more preferably, CCOHIn a special embodiment R 3 is In a further special embodiment R 3 .
  • R 3 is Ci-C 4 -alkoxy-C 2 -C6-alkynyl, more preferably Ci- C4-alkoxy-C2-C4-alkynyl.
  • R 3 is CCOCH3.
  • R 3 is CH2CCOCH3.
  • R 3 is Ci-C4-haloalkoxy-C2-C6- alkynyl, more preferably Ci-C 4 -haloalkoxy-C 2 -C 4 -alkynyl.
  • R 3 is CCOCF3.
  • R 3 is CH2CCOCF3.
  • R 3 is
  • R 3 is CH2CCOCCI3.
  • R 3 is C3-C8-cycloalkyl-C 2 -C6-alkynyl, preferably C3-C6-cycloalkyl-C 2 -C 4 -alkynyl.
  • R 3 is C3-C6-halocycloalkyl-C2-C4-alkynyl, preferably C3- C8-halocycloalkyl-C 2 -C6-alkynyl.
  • R 3 is Cs-Cs-cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl.
  • R 3 is cyclopropyl.
  • R 3 is cyclobutyl.
  • R 3 is cyclopentyl.
  • R 3 is cyclohexyl.
  • R 3 is C3-C8-cycloalkoxy, preferably C3-C6-cycloalkoxy.
  • R 3 is Cs-Ce-cycloalkyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 3 is C3-Cs-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl.
  • R 3 is fully or partially halogenated cyclo- propyl.
  • R 3 is 1 -CI-cyclopropyl.
  • R 3 is 2-CI-cyclopropyl.
  • R 3 is 1-F-cyclopropyl.
  • R 3 is 2-F-cyclopropyl.
  • R 3 is fully or partially halogenated cyclobutyl.
  • R 3 is 1-CI-cyclobutyl.
  • R 3 is 1 -F-cyclobutyl.
  • R 3 is Cs-Cs-cycloalkyl substituted by Ci- C4-alkyl, more preferably is C3-C6-cycloalkyl substituted by Ci-C4-alkyl.
  • R 3 is 1 -CH 3 -cyclopropyl.
  • R 3 is C3-Cs-cycloalkyl substituted by CN, more preferably is C3-C6-cycloalkyl substituted by CN.
  • R 3 is 1 -CN- cyclopropyl .
  • R 3 is C 3 -C8-cycloalkyl-C 3 -C8-cycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-cycloalkyl.
  • I n a special embodiment R 3 is cyclopropyl- cyclopropyl.
  • R 3 is Cs-Cs-cycloalkyl-Cs-Cs- halocycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-halocycloalkyl.
  • R 3 is C3-C8-cycloalkyl-Ci-C4-alkyl, preferably C3-C6- cycloalkyl-Ci-C4-alkyl.
  • R 3 is CH(CH 3 )(cyclopropyl).
  • R 3 is CH2-(cyclopropyl).
  • R 3 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 3 is C3-C8-cycloalkyl-Ci-C4-haloalkyl, C3-C6-cycloalkyl-Ci- C4-haloalkyl. According to a specific embodiment R 3 is C3-Ce-halocycloalkyl-Ci-C4-alkyl, C3-C6- halocycloalkyl-Ci-C4-alkyl. I n a special embodiment R 3 is fully or partially halogenated cyclopro- pyl-Ci-C4-alkyl. In a further special embodiment R 3 is 1-CI-cyclopropyl-Ci-C4-alkyl. In a further special embodiment R 3 is 1 -F-cyclopropyl-Ci-C4-alkyl.
  • R 3 is N H2.
  • R 3 is NH(Ci-C4-alkyl). According to a specific embodiment R 3 is NH(CH3). According to a specific embodiment R 3 is NH(CH2CH3). According to a specific embodiment R 3 is NH(CH 2 CH2CH 3 ). According to a specific embodiment R 3 is NH(CH(CH 3 )2). According to a specific embodiment R 3 is NH(CH2CH2CH2CH3). According to a specific embodiment R 3 is NH(C(CH 3 ) 3 ).
  • R 3 is N(Ci-C4-alkyl)2. According to a specific embodiment R 3 is N(CH3)2. According to a specific embodiment R 3 is N(CH2CH3)2. According to a specific embodiment R 3 is N(CH2CH2CH3)2. According to a specific embodiment R 3 is N(CH(CH3)2)2. According to a specific embodiment R 3 is N(CH2CH2CH2CH3)2. According to a specific embodiment R 3 is NH(C(CH 3 ) 3 ) 2 .
  • R 3 is NH(C3-C8-cycloalkyl) preferably NH(C3-C6-cycloalkyl). According to a specific embodiment R 3 is NH (cyclopropyl). According to a specific embodiment R 3 is NH(cyclobutyl). According to a specific embodiment R 3 is NH(cyclopentyl). According to a specific embodiment R 3 is NH(cyclohexyl).
  • R 3 is N(C3-Ce-cycloalkyl) 2 preferably N(C3-C6-cycloalkyl) 2 .
  • R 3 is N(cyclopropyl)2.
  • R 3 is N(cyclobutyl)2.
  • R 3 is N(cyclopentyl)2.
  • R 3 is N(cyclohexyl)2.
  • R 3 is S(0) p (Ci-C4-alkyl) wherein p is 0, 1 , 2, preferably S(0) (Ci-C4-alkyl) wherein p is 2.
  • R 3 is SO 2 CH3.
  • R 3 is SO2CF3.
  • said R 2 is in the 2-positon of the phenyl ring.
  • said R 3 is in the 3-positon of the phenyl ring.
  • said R 3 is in the 4-positon of the phenyl ring.
  • said R 3 is in the 2, 3-positon of the phenyl ring.
  • said R 3 is in the 2,4-positon of the phenyl ring.
  • said R 3 is in the 2,5-positon of the phenyl ring.
  • said R 3 is in the 2,6-positon of the phenyl ring.
  • said R 3 is in the 3,4-positon of the phenyl ring. According to one specific embodiment thereof, said R 3 is in the 3,5-positon of the phenyl ring. According to one specific embodiment thereof, said R 3 is in the 3,6-positon of the phenyl ring. According to one specific embodiment thereof, said R 3 is in the 2,4,6-positon of the phenyl ring.
  • P6b-4 3-F P6b-12 3-SOCH 3 P6b-20 2,6-CI 2
  • P6b-6 3-CN P6b-14 3-S0 2 CH 3 P6b-22 2,5-F 2
  • P6b-8 3-N0 2 P6b-16 3-C0 2 CH 3 P6b-24 2,6-F 2
  • One specific embodiment relates to the inventive compounds wherein x is 1 and n is 0.
  • Y in the compounds according to the invention is, according to one embodiment, as defined in claim 1.
  • Y in the compounds according to the invention is, according to a further embodiment, a direct bond or a divalent group selected from the group consisting of -0-, -S-, SO-, -SO2-.
  • Y is a direct bond. According to a further specific embodiment Y is -0-. According to a further specific embodiment Y is -S-. According to a further specific embodiment Y is -SO-. According to a further specific embodiment Y is -SO2-. According to a further specific embodiment Y is -NH-. According to a further specific embodiment Y is -N(Ci- C4-alkyl)-, wherein Ci-C4-alkyl is preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t- butyl.
  • Y is -C ⁇ C-.
  • Z in the compounds according to the invention is, according to one embodiment, as defined in claim 1.
  • Z in the compounds according to the invention is, according to a further embodiment, is phenyl or a five- or six-membered heteroaryl selected from the group consisting of pyrimidin- 2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazin-2-yl, pyridazin-3-yl, 1 ,3,5- triazin-2-yl and 1 ,2,4-triazin-3-yl; and wherein the phenyl is unsubstituted carries one, two, three or four independently selected radicals R 4 , and wherein the heteroaryl is unsubstitutedcarries one, two or three
  • Z is phenyl which carries one, two, three or four independently selected radicals R 4 as defined or preferably defined below.
  • Z is pyrimidin-2-yl which carries one, two, three or four independently selected radicals R 4 as defined or preferably defined below.
  • Z is pyri- din-3-yl, which carries one, two, three or four independently selected radicals R 4 as defined or preferably defined below.
  • Z is pyridin-4-yl, which carries one, two, three or four independently selected radicals R 4 as defined or preferably defined below.
  • Z is thiazol-2-yl, which carries one, two, three or four independently selected radicals R 4 as defined or preferably defined below.
  • x is 0. According to one further embodiment x is 1. According to one further embodiment x is 2. According to one further embodiment x is 3. According to one further embodiment x is 4.
  • R is O and Q is CH2 x is not 0.
  • R 4 in the compounds according to the invention is, according to one embodiment, as defined in claim 1.
  • R 4 in the compounds according to the invention is, according to a further embodiment, halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, wherein R 4 is substituted by one, two, three or four R 4a ; wherein R 4a is independently selected from halogen, CN, NO2, OH, C1-C4- alkyl, Ci-C4-haloalkyl, Ca-Ce-cycloalkyl, Ca-Ce-halocycloalkyl, Ci-C4-alkoxy and C 1 -C4- haloalkoxy; wherein m is 1 , 2 or 3.
  • m is 0. According to one embodiment m is 1 . According to one further embodiment m is 2. According to one further embodiment m is 3. According to one further embodiment m is 4.
  • said R 4 is in the 2-positon of the phenyl ring.
  • said R 4 is in the 3-positon of the phenyl ring.
  • said R 4 is in the 4-positon of the phenyl ring. According to one specific embodiment thereof, said R 4 is in the 2, 3-positon of the phenyl ring. According to one specific embodiment thereof, said R 4 is in the 2,4-positon of the phenyl ring. According to one specific embodiment thereof, said R 4 is in the 2,5-positon of the phenyl ring. According to one specific embodiment thereof, said R 4 is in the 2,6-positon of the phenyl ring. According to one specific embodiment thereof, said R 4 is in the 3,4-positon of the phenyl ring.
  • said R 4 is in the 3,5-positon of the phenyl ring. According to one specific embodiment thereof, said R 4 is in the 3,6-positon of the phenyl ring. According to one specific embodiment thereof, said R 4 is in the 2,4,6-positon of the phenyl ring.
  • R 4 is halogen. According to a specific embodiment R 4 is CI. According to a further specific embodiment R 4 is F. According to a further specific embodiment R 4 is Br. According to a further specific embodiment R 4 is CN. According to a further specific embodiment R 4 is NO 2 . According to a further specific embodiment R 4 is OH. According to a further specific embodiment R 4 is SH.
  • R 4 is Ci-C6-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • R 4 is methyl.
  • R 4 is ethyl.
  • R 4 is n-propyl.
  • R 4 is i- propyl.
  • R 4 is 1 -methylpropyl.
  • R 4 is n-butyl.
  • R 4 is i-butyl.
  • R 4 is t- butyl.
  • R 4 is Ci-C6-alkyl substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 4 is Ci-C6-haloalkyl, more preferably fully or partially halo- genated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • R 4 is CF3.
  • R 4 is CHF2.
  • R 4 is CFH2.
  • R 4 is CCI3.
  • R 4 is CHCI2.
  • R 4 is CCIH2.
  • R 4 is Ci-C6-alkyl, preferably Ci-C 4 -alkyl substituted by OH, more preferably CH 2 OH, CH 2 CH 2 OH, CH 2 CH 2 CH 2 OH, CH(CH 3 )CH 2 OH, CH 2 CH(CH 3 )OH, CH 2 CH 2 CH 2 CH 2 OH.
  • 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 2 CH 2 CH 2 CN.
  • R 4 is CH 2 CH 2 CN.
  • R 4 is CH(CH3)CN.
  • R 4 is Ci-C4-alkoxy-Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl.
  • R 4 is CH 2 OCH3.
  • R 4 is CH 2 CH 2 OCH 3 . In a further special embodiment R 4 is CH(CH 3 )OCH 3 . In a further special embodiment R 4 is CH(CH 3 )OCH 2 CH 3 . In a further special embodiment R 4 is CH2CH2OCH2CH3. According to a further specific embodiment R 4 is Ci-C4-haloalkoxy-Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl. In a special embodiment R 4 is CH 2 OCF 3 . In a further special embodiment R 4 is CH 2 CH 2 OCF3. In a further special embodiment R 4 is CH 2 OCCI 3 . In a further special embodiment R 4 is CH 2 CH 2 OCCI 3 .
  • R 4 is Ci-C6-alkoxy, preferably Ci-C4-alkoxy.
  • R 4 is OCH 3 .
  • R 4 is OChbCH .ln a further special embodiment of the invention R 4 is OCH(CH 3 )2.
  • R 4 is OCH 2 CH 2 CH 3 .
  • R 4 is OC(CH 3 ) 3 .
  • R 4 is Ci-C6-haloalkoxy, preferably Ci-C4-haloalkoxy.
  • R 4 is OCF 3 .
  • R 4 is
  • R 4 is C 2 -C6-alkenyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 4 is Ci-C4-alkoxy-C 2 -C6-alkenyl, more preferably Ci-C4-alkoxy-C 2 -C4-alkenyl.
  • R 4 is Ci-C4-haloalkoxy-C 2 -C6-alkenyl, more preferably Ci-C4-haloalkoxy-C 2 -C4-alkenyl.
  • R 4 is C2-C6-alkynyl, preferably CCH, CH2CCH, CH2CCCH3.
  • R 4 is CCH.
  • R 4 is CCCH3.
  • R 4 is CH2CCH.
  • R 4 is CH2CCCH3.
  • R 4 is CH 2 CCH 2 CH 3 .
  • R 4 is C 2 -C6-alkynyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 4 is C2-C6-haloalkynyl, more preferably fully or partially hal- ogenated C2-C6-alkynyl. In a special embodiment R 4 is fully or partially halogenated C2-alkynyl. In a further special embodiment R 4 is fully or partially halogenated C3-alkynyl. According to a further specific embodiment R 4 is C2-C6-alkynyl, preferably C2-C4-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 CH 2 CCOH.
  • R 4 is Ci-C4-alkoxy-C 2 -C6-alkynyl, more preferably Ci-C4-alkoxy-C2-C4-alkynyl.
  • R 4 is CCOCH3.
  • R 4 is CH2CCOCH3.
  • R 4 is C1-C4- haloalkoxy-C2-C6-alkynyl, more preferably Ci-C4-haloalkoxy-C2-C4-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- C4-alkynyl.
  • R 4 is C3-C6-halocycloalkyl-C 2 -C4-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-Ce-cycloalkoxy, preferably C3-C6-cycloalkoxy.
  • R 4 is O-cyclopropyl.
  • R 4 is Cs-Ce-cycloalkyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 4 is C3-Cs-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl.
  • R 4 is fully or partially halogenated cyclo- propyl.
  • 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-(CI) 2 -cyclobutyl. In a further special embodiment R 4 is 3,3-(F)2-cyclobutyl.According to a specific embodiment R 4 is Cs-Ce-cycloalkyl substituted by Ci-C4-alkyl, more preferably is C3-C6-cycloalkyl substituted by Ci-C4-alkyl. In a spe- cial embodiment R 4 is 1 -CH3-cyclopropyl.
  • R 4 is C3-C8- 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-Ce-cycloalkyl-C3-C8-halocycloalkyl, preferably C3-C6- cycloalkyl-C3-C6-halocycloalkyl.
  • R 4 is C3-C8-cycloalkyl-Ci-C4-alkyl, preferably C3-C6- cycloalkyl-Ci-C4-alkyl.
  • R 4 is CH(CH3)(cyclopropyl).
  • R 4 is In a special embodiment 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-Cs-cycloalkyl-Ci-C4-haloalkyl, C3-C6-cycloalkyl-Ci- C4-haloalkyl.
  • R 4 is C3-C8-halocycloalkyl-Ci-C4-alkyl, C3-C6- halocycloalkyl-Ci-C4-alkyl.
  • R 4 is fully or partially halogenated cyclopro- pyl-Ci-C4-alkyl.
  • R 4 is 1-CI-cyclopropyl-Ci-C4-alkyl.
  • R 4 is 1 -F-cyclopropyl-Ci-C4-alkyl.
  • R 4 is NH 2 .
  • 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(CH 2 CH2CH 3 ). According to a specific embodiment R 4 is NH(CH(CH 3 )2). According to a specific embodiment R 4 is NH(CH2CH2CH2CH3). 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 CH3)2. According to a specific embodiment R 4 is N(CH(CH 3 )2)2. Accord- ing to a specific embodiment R 4 is N(CH2CH2CH 2 CI-l3)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 spe- cific embodiment R 4 is NH(cyclohexyl).
  • R 4 is N(C3-C8-cycloalkyl) 2 preferably N(C3-C6-cycloalkyl) 2 .
  • R 4 is N(cyclopropyl)2.
  • R 4 is N(cyclobutyl)2.
  • R 4 is N(cyclopentyl)2.
  • R 4 is N(cyclohexyl)2.
  • R 4 is S(0) p (Ci-C4-alkyl) wherein p is 0, 1 , 2, preferably S(0) (Ci-C4-alkyl) wherein p is 2.
  • R 4 is SO 2 CH3.
  • R 4 is SO2CF3.
  • R 4 m is in Table X below, where- in each line of lines X1 -1 to X1 -145 corresponds to one particular embodiment of the invention, wherein X1-1 to X1-145 are also in any combination a preferred embodiment of the present invention Table X
  • Z-R 4 m are in Table Y below, wherein each line of lines Y-1 to Y-145 corresponds to one particular embodiment of the invention, wherein Y-1 to Y-145 are also in any combination a preferred embodiment of the present invention
  • Z-R 4 m Particularly preferred embodiments of Z-R 4 m according to the invention are in Table Z below, wherein each line of lines Z-1 to Z-103 corresponds to one particular embodiment of the invention, wherein Z-1 to Z-103 are also in any combination a preferred embodiment of the present invention
  • R 5 and R 6 in the compounds according to the invention are independently of another, according to one embodiment, as defined in claim 1.
  • R 5 and R 6 in the compounds according to the invention are independently of another, according to a further embodiment, H.
  • R 5 and R 6 in the compounds according to the invention are independently of another halogen.
  • R 5 and R 5 are independently CI.
  • R 5 and R 6 are independently F.
  • R 5 and R 6 are independently Br.
  • R 5 and R 6 are independently CN.
  • R 5 and R 6 are independently NO2.
  • R 5 and R 6 are independently OH.
  • R 5 and R 6 are independently SH.
  • R 5 is H and R s is CI.
  • R 5 is H and R 6 is Br.
  • R 5 is H and R 6 is F.
  • R 5 and R 6 are both F.
  • R 5 and R 5 are both CI.
  • R 5 and R 5 are both Br.
  • R 5 and R 6 are independently selected from Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ca-Ce-cycloalkyl, wherein the R 1 are in each case un- substituted or are substituted by R a and/or R b as defined and preferably herein.
  • R 5 and R 6 are independently selected from Ci-C3-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-Cs-cycloalkyl, wherein the R 5 and R 6 are inde- pendently in each case unsubstituted or are substituted by R a and/or R b as defined and preferably herein.
  • R 5 and R 6 are independently Ci-C6-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • R 5 and R 6 are independently methyl.
  • R 5 and R 6 are independently ethyl.
  • R 5 and R 6 are independently n-propyl.
  • R 5 and R 6 are independently i-propyl.
  • R 5 and R 6 are independently 1- methylpropyl.
  • R 5 and R 6 are independently n-butyl.
  • R 5 and R 6 are independently i-butyl. In a further special embodiment R 5 and R 6 are independently t-butyl. In a further special embodiment R 5 is H and R 6 is CH3. In a further special embodiment R 5 is H and R 6 is CH2CH3. In a further special embodiment R 5 is H and R 6 is CH2CH2CH3. In a further special embodiment R 5 is H and R 6 is CH(CH3)2. In a further special embodiment R 5 is CH3 and R 6 is CH3. In a further special embodiment R 5 is CH2CH3 and R 6 is CH2CH3.
  • R 5 and R 6 are independently Ci-C6-alkyl substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 5 and R 6 are independently Ci-C6-haloalkyl, more preferably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • R 5 and R 6 are independently CF3.
  • R 5 and R 6 are independently CHF2.
  • R 5 and R 6 are independently CFH2.
  • R 5 and R 6 are independently CCI3.
  • R 5 and R 6 are independently CHCI2.
  • R 5 and R 6 are independently CCIH2.
  • R 5 and R 6 are independently Ci-C 6 -alkyl, pref- erably Ci-C 4 -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, CH 2 CH(CH 3 )OH, CH2CH2CH2CH2OH.
  • R 5 and R 6 are independently CH2OH.
  • R 5 and R 6 are independently CH2CH2OH.
  • R 5 and R 6 are independently Ci-C 6 -alkyl, preferably Ci-C 4 -alkyl substituted by CN, more preferably CH 2 CN, CH2CH2CN, CH 2 CH 2 CH 2 CN, CH(CH 3 )CH 2 CN, CH 2 CH(CH 3 )CN, CH2CH2CH2CH2CN.
  • R 5 and R 6 are independently CH2CH2CN.
  • R 5 and R 6 are independently CH(CH3)CN.
  • R 5 and R 6 are independently C1-C4- alkoxy-Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl.
  • R 5 and R 6 are independently CH2OCH3. In a further special embodiment R 5 and R 6 are independently CH2CH2OCH3. In a further special embodiment R 5 and R 6 are independently CH(CH 3 )OCH 3 . In a further special embodiment R 5 and R 6 are independently CH(CH3)OCH2CH3. In a further special embodiment R 5 and R 6 are independently CH2CH2OCH2CH3. According to a further specific embodiment R 5 and R 6 are independently Ci-C4-haloalkoxy-Ci-C6-alkyl, more preferably C1-C4- alkoxy-Ci-C4-alkyl. In a special embodiment R 5 and R 6 are independently CH2OCF3. In a further special embodiment R 5 and R 6 are independently CH2CH2OCF3. In a further special embodiment R 5 and R 6 are independently CH2OCCI3. In a further special embodiment R 5 and R 6 are independently CH2CH2OCCI3.
  • R 5 and R 6 are independently Ci-C6-alkoxy, preferably Ci- C4-alkoxy.
  • R 5 and R 6 are independently OCH3.
  • R 5 and R 6 are independently OCH2CH3.
  • R 5 and R 6 are independently OCH(CH3)2.
  • R 5 and R 6 are independentlyOChbCh CI- .
  • R 5 and R 6 are independently OC(CH3)3-
  • R 5 and R 6 are independently C2-C6-alkenyl, substi- tuted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 5 and R 6 are independently C 2 -C6-haloalkenyl, more preferably fully or partially halogenated C2-C6-alkenyl.
  • R 5 and R 6 are independently fully or partially halogenated C 2 -alkenyl.
  • R 5 and R 6 are independently fully or partially halogenated C3-alkenyl.
  • R 5 and R 6 are independently C 2 -C 6 -alkynyl, preferably CCH, CH 2 CCH, CH2CCCH3.
  • R 5 and R 6 are independently CCH.
  • R 5 and R 6 are independently CCCH3.
  • R 5 and R 6 are independently CCCH(CH3)2.
  • R 5 and R 6 are independently CCC(CH3)3-
  • R 5 and R 6 are independently CH2CCH.
  • R 5 and R 6 are independently CH2CCCH3.
  • R 5 and R 6 are independently CC ⁇ Hs) In a further special embodiment R 5 and R 6 are independently CH2CCH2CH3.
  • R 5 and R 6 are independently C 2 -C6-alkynyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 5 and R 6 are independently C 2 -C6-haloalkynyl, more preferably fully or partially halogenated C2-C6-alkynyl.
  • R 5 and R s are independently fully or partially halogenated C 2 -alkynyl.
  • R 5 and R 6 are independently fully or partially halogenated C3-alkynyl.
  • R 5 and R 6 are independently CCCI.
  • R 5 and R s are independently CCBr.
  • R 5 and R 6 are independently CC-I.
  • R 5 and R 6 are independently CH2-CCCI.
  • R 5 and R 6 are independently CH 2 -CCBr. In a further special embodiment R 5 and R 6 are independently CH 2 -CC-I. According to a further specific embodiment R 5 and R 6 are independently C2-C 6 -alkynyl, preferably C2-C4- alkynyl, substituted by OH. In a special embodiment R 5 and R s are independently CC- C(OH)(CH3)2. According to a further specific embodiment R 5 and R 6 are independently C1-C4- alkoxy-C2-C6-alkynyl, more preferably Ci-C4-alkoxy-C2-C4-alkynyl. In a special embodiment R 5 and R 6 are independently CCOCH3.
  • R 5 and R 6 are independently CC- CH2-OCH3. In a special embodiment R 5 and R 6 are independently CC-C(OCH 3 )(CH 3 )2. In a further special embodiment R 5 and R 6 are independently CH2CCOCH3. According to a further specific embodiment R 5 and R 6 are independently Ci-C 4 -haloalkoxy-C 2 -C 6 -alkynyl, more preferably C 1 -C 4 - haloalkoxy-C2-C 4 -alkynyl. In a further special embodiment R 5 and R 6 are independently CC- CH2OCCI3.
  • R 5 and R 6 are independently CC-CH2OCF3 According to a further specific embodiment R 5 and R 6 are independently C3-C8-cycloalkyl-C2-CB-alkynyl, preferably C3-C 6 -cycloalkyl-C 2 -C 4 -alkynyl. In a special embodiment R 5 and R 6 are independently CC(C3H 5 ). In a special embodiment R 5 and R 6 are independently CC(C4H 7 ). In a special embodiment R 5 and R 6 are independently CCCH2(C3H5). In a special embodiment R 5 and R 6 are independently CC-CH2-C4H7).
  • R 5 and R 6 are independently C3-C6-halocycloalkyl-C2-C4-alkynyl, preferably C3-C8-halocycloalkyl-C2-C6-alkynyl.
  • R 5 and R 6 are independently CC(C3H 4 CI).
  • R 5 and R 6 are independently CC(C3H 4 F).
  • R 5 and R 6 are independently CC(C 4 H6CI).
  • R 5 and R 6 are independently CC(C 4 HeF).
  • R 5 and R 6 are independently Cs-Cs-cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl.
  • R 5 and R 6 are independently cyclopropyl.
  • R 5 and R 6 are independently cyclobutyl.
  • R 5 and R s are independently cyclopentyl.
  • R 5 and R 6 are independently cyclohexyl.
  • R 5 and R 6 are independently C3-Cs-cycloalkyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 5 and R 6 are independently C3-Cs-halocycloalkyl, more pref- erably fully or partially halogenated C3-C 6 -cycloalkyl.
  • R 5 and R 6 are independently fully or partially halogenated cyclopropyl.
  • R 5 and R 6 are independently 1-CI-cyclopropyl.
  • R 5 and R 6 are independently 2- Cl-cyclopropyl.
  • R 5 and R 6 are independently 1 -F-cyclopropyl.
  • R 5 and R 6 are independently 2-F-cyclopropyl.
  • R 5 and R 6 are independently fully or partially halogenated cyclobutyl.
  • R 5 and R 6 are independently 1-CI-cyclobutyl.
  • R 5 and R 6 are independently 1-F-cyclobutyl.
  • R 5 and R 6 are independently
  • R 5 and R 6 are independently 3-CI-cyclobutyl.
  • R 5 and R 6 are independently 2-F-cyclobutyl.
  • R 5 and R 6 are independently 3-F-cyclobutyl.
  • R 5 and R 6 are independently 3,3-(CI)2-cyclobutyl.
  • R 5 and R 6 are independently 3,3-(F)2-cyclobutyl.
  • R 5 and R 6 are independently C3-C8-cycloalkyl substituted by Ci-C4-alkyl, more preferably is C3-C 6 -cycloalkyl substituted by Ci- C4-alkyl.
  • R 5 and R 6 are independently 1 -CH3-cyclopropyl.
  • R 5 and R 6 are independently 2-CH3-cyclopropyl.
  • R 5 and R 6 are independently 1 -CH3-cyclobutyl.
  • R 5 and R 6 are independently 2-CH3-cyclobutyl.
  • R 5 and R 6 are independently
  • R 5 and R 6 are independently 3,3-(CH3)2- cyclobutyl.
  • R 5 and R 6 are independently Cs-Cs-cycloalkyl substituted by CN, more preferably is C3-C 6 -cycloalkyl substituted by CN.
  • R 5 and R 6 are independently 1-CN-cyclopropyl.
  • R 5 and R s are independently 2-CN-cyclopropyl.
  • R 5 and R 6 are independently C3-C8-cycloalkyl-C3-C8-cycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-cycloalkyl.
  • R 5 and R 6 are independently 1-cyclopropyl-cyclopropyl.
  • R 5 and R 6 are independently 2-cyclopropyl-cyclopropyl.
  • R 5 and R 6 are independently Cs-Cs-cycloalkyl-Cs-Cs-halocycloalkyl, preferably C3-C6- cycloalkyl-C3-C 6 -halocycloalkyl.
  • R 5 and R 6 are independently C3-Cs-cycloalkyl-Ci-C4-alkyl, preferably C3-C 6 -cycloalkyl-Ci-C4-alkyl.
  • R 5 and R 6 are independently CH(CH 3 )(cyclopropyl).
  • R 5 and R 6 are independently CH 2 -(cyclopropyl).
  • R 5 and R 6 are independently CH(CH3)(cyclobutyl).
  • R 5 and R 6 are independently CH2-(cyclobutyl).
  • R 5 and R 6 are independently CH2CH2-(cyclopropyl).
  • R 5 and R 6 are independently CH2CH2- (cyclobutyl).
  • R 5 and R 6 are independently C3-Cs-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 cycloalkyl 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 5 and R 6 are independently C3-C8-cycloalkyl-Ci-C4- haloalkyl, C3-C 6 -cycloalkyl-Ci-C4-haloalkyl. According to a specific embodiment R 5 and R 6 are independently C3-C8-halocycloalkyl-Ci-C4-alkyl, C3-C 6 -halocycloalkyl-Ci-C4-alkyl. In a special embodiment R 5 and R 6 are independently fully or partially halogenated cyclopropyl-Ci-C4-alkyl.
  • R 5 and R 6 are independently 1 -CI-cyclopropyl-Ci-C4-alkyl. In a further special embodiment R 5 and R 6 are independently 1 -F-cyclopropyl-Ci-C4-alkyl. In a further very special embodiment R 5 and R s are independently Chb-l -CI-cyclopropyl. In a further very special embodiment R 5 and R 6 are independently Chb-l -F-cyclopropyl. In a further very special embodiment R 5 and R 6 are independently CH(CH3)-1 -CI-cyclopropyl. In a further very special embodiment R 5 and R 6 are independently C(CH3)2-1 -F-cyclopropyl. In a further very special embodiment R 5 and R 6 are independently CH2-1 -F-cyclobutyl. In a further very special embodiment R 5 and R 6 are independently Chb-l -CI-cyclobutyl.
  • R 5 and R 6 are independently phenyl.
  • R 5 and R 6 are independently phenyl substituted by one, two, three or up to the maximum possible number of identical or different groups R as defined and preferably herein.
  • R 5 and R 6 are independently phenyl substituted by one, two or three halogen atoms, preferably by one, two or three CI or F.
  • R 5 and R 6 are independently 2-CI-phenyl.
  • R 5 and R 6 are independently 2- F-phenyl.
  • R 5 and R 6 are independently 4-CI-phenyl.
  • R 5 and R 6 are independently 4-CI-phenyl.
  • R 5 and R 6 are independently 4-F-phenyl.
  • R 5 and R 6 are inde- pendently 4-F-phenyl.
  • R 5 and R 6 are independently 2,4-C - phenyl. In a further special embodiment R 5 and R 6 are independently 2,4-F2-phenyl. In a further special embodiment R 5 and R 6 are independently 2-CI-4-F-phenyl. In a further special embodiment R 5 and R 6 are independently 2-F-4-CI-phenyl. In a further special embodiment R 5 and R 6 are independently 2,4,6-Cl3-phenyl. In a further special embodiment R 5 and R 6 are independently 2,4,6-F 3 -phenyl.
  • R 5 and R 6 are independently phenyl substituted by one, two or three CN or OH groups.
  • R 5 and R 6 are independently 2-OH-phenyl.
  • R 5 and R 6 are independently 4-OH-phenyl.
  • R 5 and R 6 are independently 2,4-OH2-phenyl.
  • R 5 and R 6 are independently 2,4, 6-OH 3 -phenyl.
  • R 5 and R 6 are independently phenyl substituted by one, two or three Ci-C4-alkyl or Ci-C4-haloalkyl groups, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or CF 3 , CHF 2 , CFH 2 , CCI 3 , CHC , CCIH 2 .
  • R 5 and R 6 are independently 2-CH3-phenyl.
  • R 5 and R 6 are independently 2-CF3- phenyl.
  • R 5 and R 6 are independently 4-CH 3 -phenyl.
  • R 5 and R 6 are independently 4-CF3-phenyl.
  • R 5 and R 6 are independently phenyl substituted by one, two or three Ci-C4-alkoxy or Ci-C4-haloalkoxy groups, preferably preferably Ci-C4-alkoxy, more preferably CH3O, CH3CH2O, CH3CH2CH2O, CH 2 (CH 3 )CH 2 0, CH 3 CH(CH 3 )0, CH3CH2CH2CH2O, CF3O, CCI3O.
  • R 5 and R 6 are independently 2-CH30-phenyl.
  • R 5 and R 6 are independently 2-CF30-phenyl.
  • R 5 and R 6 are independently 4-CH30-phenyl.
  • R 5 and R 6 are independently 4-CF 3 0-phenyl.
  • R 5 and R 6 are independently phenyl-Ci-C4-alkyl, preferably phenyl- Ci-C2-alkyl.
  • R 5 and R s are independently benzyl.
  • R 5 and R 6 are independently phenyl-Ci-C4-alkyl therein 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, in particular selected from halogen, in particular CI and F, Ci-C 4 -alkoxy, in particular OCH 3 , Ci-C 4 -alkyl, in particular CH 3 or C 2 H 5 , and CN, and phenyl can be substituted by one, two, three or up to the maximum possible number of identical or different groups R as defined and preferably herein in particular selected from halogen, in particular CI and F, Ci-C4-alkoxy, in particular OCH3, Ci-C4-alkyl, in particular CH3 or C 2 H 5 , and CN.
  • R a as defined and preferably herein, in particular selected from halogen, in particular CI and F, Ci-C 4 -alkoxy, in particular OCH 3 , Ci-
  • R 5 and R 6 are independently CH 2 -(4-CI)-phenyl. In a further special embodiment R 5 and R 6 are independently CH 2 -(4-CH3)-phenyl. In a further special embodiment R 5 and R 6 are independently CH 2 -(4-OCH3)-phenyl. In a further special embodiment R 5 and R 6 are independently CH 2 -(4-F)-phenyl. In a further special embodiment R 5 and R 6 are independently CH2-(2,4-Cl2)-phenyl. In a further special embodiment R 5 and R 6 are independently CH 2 -(2,4-F 2 )-phenyl.
  • R 5 and R 6 together with the carbon atom to which they are bound form a saturated or partially unsaturated three-, four-, five-, six- or seven- membered carbocycle.
  • R 5 and R 6 form cyclopropyl.
  • R 5 and R 6 form cyclobutyl.
  • R 5 and R 6 form cyclo- penyl.
  • R 5 and R 6 form cyclohexyl. Further preffered are cyclo- pentenyl, cyclopentadienyl and cyclohexenyl.
  • Preferred are halogen such as CI, Br, F, Ci-C6-haloalkyl and Ci-C6-alkoxy.
  • R 5 and R 6 together with the carbon atom to which they are bound form a a saturated or partially unsaturated three-, four-, five-, six- or seven- membered heterocycle, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the carbo- or heterocycle is unsubstituted or carries one, two, three or four substituents independently selected from halogen, CN, N0 2 , OH, SH, NH2, d-Ce-alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 3 -haloalkoxy, Ci-C 6 -alkylthio, Ci-C 6 - haloalkylthio, Ci-C4-alkoxy-Ci-C4-alkyl, phenyl and phenoxy; and wherein one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently
  • R 5 and R s form cyclopropanone, cyclopentanone, cyclopropanethi- one, cyclopentanethione, 5-oxazolone, cyclohexane-1 ,4-dione, cyclohexane-1 ,4-dithione, cy- clohex-2-ene-1 ,4-dione or cyclohex-2-ene-1 ,4-dithione.
  • Further preffered are oxirane, aziridine, thiirane, oxetane, azetidine, thiethane, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl,
  • C* CCl2.
  • C * CHBr.
  • R 5 and R 6 C(CH3)2.
  • R 7 in the compounds according to the invention is, according to one embodiment, as defined in claim 1.
  • R 7 in the compounds according to the invention is, according to a further embodiment, C1-C6- alkyl or C3-C6-cycloalkyl, wherein R 7 is substituted by one, two, three or four R 7a ; wherein R 7a is independently selected from halogen.
  • o 0.
  • o is 1. According to one further embodiment o is 2. According to one further embodiment o is 3. According to one further embodiment o is 4.
  • R 7 is Ci-C6-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • R 7 is methyl.
  • R 7 is ethyl.
  • R 7 is n-propyl.
  • R 7 is i- propyl.
  • R 7 is 1 -methylpropyl.
  • R 7 is n-butyl.
  • R 7 is i-butyl.
  • R 7 is t- butyl.
  • R 4 is Ci-C6-alkyl substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 7 is Ci-C6-haloalkyl, more preferably fully or partially halo- genated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • R 7 is CF3.
  • R 7 is CHF2.
  • R 7 is CFH2.
  • R 7 is CCI3.
  • R 7 is CHCI2.
  • R 7 is CCIH2.
  • R 7 is Ci-C6-alkyl, preferably Ci-C 7 -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, CH 2 CH(CH 3 )OH, CH2CH2CH2CH2OH.
  • R 7 is CH2OH.
  • R 7 is Ci-C 7-alkoxy-Ci-C6-alkyl, more preferably C 1 -C 7-alkoxy-Ci-C 7-alkyl.
  • R 7 is CH2OCH3.
  • R 7 is CH2CH2OCH3.
  • R 7 is CH(CH3)OCH 3 . In a further special embodiment R 7 is CH(CH3)OCH 2 CH3. In a further special embodiment R 7 is CH2CH2OCH2CH3. According to a further preferred embodiment R 7 is C2-C6-alkenyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 7 is Ci-C 7-alkoxy-C 2 -C6-alkenyl, more preferably Ci-C 7-alkoxy-C 2 -C 7-alkenyl.
  • R 7 is
  • R 7 is C 2 -C6-alkynyl, preferably CCH, CH 2 CCH,
  • R 7 is CCH. in a further special embodiment R 7 is CCCH 3 . In a further special embodiment R 7 is CH2CCH. In a further special embodiment R 7 is CH2CCCH3. In a further special embodiment R 7 is CH2CCH2CH3.
  • R 7 is C2-C6-alkynyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and preferably herein.
  • R 7 is C2-C6-haloalkynyl, more preferably fully or partially hal- ogenated C2-C6-alkynyl. In a special embodiment R 7 is fully or partially halogenated C2-alkynyl. In a further special embodiment R 7 is fully or partially halogenated C3-alkynyl. According to a further specific embodiment R 7 is C 2 -C6-alkynyl, preferably C 2 -C 7 -alkynyl, substituted by OH, more preferably, CCOH, CH 2 CCOH. In a special embodiment R 7 is CCOH. In a further special embodiment R 7 is CH2CCOH.
  • R 7 is C1-C 7-alkoxy-C2-C6-alkynyl, more preferably Ci-C 7-alkoxy-C2-C 7-alkynyl.
  • R 7 is CCOCH3.
  • R 7 is CH2CCOCH 3 .
  • R 7 is Cs-Ce-cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl.
  • R 7 is cyclopropyl.
  • R 7 is cyclobutyl.
  • R 7 is cyclopentyl.
  • R 7 is cyclohexyl.
  • 7 is C3-Ce-cycloalkoxy, preferably C3-C6-cycloalkoxy.
  • R 7 is O-cyclopropyl.
  • R 7 is C3-C8-cycloalkyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R a as defined and prefera- bly herein.
  • R 7 is C3-C8-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl. In a special embodiment R 7 is fully or partially halogenated cyclo- propyl. In a further special embodiment R 7 is 1-CI-cyclopropyl. In a further special embodiment R 7 is 2-CI-cyclopropyl. In a further special embodiment R 7 is 1 -F-cyclopropyl. In a further special embodiment R 7 is 2-F-cyclopropyl. In a further special embodiment R 7 is fully or partially halogenated cyclobutyl. In a further special embodiment R 7 is 1 -CI-cyclobutyl. In a further special embodiment R 7 is 1-F-cyclobutyl. In a further special embodiment R 7 is 3,3-(CI)2-cyclobutyl. In a further special embodiment R 7 is 3,3-(F)2-cyclobutyl.
  • R 71 and R 72 together with the carbon atom to which they are bound form a saturated or partially unsaturated three-, four-, five-, six- or seven- membered carbocycle.
  • R 5 and R 6 form cyclopropyl.
  • R 5 and R 6 form cyclobutyl.
  • R 5 and R 6 form cyclo- penyl.
  • R 5 and R 6 form cyclohexyl. Further preffered are cyclo- pentenyl, cyclopentadienyl and cyclohexenyl.
  • R 71 and R 72 form cyclopropanone, cyclopentanone, cyclopro- panethione, cyclopentanethione, 5-oxazolone, cyclohexane-1 ,4-dione, cyclohexane-1 ,4- dithione, cyclohex-2-ene-1 ,4-dione or cyclohex-2-ene-1 ,4-dithione.
  • oxirane aziridine, thiirane, oxetane, azetidine, thiethane, 2-tetrahydrofuranyl, 3- tetrahydrofuranyl, 2-tetrahydrothienyl and 3-tetrahydrothienyl.
  • the present invention relates to compounds of the formulae I. A to I.H, each of them representing a specific embodiment of the invention, wherein the variables are defined and preferably defined as given herein for compounds I:
  • the present invention relates to compounds of the formulae 11. A to II. H, each of them representing a specific embodiment of the invention, wherein the variables are defined and preferably defined as given herein for compounds I:
  • I.C.A6.B1 to I.C.A6.B2340 compounds I.D.A6.B1 to I.D.A6.B2340; compounds I.E.A6.B1 to I.E.A6.B2340; compounds I.F.A6.B1 to I.F.A6.B2340; compounds I.G.A6.B1 to I.G.A6.B2340; compounds I.H.A6.B1 to I.H.A6.B2340).
  • I.C.A8.B1 to I.C.A8.B2340 compounds I.D.A8.B1 to I.D.A8.B2340; compounds I.E.A8.B1 to I.E.A8.B2340; compounds I.F.A8.B1 to I.F.A8.B2340; compounds I.G.A8.B1 to I.G.A8.B2340; compounds I.H.A8.B1 to I.H.A8.B2340).
  • D.A1 1.B2340 compounds I.E.A1 1.B1 to I.E.A1 1.B2340; compounds I.F.A11.B1 to I.F.A1 1.B2340; compounds I.G.A1 1.B1 to I.G.A1 1.B2340; compounds I.H.A11.B1 to I.H.A1 1.B2340).
  • R 4 )m, R 7 and R 72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A14.B1 to II.A.A14.B2340, compounds II.B.A14.B1 to II.B.A14.B2340; compounds II.C.A14.B1 to II.C.A14.B2340; compounds II.D.A14.B1 to II.D.A14.B2340; compounds II.E.A14.B1 to II.E.A14.B2340; compounds II.F.A14.B1 to II.F.A14.B2340; compounds
  • I.C.A1.Bb1 to I.C.A1.Bb260 compounds I.D.A1.Bb1 to I.D.A1.Bb260; compounds I.E.A1.Bb1 to I.E.A1.Bb260; compounds I.F.A1.BM to I.F.A1.Bb260; compounds I.G.A1 .BM to I.G.A1.Bb260; compounds I.H.A1 .Bb1 to I.H.A1.Bb260).
  • I.C.A2.Bb1 to I.C.A2.Bb260 compounds I.D.A2.Bb1 to I.D.A2.Bb260; compounds I.E.A2.Bb1 to I.E.A2.Bb260; compounds I.F.A2.Bb1 to I.F.A2.Bb260; compounds I.G.A2.Bb1 to I.G.A2.Bb260; compounds I.H.A2.Bb1 to I.H.A2.Bb260).
  • I.C.A3.BM to I.C.A3.Bb260 compounds I.D.A3.BM to I.D.A3.Bb260; compounds LE.A3.Bb1 to I.E.A3.Bb260; compounds I.F.A3.Bb1 to I.F.A3.Bb260; compounds I.G.A3.Bb1 to I.G.A3.Bb260; compounds I.H.A3.Bb1 to I.H.A3.Bb260).
  • I.C.A4.Bb1 to I.C.A4.Bb260 compounds I.D.A4.Bb1 to I.D.A4.Bb260; compounds I.E.A4.Bb1 to I.E.A4.Bb260; compounds I.F.A4.Bb1 to I.F.A4.Bb260; compounds I.G.A4.Bb1 to I.G.A4.Bb260; compounds I.H.A4.Bb1 to I.H.A4.Bb260).
  • I.C.A6.Bb1 to I.C.A6.Bb260 compounds I.D.A6.Bb1 to I.D.A6.Bb260; compounds I.E.A6.Bb1 to I.E.A6.Bb260; compounds I.F.A6.Bb1 to I.F.A6.Bb260; compounds I.G.A6.Bb1 to I.G.A6.Bb260; compounds I.H.A6.Bb1 to I.H.A6.Bb260).
  • I.C.A7.Bb1 to I.C.A7.Bb260 compounds I.D.A7.Bb1 to I.D.A7.Bb260; compounds LE.A7.Bb1 to I.E.A7.Bb260; compounds I.F.A7.Bb1 to I.F.A7.Bb260; compounds I.G.A7.Bb1 to I.G.A7.Bb260; compounds I.H.A7.Bb1 to I.H.A7.Bb260).
  • I.C.A8.Bb1 to I.C.A8.Bb260 compounds I.D.A8.Bb1 to I.D.A8.Bb260; compounds I.E.A8.Bb1 to I.E.A8.Bb260; compounds I.F.A8.Bb1 to I.F.A8.Bb260; compounds I.G.A8.Bb1 to I.G.A8.Bb260; compounds I.H.A8.Bb1 to I.H.A8.Bb260).
  • I.C.A9.Bb1 to I.C.A9.Bb260 compounds I.D.A9.Bb1 to I.D.A9.Bb260; compounds I.E.A9.Bb1 to I.E.A9.Bb260; compounds I.F.A9.Bb1 to I.F.A9.Bb260; compounds I.G.A9.Bb1 to I.G.A9.Bb260; compounds I.H.A9.Bb1 to I.H.A9.Bb260).
  • the present invention relates to compounds of the formulae III.A to III. F each of them representing a specific embodiment of the invention, wherein the variables are defined and preferably defined as given herein for compounds I:
  • the present invention relates to compounds of the formulae IV.A to IV.R, each of them representing a specific embodiment of the invention, wherein the variables are defined and preferably defined as given herein for compounds I:
  • III.Q.C1 .P180 compounds III.R.C1.P1 to III.R.C1 P180;).
  • III.D.C2.P180 compounds III.E.C2.P1 to III.E.C2.P180; compounds III.F.C2.P1 to
  • III.H.C2.P180 compounds III.I.C2.P1 to III.I.C2.P180; compounds III.J.C2.P1 to III.J.C2.P180; compounds III.K.C2.P1 to III.K.C2.P180; compounds III.L.C2.P1 to III.L.C2.P180; compounds III.M.C2P1 to III.M.C2P180; compounds III.N.C2P1 to III.N.C2P180; compounds III.O.C2P1 to III.O.C2.P180; compounds III.P.C2.P1 to III.P.C2.P180; compounds III.Q.C2.P1 to
  • III.Q.C2.P180 compounds III.R.C2.P1 to III.R.C2.P180;).
  • III.D.C3.P180 compounds III.E.C3.P1 to III.E.C3.P180; compounds III.F.C3.P1 to
  • III.F.C3.P180 compounds III.G.C3.P1 to III.G.C3.P180; compounds III.H.C3.P1 to
  • III.H.C3.P180 compounds III.I.C3P1 to III.I.C3P180; compounds III.J.C3P1 to III.J.C3P180; compounds III.K.C3.P1 to III.K.C3.P180; compounds III.L.C3.P1 to I II.L.C3.P180; compounds III.M.C3.P1 to III.M.C3.P180; compounds III.N.C3.P1 to III.N.C3.P180; compounds III.O.C3.P1 to III.O.C3.P180; compounds III.P.C3.P1 to III.P.C3.P180; compounds III.Q.C3.P1 to
  • III.Q.C3.P180 compounds III.R.C3.P1 to III.R.C3.P180;).
  • Table 4a-lll Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III. K, III.L, III.M, III.N, III.O, III.P, III.Q, MLR in which the combination of R 71 and R 72 corresponds to line C-4 of Table C and the meaning for (R 3 ) n for each individual compound corresponds in each case to one line of Table P (compounds III.A. C4P1 to III.A.C4.P180; compounds III.B.C4.P1 to III.B.C4.P180; compounds III.C.C4.P1 to III.C.C4.P180; compounds III.D.C4.P1 to
  • III.D.C4.P180 compounds III.E.C4.P1 to III.E.C4.P180; compounds III.F.C4.P1 to
  • III.F.C4.P180 compounds III.G.C4.P1 to III.G.C4.P180; compounds III.H.C4.P1 to
  • III.H.C4.P180 compounds III.I.C4.P1 to III.I.C4P180; compounds III.J.C4P1 to III.J.C4P180; compounds III.K.C4.P1 to III.K.C4.P180; compounds III.L.C4.P1 to I II.L.C4.P180; compounds III.M.C4.P1 to III.M.C4.P180; compounds III.N.C4.P1 to III.N.C4.P180; compounds III.O.C4.P1 to III.O.C4.P180; compounds III.P.C4.P1 to III.P.C4.P180; compounds III.Q.C4.P1 to
  • III.Q.C4.P180 compounds III.R.C4.P1 to III.R.C4.P180;).
  • III.F.C5P180 compounds III.G.C5P1 to III.G.C5P180; compounds IILH.C5.P1 to
  • III.H.C5.P180 compounds III.LC5P1 to III.I.C5P180; compounds IILJ.C5P1 to III.J.C5P180; compounds III.K.C5.P1 to III.K.C5.P180; compounds III.L.C5.P1 to I II.L.C5.P180; compounds III.M.C5P1 to III.M.C5P180; compounds III.N.C5.P1 to III.N.C5.P180; compounds III.O.C5.P1 to III.O.C5.P180; compounds III.P.C5.P1 to III.P.C5.P180; compounds III.Q.C5.P1 to
  • III.Q.C5.P180 compounds III.R.C5P1 to III.R.C5.P180;).
  • III.F.C6P180 compounds III.G.C6.P1 to III.G.C6P180; compounds IILH.C6.P1 to
  • III.H.C6.P180 compounds III.I.C6.P1 to I II.I.C6.P180; compounds III.J.C6.P1 to I II.J.C6.P180; compounds III.K.C6.P1 to III.K.C6.P180; compounds III.L.C6.P1 to I II.L.C6.P180; compounds III.M.C6P1 to III.M.C6P180; compounds IILN.C6.P1 to III.N.C6P180; compounds III.O.C6.P1 to III.O.C6.P180; compounds III.P.C6.P1 to III.P.C6.P180; compounds III.Q.C6.P1 to
  • III.Q.C6.P180 compounds III.R.C6.P1 to III.R.C6.P180;).
  • Table 7a-lll Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III I, III.K, III.L, III.M,
  • III.N, III.O, III.P, III.Q, NIP in which the combination of R 71 and R 72 corresponds to line C-7 of Table C and the meaning for (R 3 ) n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C7P1 to III.A.C7P180; compounds III.B.C7P1 to III.B.C7P180; compounds III.C.C7P1 to III.C.C7P180; compounds III.D.C7P1 to
  • III.D.C7P180 compounds III.E.C7P1 to III.E.C7P180; compounds IILF.C7P1 to
  • III.H.C7P180 compounds III.I.C7P1 to III.I.C7P180; compounds III.J.C7P1 to III.J.C7P180; compounds III.K.C7P1 to III.K.C7P180; compounds III.L.C7P1 to III.L.C7P180; compounds III.M.C7P1 to III.M.C7P180; compounds III.N.C7P1 to III.N.C7P180; compounds III.O.C7P1 to III.O.C7P180; compounds IIIP.C7P1 to IIIP.C7P180; compounds III.Q.C7P1 to
  • III.Q.C7P180 compounds IIIP.C7P1 to IIIP.C7P180;).
  • III.F.C8P180 compounds III.G.C8.P1 to III.G.C8P180; compounds III.H.C8.P1 to
  • III.H.C8.P180 compounds III.I.C8P1 to III.I.C8P180; compounds III.J.C8P1 to III.J.C8P180; compounds III.K.C8.P1 to III.K.C8.P180; compounds III.L.C8.P1 to I II.L.C8.P180; compounds III.M.C8P1 to III.M.C8P180; compounds III.N.C8.P1 to III.N.C8P180; compounds III.O.C8P1 to III.O.C8.P180; compounds III.P.C8.P1 to III.P.C8.P180; compounds III.Q.C8.P1 to
  • III.Q.C8.P180 compounds IIIP.C8P1 to III.R.C8.P180;).
  • III.H.C9.P180 compounds III.I.C9.P1 to I II.I.C9.P180; compounds III.J.C9.P1 to I II.J.C9.P180; compounds III.K.C9.P1 to III.K.C9.P180; compounds III.L.C9.P1 to I II.L.C9.P180; compounds III.M.C9.P1 to III.M.C9.P180; compounds III.N.C9.P1 to III.N.C9.P180; compounds III.O.C9.P1 to III.O.C9.P180; compounds III.P.C9.P1 to IIIP.C9.P180; compounds III.Q.C9.P1 to
  • III.Q.C9.P180 compounds III.R.C9.P1 to III.R.C9.P180;).
  • Table 1 a-IV Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III.K, III.L, III.M, III.N, III.O, III.P, III.Q, IMP in which the combination of R 71 and R 72 corre- sponds to line C-10 of Table C and the meaning for ( 3 ) n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C10.P1 to III.A.C10.P180; compounds III.B.C10.P1 to III.B.C10.P180; compounds III.C.C10.P1 to I II.C.C10.P180; compounds III.D.C10.P1 to III.D.C10.P180; compounds III.E.C10.P1 to I II.E.C10.P180; compounds III.F.C10.P1 to III.F.C10.P180; compounds III.
  • III.L.C10.P1 to III.L.C10.P180 compounds III.M.C10.P1 to III.M.C10.P180; compounds III.N.C10.P1 to III.N.C10.P180; compounds III.O.C10.P1 to 111.O.C10.P180; compounds III.P.C10.P1 to III.P.C10.P180; compounds III.Q.C10.P1 to III.Q.C10.P180; compounds
  • IV.B.C5.P 80 compounds IV.C.C5.P1 to IV.C.C5.P 80; compounds IV.D.C5.P1 to
  • IV.J.C10.P180 compounds IV.K.C10.P1 to IV.K.C10.P180; compounds IV.L.C10.P1 to IV.LC10.P180; compounds IV.M.C10.P1 to IV.M.C10.P180; compounds IV.N.C10.P1 to IV.N.C10.P180; compounds IV.O.C10.P1 to IV.O.C10.P180; compounds IV.P.C10.P1 to IV.P.C10.P180; compounds IV.Q.C10.P1 to IV.Q.C10.P180; compounds IV.R.C10.P1 to IV.R.C10.P180).
  • the compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungi- cides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • compounds I and compositions thereof are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
  • The- se young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • treatment of plant propagation materials with compounds I and compositions thereof, respectively is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g.
  • herbicides e. bromoxynil or ioxynil herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from anoth- er class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci.
  • cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield ® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ -endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • VIP1 , VIP2, VIP3 or VIP3A vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins pro- prised by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdyster- oid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ).
  • Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coelop- tera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called "pathogenesis- related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Er- winia amylvora).
  • PR proteins pathogenesis- related proteins
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lysozym e. g. potato
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral patho- gens of those plants.
  • productivity e. g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Cana- da).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • a modified amount of substances of content or new substances of content specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • the compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A tragopogonis); Alternaria 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 alternata), tomatoes (e. g. A solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g.
  • a ir/f c (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 (S. zeicola) on corn, e. g. spot blotch (S. sorokiniana) on cereals and e.g. 6. oryzae on rice and turfs; Blumeria (formerly Erysiphe) gram- inis (powdery mildew) on cereals (e. g.
  • Botrytis cinerea (teleomorph: Botry- ofr ' n/a fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp.
  • Crocospora 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.
  • Gray leaf spot C. zeae-maydis
  • rice sugar beets
  • sugar cane e. g. C. beticola
  • sugar cane vegetables
  • coffee e. g. C. sojina or C. kiku
  • 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.
  • Phaeomoniella chlamydospora (earlier Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa
  • 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: Cibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F.
  • cucurbits e. g. E. cichoracearum
  • cabbages rape (e. g. E. cruciferarum)
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertell
  • fujikuroi Bakanae disease
  • G. gossypii Gossypii on cotton
  • Grainstaining complex on rice Guignardia bidwellii (black rot) on vines
  • Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H.
  • fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas
  • Peronospora spp. downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica);
  • Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P.
  • phaseoli, teleomorph Diaporthe phaseolorum
  • Phy- soderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • paprika and cucurbits e. g. P. capsici
  • soybeans e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew
  • Puccinia spp. rusts on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P.
  • Pyrenophora anamorph: Drechslera
  • tritici-repentis tan spot
  • P. teres net blotch
  • Pyricularia spp. e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals
  • Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum);
  • Ramularia spp. e. g. R.
  • collo-cygni Roso-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R.
  • S. reiliana head smut
  • Sphaerotheca fuliginea powdery mildew
  • Spongospora subterranea powdery scab
  • Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lepto- sphaeria [syn. Phaeosphaeria] nodorum) on wheat
  • Synchytrium endobioticum on potatoes potato wart disease
  • Taphrina spp. e. g. T.
  • deformans leaf curl disease
  • T. pruni plum pocket
  • plums Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U.
  • occulta stem smut
  • Uromyces spp. rust
  • vegetables such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae)
  • Ustilago spp. loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane
  • Venturia spp. scab
  • apples e. g. V. inaequalis
  • pears Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
  • the compounds I and compositions thereof, respectively, are also suitable for controlling harm- ful 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 nonliving materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, colling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Tyromyces spp. Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
  • the method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms.
  • the term "stored products” is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired.
  • Stored products of crop plant origin such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment.
  • stored products are timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.
  • Stored products of animal origin are hides, leather, furs, hairs and the like.
  • the combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.
  • Preferably "stored products” is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
  • the compounds I and compositions thereof may be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • the compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
  • the compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
  • An agrochemical composition comprises a fungicidally effective amount of a compound I.
  • the term "effective amount” denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
  • the compounds I, their N-oxides and salts can be converted into customary types of agrochem- ical compositions, e. g.
  • 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.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene, alkylated
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and compositions thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and compositions thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e.g. cellulose, starch
  • fertilizers
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and compositions 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 & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North Amer- ican Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and compositions thereof.
  • sulfonates are alkylaryl- sulfonates, 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 ethox- ylated 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 compositions thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.

Abstract

The present invention relates to new substituted triazoles and imidazoles compounds of formula I as defined in the description, and the N-oxides, and salts thereof, their preparation and intermediates for preparing them. The invention also relates to the use of these compounds for combating harmful fungi and seed coated with at least one such compound and also to compositions comprising at least one such compound.

Description

New substituted triazoles and imidazoles and their use as fungicides
Description
The present invention relates to new substituted triazoles and imidazoles of the formula I
Figure imgf000002_0001
Furthermore the present invention relates to a process for preparing compounds of the formula
Furthermore the present invention relates to agrochemical compositions, comprising an auxilia- ry and at least one compound of formula I an N-oxide or an agriculturally acceptable salt thereof.
Furthermore the present invention relates to the use of a compound of the formula I and/or of an agriculturally acceptable salt thereof or of the compositions for combating phytopathogenic fungi.
Furthermore the present invention relates to a method for combating harmful fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I or with a composition.
Furthermore the present invention relates to seed, coated with at least one compound of the formula I and/or an agriculturally acceptable salt thereof or with a composition in an amount of from 0.1 to 10 kg per 100 kg of seed.
The preparations of azolylmethyloxirane and their use for controlling phytopathogenic fungi is known from e.g. DE 0 388 871 , DE 3 325 313, DE 3 218 129, EP 0 131 845, EP 0 180 835, EP 0 196 038, EP 0 315 850.
The compounds according to the present invention differ from those described in the above- mentioned publications inter alia by the substitution of the phenyl ring and the oxetane group. 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 harmful fungi.
Accordingly, it is an object of the present invention to provide compounds having better fungi- cidal activity and/or better crop plant compatibility.
Surprisingly, these objects are achieved by compounds of the general formula I, as defined below, and by the agriculturally acceptable salts of the compounds of the general formula I.
Accordingly, the present invention relates to compounds of formula I
Figure imgf000003_0001
wherein:
R is O or CH2;
Q is O or CH2;
wherein either R or Q is O;
A is CH or N ;
D is H , halogen or SRD, wherein
RD is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl , C2-C6-haloalkenyl, C2-C6- alkynyl, C2-C6-haloalkynyl or CN ;
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, N H2, N H(Ci-C4-alkyl), N(Ci-C4-alkyl)2, N H(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl), C(=0)(Ci- C4-alkyl), C(=0)(OH),
Figure imgf000003_0002
C(=0)(N H(d-C4-alkyl)),
alkyl)2), C(=0)(N H(C3-C3-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, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy; n is 0, 1 , 2, 3 or 4;
Y is a direct bond or a divalent group selected from the group consisting of -0-, -S-, SO-,
-SO2-; -NH-, -N(Ci-C4-alkyl)-, CR15R8-, -CR9R10-CR11 R12-, -CR13=CR14 and -C≡C-; wherein
R8, R9,R10, R11 , R12, R13, R14, R15 are independently selected from hydrogen, halogen, CN, nitro, OH , Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy;
Z is five or six-membered heteroaryl, wherein the heteroaryl contains 1 , 2, 3 or 4 heteroa- toms selected from the group consisting of O, N and S, or phenyl, wherein the heteroaryl or phenyl is unsubstituted (m=0) or substituted by (R4)m, wherein
m is 0, 1 , 2, 3, 4 or 5;
R4 is independently selected from halogen, CN, N02, OH, SH , Ci-C6-alkyl, Ci-C6- alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-Cs-cycloalkyl, C3-C8-cycloalkyloxy, N H2, N H(Ci-C4-alkyl), N(Ci-C4-alkyl)2, N H(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl),
Figure imgf000003_0003
C(=0)(OH) , C(=0)(0-Ci-C4-alkyl),
Figure imgf000004_0001
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, NO2, OH, Ci-C4-alkyl, C1-C4- haloalkyl, C3-Cs-cycloalkyl, C3-C8-halocycloalkyl, Ci-C4-alkoxy and C1-C4- haloalkoxy;
p is 0, 1 or 2;
x is 0, 1 , 2, 3 or 4;
R5 is H, halogen, CN, N02, OH, SH, Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsul- finyl, Ci-C6-alkylsulfonyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-Cs-cycloalkyl, C3-Ce- cycloalkyloxy, C3-C8-cycloalkyl-Ci-C4-alkyl, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2,
Figure imgf000004_0002
alkyl, C(=0)-NH(Ci-C4-alkyl),C(=0)-N(Ci-C4-alkyl)2, C(=0)-NH(C3-C6-cycloalkyl), C(=0)- N(C3-C6-cycloalkyl)2, phenyl, heteroaryl, phenyl-Ci-C4-alkyl and heteroaryl-Ci-C4-alkyl, wherein the heteroaryl radical in the last-mentioned groups is 5- or 6-membered and wherein the aliphatic, alicyclic and aromatic moieties of R5 are unsubstituted or substituted by one, two, three or four or up to the maximum possible number of R5a; wherein
R5a is independently selected from halogen, CN, N02, OH, SH, NH2, Ci-C6-alkyl, Ci-C6- haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, d-Ce-alkylthio, Ci-C6-haloalkylthio and Ci-C4-alkoxy-Ci-C4-alkyl;
R6 is H or is selected from the substituents defined for R5, wherein the aliphatic, alicyclic and aromatic moieties of R6 are unsubstituted or substituted by one, two, three or four or up to the maximum possible number of R6a, wherein R6a is defined as R5a;
or
R5 and R6 together with the carbon atom to which they are bound form a saturated or partially unsaturated three-, four-, five-, six- or seven-membered carbocycle or a saturated or partially unsaturated three-, four-, five-, six- or seven-membered heterocycle, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the carbo- or heterocycle is unsubstituted or carries one, two, three or four substituents independently se- lected from halogen, CN, N02, OH, SH, NH2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy,
Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C4-alkoxy-Ci-C4-alkyl, phenyl and phenoxy; and wherein one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S);
or R5 and R6 together with the carbon atom to which they are bound (denominated C*) form a group (C*=CR55R66), wherein
R55, R56 are independently selected from hydrogen, halogen, CN, NO2, OH, SH, NH2,
Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio and Ci-C4-alkoxy-Ci-C4-alkyl; R7 is independently selected from Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ca-Ce-cycloalkyl, wherein each of R7 is unsubstituted or further substituted by one, two, three or four R7a; wherein
R7a is independently selected from halogen, OH and Ci-C6-alkoxy;
or
two substituents R7: R71 and R72 together with the carbon atom(s) to which they are bound form a saturated three-, four-, five-, six- or seven-membered carbocycle or heterocycle, wherein the heterocycle contains one, two, three or four O atoms.
o is 0, 1 , 2, 3 or 4;
and the N-oxides and the agricucturally acceptable salts thereof
with the proviso that
if R is O and Q is CH2 x is not 0.
Furthermore the present invention provides a process for preparing compounds of the formula I.
Furthermore the present invention provides an agrochemical composition, comprising an auxil- iary and at least one compound of formula I an N-oxide or an agriculturally acceptable salt thereof.
Furthermore compounds of the formula I and/or of an agriculturally acceptable salt thereof or of the compositions can be used for combating phytopathogenic fungi.
Furthermore the present invention provides a method for combating harmful fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I or with a composition.
Furthermore the present invention provides seed, coated with at least one compound of the formula I and/or an agriculturally acceptable salt thereof or with a composition in an amount of from 0.1 to 10 kg per 100 kg of seed.
The terms used for organic groups in the definition of the variables are, for example the expression "halogen", collective terms which represent the individual members of these groups of organic units.
The prefix Cx-Cy denotes the number of possible carbon atoms in the particular case,
halogen: fluorine, bromine, chlorine or iodine, especially fluorine, chlorine or bromine;
alkyl and the alkyl moieties of composite groups such as, for example, alkoxy, alkylamino, alkoxycarbonyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 10 carbon atoms, for example Ci-Cio-akyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1- methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethyl butyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2- ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl and 1 -ethyl-2- methylpropyl; heptyl, octyl, 2-ethylhexyl and positional isomers thereof; nonyl, decyl and positional isomers thereof; Likewise, 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- methylpropylLikewise, the term "Ci-C4-alkyl" refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl (n-propyl), 1 -methylethyl (iso-propoyl), butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (iso-butyl), 1 ,1-dimethylethyl (tert. -butyl).
haloalkyl: straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above. In one embodiment, the alkyl groups are substituted at least once or completely by a particular halogen atom, preferably fluorine, chlorine or bromine. In a further embodi- ment, the alkyl groups are partially or fully halogenated by different halogen atoms; in the case of mixed halogen substitutions, the combination of chlorine and fluorine is preferred. Particular preference is given to (Ci-C3)-haloalkyl, more preferably (Ci-C2)-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1 -bromoethyl, 1 - fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1 ,1 ,1 -trifluoroprop-
2- yl;
alkenyl and also the alkenyl moieties in composite groups, such as alkenyloxy: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and one double bond in any position. According to the invention, it may be preferred to use small alkenyl groups, such as (C2-C4)-alkenyl; on the other hand, it may also be preferred to employ larger alkenyl groups, such as (C5-Ce)-alkenyl. Examples of alkenyl groups are, for example, C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1 -methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1- methyl-1 -propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2- pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1-butenyl, 1 - methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl,
3- methyl-3-butenyl, 1 ,1-dimethyl-2-propenyl, 1 ,2-dimethyl-1 -propenyl, 1 ,2-dimethyl-2-propenyl, 1- ethyl-1 -propenyl, 1 -ethyl-2-propenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 - methyl-1 -pentenyl, 2-methyl-1 -pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1 -pentenyl, 1-methyl-2- pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl, 2- methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4- pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1-dimethyl-2-butenyl, 1 ,1 -dimethyl-3- butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 - butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 - butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1 -butenyl, 3,3-dimethyl-2- butenyl, 1 -ethyl-1 -butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2- butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 -ethyl-1-methyl-2-propenyl, 1 -ethyl-2- methyl-1 -propenyl and 1 -ethyl-2-methyl-2-propenyl; alkynyl and the alkynyl moieties in composite groups: straight-chain or branched hydrocarbon groups having 2 to 10 carbon atoms and one or two triple bonds in any position, for example C2- C6-alkynyl, such as ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1-methyl-2- propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1 -methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1 -butynyl, 1 ,1-dimethyl-2-propynyl, 1 -ethyl-2-propynyl, 1-hexynyl, 2- hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1 -methyl-3-pentynyl, 1-methyl-4- pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4- methyl-1 -pentynyl, 4-methyl-2-pentynyl, 1 ,1 -dimethyl-2-butynyl, 1 ,1 -dimethyl-3-butynyl, 1 ,2- dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1 -ethyl-2-butynyl, 1 -ethyl-3- butynyl, 2-ethyl-3-butynyl and 1 -ethyl-1-methyl-2-propynyl;
cycloalkyl and also the cycloalkyl moieties in composite groups: mono- or bicyclic saturated hydrocarbon groups having 3 to 10, in particular 3 to 6, carbon ring members, for example C3-C6- cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1 .1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl. In this connection, optionally substituted C3-Ce-cycloalkyl means a cycloalkyl radical having from 3 to 8 carbon atoms, in which at least one hydrogen atom, for example 1 , 2, 3, 4 or 5 hydrogen atoms, is/are replaced by substituents which are inert under the conditions of the reaction. Examples of inert substituents are CN, Ci-C6-alkyl, Ci-C4-haloalkyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, and Ci-C4-alkoxy-Ci-C6-alkyl;
halocycloalkyl and the halocycloalkyl moieties in halocycloalkoxy, halocycloalkylcarbonyl and the like: monocyclic saturated hydrocarbon groups having 3 to 10 carbon ring members (as mentioned above) in which some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
alkoxy: an alkyl group as defined above which is attached via an oxygen, preferably having 1 to 10, more preferably 2 to 6, carbon atoms. Examples are: methoxy, ethoxy, n-propoxy, 1 -methyl- ethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy, and also for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethyl- propoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2, 3-d i methyl butoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2- trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy; Likewise, 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 "Ci-C4-alkoxy" groups, such as methoxy, ethoxy, n-propoxy, 1 -methylethoxy, butoxy, 1- methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy. Likewise, the term "Ci-C4-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms which is bonded via an oxygen, at any position in the alkyl group, examples are methoxy, ethoxy, n-propoxy, 1 - methylethoxy, butoxy, 1 -methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
halogenalkoxy: alkoxy as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular by fluorine, chlorine or bromine. Examples are OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chloro- fluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2- bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2- chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2- fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3- chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1 -(CH2F)-2-fluoroethoxy, 1-(CH2CI)-2- chloroethoxy, 1-(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or no- nafluorobutoxy; and also 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, un- decafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluo- rohexoxy.
Depending on the substitution pattern, the compounds according to the invention may have one or more centers of chirality, and are generally obtained in the form of racemates or as diastere- omer compositions of erythro and threo forms. The erythro and threo diastereomers of the compounds according to the invention can be separated and isolated in pure form, for example, on the basis of their different solubilities or by column chromatography. Using known methods, such uniform pairs of diastereomers can be used to obtain uniform enantiomers. Suitable for use as antimicrobial agents are both the uniform diastereomers or enantiomers and compositions thereof obtained in the synthesis. This applies correspondingly to the fungicidal compositions.
Accordingly, the invention provides both the pure enantiomers or diastereomers and compositions thereof. This applies to the compounds according to the invention and, if appropriate, correspondingly to their precursors. The scope of the present invention includes in particular the (R) and (S) isomers and the racemates of the compounds according to the invention, in particular of the formula I, which have centers of chirality. Suitable compounds of the formula I according to the invention also comprise all possible stereoisomers (cis/trans isomers) and compositions thereof.
The compounds according to the invention may be present in various crystal modifications which may differ in their biological activity. They are likewise provided by the present invention.
Owing to the basic character of their heteroatoms, the compounds according to the invention are capable of forming salts or adducts with inorganic or organic acids or with metal ions.
Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds of the formula I. Thus, suitable cations are in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium 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, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hex- afluorosilicate, hexafluorophosphate, benzoate, and also the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
Depending on the substitution pattern, the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer compositions. Both, the pure enantiomers or diastereomers and their compositions are subject matter of the present invention.
The compounds of the formula I according to the invention can be prepared by different routes analogously to processes known per se of the prior art (see, for example, the prior art cited at the outset).
The compounds of the formula I in which R is O and Q is CH2 can be prepared as follows:
Figure imgf000009_0001
Compounds of formula III can be prepared from ketone compounds II using sulfonium or sulfox- onium chemistry ( Fukuoka Daigaku Rigaku, Shuho (1990), 20(2), 83-7 ; Synthesis, (9), 1613-1624; 1999; Chemical & Pharmaceutical Bulletin, 51 (9), 1 113-1 1 16; 2003; Organic Letters, 9(13), 2541 -2544; 2007; Tetrahedron, 64(52), 11839-11845; 2008; Angewandte Chemie, International Edition, 48(9), 1677-1680; 2009; Angewandte Chemie, International Edition, 51 (30), 7532-7536, S7532/1 -S7532/48; 2012). Compounds III can be optionally substituted using a strong base such as BuLi, LDA, LHMDS, KHMDS, BuLi, LTMP, Zn-TMP and an electro- phile E+ (S8, l2, ICI, C2F4Br2) (WO 2012025506 A1 , Synthesis, (1 ), 100-106; 1999).
Alternatively, compounds I can be prepared by adding a C2 nucleophile G (Synthetic Communications, 19(1 1-12), 2167-73; 1989) to ketone compound II, or by the addition of allyl magnesium bromide, to obtain compound of formula IV. A transformation of G into OH e.g. via reduction with LiAIH4, LiBH4, DiBAH leads to a compound of formula V, or e.g. in the case of the allyl alcohol via first a well known ozonolysis. Compound of formula V can then be cyclized to obtain the precursor III (Angewandte Chemie, International Edition, 51 (23), 5675-5678, S5675/1- S5675/105; 2012, Organic Letters, 2(12), 1685-1687; 2000; Organic Letters, 4(26), 4591-4593; 2002; Organic Letters, 7(20), 4333-4335; 2005; Angewandte Chemie, International Edition, g
51 (23), 5675-5678, S5675/1 -S5675/105; 2012). Compounds III can be optionally substituted using a strong base such as BuLi, LDA, LHMDS, KHMDS, BuLi, LTMP, Zn-TMP and an elec- trophile E+ (S8, \2, ICI, C2F4Br2) (WO 2012025506 A1 , Synthesis, (1 ), 100-106; 1999).
Figure imgf000010_0001
The com ounds of the formula I in which R is CH2 and Q is O can be prepared as follows:
Figure imgf000010_0002
IX
Compounds VI are known in literature or the expert knows how to synthesize. An aldol reaction with formaldehyde leads to diol VII (Chemical & Pharmaceutical Bulletin, 42(10), 2055-62; 1994; Justus Liebigs Annalen der Chemie, 671 , 108-11 ; 1964), a cyclization reaction delivers compounds VIII (WO2010010017A1 , Journal of the American Chemical Society, 131 (8), 2786-2787; 2009; ). Reduction of keto compound will lead to an alcohol that will be transformed to IX containing a leaving group (LG). Reaction with an azole compound and a base in analogy to many precedences will give compounds X which can be optionally substituted using a strong base such as BuLi, LDA, LHMDS, KHMDS, BuLi, LTMP, Zn-TMP and an electrophile E+ (S8, l2, ICI, C2F4Br2) (WO 2012025506 A1 , Synthesis, (1), 100-106; 1999).
One aspect of the invention is also the synthesis process as follows:
A process for preparing compounds of formula I as defined herein, which comprises reacting a compound of formula which comprises following steps:
converting of a compound of formula II
Figure imgf000011_0001
II
wherein Z, Y, A, R3, R5, Rs, n are as defined herein to compound of formula IV
Figure imgf000011_0002
wherein A, Z, Y, R3, R5, R6, n are as defined herein and G is preferably C02Me,C02Et, CN, CHO;
reduction of the compound of formula IV using an reductions agent to obtain an intermediate V
Figure imgf000011_0003
wherein A, Z, Y, R3, R5, RS,R7, o, n are as defined herein;
cyclisation of the intermediate V to provide a compound of the formula III
Figure imgf000012_0001
wherein A, Z, Y, R3, R5, R6,R7, o, n are as defined herein;
and optionally substitution of the azole ring to obtain compounds of formula I. Furthermore, the invention relates to a process for preparing compounds of formula I as defined herein, which comprises reacting a compound of formula which comprises following steps:
converting of a ketone of formula VI
Figure imgf000012_0002
VI
wherein Z, Y, R3, n, x are as defined herein to com ound of formula VII
Figure imgf000012_0003
wherein Z, Y, R3, R5, R6, n, x are as defined herein;
cyclisation of the intermediate V to provide a com ound of the formula VIII
Figure imgf000012_0004
wherein Z, Y, R3, R5, R7, o, n, x are as defined herein;
transformation of the intermediate VIII to provide a com ound of the formula IX
Figure imgf000012_0005
IX
wherein Z, Y, R3, R5, R6,R7, o, n, x are as defined herein and LG is a leaving group;
reaction of the compound of formula IX with an azole group to provide a compound of formula X
Figure imgf000013_0001
X
wherein Z, Y,A, R3, R5, R6, R7, o, n, x are as defined herein;
and optionally substitution of the azole ring to obtain compounds of formula I.
Furthermore, an aspect of the invention is the intermediate Compounds of formulae V, VI, VII, VIII, IX, wherein Z, Y, A, R3, R5, R6, R7, o, n, x if applicable, are as defined and preferably defined herein for compounds I.
If individual inventive compounds cannot be directly obtained by the routes described above, they can be prepared by derivatization of other inventive compounds.
The N-oxides may be prepared from the inventive compounds according to conventional 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 composition of different N-oxides, which can be separated by conven- tional methods such as chromatography.
If the synthesis yields compositions of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be intercon verted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
In the following, the intermediate compounds are further described. A skilled person will readily understand that the preferences for the substituents given herein in connection with compounds I apply for the intermediates accordingly. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein. A further embodiment of the present invention is compounds of formulae V (see above), wherein the variables Z, Y, R3, R5, R6,R7, o, n are as defined and preferably defined for formula I herein. In specific embodiments of compounds V according to the present invention, variables Z, Y, R3, R5, R6,R7, o, n are as defined in tables 1a-l to 1a-18, 1 a-ll to 18a-ll, 1a-lll to 9a-lll, 1a-IV to 9a-IV for compounds I, wherein the substituents are specific embodiments independently of each other or in any combination.
A further embodiment of the present invention is compounds of formula VI (see above), wherein variables Z, Y, R3, R5, R6,R7, o, n are as defined and preferably defined for formula I herein, and wherein G is an ester group or CH2OR. In specific embodiments of compounds VI according to the present invention, the variables Z, Y, R3, R5, R6,R7, o, n are as defined in tables 1 a-l to 1a- 18, 1 a-l I to 18a-l I, 1 a-l 11 to 9a-l 11 , 1 a-l V to 9a-IV for compounds I, wherein the substituents are specific embodiments independently of each other or in any combination. A further embodiment of the present invention is compounds of formula VII (see above), wherein the variables variables Z, Y, R3, R5, R6,R7, o, n are as defined and preferably defined for formula I herein and LG is a nucleophilically replaceable leaving group. In specific embodiments of compounds VII according to the present invention, the variables Z, Y, R3, R5, R5,R7, o, n are as defined in tables 1a-l to 1 a-18, 1a-ll to 18a-ll, 1 a-lll to 9a-lll, 1 a-IV to 9a-IV for compounds I, wherein the substituents are specific embodiments independently of each other or in any combination.
A further embodiment of the present invention is compounds of formula IX (see above), wherein the variables Z, Y, R3, R5, R6,R7, o, n are as defined and preferably defined for formula I herein and X stands for halogen, in particular CI or Br. According to one preferred embodiment, Hal in compounds VI stands for Br. In specific embodiments of compounds IX according to the present invention, the variables Z, Y, R3, R5, R6,R7, o, n are as defined in tables 1 a-l to 1 a-18, 1a-ll to 18a-ll, 1 a-lll to 9a-lll, 1a-IV to 9a-IV a for compounds I, wherein the substituents are specific embodiments independently of each other or in any combination.
A further embodiment of the present invention is compounds of formula X, wherein the variables Z, Y, R3, R5, R6,R7, o, n are as defined and preferably defined for formula I herein. In specific embodiments of compounds X according to the present invention, the variables Z, Y, R3, R5, R6,R7, o, n are as defined in tables in tables 1 a-l to 1a-18, 1a-ll to 18a-ll, 1a-lll to 9a-lll, 1 a-IV to 9a-IV for compounds I , wherein the substituents are specific embodiments independently of each other or in any combination.
In the compounds according to the invention I, particular preference is given to the following meanings of the substituents, in each case on their own or in combination.
A in the compounds according to the invention is, according to one embodiment, CH.
A in the compounds according to the invention is, according to one further embodiment, N.
According to one embodiment of the invention, R is O and Q is CH2.
According to one embodiment of the invention, R is CH2 and Q is O.
D in the compounds according to the invention is as defined in claim 1 .
According to a further embodiment of the invention, D is selected from H, halogen, SH or S-C1- Ce-alkyl.
According to one embodiment D is H. According to one further embodiment D is SH . According to one further embodiment D is S-CN.
According to one further embodiment D is halogen. In a special embodiment D is I. In a further special embodiment D is Br. In a further special embodiment D is CI.
According to one further embodiment D is S-Ci-C6-alkyl preferably S-methyl, S-ethyl, S-n-propyl, S-i-propyl, S-n-butyl, S-i-butyl or S-t-butyl. In a special embodiment D is S-methyl. In a further special embodiment D is S-ethyl. In a further special embodiment D is S-n-propyl. In a further special embodiment D is S-t-butyl.
According to one further embodiment D is S-Ci-C6-haloalkyl wherein Ci-C6-haloalkyl is preferably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. In a special embodiment D is S-CF3. In a further special embodiment D is S-CHF2. In a further special embodiment D is S-CFH2. In a further special embodiment D is S-CCI3. In a further special embodiment D is S-CHC . In a further special embodiment D is S-CCIH2. According to one another embodiment D is S-C2-C6-alkenyl, wherein C2-C6-alkenyl is preferably CH=CH2,
CH2CH=CH2, CH=CHCH3 or C(CH3)=CH2. According to one another embodiment D is S-C2-C6- haloalkenyl, preferably fully or partially halogenated CH=CH2, CH2CH=CH2, CH=CHCH3 or C(CH3)=CH2. According to one another embodiment D is S-C2-C6-alkynyl, wherein C2-C6-alkynyl is preferably CCH, CH2CCH, CH2CCCH3. In a special embodiment D is S-CCH. In a further special embodiment D is S-CCCH3. In a further special embodiment D is S-CCCH(CH3)2. In a further special embodiment D is S-CCC(CH3)3. According to a specific embodiment D is C2-C6- haloalkynyl, more preferably fully or partially halogenated C2-C4-alkynyl. In a special embodiment D is fully or partially halogenated C2-alkynyl.
R3 in the compounds according to the invention is, according to one embodiment, as defined in claim 1.
According to one embodiment n is 0. According to one further embodiment n is 1. According to one further embodiment n is 2. According to one further embodiment n is 3. According to one further embodiment n is 4.
R3 in the compounds according to the invention is, according to a further embodiment, halogen, CN, NO2, d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, S(0)p(Ci-C4-alkyl), wherein R3 is unsubsti- tuted or further substituted by one, two, three or four R3a; wherein R3a is independently selected from halogen, CN, NO2, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cs-cycloalkyl, C3-C8-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy; p is an integrer and is 0, 1 , 2.
According to one embodiment R3 is halogen. According to a specific embodiment R3 is CI. According to a further specific embodiment R3 is F. According to a further specific embodiment R3 is Br. According to one further embodiment R3 is CN. According to one further embodiment R3 is NO2. According to one further embodiment R3 is OH. According to one further embodiment R3 is SH.
According to one further embodiment R3 is Ci-C6-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. In a special embodiment R3 is methyl. In a further special embodiment R3 is ethyl. In a further special embodiment R3 is n-propyl. In a further special embodiment R3 is i- propyl. In a further special embodiment R3 is 1 -methylpropyl. In a further special embodiment R3 is n-butyl. In a further special embodiment R3 is i-butyl. In a further special embodiment R3 is t- butyl.
According to a one preferred embodiment R3 is Ci-C6-alkyl substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R3 is Ci-Cs-haloalkyl, more preferably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. In a special embodiment R3 is CF3. In a further special embodiment R3 is CHF2. In a further special embodiment R3 is CFH2. In a further special embodiment R3 is CCI3. In a further special embodiment R3 is CHCI2. In a further special embodiment R3 is CCIH2. According to a further specific embodiment R3 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 R3 is CH2OH. According to a further specific embodiment R3 is Ci-C6-alkyl, preferably d-Gralkyl substituted by CN, more preferably CH2CN, CH2CH2CN, CH2CH2CH2CN, CH(CH3)CH2CN, CH2CH(CH3)CN, CH2CH2CH2CH2CN. In a special embodiment R3 is CH2CH2CN. In a further special embodiment R3 is CH(CH3)CN. According to a further specific embodiment R3 is Ci-C4-alkoxy-Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl. In a special embodiment R3 is CH2OCH3. In a further special embodiment R3 is CH2CH2OCH3. In a further special embodiment R3 is CH(CH3)OCH3. In a further special embodiment R3 is CH(CH3)OCH2CH3. In a further special embodiment R3 is CH2CH2OCH2CH3. According to a further specific embodiment R3 is Ci-C4-haloalkoxy-C-i-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl. In a special embodiment R3 is CH2OCF3. In a further special embodiment R3 is CH2CH2OCF3. In a further special embodiment R3 is CH2OCCI3. In a further special embodiment R3 is CH2CH2OCCI3.
According to one another embodiment R3 is Ci-C6-alkoxy, preferably Ci-C4-alkoxy. In a special embodiment of the invention R3 is OCH3. In a further special embodiment of the invention R3 is OCH2CH3. In a further special embodiment of the invention R3 is OCH(CH3)2. In a further special embodiment of the invention R3 is OCH2CH2CH3. In a further special embodiment of the invention R3 is OC(CH3)3.
According to one another embodiment R3 is C2-C6-alkenyl, preferably CH=CH2, CH2CH=CH2, CH=CHCH3 or C(CH3)=CH2. In a special embodiment R3 is CH=CH2. In a further special embodiment R3 is CH2CI- CH2. In a further special embodiment R3 is CH2CH=CHCH3. In a further spe- cial embodiment R3 is CH=CHCH3 In a further special embodiment R3 is CH2C(CH3)=CH2. In a further special embodiment R3 is C(CH3)=CH2. In a further special embodiment R3 is
C(CH3)=C(CH3)H. In a further special embodiment R3 is C(CH3)=C(CH3)2. In a further special embodiment R3 is CH=C(CH3)2.
According to a further preferred embodiment R3 is C2-C6-alkenyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R3 is C2-C6-haloalkenyl, more preferably fully or partially halogenated C2-Cs-alkenyl. In a special embodiment R3 is fully or partially halogenated C2-alkenyl. In a further special embodiment R3 is CH CF2. In a further special embodiment R3 is C=CHF. In a further special embodiment R3 is CF=CF2. In a further special embodiment R3 is CF=CHF. In a further special embodiment R3 is CF=CH2. In a further special embodiment R3 is CH=CCl2. . In a further special embodiment R3 is C=CHCI. In a further special embodiment R3 is CCI=CCl2. In a further special embodiment R3 is CCI=CHCI. In a further special embodiment R3 is CCI=CH2. In a further special embodiment R3 is fully or partially halogenated C3-alkenyl. According to a further specific embodiment R3 is C2-C6-alkenyl, preferably C2-C4-alkenyl, substituted by OH, more preferably, CH=CHCH2OH, , CH=C(CH3)OH. In a further special embodiment R3 is CH=CHCH2OH. According to a further specific embodiment R3 is Ci-C4-alkoxy-C2-C6-alkenyl, more preferably Ci- C4-alkoxy-C2-C4-alkenyl. In a special embodiment R3 is CH=CHOCH3. In a further special embodiment R3 is CH CHCH2OCH3. According to a further specific embodiment R3 is CrC4-haloalkoxy- C2-C6-alkenyl, more preferably Ci-C4-haloalkoxy-C2-C4-alkenyl. In a special embodiment R3 is
CH=CHOCF3. In a further special embodiment R3 is CH=CHCH20CF3. In a further special embodiment R3 is CH=CHOCCI3. In a further special embodiment R3 is CH=CHCH2OCCI3. According to a further specific embodiment R3 is C3-Ce-cycloalkyl-C2-C6-alkenyl, preferably C3-C6-cycloalkyl-C2- C4-alkenyl. According to a further specific embodiment R3 is C3-C6-halocycloalkyl-C2-C4-alkenyl, preferably C3-C8-halocycloalkyl-C2-C6-alkenyl.
According to one another embodiment R3 is C2-C6-alkynyl, preferably CCH, CH2CCH, CH2CCCH3. In a special embodiment R3 is CCH. in a further special embodiment R3 is CCCH3. In a further special embodiment R3 is CH2CCH. In a further special embodiment R3 is CH2CCCH3. In a further special embodiment R3 is CH2CCH2CH3.
According to a further preferred embodiment R3 is C2-C6-alkynyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein. In a further special embodiment R3 is CC-CH3.
According to a specific embodiment R3 is C2-C6-haloalkynyl, more preferably fully or partially hal- ogenated C2-C6-alkynyl. In a special embodiment R3 is CC-CI. In a special embodiment R3 is CC- Br. In a special embodiment R3 is CC-l.ln a special embodiment R3 is fully or partially halogenated C2-alkynyl. In a further special embodiment R3 is fully or partially halogenated C3-alkynyl. According to a further specific embodiment R3 is C2-C6-alkynyl, preferably C2-C4-alkynyl, substituted by OH, more preferably, CCOHIn a special embodiment R3 is In a further special embodiment R3. According to a further specific embodiment R3 is Ci-C4-alkoxy-C2-C6-alkynyl, more preferably Ci- C4-alkoxy-C2-C4-alkynyl. In a special embodiment R3 is CCOCH3. In a further special embodiment R3 is CH2CCOCH3. According to a further specific embodiment R3 is Ci-C4-haloalkoxy-C2-C6- alkynyl, more preferably Ci-C4-haloalkoxy-C2-C4-alkynyl. In a special embodiment R3 is CCOCF3. In a further special embodiment R3 is CH2CCOCF3. In a further special embodiment R3 is
CCOCCI3. In a further special embodiment R3 is CH2CCOCCI3. According to a further specific embodiment R3 is C3-C8-cycloalkyl-C2-C6-alkynyl, preferably C3-C6-cycloalkyl-C2-C4-alkynyl. According to a further specific embodiment R3 is C3-C6-halocycloalkyl-C2-C4-alkynyl, preferably C3- C8-halocycloalkyl-C2-C6-alkynyl.
According to one another embodiment R3 is Cs-Cs-cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl. In a special embodiment R3 is cyclopropyl. In a further special embodiment R3 is cyclobutyl. In a further special embodiment R3 is cyclopentyl. In a further special embodiment R3 is cyclohexyl.
According to one another embodiment R3 is C3-C8-cycloalkoxy, preferably C3-C6-cycloalkoxy. According to a further preferred embodiment R3 is Cs-Ce-cycloalkyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R3 is C3-Cs-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl. In a special embodiment R3 is fully or partially halogenated cyclo- propyl. In a further special embodiment R3 is 1 -CI-cyclopropyl. In a further special embodiment R3 is 2-CI-cyclopropyl. In a further special embodiment R3 is 1-F-cyclopropyl. In a further special embodiment R3 is 2-F-cyclopropyl. In a further special embodiment R3 is fully or partially halogenated cyclobutyl. In a further special embodiment R3 is 1-CI-cyclobutyl. In a further special embodiment R3 is 1 -F-cyclobutyl. According to a specific embodiment R3 is Cs-Cs-cycloalkyl substituted by Ci- C4-alkyl, more preferably is C3-C6-cycloalkyl substituted by Ci-C4-alkyl. In a special embodiment R3 is 1 -CH3-cyclopropyl. According to a specific embodiment R3 is C3-Cs-cycloalkyl substituted by CN, more preferably is C3-C6-cycloalkyl substituted by CN. In a special embodiment R3 is 1 -CN- cyclopropyl .According to a further specific embodiment R3 is C3-C8-cycloalkyl-C3-C8-cycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-cycloalkyl. I n a special embodiment R3 is cyclopropyl- cyclopropyl. According to a further specific embodiment R3 is Cs-Cs-cycloalkyl-Cs-Cs- halocycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-halocycloalkyl.
According to one another embodiment R3 is C3-C8-cycloalkyl-Ci-C4-alkyl, preferably C3-C6- cycloalkyl-Ci-C4-alkyl. In a special embodiment R3 is CH(CH3)(cyclopropyl). In a special embodiment R3 is CH2-(cyclopropyl).
According to a further preferred embodiment R3 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 R3 is C3-C8-cycloalkyl-Ci-C4-haloalkyl, C3-C6-cycloalkyl-Ci- C4-haloalkyl. According to a specific embodiment R3 is C3-Ce-halocycloalkyl-Ci-C4-alkyl, C3-C6- halocycloalkyl-Ci-C4-alkyl. I n a special embodiment R3 is fully or partially halogenated cyclopro- pyl-Ci-C4-alkyl. In a further special embodiment R3 is 1-CI-cyclopropyl-Ci-C4-alkyl. In a further special embodiment R3 is 1 -F-cyclopropyl-Ci-C4-alkyl.
According to one another embodiment R3 is N H2.
According to one another embodiment R3 is NH(Ci-C4-alkyl). According to a specific embodiment R3 is NH(CH3). According to a specific embodiment R3 is NH(CH2CH3). According to a specific embodiment R3 is NH(CH2CH2CH3). According to a specific embodiment R3 is NH(CH(CH3)2). According to a specific embodiment R3 is NH(CH2CH2CH2CH3). According to a specific embodiment R3 is NH(C(CH3)3).
According to one another embodiment R3 is N(Ci-C4-alkyl)2. According to a specific embodiment R3 is N(CH3)2. According to a specific embodiment R3 is N(CH2CH3)2. According to a specific embodiment R3 is N(CH2CH2CH3)2. According to a specific embodiment R3 is N(CH(CH3)2)2. According to a specific embodiment R3 is N(CH2CH2CH2CH3)2. According to a specific embodiment R3 is NH(C(CH3)3)2.
According to one another embodiment R3 is NH(C3-C8-cycloalkyl) preferably NH(C3-C6-cycloalkyl). According to a specific embodiment R3 is NH (cyclopropyl). According to a specific embodiment R3 is NH(cyclobutyl). According to a specific embodiment R3 is NH(cyclopentyl). According to a specific embodiment R3 is NH(cyclohexyl).
According to one another embodiment R3 is N(C3-Ce-cycloalkyl)2 preferably N(C3-C6-cycloalkyl)2. According to a specific embodiment R3 is N(cyclopropyl)2. According to a specific embodiment R3 is N(cyclobutyl)2. According to a specific embodiment R3 is N(cyclopentyl)2. According to a specific embodiment R3 is N(cyclohexyl)2.
According to one another embodiment R3 is S(0)p(Ci-C4-alkyl) wherein p is 0, 1 , 2, preferably S(0) (Ci-C4-alkyl) wherein p is 2. According to a specific embodiment R3 is SO2CH3. According to a specific embodiment R3 is SO2CF3.
According to one another embodiment R3 is C(=0)(-Ci-C4-alkyl). According to a specific embodiment R3 is C(=0)CH3.. According to a further specific embodiment R3 is C(=0)CH2CH3. According to a further specific embodiment R3 is C(=0)CH2CH2CH3. According to a further specific embodiment R3 is C(=0)CH(CH3)2. According to a further specific embodiment R3 is C(=0)C(CH3)3.
According to one another embodiment R3 is C(=0)OH.
According to one another embodiment R3 is C(=0)(-0-Ci-C4-alkyl). According to a specific em- bodiment R3 is C(=0)OCH3, According to a further specific embodiment R3 is C(=0)OCH2CH3. According to a further specific embodiment R3 is C(=0)OCH2CH2CH3. According to a further specific embodiment R3 is C(=0)OCH(CH3)2. According to a further specific embodiment R3 is C(=0)OC(CH3)3.
According to one another embodiment R3 is C(=0)-NH(Ci-C4-alkyl). According to a specific em- bodiment R3 is C(=0)NHCH3.. According to a further specific embodiment R3 is C(=0)NHCH2CH3. According to a further specific embodiment R3 is C(=0)NHCH2CH2CH3. According to a further specific embodiment R3 is C(=0)NHCH(CH3)2. According to a further specific embodiment R3 is
Figure imgf000019_0001
According to one another embodiment R3 is C(=0)-N(Ci-C4-alkyl)2. According to a specific em- bodiment R3 is
Figure imgf000019_0002
According to a further specific embodiment R3 is
C(=0)N(CH2CH3)2. According to a further specific embodiment R3 is C(=0)N(CH2CH2CH3)2. According to a further specific embodiment R3 is C(=0)N(CH(CH3)2)2. According to a further specific embodiment R3 is C(=0)N(C(CH3)3)2.
According to one another embodiment R3 is C(=0)-NH(C3-C6-cycloalkyl). According to a specific embodiment R3 is C(=0)NH(cyclopropyl).. According to a further specific embodiment R3 is
C(=0)NH(cyclobutyl). According to a further specific embodiment R3 is C(=0)NH(cyclopentyl). According to a further specific embodiment R3 is C(=0)NH(cyclohexyl).
According to one another embodiment R3 is C(=0)-N(C3-C6-cycloalkyl)2. According to a specific embodiment R3 is C(=0)N(cyclopropyl)2. According to a further specific embodiment R3 is C(=0)N(cyclobutyl)2. According to a further specific embodiment R3 is C(=0)N(cyclopentyl)2. According to a further specific embodiment R3 is C(=0)N(cyclohexyl)2.
According to one specific embodiment thereof, said R2 is in the 2-positon of the phenyl ring. According to one specific embodiment thereof, said R3 is in the 3-positon of the phenyl ring. According to one further specific embodiment thereof, said R3 is in the 4-positon of the phenyl ring. According to one specific embodiment thereof, said R3 is in the 2, 3-positon of the phenyl ring. According to one specific embodiment thereof, said R3 is in the 2,4-positon of the phenyl ring. According to one specific embodiment thereof, said R3 is in the 2,5-positon of the phenyl ring. According to one specific embodiment thereof, said R3 is in the 2,6-positon of the phenyl ring. According to one specific embodiment thereof, said R3 is in the 3,4-positon of the phenyl ring. According to one specific embodiment thereof, said R3 is in the 3,5-positon of the phenyl ring. According to one specific embodiment thereof, said R3 is in the 3,6-positon of the phenyl ring. According to one specific embodiment thereof, said R3 is in the 2,4,6-positon of the phenyl ring.
Particularly preferred embodiments of (R3)n according to the invention are in Table P below, wherein each line of lines P1 to P180 corresponds to one particular embodiment of the invention, wherein P1 to P180 are also in any combination a preferred embodiment of the present invention. The positions of R3 are, of course, dependent on the attachment of a possible Z-Y- group.
Table P:
No. (R3)n No. (R3)n No. (R3)n
P-1 * P-39 2-F-4-CI P-77 4-OCH2CH3
P-2 2-CI P-40 3-F-4-CI P-78 2-OCF3
P-3 3-CI P-41 2-F-6-CI P-79 3-OCF3
P-4 4-CI P-42 2-CI-3-F P-80 4-OCF3
P-5 2-F P-43 2-CI-4-F P-81 2-OCHF2
P-6 3-F P-44 3-CI-4-F P-82 3-OCHF2
P-1 4-F P-45 2,3,4-CI3 P-83 4-OCHF2
P-8 2-CN P-46 2,4,5-Cls P-84 2,3-(CH3)2
P-9 3-CN P-47 3,4,5-CI3 P-85 2,4-(CH3)2
P-10 4-CN P-48 2,4,6-Cls P-86 3,4-(CH3)2
P-1 1 2-N02 P-49 2,3,4-F3 P-87 2,6-(CH3)2
P-12 3-NO2 P-50 2,4,5-Fs P-88 2,3-(CH2CH3)2
P-13 4-NO2 P-51 3,4,5-F3 P-89 2,4-(CH2CH3)2
P-14 2-SCHs P-52 2,4,6-Fs P-90 3,4-(CH2CH3)2
P-15 3-SCH3 P-53 2,3-4-F3 P-91 2,6-(CH2CH3)2
P-16 4-SCH3 P-54 2,4-F2-3-CI P-92 2,3-(CF3)2
P-17 2-SOCH3 P-55 2,6-F2-4-CI P-93 2,4-(CF3)2
P-18 3-SOCH3 P-56 2,5-F2-4-CI P-94 3,4-(CF3)2
P-19 4-SOCH3 P-57 2.4-CI2-3-F P-95 2,6-(CF3)2
P-20 2-SO2CH3 P-58 2,6-CI2-4-F P-96 2,3-(CHF2)2
P-21 3-SO2CH3 P-59 2,5-CI2-4-F P-97 2,4-(CHF2)2
P-22 4-SO2CH3 P-60 2-CH3 P-98 3,4-(CHF2)2
P-23 2-CO2CH3 P-61 3-CH3 P-99 2,6-(CHF2)2
P-24 3-CO2CH3 P-62 4-CH3 P-100 2,3-(OCH3)2
P-25 4-CO2CH3 P-63 2-CH2CH3 P-101 2,4-(OCH3)2
P-26 2,3-CI2 P-64 3-CH2CH3 P-102 3,4-(OCH3)2
P-27 2,4-Cb P-65 4-CH2CH3 P-103 2,6-(OCH3)2
P-28 2,5-CI2 P-66 2-CF3 P-104 2,3-(OCH2CH3)2
P-29 3,4-Cb P-67 3-CF3 P-105 2,4-(OCH2CH3)2
P-30 3,5-CI2 P-68 4-CF3 P-106 3,4-(OCH2CH3)2
P-31 2,6-Cb P-69 2-CHF2 P-107 2,6-(OCH2CH3)2
P-32 2,3-F2 P-70 3-CHF2 P-108 2,3-(OCF3)2
P-33 2,4-F2 P-71 4-CHF2 P-109 2,4-(OCF3)2
P-34 2,5-F2 P-72 2-OCHs P-110 3,4-(OCF3)2
P-35 3,4-F2 P-73 3-OCH3 P-11 1 2,6-(OCF3)2
P-36 3,5-F2 P-74 4-OCHs P-112 2,3-(OCHF2)2
P-37 2,6-F2 P-75 2-OCH2CH3 P-113 2,4-(OCHF2)2
P-38 2-F-3-CI P-76 3-OCH2CH3 P-114 3,4-(OCHF2)2 No. (R3)n No. (R3)n
P-115 2,6-(OCHF2)2 P-157 3-Br
P-116 2,3,4-(CH3)3 P-158 4-Br
P-117 2,4,5-(CH3)3 P-159 2,3-Br2
P-118 3,4,5-(CH3)3 P-160 2,4-Br2
P-119 2,4,6-(CH3)3 P-161 2,5-Br2
P-120 2,3,4-(CH2CH3)3 P-162 3,4-Br2
P-121 2,4,5-(CH2CH3)3 P-163 3,5-Br2
P-122 3,4,5-(CH2CH3)3 P-164 2,6-Br2
P-123 2,4,6-(CH2CH3)3 P-165 2,3,4-Br3
P-124 2,3,4-(CF3)3 P-166 2,4,5-Br3
P-125 2,4,5-(CF3)3 P-167 3,4,5-Br3
P-126 3,4,5-(CF3)3 P-168 2,4,6-Br3
P-127 2,4,6-(CF3)3 P-169 2-CF3-4-Br
P-128 2,3,4-(CHF2)3 P-170 4-CF3-2-Br
P-129 2,4,5-(CHF2)3 P-171 2-Br-4-CF3
P-130 3,4,5-(CHF2)3 P-172 4-Br-2-CF3
P-131 2,4,6-(CHF2)3 P-173 2-CN-4-Br
P-132 2,3,4-(OCH3)3 P-174 4-CN-2-Br
P-133 2,4,5-(OCH3)3 P-175 2-Br-4-CN
P-134 3,4,5-(OCH3)3 P-176 4-BI--2-CN
P-135 2,4,6-(OCH3)3 P-177 2-CF3-4-CN
P-136 2,3,4-(OCH2CH3)3 P-178 2-CN-4-CF3
P-137 2,4,5-(OCH2CH3)3 P-179 2-OCH3-4-CF3
P-138 3,4,5-(OCH2CH3)3 P-180 4-OCH3-2-CF3
P-139 2,4,6-(OCH2CH3)3
P-140 2,3,4-(OCF3)3
P-141 2,4,5-(OCF3)3
P-142 3,4,5-(OCF3)3
P-143 2,4,6-(OCF3)3
P-144 2,3,4-(OCHF2)3
P-145 2,4,5-(OCHF2)3
P-146 3,4,5-(OCHF2)3
P-147 2,4,6-(OCHF2)3
P-148 2-CF3-4-CI
P-149 2-CF3-4-F
P-150 2-CI-4-CF3
P-151 2-F-4-CF3
P-152 2-CN-4-CI
P-153 2-CN-4-F
P-154 2-CI-4-CN
P-155 2-F-4-CN
P-156 2-Br * means that n=0
Particularly preferred embodiments of (R3)n if x is 1 and Z-Y is attached in meta-(3)-position, are in Table P6a below, wherein each line of lines P6a-1 to P6a-187 corresponds to one particular embodiment of the invention, wherein P6a-1 to P6a-187 are also in any combination a preferred embodiment of the present invention.
Figure imgf000022_0001
No. (R3)n No. (R3)n No. (R3)n
P6a-108 2,4-(CHF2)2 P6a-135 4,5-(OCHF2)2 P6a-162 2-Br
P6a-109 2,5-(CHF2)2 P6a-136 4,6-(OCHF2)2 P6a-163 4-Br
P6a-110 2,6-(CHF2)2 P6a-137 5,6-(OCHF2)2 P6a-164 5-Br
P6a-11 1 4,5-(CHF2)2 P6a-138 2,4,5-(CH3)3 P6a-165 6-Br
P6a-112 4,6-(CHF2)2 P6a-139 2,4,6-(CH3)3 P6a-166 2,6-Br2
P6a-113 5,6-(CHF2)2 P6a-140 2,4,5-(CH2CH3)3 P6a-167 2,4-Br2
P6a-114 2,4-(OCH3)2 P6a-141 2,4,6-(CH2CH3)3 P6a-168 2,5-Br2
P6a-115 2,5-(OCH3)2 P6a-142 2,4,5-(CF3)3 P6a-169 4,5-Br2
P6a-116 2,6-(OCH3)2 P6a-143 2,4,6-(CF3)3 P6a-170 4,6-Br2
P6a-117 4,5-(OCH3)2 P6a-144 2,4,5-(CHF2)3 P6a-171 5,6-Br2
P6a-118 4,6-(OCH3)2 P6a-145 2,4,6-(CHF2)3 P6a-172 2,3,4-Br3
P6a-119 5,6-(OCH3)2 P6a-146 2,4,5-(OCH3)3 P6a-173 2,4,5-Br3
P6a-120 2,4-(OCH2CH3)2 P6a-147 2,4,6-(OCH3)3 P6a-174 3,4,5-Br3
P6a-121 2,5-(OCH2CH3)2 P6a-148 2,4,5-(OCH2CH3)3 P6a-175 2,4,6-Br3
P6a-122 2,6-(OCH2CH3)2 P6a-149 2,4,6-(OCH2CH3)3 P6a-176 2-CF3-4-Br
P6a-123 4,5-(OCH2CH3)2 P6a-150 2,4,5-(OCF3)3 P6a-177 4-CF3-2-Br
P6a-124 4,6-(OCH2CH3)2 P6a-151 2,4,6-(OCF3)3 P6a-178 2-B1--4-CF3
P6a-125 5,6-(OCH2CH3)2 P6a-152 2,4,5-(OCHF2)3 P6a-179 4-Br-2-CF3
P6a-126 2,4-(OCF3)2 P6a-153 2,4,6-(OCHF2)3 P6a-180 2-CN-4-Br
P6a-127 2,5-(OCF3)2 P6a-154 2-CF3-4-CI P6a-181 4-CN-2-Br
P6a-128 2,6-(OCF3)2 P6a-155 2-CF3-4-F P6a-182 2-Br-4-CN
P6a-129 4,5-(OCF3)2 P6a-156 2-CI-4-CF3 P6a-183 4-BI--2-CN
P6a-130 4,6-(OCF3)2 P6a-157 2-F-4-CF3 P6a-184 2-CF3-4-CN
P6a-131 5,6-(OCF3)2 P6a-158 2-CN-4-CI P6a-185 2-CN-4-CF3
P6a-132 2,4-(OCHF2)2 P6a-159 2-CN-4-F P6a-186 2-OCH3-4-CF3
P6a-133 2,5-(OCHF2)2 P6a-160 2-CI-4-CN P6a-187 4-OCH3-2-CF3
P6a-134 2,6-(OCHF2)2 P6a-161 2-F-4-CN
Particularly preferred embodiments of (R3)n if x is 1 and Z-Y is attached in para-(4)-position, are in Table P6b below, wherein each line of lines P6b-1 to P6b-65 corresponds to one particular embodiment of the invention, wherein P6b-1 to P6b-65 are also in any combination a preferred embodiment of the present invention.
Table P6b:
No. (R3)n No. (R3)n No. (R3)n
P6b-1 2-CI P6b-9 2-SCH3 P6b-17 2,3-CI2
P6b-2 3-CI P6b-10 3-SCH3 P6b-18 2,5-CI2
P6b-3 2-F P6b-1 1 2-SOCH3 P6b-19 3,5-CI2
P6b-4 3-F P6b-12 3-SOCH3 P6b-20 2,6-CI2
P6b-5 2-CN P6b-13 2-S02CH3 P6b-21 2,3-F2
P6b-6 3-CN P6b-14 3-S02CH3 P6b-22 2,5-F2
P6b-7 2-N02 P6b-15 2-C02CH3 P6b-23 3,5-F2
P6b-8 3-N02 P6b-16 3-C02CH3 P6b-24 2,6-F2
Figure imgf000024_0001
One specific embodiment relates to the inventive compounds wherein x is 1 and n is 0.
Y in the compounds according to the invention is, according to one embodiment, as defined in claim 1.
Y in the compounds according to the invention is, according to a further embodiment, a direct bond or a divalent group selected from the group consisting of -0-, -S-, SO-, -SO2-.
According to a specific embodiment Y is a direct bond. According to a further specific embodiment Y is -0-. According to a further specific embodiment Y is -S-. According to a further specific embodiment Y is -SO-. According to a further specific embodiment Y is -SO2-. According to a further specific embodiment Y is -NH-. According to a further specific embodiment Y is -N(Ci- C4-alkyl)-, wherein Ci-C4-alkyl is preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t- butyl.
According to a further specific embodiment Y is -CH2-. According to a further specific embodiment Y is -CH2CH2-. According to a further specific embodiment Y is -CH=CH-.
According to a further specific embodiment Y is -C≡C-.
Z in the compounds according to the invention is, according to one embodiment, as defined in claim 1.
Z in the compounds according to the invention is, according to a further embodiment, is phenyl or a five- or six-membered heteroaryl selected from the group consisting of pyrimidin- 2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazin-2-yl, pyridazin-3-yl, 1 ,3,5- triazin-2-yl and 1 ,2,4-triazin-3-yl; and wherein the phenyl is unsubstituted carries one, two, three or four independently selected radicals R4 , and wherein the heteroaryl is unsubstitutedcarries one, two or three radicals R4, wherein R4 is as defined or preferably defined below.
According to one specific embodiment Z is phenyl which carries one, two, three or four independently selected radicals R4 as defined or preferably defined below. According to one specific embodiment Z is pyrimidin-2-yl which carries one, two, three or four independently selected radicals R4 as defined or preferably defined below. According to one specific embodiment Z is pyri- din-3-yl, which carries one, two, three or four independently selected radicals R4 as defined or preferably defined below. According to one specific embodiment Z is pyridin-4-yl, which carries one, two, three or four independently selected radicals R4 as defined or preferably defined below. According to one specific embodiment Z is thiazol-2-yl, which carries one, two, three or four independently selected radicals R4 as defined or preferably defined below.
According to one embodiment x is 0. According to one further embodiment x is 1. According to one further embodiment x is 2. According to one further embodiment x is 3. According to one further embodiment x is 4.
According to one embodiment if R is O and Q is CH2 x is not 0.
R4 in the compounds according to the invention is, according to one embodiment, as defined in claim 1. R4 in the compounds according to the invention is, according to a further embodiment, halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, wherein R4 is substituted by one, two, three or four R4a; wherein R4a is independently selected from halogen, CN, NO2, OH, C1-C4- alkyl, Ci-C4-haloalkyl, Ca-Ce-cycloalkyl, Ca-Ce-halocycloalkyl, Ci-C4-alkoxy and C1-C4- haloalkoxy; wherein m is 1 , 2 or 3.
According to one embodiment m is 0. According to one embodiment m is 1 . According to one further embodiment m is 2. According to one further embodiment m is 3. According to one further embodiment m is 4.
According to one specific embodiment thereof, said R4 is in the 2-positon of the phenyl ring.
According to one specific embodiment thereof, said R4 is in the 3-positon of the phenyl ring.
According to one further specific embodiment thereof, said R4 is in the 4-positon of the phenyl ring. According to one specific embodiment thereof, said R4 is in the 2, 3-positon of the phenyl ring. According to one specific embodiment thereof, said R4 is in the 2,4-positon of the phenyl ring. According to one specific embodiment thereof, said R4 is in the 2,5-positon of the phenyl ring. According to one specific embodiment thereof, said R4 is in the 2,6-positon of the phenyl ring. According to one specific embodiment thereof, said R4 is in the 3,4-positon of the phenyl ring. According to one specific embodiment thereof, said R4 is in the 3,5-positon of the phenyl ring. According to one specific embodiment thereof, said R4 is in the 3,6-positon of the phenyl ring. According to one specific embodiment thereof, said R4 is in the 2,4,6-positon of the phenyl ring.
According to one embodiment R4 is halogen. According to a specific embodiment R4 is CI. According to a further specific embodiment R4 is F. According to a further specific embodiment R4 is Br. According to a further specific embodiment R4 is CN. According to a further specific embodiment R4 is NO2. According to a further specific embodiment R4 is OH. According to a further specific embodiment R4 is SH.
According to one further embodiment R4 is Ci-C6-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. In a special embodiment R4 is methyl. In a further special embodiment R4 is ethyl. In a further special embodiment R4 is n-propyl. In a further special embodiment R4 is i- propyl. In a further special embodiment R4 is 1 -methylpropyl. In a further special embodiment R4 is n-butyl. In a further special embodiment R4 is i-butyl. In a further special embodiment R4 is t- butyl.
According to a one preferred embodiment R4 is Ci-C6-alkyl substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R4 is Ci-C6-haloalkyl, more preferably fully or partially halo- genated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. In a special embodiment R4 is CF3. In a further special embodiment R4 is CHF2. In a further special embodiment R4 is CFH2. In a further special embodiment R4 is CCI3. In a further special embodiment R4 is CHCI2. In a further special embodiment R4 is CCIH2. 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, CH2CH2CH2CH2CN. 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 CH2OCH3. 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 CH2CH2OCH2CH3. 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 CH2OCF3. In a further special embodiment R4 is CH2CH2OCF3. In a further special embodiment R4 is CH2OCCI3. In a further special embodiment R4 is CH2CH2OCCI3.
According to one another embodiment R4 is Ci-C6-alkoxy, preferably Ci-C4-alkoxy. In a special embodiment of the invention R4 is OCH3. In a further special embodiment of the invention R4 is OChbCH .ln a further special embodiment of the invention R4 is OCH(CH3)2. In a further special embodiment of the invention R4 is OCH2CH2CH3. In a further special embodiment of the invention R4 is OC(CH3)3.
According to one another embodiment R4 is Ci-C6-haloalkoxy, preferably Ci-C4-haloalkoxy. In a special embodiment of the invention R4 is OCF3. In a further special embodiment of the invention
According to one another embodiment R4 is C2-C6-alkenyl, preferably CH=CH2, CH2CH=CH2, CH=CHCH3 or C(CH3)=CH2. In a special embodiment R4 is CH=CH2. In a further special embodiment R4 is CH2CH=CH2. In a further special embodiment R4 is CH2CH=CHCH3. In a further special embodiment R4 is CH=CHCH3 In a further special embodiment R4 is CH2C(CH3)=CH2. In a further special embodiment R4 is C(CH3)=CH2. In a further special embodiment R4 is
C(CH3)=C(CH3)H. In a further special embodiment R4 is C(CH3)=C(CH3)2. In a further special em- bodiment R4 is CH=C(CH3)2.
According to a further preferred embodiment R4 is C2-C6-alkenyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R4 is C2-C6-haloalkenyl, more preferably fully or partially hal- ogenated C2-C6-alkenyl. In a special embodiment R4 is fully or partially halogenated C2-alkenyl. In a further special embodiment R4 is fully or partially halogenated C3-alkenyl. 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 specif- ic 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=CHCH2OCH3. According to a further specific embodiment R4 is Ci-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-C6-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 one another embodiment R4 is C2-C6-alkynyl, preferably CCH, CH2CCH, CH2CCCH3. In a special embodiment R4 is CCH. in a further special embodiment R4 is CCCH3. In a further special embodiment R4 is CH2CCH. In a further special embodiment R4 is CH2CCCH3. In a further special embodiment R4 is CH2CCH2CH3.
According to a further preferred embodiment R4 is C2-C6-alkynyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R4 is C2-C6-haloalkynyl, more preferably fully or partially hal- ogenated C2-C6-alkynyl. In a special embodiment R4 is fully or partially halogenated C2-alkynyl. In a further special embodiment R4 is fully or partially halogenated C3-alkynyl. 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 C1-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 em- bodiment 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-Ce-cycloalkoxy, preferably C3-C6-cycloalkoxy. In a special embodiment R4 is O-cyclopropyl.
According to a further preferred embodiment R4 is Cs-Ce-cycloalkyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R4 is C3-Cs-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl. In a special embodiment R4 is fully or partially halogenated cyclo- propyl. 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-(CI)2-cyclobutyl. In a further special embodiment R4 is 3,3-(F)2-cyclobutyl.According to a specific embodiment R4 is Cs-Ce-cycloalkyl substituted by Ci-C4-alkyl, more preferably is C3-C6-cycloalkyl substituted by Ci-C4-alkyl. In a spe- cial embodiment R4 is 1 -CH3-cyclopropyl. According to a specific embodiment R4 is C3-C8- 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-Ce-cycloalkyl-C3-C8-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 In a 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-Cs-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(CH2CH2CH3)2. According to a specific embodiment R4 is N(CH(CH3)2)2. Accord- ing to a specific embodiment R4 is N(CH2CH2CH2CI-l3)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 spe- cific 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 one another embodiment R4 is S(0)p(Ci-C4-alkyl) wherein p is 0, 1 , 2, preferably S(0) (Ci-C4-alkyl) wherein p is 2. According to a specific embodiment R4 is SO2CH3. According to a specific embodiment R4 is SO2CF3.
According to one another embodiment R4 is C(=0)(-Ci-C4-alkyl). According to a specific embodi- ment 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 em- bodiment 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 specific 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 em- bodiment 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 em- bodiment 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. According to a further specific embodiment R4 is
Figure imgf000030_0001
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). According 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.
The above mentioned list of particularly preferred embodiments of R4 is independent for each m = 1 , m = 2, m = 3, m = 4 and m= 5 and is independent within m = 2, m = 3, m = 4 and m= 5.
Particularly preferred embodiments of R4 m according to the invention are in Table X below, where- in each line of lines X1 -1 to X1 -145 corresponds to one particular embodiment of the invention, wherein X1-1 to X1-145 are also in any combination a preferred embodiment of the present invention Table X
No. R4m No. R4m No. R4m
X-1 2-CI X-40 2,4,5-F3 X-79 2,4-(CH2CH3)2
X-2 3-CI X-41 3,4,5-Fs X-80 3,4-(CH2CH3)2
X-3 4-CI X-42 2,4,6-F3 X-81 2,6-(CH2CH3)2
X-4 2-F X-43 2,3-4-F3 X-82 2,3-(CF3)2
X-5 3-F X-44 2,4-F2-3-CI X-83 2,4-(CF3)2
X-6 4-F X-45 2,6-F2-4-CI X-84 3,4-(CF3)2
X-7 2-CN X-46 2,5-F2-4-CI X-85 2,6-(CF3)2
X-8 3-CN X-47 2,4-CI2-3-F X-86 2,3-(CHF2)2
X-9 4-CN X-48 2,6-CI2-4-F X-87 2,4-(CHF2)2
X-10 2-N02 X-49 2,5-CI2-4-F X-88 3,4-(CHF2)2
X-1 1 3-NO2 X-50 2-CH3 X-89 2,6-(CHF2)2
X-12 4-NO2 X-51 3-CH3 X-90 2,3-(OCH3)2
X-13 2-CO2CH3 X-52 4-CH3 X-91 2,4-(OCH3)2
X-14 3-CO2CH3 X-53 2-CH2CH3 X-92 3,4-(OCH3)2
X-15 4-CO2CH3 X-54 3-CH2CH3 X-93 2,6-(OCH3)2
X-16 2,3-Cb X-55 4-CH2CH3 X-94 2,3-(OCH2CH3)2
X-17 2,4-CI2 X-56 2-CF3 X-95 2,4-(OCH2CH3)2
X-18 2,5-CI2 X-57 3-CF3 X-96 3,4-(OCH2CH3)2
X-19 3,4-CI2 X-58 4-CF3 X-97 2,6-(OCH2CH3)2
X-20 3,5-CI2 X-59 2-CHF2 X-98 2,3-(OCF3)2
X-21 2,6-CI2 X-60 3-CHF2 X-99 2,4-(OCF3)2
X-22 2,3-F2 X-61 4-CHF2 X-100 3,4-(OCF3)2
X-23 2,4-F2 X-62 2-OCH3 X-101 2,6-(OCF3)2
X-24 2,5-F2 X-63 3-OCH3 X-102 2,3-(OCHF2)2
X-25 3,4-F2 X-64 4-OCH3 X-103 2,4-(OCHF2)2
X-26 3,5-F2 X-65 2-OCH2CH3 X-104 3,4-(OCHF2)2
X-27 2,6-F2 X-66 3-OCH2CH3 X-105 2,6-(OCHF2)2
X-28 2-F-3-CI X-67 4-OCH2CH3 X-106 2,3,4-(CH3)3
X-29 2-F-4-CI X-68 2-OCF3 X-107 2,4,5-(CH3)3
X-30 3-F-4-CI X-69 3-OCF3 X-108 3,4,5-(CH3)3
X-31 2-F-6-CI X-70 4-OCF3 X-109 2,4,6-(CH3)3
X-32 2-CI-3-F X-71 2-OCHF2 X-1 10 2,3,4-(CH2CH3)3
X-33 2-CI-4-F X-72 3-OCHF2 X-1 1 1 2,4,5-(CH2CH3)3
X-34 3-CI-4-F X-73 4-OCHF2 X-1 12 3,4,5-(CH2CH3)3
X-35 2,3,4-Cb X-74 2,3-(CH3)2 X-1 13 2,4,6-(CH2CH3)3
X-36 2,4,5-CI3 X-75 2,4-(CH3)2 X-1 14 2,3,4-(CF3)3
X-37 3,4,5-Cb X-76 3,4-(CH3)2 X-1 15 2,4,5-(CF3)3
X-38 2,4,6-CI3 X-71 2,6-(CH3)2 X-1 16 3,4,5-(CF3)3
X-39 2,3,4-Fs X-78 2,3-(CH2CH3)2 X-1 17 2,4,6-(CF3)3 No. R4m No. R4m No. R4m
X-1 18 2,3,4-(CHF2)3 (OCH2CH3)3 X-136 3,4,5-(OCHF2)3
X-1 19 2,4,5-(CHF2)3 X-128 3,4,5- X-137 2,4,6-(OCHF2)3
X-120 3,4,5-(CHF2)3 (OCH2CH3)3 X-138 2-CF3-4-CI
X-121 2,4,6-(CHF2)3 X-129 2,4,6- X-139 2-CF3-4-F
X-122 2,3,4-(OCH3)3 (OCH2CH3)3 X-140 2-CI-4-CF3
X-123 2,4,5-(OCH3)3 X-130 2,3,4-(OCF3)3 X-141 2-F-4-CF3
X-124 3,4,5-(OCH3)3 X-131 2,4,5-(OCF3)3 X-142 2-CN-4-CI
X-125 2,4,6-(OCH3)3 X-132 3,4,5-(OCF3)3 X-143 2-CN-4-F
X-126 2,3,4- X-133 2,4,6-(OCF3)3 X-144 2-CI-4-CN
(OCH2CH3)3 X-134 2,3,4-(OCHF2)3 X-145 2-F-4-CN
X-127 2,4,5- X-135 2,4,5-(OCHF2)3
Particularly preferred embodiments of Z-R4 m according to the invention are in Table Y below, wherein each line of lines Y-1 to Y-145 corresponds to one particular embodiment of the invention, wherein Y-1 to Y-145 are also in any combination a preferred embodiment of the present invention
Table Y
No. Z-R4m No. Z-R4m
Y-1 2-CI-C6H4 Y-25 3,4-F2-C6H3
Y-2 3-CI-CsH4 Y-26 3,5-F2-CeH3
Y-3 4-CI-C6H4 Y-27 2,6-F2-C6H3
Y-4 2-F-C6H4 Y-28 2-F-3-CI-C6H3
Y-5 3-F-C6H4 Y-29 2-F-4-CI-C6H3
Y-6 4-F-C6H4 Y-30 3-F-4-CI-C6H3
Y-7 2-CN-C6H4 Y-31 2-F-6-CI-C6H3
Y-8 3-CN-C6H4 Y-32 2-CI-3-F-C6H3
Y-9 4-CN-C6H4 Y-33 2-CI-4-F-C6H3
Y-10 2-N02-C6H4 Y-34 3-CI-4-F-C6H3
Y- 1 3-N02-C6H4 Y-35 2,3,4-CI3-C6H2
Y-12 4-N02-C6H Y-36 2,4,5-CI3-C6H2
Y-13 2-C02CH3-C6H4 Y-37 3,4,5-CI3-C6H2
Y-14 3-C02CH3-C6H4 Y-38 2,4,6-CI3-C6H2
Y-15 4-C02CH3-C6H4 Y-39 2,3,4-F3-C6H2
Y-16 2,3-CI2-C6H3 Y-40 2,4,5-F3-C6H2
Y-17 2,4-CI2-C6H3 Y-41 3,4,5-F3-C6H2
Y-18 2,5-CI2-C6H3 Y-42 2,4,6-F3-C6H2
Y-19 3,4-CI2-C6H3 Y-43 2,3-4-F3-C6H2
Y-20 3,5-CI2-C6H3 Y-44 2,4-F2-3-CI-C6H2
Y-21 2,6-CI2-C6H3 Y-45 2,6-F2-4-CI-C6H2
Y-22 2,3-F2-CsH3 Y-46 2,5-F2-4-CI-C6H2
Y-23 2,4-F2-C6H3 Y-47 2,4-CI2-3-F-C6H2
Y-24 2,5-F2-CsH3 Y-48 2,6-CI2-4-F-C6H2 . Z-R4m No. Z-R4m
Y-49 2,5-CI2-4-F-C3H2 Y-90 2,3-(OCH3)2
Y-50 2-CH3-C6H4 Y-91 2,4-(OCH3)2-C6H3
Y-51 3-CH3-C6H4 Y-92 3,4-(OCH3)2-C6H3
Y-52 4-CH3-C6H4 Y-93 2,6-(OCH3)2-C6H3
Y-53 2-CH2CH3-C6H4 Y-94 2,3-(OCH2CH3)2-C6H3
Y-54 3-CH2CH3-C6H4 Y-95 2,4-(OCH2CH3)2-C6H3
Y-55 4-CH2CH3-C6H4 Y-96 3,4-(OCH2CH3)2-C6H3
Y-56 2-CF3-C6H4 Y-97 2,6-(OCH2CH3)2-C6H3
Y-57 3-CF3-C6H4 Y-98 2,3-(OCF3)2-C6H3
Y-58 4-CF3-C6H4 Y-99 2,4-(OCF3)2-C6H3
Y-59 2-CHF2-CeH4 Y-100 3,4-(OCF3)2-C6H3
Y-60 3-CH F2-C6H4 Y-101 2,6-(OCF3)2
Y-61 4-CHF2-C6H4 Y-102 2,3-(OCHF2)2-C6H3
Y-62 2-OCH3-C6H4 Y-103 2,4-(OCHF2)2
Y-63 3-OCH3-C6H4 Y-104 3,4-(OCHF2)2-C6H3
Y-64 4-OCH3-C6H4 Y-105 2,6-(OCHF2)2-C6H3
Y-65 2-OCH2CH3-C6H4 Y-106 2,3,4-(CH3)3-C6H2
Y-66 3-OCH2CH3-C6H4 Y-107 2,4,5-(CH3)3-C6H2
Y-67 4-OCH2CH3-C6H4 Y-108 3,4,5-(CH3)3-C6H2
Y-68 2-OCF3-C6H4 Y-109 2,4,6-(CH3)3-C6H2
Y-69 3-OCF3-C6H4 Y-1 10 2,3,4-(CH2CH3)3-C6H2
Y-70 4-OCF3-C6H4 Y-1 1 1 2,4,5-(CH2CH3)3-C6H2
Y-71 2-OCHF2-C6H4 Y-1 12 3,4,5-(CH2CH3)3-C6H2
Y-72 3-OCHF2-C6H4 Y-1 13 2,4,6-(CH2CH3)3-C6H2
Y-73 4-OCHF2-C6H4 Y-1 14 2,3,4-(CF3)3-C6H2
Y-74 2,3-(CH3)2-C6H3 Y-1 15 2,4,5-(CF3)3-C6H2
Y-75 2,4-(CH3)2-C6H3 Y-1 16 3,4,5-(CF3)3-C6H2
Y-76 3,4-(CH3)2-C6H3 Y-1 17 2,4,6-(CF3)3-C6H2
Y-77 2,6-(CH3)2-C6H3 Y-1 18 2,3,4-(CHF2)3-C3H2
Y-78 2,3-(CH2CH3)2-C6H3 Y-1 19 2,4,5-(CHF2)3-C6H2
Y-79 2,4-(CH2CH3)2-C6H3 Y-120 3,4,5-(CHF2)3-C3H2
Y-80 3,4-(CH2CH3)2-C6H3 Y-121 2,4,6-(CHF2)3-C6H2
Y-81 2,6-(CH2CH3)2-C6H3 Y-122 2,3,4-(OCH3)3-C6H2
Y-82 2,3-(CF3)2-C6H3 Y-123 2,4,5-(OCH3)3
Y-83 2,4-(CF3)2-C3H3 Y-124 3,4,5-(OCH3)3-C6H2
Y-84 3,4-(CF3)2-CsH3 Y-125 2,4,6-(OCH3)3-C6H2
Y-85 2,6-(CF3)2-C3H3 Y-126 2,3,4-(OCH2CH3)3-C6H2
Y-86 2,3-(CHF2)2-C6H3 Y-127 2,4,5-(OCH2CH3)3-C6H2
Y-87 2,4-(CHF2)2-C6H3 Y-128 3,4,5-(OCH2CH3)3-C6H2
Y-88 3,4-(CHF2)2 Y-129 2,4,6-(OCH2CH3)3-C6H2
Y-89 2,6-(CHF2)2-C6H3 Y-130 2,3,4-(OCF3)3-C6H2 o. Z-R4 m No. Z-R4 m
Y-131 2,4,5-(OCF3)3 Y-139 2-CF3-4-F-C6H3
Y-132 3,4,5-(OCF3)3-C6H2 Y-140 2-CI-4-CF3-C6H3-C6H2
Y-133 2,4,6-(OCF3)3-C6H2 Y-141 2-F-4-CF3-C6H3
Y-134 2,3,4-(OCHF2)3-C6H2 Y-142 2-CN-4-CI-C6H3-C6H2
Y-135 2,4,5-(OCHF2)3 Y-143 2-CN-4-F-C6H3-C6H2
Y-136 3,4,5-(OCHF2)3-C6H2 Y-144 2-CI-4-CN-C6H3-C6H2
Y-137 2,4,6-(OCHF2)3-C6H2 Y-145 2-F-4-CN-C6H3-C6H2
Y-138 2-CF3-4-CI-C6H3-C6H2
Particularly preferred embodiments of Z-R4 m according to the invention are in Table Z below, wherein each line of lines Z-1 to Z-103 corresponds to one particular embodiment of the invention, wherein Z-1 to Z-103 are also in any combination a preferred embodiment of the present invention
Table Z
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
R5 and R6 in the compounds according to the invention are independently of another, according to one embodiment, as defined in claim 1.
R5 and R6 in the compounds according to the invention are independently of another, according to a further embodiment, H.
According to one embodiment R5 and R6 in the compounds according to the invention are independently of another halogen. According to a specific embodiment R5 and R5 are independently CI. According to a further specific embodiment R5 and R6 are independently F. According to a further specific embodiment R5 and R6 are independently Br. According to a further specific embodiment R5 and R6 are independently CN. According to a further specific embodiment R5 and R6 are independently NO2. According to a further specific embodiment R5 and R6 are independently OH. According to a further specific embodiment R5 and R6 are independently SH. In a further special embodiment R5 is H and Rs is CI. In a further special embodiment R5 is H and R6 is Br. In a further special embodiment R5 is H and R6 is F.
According to a further embodiment, in particular in any one of formulae I .A to I.H, 11.A to II. H, III.A to III.R and IV.A to IV.R, R5 and R6 are both F.
According to still a further embodiment, in particular in any one of formulae I .A to I.H, II.A to II. H, III.A to III.R and IV.A to IV.R, R5 and R5 are both CI.
According to still a further embodiment, in particular in any one of formulae I .A to I.H, II.A to II. H, III.A to III.R and IV.A to IV.R, R5 and R5 are both Br.
According to a further embodiment of the invention, R5 and R6 are independently selected from Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ca-Ce-cycloalkyl, wherein the R1 are in each case un- substituted or are substituted by Ra and/or Rb as defined and preferably herein.
According to a further embodiment of the invention, R5 and R6 are independently selected from Ci-C3-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-Cs-cycloalkyl, wherein the R5 and R6 are inde- pendently in each case unsubstituted or are substituted by Ra and/or Rb as defined and preferably herein.
According to one embodiment R5 and R6 are independently Ci-C6-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. In a special embodiment R5 and R6 are independently methyl. In a further special embodiment R5 and R6 are independently ethyl. In a further special embodiment R5 and R6 are independently n-propyl. In a further special embodiment R5 and R6 are independently i-propyl. In a further special embodiment R5 and R6 are independently 1- methylpropyl. In a further special embodiment R5 and R6 are independently n-butyl. In a further special embodiment R5 and R6 are independently i-butyl. In a further special embodiment R5 and R6 are independently t-butyl. In a further special embodiment R5 is H and R6 is CH3. In a further special embodiment R5 is H and R6 is CH2CH3. In a further special embodiment R5 is H and R6 is CH2CH2CH3. In a further special embodiment R5 is H and R6 is CH(CH3)2. In a further special embodiment R5 is CH3 and R6 is CH3. In a further special embodiment R5 is CH2CH3 and R6 is CH2CH3.
According to a one preferred embodiment R5 and R6 are independently Ci-C6-alkyl substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R5 and R6 are independently Ci-C6-haloalkyl, more preferably fully or partially halogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. In a special embodiment R5 and R6 are independently CF3. In a further special embodiment R5 and R6 are independently CHF2. In a further special embodiment R5 and R6 are independently CFH2. In a further special embodiment R5 and R6 are independently CCI3. In a further special embodiment R5 and R6 are independently CHCI2. In a further special embodiment R5 and R6 are independently CCIH2. According to a further specific embodiment R5 and R6 are independently Ci-C6-alkyl, pref- erably Ci-C4-alkyl substituted by OH, more preferably CH2OH, CH2CH2OH, CH2CH2CH2OH, CH(CH3)CH2OH, CH2CH(CH3)OH, CH2CH2CH2CH2OH. In a special embodiment R5 and R6 are independently CH2OH. In a further special embodiment R5 and R6 are independently CH2CH2OH. According to a further specific embodiment R5 and R6 are independently Ci-C6-alkyl, preferably Ci-C4-alkyl substituted by CN, more preferably CH2CN, CH2CH2CN, CH2CH2CH2CN, CH(CH3)CH2CN, CH2CH(CH3)CN, CH2CH2CH2CH2CN. In a special embodiment R5 and R6 are independently CH2CH2CN. In a further special embodiment R5 and R6 are independently CH(CH3)CN. According to a further specific embodiment R5 and R6 are independently C1-C4- alkoxy-Ci-C6-alkyl, more preferably Ci-C4-alkoxy-Ci-C4-alkyl. In a special embodiment R5 and R6 are independently CH2OCH3. In a further special embodiment R5 and R6 are independently CH2CH2OCH3. In a further special embodiment R5 and R6 are independently CH(CH3)OCH3. In a further special embodiment R5 and R6 are independently CH(CH3)OCH2CH3. In a further special embodiment R5 and R6 are independently CH2CH2OCH2CH3. According to a further specific embodiment R5 and R6 are independently Ci-C4-haloalkoxy-Ci-C6-alkyl, more preferably C1-C4- alkoxy-Ci-C4-alkyl. In a special embodiment R5 and R6 are independently CH2OCF3. In a further special embodiment R5 and R6 are independently CH2CH2OCF3. In a further special embodiment R5 and R6 are independently CH2OCCI3. In a further special embodiment R5 and R6 are independently CH2CH2OCCI3.
According to one another embodiment R5 and R6 are independently Ci-C6-alkoxy, preferably Ci- C4-alkoxy. In a special embodiment of the invention R5 and R6 are independently OCH3. In a fur- ther special embodiment of the invention R5 and R6 are independently OCH2CH3. In a further special embodiment of the invention R5 and R6 are independently OCH(CH3)2. In a further special embodiment of the invention R5 and R6 are independentlyOChbCh CI- . In a further special embodiment of the invention R5 and R6 are independently OC(CH3)3-
According to one another embodiment R5 and Rs are independently C2-C6-alkenyl, preferably CH=CH2, CH2CH=CH2, CH=CHCH3 or C(CH3)=CH2. In a special embodiment R5 and R6 are independently CH=CH2. In a further special embodiment R5 and R6 are independently CH2CH=CH2. In a further special embodiment R5 and R6 are independently CH2C(CH3)=CH2. In a further special embodiment R5 and R6 are independently CH2C(CH3)=CHCH3. In a further special embodiment R5 and R6 are independently CH2C(CH3)=C(CH3)2. In a further special embodiment R5 and R6 are independently CH2CH=CHCH3. In a further special embodiment R5 and R6 are independently CH=CHCH3 In a further special embodiment R5 and R6 are independently CH2C(CH3)=CI-l2. In a further special embodiment R5 and R6 are independently C(CH3)=CH2. In a further special embodiment R5 and R6 are independently C(CH3)=C(CH3)H. In a further special embodiment R5 and R6 are independently C(CH3)=C(CH3)2. In a further special embodiment R5 and R6 are independently CH=C(CH3)2.
According to a further preferred embodiment R5 and R6 are independently C2-C6-alkenyl, substi- tuted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R5 and R6 are independently C2-C6-haloalkenyl, more preferably fully or partially halogenated C2-C6-alkenyl. In a special embodiment R5 and R6 are independently fully or partially halogenated C2-alkenyl. In a further special embodiment R5 and R6 are independently fully or partially halogenated C3-alkenyl. In a special embodiment R5 and R6 are independently C(CI)=CH2. In a special embodiment R5 and R6 are independently C(CI)=CCIH. In a further special embodiment R5 and R6 are independently C(H)=CH(CI). In a further special embodiment R5 and R6 are independently C(H)=CCl2. In a further special embodiment R5 and R6 are independently C(CI)=CCl2- In a special embodiment R5 and R6 are independently C(CI)=CH2. In a further special embodiment R5 and R6 are independently C(H)=CH(F). In a further special embodiment R5 and R6 are independently C(H)=CF2. In a further special embodiment R5 and R6 are independently C(F)=CF2. In a special embodiment R5 and R6 are independently C(F)=CFH. According to a further specific embodiment R5 and R6 are independently C2-C6-alkenyl, preferably C2-C4- alkenyl, substituted by OH, more preferably, CH=CHCH20H. In a further special embodiment R5 and R6 are independently CH=CHCH20H. According to a further specific embodiment R5 and R6 are independently Ci-C4-alkoxy-C2-C6-alkenyl, more preferably Ci-C4-alkoxy-C2-C4-alkenyl. In a special embodiment R5 and R6 are independently CH=CHOCH3. In a further special embodiment R5 and R6 are independently CH=CHCH20CH3. According to a further specific embodiment R5 and R6 are independently Ci-C4-haloalkoxy-C2-C6-alkenyl, more preferably Ci-C4-haloalkoxy-C2- C4-alkenyl. In a further special embodiment R5 and R6 are independently CH=CHCH20CF3. In a further special embodiment R5 and R6 are independently CH=CHCH20CCl3. According to a further specific embodiment R5 and R6 are independently C3-Ce-cycloalkyl-C2-C6-alkenyl, preferably C3-C6-cycloalkyl-C2-C4-alkenyl. According to a further specific embodiment R5 and R6 are independently C3-C6-halocycloalkyl-C2-C4-alkenyl, preferably C3-C8-halocycloalkyl-C2-C6-alkenyl. In a further special embodiment R5 and R6 are independently CH=CH(C3H5). In a further special embodiment R5 and R6 are independently
Figure imgf000040_0001
In a further special embodiment R5 and R6 are independently
Figure imgf000040_0002
In a further special embodiment R5 and R6 are independently CH=C(H)(FC3H4). In a further special embodiment R5 and R6 are independently CH=C(H)(CIC4H6). In a further special embodiment R5 and R6 are independently CH=C(H)(FC4H6).
According to one another embodiment R5 and R6 are independently C2-C6-alkynyl, preferably CCH, CH2CCH, CH2CCCH3. In a special embodiment R5 and R6 are independently CCH. In a further special embodiment R5 and R6 are independently CCCH3. In a further special embodiment R5 and R6 are independently CCCH(CH3)2. In a further special embodiment R5 and R6 are independently CCC(CH3)3- In a further special embodiment R5 and R6 are independently CH2CCH. In a further special embodiment R5 and R6 are independently CH2CCCH3. In a further special em- bodiment R5 and R6 are independently CC^Hs) In a further special embodiment R5 and R6 are independently CH2CCH2CH3.
According to a further preferred embodiment R5 and R6 are independently C2-C6-alkynyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R5 and R6 are independently C2-C6-haloalkynyl, more preferably fully or partially halogenated C2-C6-alkynyl. In a special embodiment R5 and Rs are independently fully or partially halogenated C2-alkynyl. In a further special embodiment R5 and R6 are independently fully or partially halogenated C3-alkynyl. In a further special embodiment R5 and R6 are independently CCCI. In a further special embodiment R5 and Rs are independently CCBr. In a further special embodiment R5 and R6 are independently CC-I. In a further special embodiment R5 and R6 are independently CH2-CCCI. In a further special embodiment R5 and R6 are independently CH2-CCBr. In a further special embodiment R5 and R6 are independently CH2-CC-I. According to a further specific embodiment R5 and R6 are independently C2-C6-alkynyl, preferably C2-C4- alkynyl, substituted by OH. In a special embodiment R5 and Rs are independently CC- C(OH)(CH3)2. According to a further specific embodiment R5 and R6 are independently C1-C4- alkoxy-C2-C6-alkynyl, more preferably Ci-C4-alkoxy-C2-C4-alkynyl. In a special embodiment R5 and R6 are independently CCOCH3. In a special embodiment R5 and R6 are independently CC- CH2-OCH3. In a special embodiment R5 and R6 are independently CC-C(OCH3)(CH3)2. In a further special embodiment R5 and R6 are independently CH2CCOCH3. According to a further specific embodiment R5 and R6 are independently Ci-C4-haloalkoxy-C2-C6-alkynyl, more preferably C1-C4- haloalkoxy-C2-C4-alkynyl. In a further special embodiment R5 and R6 are independently CC- CH2OCCI3. In a further special embodiment R5 and R6 are independently CC-CH2OCF3 According to a further specific embodiment R5 and R6 are independently C3-C8-cycloalkyl-C2-CB-alkynyl, preferably C3-C6-cycloalkyl-C2-C4-alkynyl. In a special embodiment R5 and R6 are independently CC(C3H5). In a special embodiment R5 and R6 are independently CC(C4H7). In a special embodiment R5 and R6 are independently CCCH2(C3H5). In a special embodiment R5 and R6 are independently CC-CH2-C4H7). According to a further specific embodiment R5 and R6 are independently C3-C6-halocycloalkyl-C2-C4-alkynyl, preferably C3-C8-halocycloalkyl-C2-C6-alkynyl. In a special embodiment R5 and R6 are independently CC(C3H4CI). In a special embodiment R5 and R6 are independently CC(C3H4F). In a special embodiment R5 and R6 are independently CC(C4H6CI). In a special embodiment R5 and R6 are independently CC(C4HeF).
According to one another embodiment R5 and R6 are independently Cs-Cs-cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl. In a special embodiment R5 and R6 are independently cyclopropyl. In a further special embodiment R5 and R6 are independently cyclobutyl. In a further special embodiment R5 and Rs are independently cyclopentyl. In a further special embodiment R5 and R6 are independently cyclohexyl. According to a further preferred embodiment R5 and R6 are independently C3-Cs-cycloalkyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R5 and R6 are independently C3-Cs-halocycloalkyl, more pref- erably fully or partially halogenated C3-C6-cycloalkyl. In a special embodiment R5 and R6 are independently fully or partially halogenated cyclopropyl. In a further special embodiment R5 and R6 are independently 1-CI-cyclopropyl. In a further special embodiment R5 and R6 are independently 2- Cl-cyclopropyl. In a further special embodiment R5 and R6 are independently 1 -F-cyclopropyl. In a further special embodiment R5 and R6 are independently 2-F-cyclopropyl. In a further special em- bodiment R5 and R6 are independently fully or partially halogenated cyclobutyl. In a further special embodiment R5 and R6 are independently 1-CI-cyclobutyl. In a further special embodiment R5 and R6 are independently 1-F-cyclobutyl. In a further special embodiment R5 and R6 are independently
2- CI-cyclobutyl. In a further special embodiment R5 and R6 are independently 3-CI-cyclobutyl. In a further special embodiment R5 and R6 are independently 2-F-cyclobutyl. In a further special em- bodiment R5 and R6 are independently 3-F-cyclobutyl. In a further special embodiment R5 and R6 are independently 3,3-(CI)2-cyclobutyl. In a further special embodiment R5 and R6 are independently 3,3-(F)2-cyclobutyl. According to a specific embodiment R5 and R6 are independently C3-C8-cycloalkyl substituted by Ci-C4-alkyl, more preferably is C3-C6-cycloalkyl substituted by Ci- C4-alkyl. In a special embodiment R5 and R6 are independently 1 -CH3-cyclopropyl. In a further special embodiment R5 and R6 are independently 2-CH3-cyclopropyl. In a further special embodiment R5 and R6 are independently 1 -CH3-cyclobutyl. In a further special embodiment R5 and R6 are independently 2-CH3-cyclobutyl. In a further special embodiment R5 and R6 are independently
3- CH3-cyclobutyl. In a further special embodiment R5 and R6 are independently 3,3-(CH3)2- cyclobutyl. According to a specific embodiment R5 and R6 are independently Cs-Cs-cycloalkyl substituted by CN, more preferably is C3-C6-cycloalkyl substituted by CN. In a special embodiment R5 and R6 are independently 1-CN-cyclopropyl. In a special embodiment R5 and Rs are independently 2-CN-cyclopropyl. According to a further specific embodiment R5 and R6 are independently C3-C8-cycloalkyl-C3-C8-cycloalkyl, preferably C3-C6-cycloalkyl-C3-C6-cycloalkyl. In a special embodiment R5 and R6 are independently 1-cyclopropyl-cyclopropyl. In a very special em- bodiment R5 and R6 are independently 2-cyclopropyl-cyclopropyl. According to a further specific embodiment R5 and R6 are independently Cs-Cs-cycloalkyl-Cs-Cs-halocycloalkyl, preferably C3-C6- cycloalkyl-C3-C6-halocycloalkyl.
According to one another embodiment R5 and R6 are independently C3-Cs-cycloalkyl-Ci-C4-alkyl, preferably C3-C6-cycloalkyl-Ci-C4-alkyl. In a special embodiment R5 and R6 are independently CH(CH3)(cyclopropyl). In a special embodiment R5 and R6 are independently CH2-(cyclopropyl). In a special embodiment R5 and R6 are independently CH(CH3)(cyclobutyl). In a special embodiment R5 and R6 are independently CH2-(cyclobutyl). In a special embodiment R5 and R6 are independently CH2CH2-(cyclopropyl). In a special embodiment R5 and R6 are independently CH2CH2- (cyclobutyl).
According to a further preferred embodiment R5 and R6 are independently C3-Cs-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 cycloalkyl 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 R5 and R6 are independently C3-C8-cycloalkyl-Ci-C4- haloalkyl, C3-C6-cycloalkyl-Ci-C4-haloalkyl. According to a specific embodiment R5 and R6 are independently C3-C8-halocycloalkyl-Ci-C4-alkyl, C3-C6-halocycloalkyl-Ci-C4-alkyl. In a special embodiment R5 and R6 are independently fully or partially halogenated cyclopropyl-Ci-C4-alkyl. In a further special embodiment R5 and R6 are independently 1 -CI-cyclopropyl-Ci-C4-alkyl. In a further special embodiment R5 and R6 are independently 1 -F-cyclopropyl-Ci-C4-alkyl. In a further very special embodiment R5 and Rs are independently Chb-l -CI-cyclopropyl. In a further very special embodiment R5 and R6 are independently Chb-l -F-cyclopropyl. In a further very special embodiment R5 and R6 are independently CH(CH3)-1 -CI-cyclopropyl. In a further very special embodiment R5 and R6 are independently C(CH3)2-1 -F-cyclopropyl. In a further very special embodiment R5 and R6 are independently CH2-1 -F-cyclobutyl. In a further very special embodiment R5 and R6 are independently Chb-l -CI-cyclobutyl.
According to one embodiment R5 and R6 are independently phenyl.
According to a one preferred embodiment R5 and R6 are independently phenyl substituted by one, two, three or up to the maximum possible number of identical or different groups R as defined and preferably herein.
According to a specific embodiment R5 and R6 are independently phenyl substituted by one, two or three halogen atoms, preferably by one, two or three CI or F. In a special embodiment R5 and R6 are independently 2-CI-phenyl. In a further special embodiment R5 and R6 are independently 2- F-phenyl. In a further special embodiment R5 and R6 are independently 4-CI-phenyl. In a further special embodiment R5 and R6 are independently 4-CI-phenyl. In a further special embodiment R5 and R6 are independently 4-F-phenyl. In a further special embodiment R5 and R6 are inde- pendently 4-F-phenyl. In a further special embodiment R5 and R6 are independently 2,4-C - phenyl. In a further special embodiment R5 and R6 are independently 2,4-F2-phenyl. In a further special embodiment R5 and R6 are independently 2-CI-4-F-phenyl. In a further special embodiment R5 and R6 are independently 2-F-4-CI-phenyl. In a further special embodiment R5 and R6 are independently 2,4,6-Cl3-phenyl. In a further special embodiment R5 and R6 are independently 2,4,6-F3-phenyl.
According to a specific embodiment R5 and R6 are independently phenyl substituted by one, two or three CN or OH groups. In a special embodiment R5 and R6 are independently 2-OH-phenyl. In a further special embodiment R5 and R6 are independently 4-OH-phenyl. In a further special embodiment R5 and R6 are independently 2,4-OH2-phenyl. In a further special embodiment R5 and R6 are independently 2,4, 6-OH3-phenyl.
According to a specific embodiment R5 and R6 are independently phenyl substituted by one, two or three Ci-C4-alkyl or Ci-C4-haloalkyl groups, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or CF3, CHF2, CFH2, CCI3, CHC , CCIH2. In a special embodiment R5 and R6 are independently 2-CH3-phenyl. In a further special embodiment R5 and R6 are independently 2-CF3- phenyl. In a further special embodiment R5 and R6 are independently 4-CH3-phenyl. In a further special embodiment R5 and R6 are independently 4-CF3-phenyl. According to a specific embodiment R5 and R6 are independently phenyl substituted by one, two or three Ci-C4-alkoxy or Ci-C4-haloalkoxy groups, preferably preferably Ci-C4-alkoxy, more preferably CH3O, CH3CH2O, CH3CH2CH2O, CH2(CH3)CH20, CH3CH(CH3)0, CH3CH2CH2CH2O, CF3O, CCI3O. In a special embodiment R5 and R6 are independently 2-CH30-phenyl. In a further special embodiment R5 and R6 are independently 2-CF30-phenyl. In a further special embodiment R5 and R6 are independently 4-CH30-phenyl. In a further special embodiment R5 and R6 are independently 4-CF30-phenyl.
According to one embodiment R5 and R6 are independently phenyl-Ci-C4-alkyl, preferably phenyl- Ci-C2-alkyl. In a special embodiment R5 and Rs are independently benzyl.
According to a one preferred embodiment R5 and R6 are independently phenyl-Ci-C4-alkyl therein 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, 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, and phenyl can be substituted by one, two, three or up to the maximum possible number of identical or different groups R as defined and preferably 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. In a special embodiment R5 and R6 are independently CH2-(4-CI)-phenyl. In a further special embodiment R5 and R6 are independently CH2-(4-CH3)-phenyl. In a further special embodiment R5 and R6 are independently CH2-(4-OCH3)-phenyl. In a further special embodiment R5 and R6 are independently CH2-(4-F)-phenyl. In a further special embodiment R5 and R6 are independently CH2-(2,4-Cl2)-phenyl. In a further special embodiment R5 and R6 are independently CH2-(2,4-F2)-phenyl.
According to a one preferred embodiment R5 and R6 together with the carbon atom to which they are bound form a saturated or partially unsaturated three-, four-, five-, six- or seven- membered carbocycle. In a special embodiment R5 and R6form cyclopropyl. In a further special embodiment R5 and R6form cyclobutyl. In a further special embodiment R5 and R6form cyclo- penyl. In a further special embodiment R5 and R6form cyclohexyl. Further preffered are cyclo- pentenyl, cyclopentadienyl and cyclohexenyl.
According to a one preferred embodiment carbocycle as defined above carries one, two, three or four substituents independently selected from halogen, CN, NO2, OH, SH, NH2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, C1-C4- alkoxy-Ci-C4-alkyl, phenyl and phenoxy; and wherein one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S). Preferred are halogen such as CI, Br, F, Ci-C6-haloalkyl and Ci-C6-alkoxy.
According to a one preferred embodiment R5 and R6 together with the carbon atom to which they are bound form a a saturated or partially unsaturated three-, four-, five-, six- or seven- membered heterocycle, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the carbo- or heterocycle is unsubstituted or carries one, two, three or four substituents independently selected from halogen, CN, N02, OH, SH, NH2, d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C3-haloalkoxy, Ci-C6-alkylthio, Ci-C6- haloalkylthio, Ci-C4-alkoxy-Ci-C4-alkyl, phenyl and phenoxy; and wherein one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S). Preffered R5 and Rs form cyclopropanone, cyclopentanone, cyclopropanethi- one, cyclopentanethione, 5-oxazolone, cyclohexane-1 ,4-dione, cyclohexane-1 ,4-dithione, cy- clohex-2-ene-1 ,4-dione or cyclohex-2-ene-1 ,4-dithione. Further preffered are oxirane, aziridine, thiirane, oxetane, azetidine, thiethane, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl,
2-tetrahydrothienyl and 3-tetrahydrothienyl.
According to a one preferred embodiment R5 and R6 together with the carbon atom to which they are bound (denominated C*) form a group (C*=CR55R66), wherein R55, R66 are inde- pendently selected from hydrogen, halogen, CN, NO2, OH, SH, NH2, Ci-Ce-alkyI, Ci-Ce- haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio and Ci-C4-alkoxy- Ci-C4-alkyl.
According to a one preferred embodiment R5 and R6 together with the carbon atom to which they are bound (denominated C*) form a group (C*=CR55R66), wherein R55, R66 are inde- pendently selected from hydrogen, halogen and Ci-C6-alkyl.
In a special embodiment R5 and R6form C*=CH2. In a special embodiment R5 and R6form
C*=CCl2. In a special embodiment R5 and R6form C*=CHCI. In a special embodiment R5 and R6 form C*=CHBr. In a special embodiment R5 and R6form C*=CHF. In a special embodiment R5 and R6form C*=CHCH3. In a special embodiment R5 and R6form C*=C(CH3)2. In a special em- bodiment R5 and R6form C*=CH(CH2CH3). In a special embodiment R5 and R6form
C*=C(CH2CH3)2.
R7 in the compounds according to the invention is, according to one embodiment, as defined in claim 1.
R7 in the compounds according to the invention is, according to a further embodiment, C1-C6- alkyl or C3-C6-cycloalkyl, wherein R7 is substituted by one, two, three or four R7a; wherein R7a is independently selected from halogen.
According to one embodiment o is 0.
According to one embodiment o is 1. According to one further embodiment o is 2. According to one further embodiment o is 3. According to one further embodiment o is 4.
According to one further embodiment R7 is Ci-C6-alkyl, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. In a special embodiment R7 is methyl. In a further special embodiment R7 is ethyl. In a further special embodiment R7 is n-propyl. In a further special embodiment R7 is i- propyl. In a further special embodiment R7 is 1 -methylpropyl. In a further special embodiment R7 is n-butyl. In a further special embodiment R7 is i-butyl. In a further special embodiment R7 is t- butyl.
According to a one preferred embodiment R4 is Ci-C6-alkyl substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R 7 is Ci-C6-haloalkyl, more preferably fully or partially halo- genated methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. In a special embodiment R 7 is CF3. In a further special embodiment R 7 is CHF2. In a further special embodiment R 7 is CFH2. In a further special embodiment R 7 is CCI3. In a further special embodiment R 7 is CHCI2. In a further special embodiment R 7 is CCIH2. According to a further specific embodiment R 7 is Ci-C6-alkyl, preferably Ci-C 7-alkyl substituted by OH, more preferably CH2OH, CH2CH2OH, CH2CH2CH2OH, CH(CH3)CH2OH, CH2CH(CH3)OH, CH2CH2CH2CH2OH. In a special embodiment R 7 is CH2OH. According to a further specific embodiment R 7 is Ci-C 7-alkoxy-Ci-C6-alkyl, more preferably C1-C 7-alkoxy-Ci-C 7-alkyl. In a special embodiment R 7 is CH2OCH3. In a further special embodiment R 7 is CH2CH2OCH3. In a further special embodiment R 7 is CH(CH3)OCH3. In a further special embodiment R 7 is CH(CH3)OCH2CH3. In a further special embodiment R 7 is CH2CH2OCH2CH3. According to a further preferred embodiment R 7 is C2-C6-alkenyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R 7 is C2-C6-haloalkenyl, more preferably fully or partially halogenated C2-C6-alkenyl. In a special embodiment R 7 is fully or partially halogenated C2-alkenyl. In a further special embodiment R 7 is fully or partially halogenated C3-alkenyl. According to a further specific embodiment R 7 is C2-C6-alkenyl, preferably C2-C 7-alkenyl, substituted by OH, more preferably, CH=CHOH, CH=CHCH2OH, C(CH3)=CHOH, CH=C(CH3)OH. In a special embodiment R 7 is CH=CHOH. In a further special embodiment R 7 is CH=CHCH20H. According to a further specific embodiment R 7 is Ci-C 7-alkoxy-C2-C6-alkenyl, more preferably Ci-C 7-alkoxy-C2-C 7-alkenyl. In a special embodiment R 7 is CH=CHOCH3. In a further special embodiment R 7 is
CH=CHCH2OCH3.
According to one another embodiment R 7 is C2-C6-alkynyl, preferably CCH, CH2CCH,
CH2CCCH3. In a special embodiment R 7 is CCH. in a further special embodiment R 7 is CCCH3. In a further special embodiment R 7 is CH2CCH. In a further special embodiment R 7 is CH2CCCH3. In a further special embodiment R 7 is CH2CCH2CH3.
According to a further preferred embodiment R 7 is C2-C6-alkynyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and preferably herein.
According to a specific embodiment R 7 is C2-C6-haloalkynyl, more preferably fully or partially hal- ogenated C2-C6-alkynyl. In a special embodiment R 7 is fully or partially halogenated C2-alkynyl. In a further special embodiment R 7 is fully or partially halogenated C3-alkynyl. According to a further specific embodiment R 7 is C2-C6-alkynyl, preferably C2-C 7-alkynyl, substituted by OH, more preferably, CCOH, CH2CCOH. In a special embodiment R 7 is CCOH. In a further special embodiment R 7 is CH2CCOH. According to a further specific embodiment R 7 is C1-C 7-alkoxy-C2-C6-alkynyl, more preferably Ci-C 7-alkoxy-C2-C 7-alkynyl. In a special embodiment R 7 is CCOCH3. In a further special embodiment R 7 is CH2CCOCH3.
According to one another embodiment R 7 is Cs-Ce-cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular cyclopropyl or cyclobutyl. In a special embodiment R 7 is cyclopropyl. In a further special embodiment R 7 is cyclobutyl. In a further special embodiment R 7 is cyclopentyl. In a further special embodiment R 7 is cyclohexyl. According to one another embodiment 7 is C3-Ce-cycloalkoxy, preferably C3-C6-cycloalkoxy. In a special embodiment R 7 is O-cyclopropyl.
According to a further preferred embodiment R 7 is C3-C8-cycloalkyl, substituted by one, two, three or up to the maximum possible number of identical or different groups Ra as defined and prefera- bly herein.
According to a specific embodiment R 7 is C3-C8-halocycloalkyl, more preferably fully or partially halogenated C3-C6-cycloalkyl. In a special embodiment R7 is fully or partially halogenated cyclo- propyl. In a further special embodiment R7 is 1-CI-cyclopropyl. In a further special embodiment R7 is 2-CI-cyclopropyl. In a further special embodiment R 7 is 1 -F-cyclopropyl. In a further special embodiment R7 is 2-F-cyclopropyl. In a further special embodiment R 7 is fully or partially halogenated cyclobutyl. In a further special embodiment R 7 is 1 -CI-cyclobutyl. In a further special embodiment R 7 is 1-F-cyclobutyl. In a further special embodiment R7 is 3,3-(CI)2-cyclobutyl. In a further special embodiment R7 is 3,3-(F)2-cyclobutyl.
According to one another embodiment two substituents R7: R7 and R72 together with the carbon atom(s) to which they are bound form a saturated three-, four-, five-, six- or seven-membered car- bocycle or heterocycle, wherein the heterocycle contains one, two, three or four O atoms.
According to a one preferred embodiment R71 and R72 together with the carbon atom to which they are bound form a saturated or partially unsaturated three-, four-, five-, six- or seven- membered carbocycle. In a special embodiment R5 and R6form cyclopropyl. In a further special embodiment R5 and R6form cyclobutyl. In a further special embodiment R5 and R6form cyclo- penyl. In a further special embodiment R5 and R6form cyclohexyl. Further preffered are cyclo- pentenyl, cyclopentadienyl and cyclohexenyl.
According to a one preferred embodiment R71 and R72 together with the carbon atom to which they are bound form a a saturated or partially unsaturated three-, four-, five-, six- or seven- membered heterocycle, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the carbo- or heterocycle is unsubstituted or carries one, two, three or four substituents independently selected from halogen, CN, NO2, OH, SH, N H2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- haloalkylthio, Ci-C4-alkoxy-Ci-C4-alkyl, phenyl and phenoxy; and wherein one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S). Preffered R71 and R72 form cyclopropanone, cyclopentanone, cyclopro- panethione, cyclopentanethione, 5-oxazolone, cyclohexane-1 ,4-dione, cyclohexane-1 ,4- dithione, cyclohex-2-ene-1 ,4-dione or cyclohex-2-ene-1 ,4-dithione. Further preffered are oxirane, aziridine, thiirane, oxetane, azetidine, thiethane, 2-tetrahydrofuranyl, 3- tetrahydrofuranyl, 2-tetrahydrothienyl and 3-tetrahydrothienyl.
According to one embodiment, the present invention relates to compounds of the formulae I. A to I.H, each of them representing a specific embodiment of the invention, wherein the variables are defined and preferably defined as given herein for compounds I:
Figure imgf000048_0001
Figure imgf000048_0002
Here, the variables are as defined elsewhere herein for formula I, or as defined as being preferred for formula I.
According to one embodiment, the present invention relates to compounds of the formulae 11. A to II. H, each of them representing a specific embodiment of the invention, wherein the variables are defined and preferably defined as given herein for compounds I:
Figure imgf000049_0001
Here, the variables are as defined elsewhere herein for formula I, or as defined as being preferred for formula I.
Preference is given to the compounds I according to the invention compiled in Tables 1 a-l to 18a-l, 1 a-l I to 18a-ll, Tables 1a-a to 18a-a and Tables 1 a-b to 18a-b below with the proviso as defined above. The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question.
Table 1 a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of 5 and R6 corresponds to line A-1 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A1.B1 to I.A.A1.B2340, compounds I.B.A1.B1 to I.B.A1.B2340; compounds I.C.A1.B1 to I.C.A1.B2340; compounds I.D.A1.B1 to I.D.A1 .B2340; compounds I.E.A1.B1 to I.E.A1.B2340; compounds I.F.A1.B1 to I.F.A1.B2340; compounds I.G.A1.B1 to I.G.A1.B2340; compounds I.H.A1.B1 to I.H.A1.B2340).
Table 2a-l
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-2 of Table A and the meaning for the combination of (R3)n, (R4)m, R7 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A2.B1 to I.A.A2.B2340, compounds I.B.A2.B1 to I.B.A2.B2340; compounds I.C.A2.B1 to I.C.A2.B2340; compounds I.D.A2.B1 to I.D.A2.B2340; compounds I.E.A2.B1 to I.E.A2.B2340; compounds I.F.A2.B1 to I.F.A2.B2340; compounds I.G.A2.B1 to I.G.A2.B2340; compounds I.H.A2.B1 to I.H.A2.B2340).
Table 3a-l
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-3 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A3.B1 to I.A.A3.B2340, compounds I.B.A3.B1 to I.B.A3.B2340; compounds I.C.A3.B1 to I.C.A3.B2340; compounds I.D.A3.B1 to I.D.A3.B2340; compounds I.E.A3.B1 to I.E.A3.B2340; compounds I.F.A3.B1 to I.F.A3.B2340; compounds I.G.A3.B1 to I.G.A3.B2340; compounds I.H.A3.B1 to I.H.A3.B2340).
Table 4a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-4 of Table A and the meaning for the combination of (R3)n, (R4)m, R7 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A4.B1 to I.A.A4.B2340, compounds I.B.A4.B1 to I.B.A4.B2340; compounds I.C.A4.B1 to I.C.A4.B2340; compounds I.D.A4.B1 to I.D.A4.B2340; compounds I.E.A4.B1 to I.E.A4.B2340; compounds I.F.A4.B1 to I.F.A4.B2340; compounds I.G.A4.B1 to I.G.A4.B2340; compounds I.H.A4.B1 to I.H.A4.B2340).
Table 5a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-5 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A5.B1 to I.A.A5.B2340, compounds I.B.A5.B1 to I.B.A5.B2340; compounds I.C.A5.B1 to I.C.A5.B2340; compounds I.D.A5.B1 to I.D.A5.B2340; compounds I.E.A5.B1 to I.E.A5.B2340; compounds I.F.A5.B1 to I.F.A5.B2340; compounds I.G.A5.B1 to I.G.A5.B2340; compounds I.H.A5.B1 to I.H.A5.B2340).
Table 6a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-6 of Table A and the meaning for the combination of (R3)n, (R4)m, R7 and R72 for each individual compound corresponds in each case to one line of Table B (com- pounds I.A.A6.B1 to I.A.A6.B2340, compounds I.B.A6.B1 to I.B.A6.B2340; compounds
I.C.A6.B1 to I.C.A6.B2340; compounds I.D.A6.B1 to I.D.A6.B2340; compounds I.E.A6.B1 to I.E.A6.B2340; compounds I.F.A6.B1 to I.F.A6.B2340; compounds I.G.A6.B1 to I.G.A6.B2340; compounds I.H.A6.B1 to I.H.A6.B2340).
Table 7a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-7 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A7.B1 to I.A.A7.B2340, compounds I.B.A7.B1 to I.B.A7.B2340; compounds I.C.A7.B1 to I.C.A7.B2340; compounds I.D.A7.B1 to I.D.A7.B2340; compounds I.E.A7.B1 to I.E.A7.B2340; compounds I.F.A7.B1 to I.F.A7.B2340; compounds I.G.A7.B1 to I.G.A7.B2340; compounds I.H.A7.B1 to I.H.A7.B2340).
Table 8a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I. H in which the combination of R5 and R6 corresponds to line A-8 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (com- pounds I.A.A8.B1 to I.A.A8.B2340, compounds I.B.A8.B1 to I.B.A8.B2340; compounds
I.C.A8.B1 to I.C.A8.B2340; compounds I.D.A8.B1 to I.D.A8.B2340; compounds I.E.A8.B1 to I.E.A8.B2340; compounds I.F.A8.B1 to I.F.A8.B2340; compounds I.G.A8.B1 to I.G.A8.B2340; compounds I.H.A8.B1 to I.H.A8.B2340).
Table 9a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I. H in which the combination of R5 and R6 corresponds to line A-9 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A9.B1 to I.A.A9.B2340, compounds I.B.A9.B1 to I.B.A9.B2340; compounds I.C.A9.B1 to I.C.A9.B2340; compounds I.D.A9.B1 to I.D.A9.B2340; compounds I.E.A9.B1 to I.E.A9.B2340; compounds I.F.A9.B1 to I.F.A9.B2340; compounds I.G.A9.B1 to I.G.A9.B2340; compounds I.H.A9.B1 to I.H.A9.B2340).
Table 10a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I. H in which the combination of R5 and R6 corresponds to line A-10 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A10.B1 to I.A.A10.B2340, compounds I.B.A10.B1 to I.B.A10.B2340; compounds I.C.A10.B1 to I.C.A10.B2340; compounds I.D.A10.B1 to I.D.A10.B2340; compounds I.E.A10.B1 to I.E.A10.B2340; compounds I.F.A10.B1 to I.F.A10.B2340; compounds I.G.A10.B1 to I.G.A10.B2340; compounds I.H.A10.B1 to I.H.A10.B2340).
Table 1 1 a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-1 1 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A1 1.B1 to I.A.A1 1.B2340, compounds I.B.A11.B1 to I.B.A1 1.B2340; compounds I.C.A11.B1 to I.C.A1 1.B2340; compounds I . D.A1 1.B1 to I. D.A1 1.B2340; compounds I.E.A1 1.B1 to I.E.A1 1.B2340; compounds I.F.A11.B1 to I.F.A1 1.B2340; compounds I.G.A1 1.B1 to I.G.A1 1.B2340; compounds I.H.A11.B1 to I.H.A1 1.B2340).
Table 12a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-12 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A12.B1 to I.A.A12.B2340, compounds I.B.A12.B1 to I.B.A12.B2340; compounds I.C.A12.B1 to I.C.A12.B2340; compounds I.D.A12.B1 to I.D.A12.B2340; compounds I.E.A12.B1 to I.E.A12.B2340; compounds I.F.A12.B1 to I.F.A12.B2340; compounds I.G.A12.B1 to I.G.A12.B2340; compounds I.H.A12.B1 to I.H.A12.B2340).
Table 13a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I. H in which the combination of R5 and R6 corresponds to line A-13 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (com- pounds I.A.A13.B1 to I.A.A13.B2340, compounds I.B.A13.B1 to I.B.A13.B2340; compounds I.C.A13.B1 to I.C.A13.B2340; compounds I.D.A13.B1 to I.D.A13.B2340; compounds I.E.A13.B1 to I.E.A13.B2340; compounds I.F.A13.B1 to I.F.A13.B2340; compounds I.G.A13.B1 to I.G.A13.B2340; compounds I.H.A13.B1 to I.H.A13.B2340).
Table 14a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I. H in which the combination of R5 and R6 corresponds to line A-1 14 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A14.B1 to I.A.A14.B2340, compounds I.B.A14.B1 to I.B.A14.B2340; compounds I.C.A14.B1 to I.C.A14.B2340; compounds I.D.A14.B1 to I.D.A14.B2340; compounds I.E.A14.B1 to I.E.A14.B2340; compounds I.F.A14.B1 to I.F.A14.B2340; compounds I.G.A14.B1 to I.G.A14.B2340; compounds I.H.A14.B1 to I.H.A14.B2340).
Table 15a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I. H in which the combination of R5 and R6 corresponds to line A-15 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A15.B1 to I.A.A15.B2340, compounds I.B.A15.B1 to I.B.A15.B2340; compounds I.C.A15.B1 to I.C.A15.B2340; compounds I.D.A15.B1 to I.D.A15.B2340; compounds I.E.A15.B1 to I.E.A15.B2340; compounds I.F.A15.B1 to I.F.A15.B2340; compounds I.G.A15.B1 to I.G.A15.B2340; compounds I.H.A15.B1 to I.H.A15.B2340).
Table 16a-l
Compounds of the formula I.A, I.B. I.C, I.D, I.E, I.F, I.G, I. H in which the combination of R5 and R6 corresponds to line A-16 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A16.B1 to I.A.A16.B2340, compounds I.B.A16.B1 to I.B.A16.B2340; compounds I.C.A16.B1 to I.C.A16.B2340; compounds I.D.A16.B1 to I.D.A16.B2340; compounds I.E.A16.B1 to I.E.A16.B2340; compounds I.F.A16.B1 to I.F.A16.B2340; compounds I.G.A16.B1 to
I.G.A16.B2340; compounds I.H.A16.B1 to I.H.A16.B2340).
Table 17a-l
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-17 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A17.B1 to I.A.A17.B2340, compounds I.B.A17.B1 to I.B.A17.B2340; compounds I.C.A17.B1 to I.C.A17.B2340; compounds I.D.A17.B1 to I.D.A17.B2340; compounds I.E.A17.B1 to I.E.A17.B2340; compounds I.F.A17.B1 to I.F.A17.B2340; compounds I.G.A17.B1 to
I.G.A17.B2340; compounds I.H.A17.B1 to I.H.A17.B2340).
Table 18a-l
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-18 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds I.A.A18.B1 to I.A.A18.B2340, compounds I.B.A18.B1 to I.B.A18.B2340; compounds I.C.A18.B1 to I.C.A18.B2340; compounds I.D.A18.B1 to I.D.A18.B2340; compounds I.E.A18.B1 to I.E.A18.B2340; compounds I.F.A18.B1 to I.F.A18.B2340; compounds I.G.A18.B1 to
I. G.A18.B2340; compounds I.H.A18.B1 to I.H.A18.B2340).
Table 1 a-ll
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, I I.G, II. H in which the combination of R5 and R6 corresponds to line A-1 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A1.B1 to II.A.A1.B2340, compounds II.B.A1.B1 to II.B.A1.B2340; compounds II.C.A1.B1 to II.C.A1.B2340; compounds II.D.A1.B1 to II.D.A1.B2340; compounds II.E.A1.B1 to
II. E.A1 .B2340; compounds II.F.A1.B1 to II.F.A1.B2340; compounds II.G.A1.B1 to
II.G.A1.B2340; compounds II.H.A1.B1 to II.H.A1 .B2340).
Table 2a-ll
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, I I.G, II. H in which the combination of R5 and R6 corresponds to line A-2 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A2.B1 to II.A.A2.B2340, compounds II.B.A2.B1 to II.B.A2.B2340; compounds II.C.A2.B1 to II.C.A2.B2340; compounds II.D.A2.B1 to II.D.A2.B2340; compounds II.E.A2.B1 to II.E.A2.B2340; compounds II.F.A2.B1 to II.F.A2.B2340; compounds II.G.A2.B1 to
II.G.A2.B2340; compounds II.H.A2.B1 to II.H.A2.B2340).
Table 3a-ll
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, I I.G, II. H in which the combination of R5 and R6 corresponds to line A-3 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A3.B1 to II.A.A3.B2340, compounds II.B.A3.B1 to II.B.A3.B2340; compounds II.C.A3.B1 to II.C.A3.B2340; compounds II.D.A3.B1 to II.D.A3.B2340; compounds II.E.A3.B1 to II.E.A3.B2340; compounds II.F.A3.B1 to II.F.A3.B2340; compounds II.G.A3.B1 to
II.G.A3.B2340; compounds II.H.A3.B1 to II.H.A3.B2340).
Table 4a-ll
Compounds of the formula II.A, II. B. II. C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-4 of Table A and the meaning for the combination of (R3)n, (R4)m, R7 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A4.B1 to II.A.A4.B2340, compounds II.B.A4.B1 to II.B.A4.B2340; compounds II.C.A4.B1 to II.C.A4.B2340; compounds II.D.A4.B1 to II.D.A4.B2340; compounds II.E.A4.B1 to II.E.A4.B2340; compounds II.F.A4.B1 to II.F.A4.B2340; compounds II.G.A4.B1 to
II.G.A4.B2340; compounds II.H.A4.B1 to II.H.A4.B2340).
Table 5a-\\
Compounds of the formula II.A, II. B. II. C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-5 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A5.B1 to II.A.A5.B2340, compounds II.B.A5.B1 to II.B.A5.B2340; compounds II.C.A5.B1 to II.C.A5.B2340; compounds II.D.A5.B1 to II.D.A5.B2340; compounds II.E.A5.B1 to II.E.A5.B2340; compounds II.F.A5.B1 to II.F.A5.B2340; compounds II.G.A5.B1 to
II.G.A5.B2340; compounds II.H.A5.B1 to II.H.A5.B2340).
Table 6a-ll
Compounds of the formula II.A, II. B. II. C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-6 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A6.B1 to II.A.A6.B2340, compounds II.B.A6.B1 to II.B.A6.B2340; compounds II.C.A6.B1 to II.C.A6.B2340; compounds II.D.A6.B1 to II.D.A6.B2340; compounds II.E.A6.B1 to II.E.A6.B2340; compounds II.F.A6.B1 to II.F.A6.B2340; compounds II.G.A6.B1 to
II.G.A6.B2340; compounds II.H.A6.B1 to II.H.A6.B2340).
Table 7a-ll
Compounds of the formula II.A, II. B. II. C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-7 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B
(compounds II.A.A7.B1 to II.A.A7.B2340, compounds II.B.A7.B1 to II.B.A7.B2340; compounds II.C.A7.B1 to II.C.A7.B2340; compounds II.D.A7.B1 to II.D.A7.B2340; compounds II.E.A7.B1 to II.E.A7.B2340; compounds II.F.A7.B1 to II.F.A7.B2340; compounds II.G.A7.B1 to
II.G.A7.B2340; compounds II.H.A7.B1 to II.H.A7.B2340).
Table 8a-ll
Compounds of the formula II.A, II. B. II. C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-8 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A8.B1 to II.A.A8.B2340, compounds II.B.A8.B1 to II.B.A8.B2340; compounds II.C.A8.B1 to II.C.A8.B2340; compounds II.D.A8.B1 to II.D.A8.B2340; compounds II.E.A8.B1 to II.E.A8.B2340; compounds II.F.A8.B1 to II.F.A8.B2340; compounds II.G.A8.B1 to
II.G.A8.B2340; compounds II.H.A8.B1 to II.H.A8.B2340).
Table 9a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-9 of Table A and the meaning for the combination of (R3)n, (R4)m, R7 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A9.B1 to II.A.A9.B2340, compounds II.B.A9.B1 to II.B.A9.B2340; compounds II.C.A9.B1 to II.C.A9.B2340; compounds II.D.A9.B1 to II.D.A9.B2340; compounds II.E.A9.B1 to II.E.A9.B2340; compounds II.F.A9.B1 to II.F.A9.B2340; compounds II.G.A9.B1 to
II.G.A9.B2340; compounds II.H.A9.B1 to II.H.A9.B2340).
Table 10a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-10 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A10.B1 to II.A.A10.B2340, compounds II.B.A10.B1 to II.B.A10.B2340; compounds II.C.A10.B1 to II.C.A10.B2340; compounds II.D.A10.B1 to II.D.A10.B2340; compounds II.E.A10.B1 to II.E.A10.B2340; compounds II.F.A10.B1 to II.F.A10.B2340; compounds
II.G.A10.B1 to II.G.A10.B2340; compounds II.H.A10.B1 to II.H.A10.B2340).
Table 1 1 a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-1 1 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A1 1.B1 to II.A.A1 1.B2340, compounds II.B.A11.B1 to II.B.A1 1.B2340; com- pounds II.C.A11.B1 to II.C.A1 1.B2340; compounds II.D.A1 1.B1 to II.D.A1 1.B2340; compounds II.E.A1 1.B1 to II.E.A1 1 .B2340; compounds II.F.A1 1 .B1 to II.F.A11.B2340; compounds
II.G.A1 1.B1 to II.G.A11.B2340; compounds II.H.A1 1.B1 to II.H.A1 1.B2340).
Table 12a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-12 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A12.B1 to II.A.A12.B2340, compounds II.B.A12.B1 to II.B.A12.B2340; compounds II.C.A12.B1 to II.C.A12.B2340; compounds II.D.A12.B1 to II.D.A12.B2340; compounds II.E.A12.B1 to II.E.A12.B2340; compounds II.F.A12.B1 to II.F.A12.B2340; compounds
II.G.A12.B1 to II.G.A12.B2340; compounds II.H.A12.B1 to II.H.A12.B2340).
Table 13a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-13 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A13.B1 to II.A.A13.B2340, compounds II.B.A13.B1 to II.B.A13.B2340; compounds II.C.A13.B1 to II.C.A13.B2340; compounds II.D.A13.B1 to II.D.A13.B2340; compounds II.E.A13.B1 to II.E.A13.B2340; compounds II.F.A13.B1 to II.F.A13.B2340; compounds
II.G.A13.B1 to II.G.A13.B2340; compounds II.H.A13.B1 to II.H.A13.B2340).
Table 14a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-1 14 of Table A and the meaning for the combination of (R3)n,
(R4)m, R7 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A14.B1 to II.A.A14.B2340, compounds II.B.A14.B1 to II.B.A14.B2340; compounds II.C.A14.B1 to II.C.A14.B2340; compounds II.D.A14.B1 to II.D.A14.B2340; compounds II.E.A14.B1 to II.E.A14.B2340; compounds II.F.A14.B1 to II.F.A14.B2340; compounds
II.G.A14.B1 to II.G.A14.B2340; compounds II.H.A14.B1 to II.H.A14.B2340).
Table 15a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-15 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A15.B1 to II.A.A15.B2340, compounds II.B.A15.B1 to II.B.A15.B2340; compounds II.C.A15.B1 to II.C.A15.B2340; compounds II.D.A15.B1 to II.D.A15.B2340; compounds II.E.A15.B1 to II.E.A15.B2340; compounds II.F.A15.B1 to II.F.A15.B2340; compounds
II.G.A15.B1 to II.G.A15.B2340; compounds II.H.A15.B1 to II.H.A15.B2340).
Table 16a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-16 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A16.B1 to II.A.A16.B2340, compounds II.B.A16.B1 to II.B.A16.B2340; compounds II.C.A16.B1 to II.C.A16.B2340; compounds II.D.A16.B1 to II.D.A16.B2340; compounds II.E.A16.B1 to II.E.A16.B2340; compounds II.F.A16.B1 to II.F.A16.B2340; compounds
II.G.A16.B1 to II.G.A16.B2340; compounds II.H.A16.B1 to II.H.A16.B2340).
Table 17a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-17 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B
(compounds II.A.A17.B1 to II.A.A17.B2340, compounds II.B.A17.B1 to II.B.A17.B2340; compounds II.C.A17.B1 to II.C.A17.B2340; compounds II.D.A17.B1 to II.D.A17.B2340; compounds II.E.A17.B1 to II.E.A17.B2340; compounds II.F.A17.B1 to II.F.A17.B2340; compounds
II.G.A17.B1 to II.G.A17.B2340; compounds II.H.A17.B1 to II.H.A17.B2340).
Table 18a-ll
Compounds of the formula II.A, II. B. II.C, II. D, II. E, II. F, II.G, II. H in which the combination of R5 and R6 corresponds to line A-18 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table B (compounds II.A.A18.B1 to II.A.A18.B2340, compounds II.B.A18.B1 to II.B.A18.B2340; com- pounds II.C.A18.B1 to II.C.A18.B2340; compounds II.D.A18.B1 to II.D.A18.B2340; compounds II.E.A18.B1 to II.E.A18.B2340; compounds II.F.A18.B1 to II.F.A18.B2340; compounds
II.G.A18.B1 to II.G.A18.B2340; compounds II.H.A18.B1 to II.H.A18.B2340).
Table 1 a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-1 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A1.Bb1 to I.A.A1.Bb260, compounds I.B.A1 .Bb1 to I.B.A1 .Bb260; compounds
I.C.A1.Bb1 to I.C.A1.Bb260; compounds I.D.A1.Bb1 to I.D.A1.Bb260; compounds I.E.A1.Bb1 to I.E.A1.Bb260; compounds I.F.A1.BM to I.F.A1.Bb260; compounds I.G.A1 .BM to I.G.A1.Bb260; compounds I.H.A1 .Bb1 to I.H.A1.Bb260).
Table 2a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-2 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (com- pounds I.A.A2.Bb1 to I.A.A2.Bb260, compounds I.B.A2.Bb1 to I.B.A2.Bb260; compounds
I.C.A2.Bb1 to I.C.A2.Bb260; compounds I.D.A2.Bb1 to I.D.A2.Bb260; compounds I.E.A2.Bb1 to I.E.A2.Bb260; compounds I.F.A2.Bb1 to I.F.A2.Bb260; compounds I.G.A2.Bb1 to I.G.A2.Bb260; compounds I.H.A2.Bb1 to I.H.A2.Bb260).
Table 3a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-3 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A3.Bb1 to I.A.A3.Bb260, compounds I.B.A3.Bb1 to I.B.A3.Bb260; compounds
I.C.A3.BM to I.C.A3.Bb260; compounds I.D.A3.BM to I.D.A3.Bb260; compounds LE.A3.Bb1 to I.E.A3.Bb260; compounds I.F.A3.Bb1 to I.F.A3.Bb260; compounds I.G.A3.Bb1 to I.G.A3.Bb260; compounds I.H.A3.Bb1 to I.H.A3.Bb260).
Table 4a-a
Compounds of the formula LA, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-4 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A4.Bb1 to I.A.A4.Bb260, compounds I.B.A4.Bb1 to I.B.A4.Bb260; compounds
I.C.A4.Bb1 to I.C.A4.Bb260; compounds I.D.A4.Bb1 to I.D.A4.Bb260; compounds I.E.A4.Bb1 to I.E.A4.Bb260; compounds I.F.A4.Bb1 to I.F.A4.Bb260; compounds I.G.A4.Bb1 to I.G.A4.Bb260; compounds I.H.A4.Bb1 to I.H.A4.Bb260).
Table 5a-a
Compounds of the formula LA, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-5 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A5.Bb1 to I.A.A5.Bb260, compounds I.B.A5.Bb1 to I.B.A5.Bb260; compounds
I.C.A5.Bb1 to I.C.A5.Bb260; compounds I.D.A5.Bb1 to I.D.A5.Bb260; compounds I.E.A5.Bb1 to I.E.A5.Bb260; compounds I.F.A5.Bb1 to I.F.A5.Bb260; compounds I.G.A5.Bb1 to I.G.A5.Bb260; compounds I.H.A5.Bb1 to I.H.A5.Bb260). Table 6a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-6 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (com- pounds I.A.A6.BM to I.A.A6.Bb260, compounds I.B.A6.Bb1 to I.B.A6.Bb260; compounds
I.C.A6.Bb1 to I.C.A6.Bb260; compounds I.D.A6.Bb1 to I.D.A6.Bb260; compounds I.E.A6.Bb1 to I.E.A6.Bb260; compounds I.F.A6.Bb1 to I.F.A6.Bb260; compounds I.G.A6.Bb1 to I.G.A6.Bb260; compounds I.H.A6.Bb1 to I.H.A6.Bb260).
Table 7a-a
Compounds of the formula LA, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-7 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A7.Bb1 to I.A.A7.Bb260, compounds I.B.A7.Bb1 to I.B.A7.Bb260; compounds
I.C.A7.Bb1 to I.C.A7.Bb260; compounds I.D.A7.Bb1 to I.D.A7.Bb260; compounds LE.A7.Bb1 to I.E.A7.Bb260; compounds I.F.A7.Bb1 to I.F.A7.Bb260; compounds I.G.A7.Bb1 to I.G.A7.Bb260; compounds I.H.A7.Bb1 to I.H.A7.Bb260).
Table 8a-a
Compounds of the formula LA, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-8 of Table A and the meaning for the combination of (R3)n, (R4)m, R7 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A8.Bb1 to I.A.A8.Bb260, compounds I.B.A8.Bb1 to I.B.A8.Bb260; compounds
I.C.A8.Bb1 to I.C.A8.Bb260; compounds I.D.A8.Bb1 to I.D.A8.Bb260; compounds I.E.A8.Bb1 to I.E.A8.Bb260; compounds I.F.A8.Bb1 to I.F.A8.Bb260; compounds I.G.A8.Bb1 to I.G.A8.Bb260; compounds I.H.A8.Bb1 to I.H.A8.Bb260).
Table 9a-a
Compounds of the formula LA, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-9 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A9.Bb1 to I.A.A9.Bb260, compounds I.B.A9.Bb1 to I.B.A9.Bb260; compounds
I.C.A9.Bb1 to I.C.A9.Bb260; compounds I.D.A9.Bb1 to I.D.A9.Bb260; compounds I.E.A9.Bb1 to I.E.A9.Bb260; compounds I.F.A9.Bb1 to I.F.A9.Bb260; compounds I.G.A9.Bb1 to I.G.A9.Bb260; compounds I.H.A9.Bb1 to I.H.A9.Bb260).
Table 10a-a
Compounds of the formula LA, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-10 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A10.Bb1 to I.A.A10.Bb260, compounds I.B.A10.Bb1 to I.B.A10.Bb260; compounds I.C.A10.Bb1 to I.C.A10.Bb260; compounds I.D.A10.Bb1 to I.D.A10.Bb260; compounds
I.E.A10.Bb1 to I.E.A10.Bb260; compounds LF.A10.Bb1 to I.F.A10.Bb260; compounds
I.G.A10.Bb1 to I.G.A10.Bb260; compounds I.H.A10.Bb1 to I.H.A10.Bb260).
Table 1 1 a-a
Compounds of the formula LA, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-1 1 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A11 .Bb1 to I.A.A1 1.Bb260, compounds I.B.A11.Bb1 to I.B.A1 1.Bb260; compounds I.C.A11 .Bb1 to I.C.A1 1.Bb260; compounds I.D.A1 1.Bb1 to I.D.A1 1.Bb260; compounds
I.E.A1 1.Bb1 to I.E.A1 1.Bb260; compounds I.F.A1 1.Bb1 to I.F.A1 1.Bb260; compounds
I.G.A1 1.Bb1 to I.G.A1 1.Bb260; compounds I. H.A1 1.Bb1 to I.H.A1 1.Bb260).
Table 12a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-12 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (com- pounds I.A.A12.Bb1 to I.A.A12.Bb260, compounds I.B.A12.BM to I.B.A12.Bb260; compounds I.C.A12.Bb1 to I.C.A12.Bb260; compounds I.D.A12.Bb1 to I.D.A12.Bb260; compounds
I.E.A12.Bb1 to I.E.A12.Bb260; compounds I.F.A12.Bb1 to I.F.A12.Bb260; compounds
I.G.A12.Bb1 to I.G.A12.Bb260; compounds I.H.A12.Bb1 to I.H.A12.Bb260).
Table 13a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-13 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A13.Bb1 to I.A.A13.Bb260, compounds I.B.A13.Bb1 to I.B.A13.Bb260; compounds I.C.A13.Bb1 to I.C.A13.Bb260; compounds I.D.A13.Bb1 to I.D.A13.Bb260; compounds
I.E.A13.Bb1 to I.E.A13.Bb260; compounds I.F.A13.Bb1 to I.F.A13.Bb260; compounds
I.G.A13.Bb1 to I.G.A13.Bb260; compounds I.H.A13.Bb1 to I.H.A13.Bb260).
Table 14a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-14 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A14.Bb1 to I.A.A14.Bb260, compounds I.B.A14.Bb1 to I.B.A14.Bb260; compounds I.C.A14.Bb1 to I.C.A14.Bb260; compounds I.D.A14.Bb1 to I.D.A14.Bb260; compounds
I.E.A14.Bb1 to I.E.A14.Bb260; compounds I.F.A14.Bb1 to I.F.A14.Bb260; compounds
I.G.A14.Bb1 to I.G.A14.Bb260; compounds I.H.A14.BM to I.H.A14.Bb260).
Table 15a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-15 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A15.Bb1 to I.A.A15.Bb260, compounds I.B.A15.Bb1 to I.B.A15.Bb260; compounds I.C.A15.Bb1 to I.C.A15.Bb260; compounds I.D.A15.Bb1 to I.D.A15.Bb260; compounds
I.E.A15.BM to I.E.A15.Bb260; compounds I.F.A15.Bb1 to I.F.A15.Bb260; compounds
I.G.A15.BM to I.G.A15.Bb260; compounds I.H.A15.BM to I.H.A15.Bb260).
Table 16a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-16 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A16.Bb1 to I.A.A16.Bb260, compounds I.B.A16.Bb1 to I.B.A16.Bb260; compounds I.C.A16.Bb1 to I.C.A16.Bb260; compounds I.D.A16.Bb1 to I.D.A16.Bb260; compounds I.E.A16.Bb1 to I.E.A16.Bb260; compounds I.F.A16.Bb1 to I.F.A16.Bb260; compounds
I.G.A16.BM to I.G.A16.Bb260; compounds I.H.A16.BM to I.H.A16.Bb260).
Table 17a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-17 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds I.A.A17.Bb1 to I.A.A17.Bb260, compounds I.B.A17.Bb1 to I.B.A17.Bb260; compounds I.C.A17.Bb1 to I.C.A17.Bb260; compounds I.D.A17.Bb1 to I.D.A17.Bb260; compounds I.E.A17.Bb1 to I.E.A17.Bb260; compounds I.F.A17.Bb1 to I.F.A17.Bb260; compounds
I.G.A17.Bb1 to I.G.A17.Bb260; compounds I.H.A17.Bb1 to I.H.A17.Bb260).
Table 18a-a
Compounds of the formula I .A, I.B. I.C, I.D, I.E, I.F, I.G, I.H in which the combination of R5 and R6 corresponds to line A-18 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (com- pounds I.A.A18.Bb1 to I.A.A18.Bb260, compounds I.B.A18.Bb1 to I.B.A18.Bb260; compounds I.C.A18.Bb1 to I.C.A18.Bb260; compounds I.D.A18.Bb1 to I.D.A18.Bb260; compounds I.E.A18.Bb1 to I.E.A18.Bb260; compounds I.F.A18.Bb1 to I.F.A18.Bb260; compounds
I. G.A18.Bb1 to I.G.A18.Bb260; compounds I.H.A18.Bb1 to I.H.A18.Bb260).
Table 1 a-b
Compounds of the formula II.A, II. B. M.C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-1 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A1.Bb1 to II.A.A1 .Bb260, compounds II.B.A1.Bb1 to II.B.A1.Bb260; compounds II.C.A1.Bb1 to II.C.A1.Bb260; compounds II.D.A1.Bb1 to II.D.A1.Bb260; compounds II.E.A1.Bb1 to II.E.A1 .Bb260; compounds II.F.A1.Bb1 to II.F.A1.Bb260; compounds II.G.A1.Bb1 to II.G.A1.Bb260; compounds II.H.A1 .Bb1 to II.H.A1.Bb260).
Table 2a-b
Compounds of the formula II.A, II. B. M.C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-2 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A2.Bb1 to II.A.A2.Bb260, compounds II.B.A2.Bb1 to II.B.A2.Bb260; compounds II.C.A2.Bb1 to II.C.A2.Bb260; compounds II.D.A2.Bb1 to II.D.A2.Bb260; compounds
II. E.A2.Bb1 to II.E.A2.Bb260; compounds II.F.A2.Bb1 to II.F.A2.Bb260; compounds II.G.A2.Bb1 to II.G.A2.Bb260; compounds II.H.A2.Bb1 to II.H.A2.Bb260).
Table 3a-b
Compounds of the formula II.A, II. B. M.C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-3 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A3.Bb1 to II.A.A3.Bb260, compounds II.B.A3.Bb1 to II.B.A3.Bb260; com- pounds II.C.A3.Bb1 to II.C.A3.Bb260; compounds II.D.A3.Bb1 to II.D.A3.Bb260; compounds II.E.A3.Bb1 to II.E.A3.Bb260; compounds II.F.A3.Bb1 to II.F.A3.Bb260; compounds II.G.A3.Bb1 to II.G.A3.Bb260; compounds II.H.A3.Bb1 to II.H.A3.Bb260). Table 4a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-4 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A4.Bb1 to II.A.A4.Bb260, compounds II.B.A4.Bb1 to II.B.A4.Bb260; compounds II.C.A4.Bb1 to II.C.A4.Bb260; compounds II.D.A4.Bb1 to II.D.A4.Bb260; compounds II.E.A4.Bb1 to II.E.A4.Bb260; compounds II.F.A4.Bb1 to II.F.A4.Bb260; compounds II.G.A4.Bb1 to II.G.A4.Bb260; compounds II.H.A4.Bb1 to II.H.A4.Bb260).
Table 5a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-5 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A5.Bb1 to II.A.A5.Bb260, compounds II.B.A5.Bb1 to II.B.A5.Bb260; compounds II.C.A5.Bb1 to II.C.A5.Bb260; compounds II.D.A5.Bb1 to II.D.A5.Bb260; compounds II.E.A5.Bb1 to II.E.A5.Bb260; compounds II.F.A5.Bb1 to II.F.A5.Bb260; compounds II.G.A5.Bb1 to II.G.A5.Bb260; compounds II.H.A5.Bb1 to II.H.A5.Bb260).
Table 6a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-6 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A6.Bb1 to II.A.A6.Bb260, compounds II.B.A6.Bb1 to II.B.A6.Bb260; compounds II.C.A6.Bb1 to II.C.A6.Bb260; compounds II.D.A6.Bb1 to II.D.A6.Bb260; compounds II.E.A6.Bb1 to II.E.A6.Bb260; compounds II.F.A6.Bb1 to II.F.A6.Bb260; compounds II.G.A6.Bb1 to II.G.A6.Bb260; compounds II.H.A6.Bb1 to II.H.A6.Bb260).
Table 7a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-7 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A7.Bb1 to II.A.A7.Bb260, compounds II.B.A7.Bb1 to II.B.A7.Bb260; com- pounds II.C.A7.Bb1 to II.C.A7.Bb260; compounds II.D.A7.Bb1 to II.D.A7.Bb260; compounds
II.E.A7.Bb1 to II.E.A7.Bb260; compounds II.F.A7.Bb1 to II.F.A7.Bb260; compounds II.G.A7.Bb1 to II.G.A7.Bb260; compounds II.H.A7.Bb1 to II.H.A7.Bb260).
Table 8a-b
Compounds of the formula 11. A, H.B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-8 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A8.Bb1 to II.A.A8.Bb260, compounds II.B.A8.Bb1 to II.B.A8.Bb260; compounds II.C.A8.Bb1 to II.C.A8.Bb260; compounds II.D.A8.Bb1 to II.D.A8.Bb260; compounds II.E.A8.Bb1 to II.E.A8.Bb260; compounds II.F.A8.Bb1 to II.F.A8.Bb260; compounds II.G.A8.Bb1 to II.G.A8.Bb260; compounds II.H.A8.Bb1 to II.H.A8.Bb260).
Table 9a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-9 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A9.Bb1 to II.A.A9.Bb260, compounds II.B.A9.Bb1 to II.B.A9.Bb260; compounds II.C.A9.Bb1 to II.C.A9.Bb260; compounds II.D.A9.Bb1 to II.D.A9.Bb260; compounds II.E.A9.Bb1 to II.E.A9.Bb260; compounds II.F.A9.Bb1 to II.F.A9.Bb260; compounds II.G.A9.Bb1 to II.G.A9.Bb260; compounds II.H.A9.Bb1 to II.H.A9.Bb260).
Table 10a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-10 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A10.Bb1 to II.A.A10.Bb260, compounds II.B.A10.Bb1 to II.B.A10.Bb260; compounds II.C.A10.Bb1 to II.C.A10.Bb260; compounds II.D.A10.Bb1 to II.D.A10.Bb260; compounds II.E.A10.Bb1 to II.E.A10.Bb260; compounds II.F.A10.Bb1 to II.F.A10.Bb260; compounds II.G.A10.Bb1 to II.G.A10.Bb260; compounds II.H.A10.Bb1 to II.H.A10.Bb260).
Table 1 1 a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-1 1 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A11.Bb1 to II.A.A11.Bb260, compounds II.B.A11.Bb1 to II.B.A11 .Bb260; compounds II.C.A11.Bb1 to II.C.A11.Bb260; compounds II.D.A11 .Bb1 to II.D.A1 1.Bb260; com- pounds II.E.A11.Bb1 to II.E.A11.Bb260; compounds II.F.A11.Bb1 to II.F.A11.Bb260; compounds II.G.A11.Bb1 to II.G.A11 .Bb260; compounds II.H.A1 1.Bb1 to II.H.A11.Bb260).
Table 12a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-12 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb
(compounds II.A.A12.Bb1 to II.A.A12.Bb260, compounds II.B.A12.Bb1 to II.B.A12.Bb260; compounds II.C.A12.Bb1 to II.C.A12.Bb260; compounds II.D.A12.Bb1 to II.D.A12.Bb260; compounds II.E.A12.Bb1 to II.E.A12.Bb260; compounds II.F.A12.Bb1 to II.F.A12.Bb260; compounds II.G.A12.Bb1 to II.G.A12.Bb260; compounds II.H.A12.Bb1 to II.H.A12.Bb260).
Table 13a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-13 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A13.Bb1 to II.A.A13.Bb260, compounds II.B.A13.Bb1 to II.B.A13.Bb260; com- pounds II.C.A13.Bb1 to II.C.A13.Bb260; compounds II.D.A13.Bb1 to II.D.A13.Bb260; compounds II.E.A13.Bb1 to II.E.A13.Bb260; compounds II.F.A13.Bb1 to II.F.A13.Bb260; compounds II.G.A13.Bb1 to II.G.A13.Bb260; compounds II.H.A13.Bb1 to II.H.A13.Bb260).
Table 14a-b
Compounds of the formula 11. A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-1 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A14.Bb1 to II.A.A14.Bb260, compounds II.B.A14.Bb1 to II.B.A14.Bb260; compounds II.C.A14.Bb1 to II.C.A14.Bb260; compounds II.D.A14.Bb1 to II.D.A14.Bb260; com- pounds II.E.A14.Bb1 to II.E.A14.Bb260; compounds II.F.A14.Bb1 to II.F.A14.Bb260; compounds II.G.A14.Bb1 to II.G.A14.Bb260; compounds II.H.A14.Bb1 to II.H.A14.Bb260).
Table 15a-b
Compounds of the formula II.A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-15 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A15.Bb1 to II.A.A15.Bb260, compounds II.B.A15.Bb1 to II.B.A15.Bb260; compounds II.C.A15.Bb1 to II.C.A15.Bb260; compounds II.D.A15.Bb1 to II.D.A15.Bb260; compounds II.E.A15.Bb1 to II.E.A15.Bb260; compounds II.F.A15.Bb1 to II.F.A15.Bb260; com- pounds II.G.A15.Bb1 to II.G.A15.Bb260; compounds II.H.A15.Bb1 to II.H.A15.Bb260).
Table 16a-b
Compounds of the formula II.A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-16 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A16.Bb1 to II.A.A16.Bb260, compounds II.B.A16.Bb1 to II.B.A16.Bb260; compounds II.C.A16.Bb1 to II.C.A16.Bb260; compounds II.D.A16.Bb1 to II.D.A16.Bb260; compounds II.E.A16.Bb1 to II.E.A16.Bb260; compounds II.F.A16.Bb1 to II.F.A16.Bb260; compounds II.G.A16.Bb1 to II.G.A16.Bb260; compounds II.H.A16.Bb1 to II.H.A16.Bb260).
Table 17a-b
Compounds of the formula II.A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-17 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb (compounds II.A.A17.Bb1 to II.A.A17.Bb260, compounds II.B.A17.Bb1 to II.B.A17.Bb260; compounds II.C.A17.Bb1 to II.C.A17.Bb260; compounds II.D.A17.Bb1 to II.D.A17.Bb260; com- pounds II.E.A17.Bb1 to II.E.A17.Bb260; compounds II.F.A17.Bb1 to II.F.A17.Bb260; compounds II.G.A17.Bb1 to II.G.A17.Bb260; compounds II.H.A17.Bb1 to II.H.A17.Bb260).
Table 18a-b
Compounds of the formula II.A, II. B. II. C, II. D, II. E, II. F, II. G, II. H in which the combination of R5 and R6 corresponds to line A-18 of Table A and the meaning for the combination of (R3)n, (R4)m, R71 and R72 for each individual compound corresponds in each case to one line of Table Bb
(compounds II.A.A18.Bb1 to II.A.A18.Bb260, compounds II.B.A18.Bb1 to II.B.A18.Bb260; compounds II.C.A18.Bb1 to II.C.A18.Bb260; compounds II.D.A18.Bb1 to II.D.A18.Bb260; compounds II.E.A18.Bb1 to II.E.A18.Bb260; compounds II.F.A18.Bb1 to II.F.A18.Bb260; compounds II.G.A18.Bb1 to II.G.A18.Bb260; compounds II.H.A18.Bb1 to II.H.A18.Bb260).
Table A:
Figure imgf000063_0001
line R5 R6 line R5 R6
A-9 OCHs H A-14 =CH2
A-10 OCH2CH3 H A-15 cyclopropyl
A-1 1 OCH(CH3)2 H A-16 cyclobutyl
A-12 CH3 CH3 A-17 cyclopentyl
A-13 CH2CH3 CH2CH3 A-18 cyclohexyl
Table B
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Table Bb
Figure imgf000122_0002
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
According to one embodiment, the present invention relates to compounds of the formulae III.A to III. F each of them representing a specific embodiment of the invention, wherein the variables are defined and preferably defined as given herein for compounds I:
Figure imgf000130_0001
Figure imgf000130_0002
According to one embodiment, the present invention relates to compounds of the formulae IV.A to IV.R, each of them representing a specific embodiment of the invention, wherein the variables are defined and preferably defined as given herein for compounds I:
Figure imgf000131_0001
Figure imgf000131_0002
I .
Preference is given to the compounds I according to the invention compiled in Tables 1 a-lll to 10a-lll, 1 a-IV to 10a-IV below with the proviso as defined above. The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question. Table 1 a-lll
Compounds of the formula III.A, 111.13, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III. K, III.L, III.M, III.N, III. O , IMP, III.Q, IM.R in which the combination of 71 and R72 corresponds to line C-1 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C1 P1 to III.A.C1 P180; compounds III.B.C1 P1 to III.B.C1 .P180; compounds III.C.C1.P1 to III.C.C1.P180; compounds III.D.C1.P1 to
III.D.C1 .P180; compounds III.E.C1.P1 to III.E.C1.P180; compounds III.F.C1.P1 to
III.F.C1.P180; compounds III.G.C1.P1 to III.G.C1.P180; compounds III.H.C1.P1 to
III.H.C1 .P180; compounds III.I.C1.P1 to III.I.C1.P180; compounds III.J.C1.P1 to III.J.C1.P180; compounds III.K.C1.P1 to III.K.C1.P180; compounds III.L.C1.P1 to III.L.C1.P180; compounds III.M.C1.P1 to III.M.C1.P180; compounds III.N.C1.P1 to III.N.C1 P180; compounds III.O.C1.P1 to III.O.C1.P180; compounds III.P.C1 .P1 to III.P.C1.P180; compounds III.Q.C1.P1 to
III.Q.C1 .P180; compounds III.R.C1.P1 to III.R.C1 P180;).
Table 2a-lll
Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III. K, III.L, III.M, III.N, III.O, NIP, III.Q, IMP in which the combination of R71 and R72 corresponds to line C-2 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C2.P1 to 111.A.C2.P180; compounds III.B.C2.P1 to III.B.C2P180; compounds III.C.C2P1 to III.C.C2P180; compounds III.D.C2P1 to
III.D.C2.P180; compounds III.E.C2.P1 to III.E.C2.P180; compounds III.F.C2.P1 to
III.F.C2.P180; compounds III.G.C2.P1 to III.G.C2.P180; compounds III.H.C2.P1 to
III.H.C2.P180; compounds III.I.C2.P1 to III.I.C2.P180; compounds III.J.C2.P1 to III.J.C2.P180; compounds III.K.C2.P1 to III.K.C2.P180; compounds III.L.C2.P1 to III.L.C2.P180; compounds III.M.C2P1 to III.M.C2P180; compounds III.N.C2P1 to III.N.C2P180; compounds III.O.C2P1 to III.O.C2.P180; compounds III.P.C2.P1 to III.P.C2.P180; compounds III.Q.C2.P1 to
III.Q.C2.P180; compounds III.R.C2.P1 to III.R.C2.P180;).
Table 3a-lll
Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III.K, III.L, III.M, III.N, III.O, NIP, III.Q, IMP in which the combination of R71 and R72 corresponds to line C-3 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C3.P1 to III.A.C3.P180; compounds III.B.C3.P1 to III.B.C3.P180; compounds III.C.C3.P1 to III .C.C3.P180; compounds III.D.C3.P1 to
III.D.C3.P180; compounds III.E.C3.P1 to III.E.C3.P180; compounds III.F.C3.P1 to
III.F.C3.P180; compounds III.G.C3.P1 to III.G.C3.P180; compounds III.H.C3.P1 to
III.H.C3.P180; compounds III.I.C3P1 to III.I.C3P180; compounds III.J.C3P1 to III.J.C3P180; compounds III.K.C3.P1 to III.K.C3.P180; compounds III.L.C3.P1 to I II.L.C3.P180; compounds III.M.C3.P1 to III.M.C3.P180; compounds III.N.C3.P1 to III.N.C3.P180; compounds III.O.C3.P1 to III.O.C3.P180; compounds III.P.C3.P1 to III.P.C3.P180; compounds III.Q.C3.P1 to
III.Q.C3.P180; compounds III.R.C3.P1 to III.R.C3.P180;).
Table 4a-lll Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III. K, III.L, III.M, III.N, III.O, III.P, III.Q, MLR in which the combination of R71 and R72 corresponds to line C-4 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A. C4P1 to III.A.C4.P180; compounds III.B.C4.P1 to III.B.C4.P180; compounds III.C.C4.P1 to III.C.C4.P180; compounds III.D.C4.P1 to
III.D.C4.P180; compounds III.E.C4.P1 to III.E.C4.P180; compounds III.F.C4.P1 to
III.F.C4.P180; compounds III.G.C4.P1 to III.G.C4.P180; compounds III.H.C4.P1 to
III.H.C4.P180; compounds III.I.C4.P1 to III.I.C4P180; compounds III.J.C4P1 to III.J.C4P180; compounds III.K.C4.P1 to III.K.C4.P180; compounds III.L.C4.P1 to I II.L.C4.P180; compounds III.M.C4.P1 to III.M.C4.P180; compounds III.N.C4.P1 to III.N.C4.P180; compounds III.O.C4.P1 to III.O.C4.P180; compounds III.P.C4.P1 to III.P.C4.P180; compounds III.Q.C4.P1 to
III.Q.C4.P180; compounds III.R.C4.P1 to III.R.C4.P180;).
Table 5a-lll
Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III.K, III.L, III.M, III.N, III.O, III.P, III.Q, MLR in which the combination of R71 and R72 corresponds to line C-5 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C5.P1 to III.A.C5.P180; compounds III.B.C5.P1 to III.B.C5.P180; compounds III.C.C5.P1 to III .C.C5.P180; compounds III.D.C5.P1 to
III.D.C5.P180; compounds III.E.C5.P1 to III.E.C5.P180; compounds III.F.C5.P1 to
III.F.C5P180; compounds III.G.C5P1 to III.G.C5P180; compounds IILH.C5.P1 to
III.H.C5.P180; compounds III.LC5P1 to III.I.C5P180; compounds IILJ.C5P1 to III.J.C5P180; compounds III.K.C5.P1 to III.K.C5.P180; compounds III.L.C5.P1 to I II.L.C5.P180; compounds III.M.C5P1 to III.M.C5P180; compounds III.N.C5.P1 to III.N.C5.P180; compounds III.O.C5.P1 to III.O.C5.P180; compounds III.P.C5.P1 to III.P.C5.P180; compounds III.Q.C5.P1 to
III.Q.C5.P180; compounds III.R.C5P1 to III.R.C5.P180;).
Table 6a-lll
Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, II. I. III.J, III.K, III.L, III.M, III.N, III.O, III.P, III.Q, MLR in which the combination of R71 and R72 corresponds to line C-6 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C6.P1 to III.A.C6.P180; compounds III.B.C6.P1 to III.B.C6.P180; compounds III.C.C6.P1 to III.C.C6.P180; compounds III.D.C6.P1 to
III.D.C6.P180; compounds III.E.C6.P1 to III.E.C6.P180; compounds III.F.C6.P1 to
III.F.C6P180; compounds III.G.C6.P1 to III.G.C6P180; compounds IILH.C6.P1 to
III.H.C6.P180; compounds III.I.C6.P1 to I II.I.C6.P180; compounds III.J.C6.P1 to I II.J.C6.P180; compounds III.K.C6.P1 to III.K.C6.P180; compounds III.L.C6.P1 to I II.L.C6.P180; compounds III.M.C6P1 to III.M.C6P180; compounds IILN.C6.P1 to III.N.C6P180; compounds III.O.C6.P1 to III.O.C6.P180; compounds III.P.C6.P1 to III.P.C6.P180; compounds III.Q.C6.P1 to
III.Q.C6.P180; compounds III.R.C6.P1 to III.R.C6.P180;).
Table 7a-lll Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III I, III.K, III.L, III.M,
III.N, III.O, III.P, III.Q, NIP in which the combination of R71 and R72 corresponds to line C-7 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C7P1 to III.A.C7P180; compounds III.B.C7P1 to III.B.C7P180; compounds III.C.C7P1 to III.C.C7P180; compounds III.D.C7P1 to
III.D.C7P180; compounds III.E.C7P1 to III.E.C7P180; compounds IILF.C7P1 to
III.F.C7.P180; compounds III.G.C7P1 to III.G.C7P180; compounds III.H.C7P1 to
III.H.C7P180; compounds III.I.C7P1 to III.I.C7P180; compounds III.J.C7P1 to III.J.C7P180; compounds III.K.C7P1 to III.K.C7P180; compounds III.L.C7P1 to III.L.C7P180; compounds III.M.C7P1 to III.M.C7P180; compounds III.N.C7P1 to III.N.C7P180; compounds III.O.C7P1 to III.O.C7P180; compounds IIIP.C7P1 to IIIP.C7P180; compounds III.Q.C7P1 to
III.Q.C7P180; compounds IIIP.C7P1 to IIIP.C7P180;).
Table 8a-lll
Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III.K, III.L, III.M, III.N, III.O, III.P, III.Q, NIP in which the combination of R71 and R72 corresponds to line C-8 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C8.P1 to III.A.C8.P180; compounds III.B.C8.P1 to III.B.C8.P180; compounds III.C.C8.P1 to III .C.C8.P180; compounds III.D.C8.P1 to
III.D.C8.P180; compounds III.E.C8.P1 to III.E.C8.P180; compounds III.F.C8.P1 to
III.F.C8P180; compounds III.G.C8.P1 to III.G.C8P180; compounds III.H.C8.P1 to
III.H.C8.P180; compounds III.I.C8P1 to III.I.C8P180; compounds III.J.C8P1 to III.J.C8P180; compounds III.K.C8.P1 to III.K.C8.P180; compounds III.L.C8.P1 to I II.L.C8.P180; compounds III.M.C8P1 to III.M.C8P180; compounds III.N.C8.P1 to III.N.C8P180; compounds III.O.C8P1 to III.O.C8.P180; compounds III.P.C8.P1 to III.P.C8.P180; compounds III.Q.C8.P1 to
III.Q.C8.P180; compounds IIIP.C8P1 to III.R.C8.P180;).
Table 9a-lll
Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III.K, III.L, III.M, III.N, III.O, III.P, III.Q, NIP in which the combination of R71 and R72 corresponds to line C-9 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C9.P1 to III.A.C9.P180; compounds III.B.C9.P1 to III.B.C9.P180; compounds III.C.C9.P1 to III.C.C9.P180; compounds III.D.C9.P1 to
III.D.C9.P180; compounds III.E.C9.P1 to III.E.C9.P180; compounds III.F.C9.P1 to
III.F.C9.P180; compounds III.G.C9.P1 to III.G.C9.P180; compounds III.H.C9.P1 to
III.H.C9.P180; compounds III.I.C9.P1 to I II.I.C9.P180; compounds III.J.C9.P1 to I II.J.C9.P180; compounds III.K.C9.P1 to III.K.C9.P180; compounds III.L.C9.P1 to I II.L.C9.P180; compounds III.M.C9.P1 to III.M.C9.P180; compounds III.N.C9.P1 to III.N.C9.P180; compounds III.O.C9.P1 to III.O.C9.P180; compounds III.P.C9.P1 to IIIP.C9.P180; compounds III.Q.C9.P1 to
III.Q.C9.P180; compounds III.R.C9.P1 to III.R.C9.P180;).
Table 10a-lll
Table 1 a-IV Compounds of the formula III.A, III.B, III.C, III.D, III.E, III.F, III.G, III.H, III. I, III.J, III.K, III.L, III.M, III.N, III.O, III.P, III.Q, IMP in which the combination of R71 and R72 corre- sponds to line C-10 of Table C and the meaning for ( 3)n for each individual compound corresponds in each case to one line of Table P (compounds III.A.C10.P1 to III.A.C10.P180; compounds III.B.C10.P1 to III.B.C10.P180; compounds III.C.C10.P1 to I II.C.C10.P180; compounds III.D.C10.P1 to III.D.C10.P180; compounds III.E.C10.P1 to I II.E.C10.P180; compounds III.F.C10.P1 to III.F.C10.P180; compounds III.G.C10.P1 to III.G.C10.P180; compounds III.H.C10.P1 to III.H.C10.P180; compounds III.I.C10.P1 to III.I.C10.P180; compounds
III.J.C10.P1 to III.J.C10.P180; compounds III.K.C10.P1 to III.K.C10.P180; compounds
III.L.C10.P1 to III.L.C10.P180; compounds III.M.C10.P1 to III.M.C10.P180; compounds III.N.C10.P1 to III.N.C10.P180; compounds III.O.C10.P1 to 111.O.C10.P180; compounds III.P.C10.P1 to III.P.C10.P180; compounds III.Q.C10.P1 to III.Q.C10.P180; compounds
III. R.C10.P1 to III.R.C10.P180).
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H, IV.I, IV.J, IV.K, IV.L,
IV. M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C-
1 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C1.P1 to IV.A.C1.P180; compounds IV.B.C1.P1 to
IV.B.C1 .P180; compounds IV.C.C1 .P1 to IV.C.C1.P180; compounds IV.D.C1.P1 to
IV.D.C1.P180; compounds IV.E.C1 .P1 to IV.E.C1.P180; compounds IV.F.C1.P1 to
IV.F.C1 .P180; compounds IV.G.C1 .P1 to IV.G.C1.P180; compounds IV.H.C1.P1 to
IV.H.C1.P180; compounds IV.I.C1.P1 to IV.I.C1.P180; compounds IV.J.C1.P1 to IV.J.C1.P180; compounds IV.K.C1.P1 to IV.K.C1.P180; compounds IV.L.C1.P1 to IV.L.C1.P180; compounds IV.M.C1.P1 to IV.M.C1.P180; compounds IV.N.C1 .P1 to IV.N.C1.P180; compounds IV.O.C1.P1 to IV.O.C1 .P180; compounds IV.P.C1.P1 to IV.P.C1.P180; compounds IV.Q.C1.P1 to
IV.Q.C1.P180; compounds IV.R.C1.P1 to IV.R.C1.P180;).
Table 2a-IV
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H, IV.I, IV.J, IV.K, IV.L,
IV.M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C-
2 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C2.P1 to IV.A.C2.P180; compounds IV.B.C2.P1 to IV.B.C2.P180; compounds IV.C.C2.P1 to IV.C.C2.P180; compounds IV.D.C2.P1 to
IV.D.C2.P180; compounds IV.E.C2.P1 to IV.E.C2.P180; compounds IV.F.C2.P1 to
IV.F.C2.P180; compounds IV.G.C2.P1 to IV.G.C2.P180; compounds IV.H.C2.P1 to
IV.H.C2.P180; compounds IV.I.C2.P1 to IV.I.C2.P180; compounds IV.J.C2.P1 to IV.J.C2.P180; compounds IV.K.C2.P1 to IV.K.C2.P180; compounds IV.L.C2.P1 to IV.L.C2.P180; compounds IV.M.C2.P1 to IV.M.C2.P180; compounds IV.N.C2.P1 to IV.N.C2.P180; compounds IV.O.C2.P1 to IV.O.C2.P180; compounds IV.P.C2.P1 to IV.P.C2.P180; compounds IV.Q.C2.P1 to
IV.Q.C2.P180; compounds IV.R.C2.P1 to IV.R.C2.P180;).
Table 3a-IV
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H, IV.I, IV.J, IV.K, IV.L, IV.M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C- 3 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C3.P1 to IV.A.C3.P180; compounds IV.B.C3.P1 to IV.B.C3.P180; compounds IV.C.C3.P1 to IV.C.C3.P180; compounds IV.D.C3.P1 to IV.D.C3.P180; compounds IV.E.C3.P1 to IV.E.C3.P180; compounds IV.F.C3.P1 to
IV.F.C3.P180; compounds IV.G.C3.P1 to IV.G.C3.P180; compounds IV.H.C3.P1 to
IV.H.C3.P180; compounds IV.I.C3.P1 to IV.I.C3.P180; compounds IV.J.C3.P1 to IV.J.C3.P180; compounds IV.K.C3.P1 to IV.K.C3.P180; compounds IV.L.C3.P1 to IV.L.C3.P180; compounds IV.M.C3.P1 to IV.M.C3.P180; compounds IV.N.C3.P1 to IV.N.C3.P180; compounds IV.O.C3.P1 to IV.O.C3.P180; compounds IV.P.C3.P1 to IV.P.C3.P180; compounds IV.Q.C3.P1 to
IV.Q.C3.P180; compounds IV.R.C3.P1 to IV.R.C3.P180;).
Table 4a-IV
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H, IV.I, IV.J, IV.K, IV.L, IV.M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C-
4 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C4.P1 to IV.A.C4.P180; compounds IV.B.C4.P1 to IV.B.C4.P180; compounds IV.C.C4.P1 to IV.C.C4.P180; compounds IV.D.C4.P1 to
IV.D.C4.P180; compounds IV.E.C4.P1 to IV.E.C4.P180; compounds IV.F.C4.P1 to
IV.F.C4.P180; compounds IV.G.C4.P1 to IV.G.C4.P180; compounds IV.H.C4.P1 to
IV.H.C4.P180; compounds IV.I.C4.P1 to IV.I.C4.P180; compounds IV.J.C4.P1 to IV.J.C4.P180; compounds IV.K.C4.P1 to IV.K.C4.P180; compounds IV.L.C4.P1 to IV.L.C4.P180; compounds IV.M.C4.P1 to IV.M.C4.P180; compounds IV.N.C4.P1 to IV.N.C4.P180; compounds IV.O.C4.P1 to IV.O.C4.P180; compounds IV.P.C4.P1 to IV.P.C4.P180; compounds IV.Q.C4.P1 to
IV.Q.C4.P180; compounds IV.R.C4.P1 to IV.R.C4.P180;).
Table 5a-IV
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H, IV.I, IV.J, IV.K, IV.L, IV.M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C-
5 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C5.P1 to IV.A.C5.P180; compounds IV.B.C5.P1 to
IV.B.C5.P 80; compounds IV.C.C5.P1 to IV.C.C5.P 80; compounds IV.D.C5.P1 to
IV.D.C5.P180; compounds IV.E.C5.P1 to IV.E.C5.P180; compounds IV.F.C5.P1 to
IV.F.C5.P180; compounds IV.G.C5.P1 to IV.G.C5.P180; compounds IV.H.C5.P1 to
IV.H.C5.P180; compounds IV.I.C5.P1 to IV.I.C5.P180; compounds IV.J.C5.P1 to IV.J.C5.P180; compounds IV.K.C5.P1 to IV.K.C5.P180; compounds IV.L.C5.P1 to IV.L.C5.P180; compounds IV.M.C5.P1 to IV.M.C5.P180; compounds IV.N.C5.P1 to IV.N.C5.P180; compounds IV.O.C5.P1 to IV.O.C5.P180; compounds IV.P.C5.P1 to IV.P.C5.P180; compounds IV.Q.C5.P1 to
IV.Q.C5.P180; compounds IV.R.C5.P1 to IV.R.C5.P180;).
Table 6a-IV
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H, IV.I, IV.J, IV.K, IV.L,
IV.M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C-
6 of Table C and the meaning for (R3)„ for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C6.P1 to IV.A.C6.P180; compounds IV.B.C6.P1 to IV.B.C6.P180; compounds IV.C.C6.P1 to IV.C.C6.P180; compounds IV.D.C6.P1 to
IV.D.C6.P180; compounds IV.E.C6.P1 to IV.E.C6.P180; compounds IV.F.C6.P1 to
IV.F.C6.P180; compounds IV.G.C6.P1 to IV.G.C6.P180; compounds IV.H.C6.P1 to IV.H.C6.P180; compounds IV.I.C6.P1 to IV.I.C6.P180; compounds IV.J.C6.P1 to IV.J.C6.P180; compounds IV.K.C6.P1 to IV.K.C6.P180; compounds IV.L.C6.P1 to IV.L.C6.P180; compounds IV.M.C6.P1 to IV.M.C6.P180; compounds IV.N.C6.P1 to IV.N.C6.P180; compounds IV.O.C6.P1 to IV.O.C6.P180; compounds IV.P.C6.P1 to IV.P.C6.P180; compounds IV.Q.C6.P1 to
IV.Q.C6.P180; compounds IV.R.C6.P1 to IV.R.C6.P180;).
Table 7a-IV
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H, IV. I, IV.J, IV.K, IV.L, IV.M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C-
7 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C7.P1 to IV.A.C7.P180; compounds IV.B.C7.P1 to
IV.B.C7.P180; compounds IV.C.C7.P1 to IV.C.C7.P180; compounds IV.D.C7.P1 to
IV.D.C7.P180; compounds IV.E.C7.P1 to IV.E.C7.P180; compounds IV.F.C7.P1 to
IV.F.C7.P180; compounds IV.G.C7.P1 to IV.G.C7.P180; compounds IV.H.C7.P1 to
IV.H.C7.P180; compounds IV.I.C7.P1 to IV.I.C7.P180; compounds IV.J.C7.P1 to IV.J.C7.P180; compounds IV.K.C7.P1 to IV.K.C7.P180; compounds IV.L.C7.P1 to IV.L.C7.P180; compounds IV.M.C7.P1 to IV.M.C7.P180; compounds IV.N.C7.P1 to IV.N.C7.P180; compounds IV.O.C7.P1 to IV.O.C7.P180; compounds IV.P.C7.P1 to IV.P.C7.P180; compounds IV.Q.C7.P1 to
IV.Q.C7.P180; compounds IV.R.C7.P1 to IV.R.C7.P180;).
Table 8a-IV
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H, IV.I, IV.J, IV.K, IV.L,
IV.M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C-
8 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C8.P1 to IV.A.C8.P180; compounds IV.B.C8.P1 to IV.B.C8.P180; compounds IV.C.C8.P1 to IV.C.C8.P180; compounds IV.D.C8.P1 to
IV.D.C8.P180; compounds IV.E.C8.P1 to IV.E.C8.P180; compounds IV.F.C8.P1 to
IV.F.C8.P180; compounds IV.G.C8.P1 to IV.G.C8.P180; compounds IV.H.C8.P1 to
IV.H.C8.P180; compounds IV.I.C8.P1 to IV.I.C8.P180; compounds IV.J.C8.P1 to IV.J.C8.P180; compounds IV.K.C8.P1 to IV.K.C8.P180; compounds IV.L.C8.P1 to IV.L.C8.P180; compounds IV.M.C8.P1 to IV.M.C8.P180; compounds IV.N.C8.P1 to IV.N.C8.P180; compounds IV.O.C8.P1 to IV.O.C8.P180; compounds IV.P.C8.P1 to IV.P.C8.P180; compounds IV.Q.C8.P1 to
IV.Q.C8.P180; compounds IV.R.C8.P1 to IV.R.C8.P180;).
Table 9a-IV
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H, IV.I, IV.J, IV.K, IV.L, IV.M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C- 9 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C9.P1 to IV.A.C9.P180; compounds IV.B.C9.P1 to IV.B.C9.P180; compounds IV.C.C9.P1 to IV.C.C9.P180; compounds IV.D.C9.P1 to
IV.D.C9.P180; compounds IV.E.C9.P1 to IV.E.C9.P180; compounds IV.F.C9.P1 to
IV.F.C9.P180; compounds IV.G.C9.P1 to IV.G.C9.P180; compounds IV.H.C9.P1 to
IV.H.C9.P180; compounds IV.I.C9.P1 to IV.I.C9.P180; compounds IV.J.C9.P1 to IV.J.C9.P180; compounds IV.K.C9.P1 to IV.K.C9.P180; compounds IV.L.C9.P1 to IV.L.C9.P180; compounds IV.M.C9.P1 to IV.M.C9.P180; compounds IV.N.C9.P1 to IV.N.C9.P180; compounds IV.O.C9.P1 to IV.O.C9.P180; compounds IV.P.C9.P1 to IV.P.C9.P180; compounds IV.Q.C9.P1 to
IV.Q.C9.P180; compounds IV.R.C9.P1 to IV.R.C9.P180).
Table 10a-IV
Compounds of the formula IV.A, IV.B, IV.C, IV.D, IV.E, IV.F, IV.G, IV.H , IV.I, IV.J, IV.K, IV.L, IV.M, IV.N, IV.O, IV.P, IV.Q, IV.R in which the combination of R71 and R72 corresponds to line C- 10 of Table C and the meaning for (R3)n for each individual compound corresponds in each case to one line of Table P (compounds IV.A.C10.P1 to IV.A.C10.P180; compounds IV.B.C10.P1 to IV.B.C10.P180; compounds IV.C.C10.P1 to IV.C.C10.P180; compounds IV.D.C10.P1 to IV.D.C10.P180; compounds IV.E.C10.P1 to IV.E.C10.P180; compounds IV.F.C10.P1 to IV.F.C10.P180; compounds IV.G.C10.P1 to IV.G.C10.P180; compounds IV.H.C10.P1 to IV.H.C10.P180; compounds IV.I.C10.P1 to IV.I.C10.P180; compounds IV.J.C10.P1 to
IV.J.C10.P180; compounds IV.K.C10.P1 to IV.K.C10.P180; compounds IV.L.C10.P1 to IV.LC10.P180; compounds IV.M.C10.P1 to IV.M.C10.P180; compounds IV.N.C10.P1 to IV.N.C10.P180; compounds IV.O.C10.P1 to IV.O.C10.P180; compounds IV.P.C10.P1 to IV.P.C10.P180; compounds IV.Q.C10.P1 to IV.Q.C10.P180; compounds IV.R.C10.P1 to IV.R.C10.P180).
Table C
Figure imgf000138_0001
The compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungi- cides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
The compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
Preferably, compounds I and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. The- se young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties. Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides 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 sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from anoth- er class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially availa- ble 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 pro- duced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdyster- oid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); 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 capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of 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 Cry1 Ac toxin), Bollgard® I (cotton cultivars producing the CrylAc toxin), Bollgard® II (cotton cultivars producing Cry1 Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protects®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis- related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Er- winia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral 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 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); Alternaria 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 alternata), tomatoes (e. g. A solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A ir/f c (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 (S. zeicola) on corn, e. g. spot blotch (S. sorokiniana) on cereals and e.g. 6. oryzae on rice and turfs; Blumeria (formerly Erysiphe) gram- inis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botry- ofr'n/a fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (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. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose 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 (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Ery- siphe spp. (powdery mildew) on sugar beets (E. 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: Cibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme ) and F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibber- ella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica);
Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Phy- soderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P.
megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad- leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yal- lundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sa- rocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) no- dorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lepto- sphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
The compounds I and compositions thereof, respectively, are also suitable for controlling harm- ful 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 nonliving 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: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
The method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms. According to the present invention, the term "stored products" is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired. Stored products of crop plant origin, such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Stored products of animal origin are hides, leather, furs, hairs and the like. The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold. Preferably "stored products" is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
The compounds I and compositions thereof, resepectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
The compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
The compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
An agrochemical composition comprises a fungicidally effective amount of a compound I. The term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used. The compounds I, their N-oxides and salts can be converted into customary types of agrochem- ical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and compositions thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, 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 compositions thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and compositions thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and compositions 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 & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North Amer- ican Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and compositions thereof. Examples of sulfonates are alkylaryl- sulfonates, 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 ethox- ylated 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 compositions 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 and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I and 1 -10 wt% dispersant (e. g. 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 and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aro- matic hydrocarbon). This composition is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound I are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound I are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of a compound I are added to 5-30 wt% organic solvent blend (e.g. fatty acid dime- thylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alcohol ethoxylate and ar- ylphenol ethoxylate), and water ad 100 %. This composition is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4'-diisocyanatae) are dis- persed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1-10 wt% of a compound I are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%.
xii) Granules (GR, FG)
0.5-30 wt% of a compound I is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or fluidized bed.
xiii) Ultra-low volume liquids (UL)
1-50 wt% of a compound I are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%.
The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
A pesticide is generally a chemical or biological agent (such as a virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term pesticides includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of acrop plant.
Biopesticides are typically created by growing and concentrating naturally occurring organisms and/or their metabolites including bacteria and other microbes, fungi, viruses, nematodes, proteins, etc. They are often considered to be important components of integrated pest management (IPM) programmes.
Biopesticides fall into two major classes, microbial and biochemical pesticides:
(1 ) Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classed as microbial pesticides, even though they are multi-cellular.
Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary composition may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e.g seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
When living microorganisms, such as pesticides from groups L1), L3) and L5), form part of such kit, it must be taken care that choice and amounts of the components (e.g. chemcial pesti- cidal agents) and of the further auxiliaries should not influence the viability of the microbial pesticides in the composition mixed by the user. Especially for bactericides and solvents, compati- bility with the respective microbial pesticide has to be taken into account.
Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit compring a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and option- ally a further active component 3) as defined herein.
Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.
The following list of pesticides (e.g. pesticidally active substances and biopesticides), in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
A) Respiration inhibitors
- Inhibitors of complex III at Q0 site (e.g. strobilurins): azoxystrobin, coumethoxystrobin,
coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/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-di- chlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl- acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone; - 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, (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, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, isopyrazam, 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-difluoroquinazolin- 4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl deri- vates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthi- ofam;
B) Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, bromucona- zole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbu- conazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triti- conazole, 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-chloro- phenoxy)-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; 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; triazolopyrimidines: 5-chloro-7-(4-methyl- piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine
- other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil, mepanipyrim, pyrimethanil;
- 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, fenpiclonil, 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, mandipropa- mid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
- compounds affecting cell membrane permeability and fatty acides: propamocarb, propamo- carb-hydrochlorid
- fatty acid amide hydrolase inhibitors: oxathiapiprolin, 1-[4-[4-[5-(2,6-difluorophenyl)-4,5- dihydro-3-isoxazolyl]-2 hiazolyl]-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 composition, copper acetate, copper hydroxide, cop- per 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, chloro- thalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pen- tachlorphenole 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: validamycin, polyoxin B; melanin synthesis inhibitors: pyroqui- lon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
J) Plant defence inducers
- acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: 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, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, 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 - y|]-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, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetam- ide, 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 , picarbutrazox, pentyl 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]phen-yl]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;
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 michi- ganensis (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. 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. stromati- cum, T. virens (also named Gliocladium virens), T. viride, Typhula phacorrhiza, Ulo- cladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator 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. te- nebrionis, Beauveria bassiana, B. brongniartii , Burkholderia sp., Chromobacterium subtsugae, Cydia pomonella granulosis virus, Cryptophlebia leucotreta granulovirus (CrleGV), Isaria fumosorosea, Heterorhabditis bacteriophora, Lecanicillium long- isporum, L. muscarium (formerly Verticillium lecanii), Metarhizium anisopliae, M. an- isopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Pae- nibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramose, P. rene- formis, P. thornea, P. usgae, Pseudomonas fluorescens, Steinernema carpocapsae, S. feltiae, S. kraussei;
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or ne- maticidal 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- octadecadien-1-ol acetate, (E,Z)-3,13-octadecadien-1-ol, R-1 -octen-3-ol, pentater- manone, potassium silicate, sorbitol actanoate, (E,Z,Z)-3,8,11-tetradecatrienyl acetate,
(Z,E)-9,12-tetradecadien-1 -yl acetate, Z-7-tetradecen-2-one, Z-9-tetradecen-1 -yl acetate, Z-11 -tetradecenal, Z-1 1 -tetradecen-1 -ol, Acacia negra extract, extract of grapefruit seeds and pulp, extract of Chenopodium ambrosiodae, 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, Penicillium bilaiae, Rhizobium leguminosarum bv. phaseoli, R. I. 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, mefe- nacet, 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, thio- bencarb, 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, ox- yfluorfen;
- hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;
- imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
- 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;
- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfu- ron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3- (4,6-dimethoxy-pyrimidin-2-yl)urea;
- triazines: ametryn, atrazine, 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, pyrim- isulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarba- zone,benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromo- butide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlorthal, cinme- thylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl ar- sonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, py- raclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, 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, chlorpyri- fos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethi- on, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phentho- ate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosul- fan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodi- carb, 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) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juve- noids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
- nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, flupyradifurone, 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, spinosad, 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: piperonyl 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, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon.
The present invention furthermore relates to agrochemical compositions comprising a composi- tion of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if desired one suitable solvent or solid carrier. Those compositions are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Fur- thermore, combating harmful fungi with a composition of compounds I and at least one fungicide from groups A) to K), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to K). By applying compounds I together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic composi- tions).
This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or seperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.
When applying a compound of the present invention and a pesticide II sequentially the time between both applications may vary e.g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day. In case of a composition or mixture comprising a pesticide II selected from group L), it is preferred that the pesticide II is applied as last treatment.
According to the invention, the solid material (dry matter) of the biopesticides (with the exception of oils such as Neem oil, Tagetes oil, etc.) are considered as active components (e.g. to be obtained after drying or evaporation of the extraction medium or the suspension medium in case of liquid formulations of the microbial pesticides).
In accordance with the present invention, the weight ratios and percentages used herein for a biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
The total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms, can be determined using the amount of CFU of the respective microorganism to calclulate the total weight of the respective active component with the following equation that 1 x 109 CFU equals one gram of total weight of the respective active component. Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells. In addition, here "CFU" may also be understood as the number of (juvenile) individual nematodes in case of (entomopathogenic) nematode biopesticides, such as
Steinernema feltiae.
In the binary mixtures and compositions according to the invention the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active compo- nents used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1.
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1000:1 to 1 :1 , often in the range of from 100: 1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1.
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1 :1 to 1 :1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
In the ternary mixtures, i.e. compositions according to the invention comprising the component 1 ) and component 2) and a compound III (component 3), the weight ratio of component 1 ) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4: 1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1.
Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1 ).
These ratios are also suitable for inventive mixtures applied by seed treatment.
In two-component-compositions, i.e. compositions according to the invention comprising one compound I (component 1 ) and one further pesticidally 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 three-componentcompositions, i.e. compositions according to the invention comprising one compound I (component 1 ) and a first further pesticidally active substance (component 2) and a second further pesticidally 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 (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, pyra- clostrobin, trifloxystrobin; famoxadone, fenamidone; benzovindiflupyr, bixafen, boscalid, fluopy- ram, 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 (component 1 ) and at least one active substance selected from group B) (component 2) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metcona- zole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, fenarimol, triforine; dodemorph, fenprop- imorph, tridemorph, fenpropidin, spiroxamine; fenhexamid.
Preference is given to compositions comprising a compound of formula I (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 (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 (component 1 ) and at least one active substance selected from group E) (component 2) and particularly selected from cy- prodinil, mepanipyrim, pyrimethanil.
Preference is also given to compositions comprising a compound I (component 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 (component 1 ) and at least one active substance selected from group G) (component 2) and particularly selected from di- methomorph, flumorph, iprovalicarb, benthiavalicarb, mandipropamid, propamocarb.
Preference is also given to compositions comprising a compound I (component 1 ) and at least one active substance selected from group H) (component 2) and particularly selected from cop- per 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 (component 1 ) and at least one active substance selected from group I) (component 2) and particularly selected from car- propamid and fenoxanil.
Preference is also given to compositions comprising a compound I (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 (component 1 ) and at least one active substance selected from group K) (component 2) and particularly selected from cy- moxanil, proquinazid and A/-methyl-2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]- piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide.
The biopesticides from group L) of pesticides II, their preparation and their pesticidal activity e.g. against harmful fungi or insects are known (e-Pesticide Manual V 5.2 (ISBN 978 1 901396 85 0) (2008-201 1 ); http://www.epa.gov/opp00001/biopesticides/, see product lists therein; http://www.omri.org/omri-lists, see lists therein; Bio-Pesticides Database BPDB http://sitem.herts.ac.uk/aeru/bpdb/, see A to Z link therein).
The biopesticides from group L1 ) and/or L2) may also have insecticidal, acaricidal, molluscidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L3) and/or L4) may also have fun- gicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L5) and/or L6) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
Many of these biopesticides are registered and/or are commercially available: aluminium silicate (Screen™ Duo from Certis LLC, USA), Agrobacterium radiobacter K1026 (e.g. NoGall® from Becker Underwood Pty Ltd., Australia), A. radiobacter K84 (Nature 280, 697-699, 1979; e.g. GallTroll® from AG Biochem, Inc., C, USA), Ampelomyces quisqualis M-10 (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract or filtrate (e.g. ORKA GOLD from Becker Underwood, South Africa; or Goemar® from Laboratoires Goemar, France), Aspergillus flavus NRRL 21882 isolated from a peanut in Georgia in 1991 by the USDA, National Peanut Research Laboratory (e.g. in Afla-Guard® from Syngenta, CH), mixtures of Aureobasidium pullulans DSM14940 and DSM 14941 (e.g. blasto- spores in Blossom Protect® from bio-ferm GmbH, Germany), Azospirillum amazonense BR 1 1140 (SpY2T) (Proc. 9th Int. and 1st Latin American PGPR meeting, Quimara, Medellin, Colombia 2012, p. 60, ISBN 978-958-46-0908-3), A. brasilense AZ39 (Eur. J. Soil Biol 45(1 ), 28-35, 2009), A. brasilense XOH (e.g. AZOS from Xtreme Gardening, USA or RTI Reforestation Technologies International; USA), A. brasilense BR 1 1002 (Proc. 9th Int. and 1st Latin American PGPR meeting, Quimara, Medellin, Colombia 2012, p. 60, ISBN 978-958-46-0908-3), A. bra- silense BR 1 1005 (SP245; e.g. in GELFIX Gramineas from BASF Agricultural Specialties Ltd., Brazil), A. lipoferum BR 1 1646 (Sp31 ) (Proc. 9th Int. and 1st Latin American PGPR meeting, Quimara, Medellin, Colombia 2012, p. 60), Bacillus amyloliquefaciens FZB42 (e.g. in Rhi- zoVital® 42 from AbiTEP GmbH, Berlin, Germany), B. amyloliquefaciens IN937a (J. Microbiol. Biotechnol. 17(2), 280-286, 2007; e.g. in BioYield® from Gustafson LLC, TX, USA), B. amylo- liquefaciens IT-45 (CNCM I-3800) (e.g. Rhizocell C from ITHEC, France), B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595, deposited at United States Department of Agriculture) (e.g. Integral®, Subtilex® NG from Becker Underwood, USA), B. cereus CNCM 1-1562 (US 6,406,690), B. firmus CNCM 1-1582 (WO 2009/126473, WO 2009/124707, US 6,406,690; Voti- vo® from Bayer Crop Science LP, USA), B. pumilus GB34 (ATCC 700814; e.g. in YieldShield® from Gustafson LLC, TX, USA), and Bacillus pumilus KFP9F (NRRL B-50754) (e.g. in BAC-UP or FUSION-P from Becker Underwood South Africa), B. pumilus QST 2808 (NRRL B-30087) (e.g. Sonata® and Ballad® Plus from AgraQuest Inc., USA), B. subtilis GB03 (e.g. Kodiak® or BioYield® from Gustafson, Inc., USA; or Companion® from Growth Products, Ltd., White Plains, NY 10603, USA), B. subtilis GB07 (Epic® from Gustafson, Inc., USA), B. subtilis QST-713 (NRRL B-21661 in Rhapsody®, Serenade® MAX and Serenade® ASO from AgraQuest Inc., USA), B. subtilis var. amyloliquefaciens FZB24 (e.g. Taegro® from Novozyme Biologicals, Inc., USA), B. subtilis var. amyloliquefaciens D747 (e.g. Double Nickel 55 from Certis LLC, USA), B. thuringiensis ssp. aizawai ABTS-1857 (e.g. in XenTari® from BioFa AG, Munsingen, Germany), B. t. ssp. aizawai SAN 401 I, ABG-6305 and ABG-6346, Bacillus t. ssp. israelensis AM65-52 (e.g. in VectoBac® from Valent Biosciences, IL, USA), Bacillus thuringiensis ssp. kurstaki SB4 (NRRL B-50753; e.g. Beta Pro® from Becker Underwood, South Africa), B. t. ssp. kurstaki ABTS-351 identical to HD-1 (ATCC SD-1275; e.g. in Dipel® DF from Valent Biosciences, IL, USA), B. t. ssp. kurstaki EG 2348 (e.g. in Lepinox® or Rapax® from CBC (Europe) S.r.l., Italy), B. t. ssp. tenebrionis DSM 2803 (EP 0 585 215 B1 ; identical to NRRL B-15939; Mycogen Corp.), B. t. ssp. tenebrionis NB-125 (DSM 5526; EP 0 585 215 B1 ; also referred to as SAN 418 I or ABG-6479; former production strain of Novo-Nordisk), B. t. ssp. tenebrionis NB-176 (or NB- 176-1 ) a gamma-irridated, induced high-yielding mutant of strain NB-125 (DSM 5480; EP 585 215 B1 ; Novodor® from Valent Biosciences, Switzerland), Beauveria bassiana ATCC 74040 (e.g. in Naturalis® from CBC (Europe) S.r.l., Italy), B. bassiana DSM 12256 (US 200020031495; e.g. BioExpert® SC from Live Sytems Technology S.A., Colombia), B. bassiana GHA (Botani- Gard® 22WGP from Laverlam Int. Corp., USA), B. bassiana PPRI 5339 (ARSEF number 5339 in the USDA ARS collection of entomopathogenic fungal cultures; NRRL 50757) (e.g. Broad- Band® from Becker Underwood, South Africa), B. brongniartii (e.g. in Melocont® from Agrifutur, Agrianello, Italy, for control of cockchafer; J. Appl. Microbiol. 100(5), 1063-72, 2006), Bradyrhi- zobium sp. (e.g. Vault® from Becker Underwood, USA), B. japonicum (e.g. VAULT® from Becker Underwood, USA), Candida oleophila 1-182 (NRRL Y-18846; e.g. Aspire® from Ecogen Inc., USA, Phytoparasitica 23(3), 231 -234, 1995), C. oleophila strain O (NRRL Y-2317; Biologi- cal Control 51 , 403-408, 2009),, Candida saitoana (e.g. Biocure® (in mixture with lysozyme) and BioCoat® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g. Armour- Zen® from BotriZen Ltd., NZ), Clonostachys rosea f. catenulata, also named Gliocladium ca- tenulatum (e.g. isolate J 1446: Prestop® from Verdera Oy, Finland), Chromobacterium subtsu- gae PRAA4-1 isolated from soil under an eastern hemlock (Tsuga canadensis) in the Catoctin Mountain region of central Maryland (e.g. in GRANDEVO from Marrone Bio Innovations, USA), Coniothyrium minitans CON/M/91-08 (e.g. Contans® WG from Prophyta, Germany),
Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g. YIELD PLUS® from Anchor Bio-Technologies, South Africa), Cryptophlebia leucotreta granulovirus (CrleGV) (e.g. in CRYPTEX from Adermatt Biocontrol, Switzerland), Cydia pomo- nella granulovirus (CpGV) V03 (DSM GV-0006; e.g. in MADEX Max from Andermatt Biocontrol, Switzerland), CpGV V22 (DSM GV-0014; e.g. in MADEX Twin from Adermatt Biocontrol, Switzerland), Delftia acidovorans RAY209 (ATCC PTA-4249; WO 2003/57861 ; e.g. in BIOBOOST from Brett Young, Winnipeg, Canada), Dilophosphora alopecuri (Twist Fungus from Becker Underwood, Australia), Ecklonia maxima (kelp) extract (e.g. KELPAK SL from Kelp Products Ltd, South Africa), formononetin (e.g. in MYCONATE from Plant Health Care pic, U.K.), Fusarium oxysporum (e.g. BIOFOX® from S.I.A.P.A., Italy, FUSACLEAN® from Natural Plant Protection, France), Glomus intraradices (e.g. MYC 4000 from ITHEC, France), Glomus intraradices RTI- 801 (e.g. MYKOS from Xtreme Gardening, USA or RTI Reforestation Technologies International; USA), grapefruit seeds and pulp extract (e.g. BC-1000 from Chemie S.A., Chile), harpin (al- pha-beta) protein (e.g. MESSENGER or HARP-N-Tek from Plant Health Care pic, U.K.; Science 257, 1-132, 1992), Heterorhabditis bacteriophaga (e.g. Nemasys® G from Becker Underwood Ltd., UK), Isaria fumosorosea Apopka-97 (ATCC 20874) (PFR-97™ from Certis LLC, USA), cis- jasmone (US 8,221 ,736), laminarin (e.g. in VACCI PLANT from Laboratoires Goemar, St. Malo, France or Stahler SA, Switzerland), Lecanicillium longisporum KV42 and KV71 (e.g. VERTAL- EC® from Koppert BV, Netherlands), L. muscarium KV01 (formerly Verticillium lecanii) (e.g. MYCOTAL from Koppert BV, Netherlands), Lysobacter antibioticus 13-1 (Biological Control 45, 288-296, 2008), L. antibioticus HS124 (Curr. Microbiol. 59(6), 608-615, 2009), L. enzymogenes 3.1T8 (Microbiol. Res. 158, 107-1 15; Biological Control 31 (2), 145-154, 2004), Metarhizium an- isopliae var. acridum IMI 330189 (isolated from Ornithacris cavroisi in Niger; also NRRL 50758) (e.g. GREEN MUSCLE® from Becker Underwood, South Africa), M. a. var. acridum FI-985 (e.g. GREEN GUARD® SC from Becker Underwood Pty Ltd, Australia), M. anisopliae FI-1045 (e.g. BIOCANE® from Becker Underwood Pty Ltd, Australia), M. anisopliae F52 (DSM 3884, ATCC 90448; e.g. MET52® Novozymes Biologicals BioAg Group, Canada), M. anisopliae ICIPE 69 (e.g. METATHRI POL from ICIPE, Nairobe, Kenya), Metschnikowia fructicola (NRRL Y-30752; e.g. SHEMER® from Agrogreen, Israel, now distributed by Bayer CropSciences, Germany; US 6,994,849), Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France), Micro- sphaeropsis ochracea P130A (ATCC 74412 isolated from apple leaves from an abandoned or- chard, St-Joseph-du-Lac, Quebec, Canada in 1993; Mycologia 94(2), 297-301 , 2002), Mus- codor albus QST 20799 originally isolated from the bark of a cinnamon tree in Honduras (e.g. in development products Muscudor™ or QRD300 from AgraQuest, USA), Neem oil (e.g. TRILOGY®, TRIACT® 70 EC from Certis LLC, USA), Nomuraea rileyi strains SA86101 , GU87401 , SR86151 , CG128 and VA9101 , Paecilomyces fumosoroseus FE 9901 (e.g. NO FLY™ from Natural Industries, Inc., USA), P. Iilacinus 251 (e.g. in BioAct®/MeloCon® from Prophyta, Germany; Crop Protection 27, 352-361 , 2008; originally isolated from infected nematode eggs in the Philippines), P. Iilacinus DSM 15169 (e.g. NEMATA® SC from Live Systems Technology S.A., Colombia), P. Iilacinus BCP2 (NRRL 50756; e.g. PL GOLD from Becker Underwood BioAg SA Ltd, South Africa), mixture of Paenibacillus alvei NAS6G6 (NRRL B-50755), Pantoea vagans (formerly agglomerans) C9-1 (originally isolated in 1994 from apple stem tissue; Blight- Ban C9-1® from NuFrams America Inc., USA, for control of fire blight in apple; J. Bacteriol. 192(24) 6486-6487, 2010), Pasteuria spp. ATCC PTA-9643 (WO 2010/085795), Pasteuria spp. ATCC SD-5832 (WO 2012/064527), P. nishizawae (WO 2010/80169), P. penetrans (US 5,248,500), P. ramose (WO 2010/80619), P. thornea (WO 2010/80169), P. usgae (WO
2010/80169), Penicillium bilaiae (e.g. Jump Start® from Novozymes Biologicals BioAg Group, Canada, originally isolated from soil in southern Alberta; Fertilizer Res. 39, 97-103, 1994), Phle- biopsis gigantea (e.g. RotStop® from Verdera Oy, Finland), Pichia anomala WRL-076 (NRRL Y- 30842; US 8,206,972), potassium bicarbonate (e.g. Amicarb® fromm Stahler SA, Switzerland), potassium silicate (e.g. Sil-MATRIX™ from Certis LLC, USA), Pseudozyma flocculosa PF-A22 UL (e.g. Sporodex® from Plant Products Co. Ltd., Canada), Pseudomonas sp. DSM 13134 (WO 2001/40441 , e.g. in PRORADIX from Sourcon Padena GmbH & Co. KG, Hechinger Str. 262, 72072 Tubingen, Germany), P. chloraphis MA 342 (e.g. in CERALL or CEDEMON from BioAgri AB, Uppsala, Sweden), P. fluorescens CL 145A (e.g. in ZEQUANOX from Marrone Bio- Innovations, Davis, CA, USA; J. Invertebr. Pathol. 113(1 ):104-14, 2013), Pythium oligandrum DV 74 (ATCC 38472; e.g. POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep. and GOWAN, USA; US 2013/0035230), Reynoutria sachlinensis extract (e.g. REGALIA® SC from Marrone Biolnnovations, Davis, CA, USA), Rhizobium leguminosarum bv. phaseoli (e.g. RHIZO-STICK from Becker Underwood, USA), R. I. trifolii RP1 13-7 (e.g. DORMAL from Becker Underwood, USA; Appl. Environ. Microbiol. 44(5), 1096-1101 ), R. I. bv. viciae P1 NP3Cst (also referred to as 1435; New Phytol 179(1 ), 224-235, 2008; e.g. in NODULATOR PL Peat Granule from Becker Underwood, USA; or in NODULATOR XL PL bfrom Becker Underwood, Canada), R. I. bv. viciae SU303 (e.g. NODULAID Group E from Becker Underwood, Australia), R. I. bv. viciae WSM1455 (e.g. NODULAID Group F from Becker Underwood, Australia), R. tropici SEMIA 4080 (identical to PRF 81 ; Soil Biology & Biochemistry 39, 867-876, 2007), Sinorhizobi- urn meliloti MSDJ0848 (INRA, France) also referred to as strain 201 1 or RCR2011 (Mol Gen Genomics (2004) 272: 1-17; e.g. DORMAL ALFALFA from Becker Underwood, USA; Nl- TRAGIN® Gold from Novozymes Biologicals BioAg Group, Canada), Sphaerodes mycoparasiti- ca IDAC 301008-01 (WO 201 1/022809), Steinernema carpocapsae (e.g. MILLENIUM® from Becker Underwood Ltd., UK), S. feltiae (NEMASHIELD® from BioWorks, Inc., USA;
NEMASYS® from Becker Underwood Ltd., UK), S. kraussei L137 (NEMASYS® L from Becker Underwood Ltd., UK), Streptomyces griseoviridis K61 (e.g. MYCOSTOP® from Verdera Oy, Espoo, Finland; Crop Protection 25, 468-475, 2006), S. lydicus WYEC 108 (e.g. Actinovate® from Natural Industries, Inc., USA, US 5,403,584), S. violaceusniger YCED-9 (e.g. DT-9® from Natural Industries, Inc., USA, US 5,968,503), Talaromyces flavus V1 17b (e.g. PROTUS® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. asperellum ICC 012 (e.g. in TENET WP, REMDIER WP, BIOTEN WP from Isagro NC, USA, BIO-TAM from AgraQuest, USA), T. atroviride LC52 (e.g. SENTI- NEL® from Agrimm Technologies Ltd, NZ), T. atroviride CNCM 1-1237 (e.g. in Esquive WG from Agrauxine S.A., France, e.g. against pruning wound diseases on vine and plant root pathogens), T. fertile JM41 R (NRRL 50759; e.g. RICHPLUS™ from Becker Underwood Bio Ag SA Ltd, South Africa), T. gamsii ICC 080 (e.g. in TENET WP, REMDIER WP, BIOTEN WP from Isagro NC, USA, BIO-TAM from AgraQuest, USA), T. harzianum T-22 (e.g. PLANTSHIELD® der Firma BioWorks Inc., USA), T. harzianum TH 35 (e.g. ROOT PRO® from Mycontrol Ltd., Israel), T. harzianum T-39 (e.g. TRICHODEX® and TRICHODERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum ICC012 and T. viride ICC080 (e.g. REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T. harzianum (e.g. BINAB® from BINAB Bio- Innovation AB, Sweden), T. stromaticum (e.g. TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (also named Gliocladium virens) (e.g. SOILGARD® from Certis LLC, USA), T. viride (e.g. TRIECO® from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE® F from T. Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1 from Agribiotec srl, Italy) and Ulocladium oudemansii HRU3 (e.g. in BOTRY-ZEN® from Botry-Zen Ltd, NZ).
Strains can be sourced from genetic resource and deposition centers: American Type Culture Collection, 10801 University Blvd., Manassas, VA 20110-2209, USA (strains with ATCC prefic); CABI Europe - International Mycological Institute, Bakeham Lane, Egham, Surrey, TW20 9TYNRRL, UK (strains with prefices CABI and I Ml); Centraalbureau voor Schimmelcultures, Fungal Biodiversity Centre, Uppsalaan 8, PO Box 85167, 3508 AD Utrecht, Netherlands (strains with prefic CBS); Division of Plant Industry, CSIRO, Canberra, Australia (strains with prefix CC); Collection Nationale de Cultures de Microorganismes, Institut Pasteur, 25 rue du Docteur Roux, F-75724 PARIS Cedex 15 (strains with prefix CNCM); Leibniz-lnstitut DSMZ-Deutsche
Sammlung von Mikroorganismen und Zellkulturen GmbH, Inhoffenst^e 7 B, 38124 Braunschweig, Germany (strains with prefix DSM); International Depositary Authority of Canada Col- lection, Canada (strains with prefix IDAC); Interntional Collection of Micro-orgniasms from Plants, Landcare Research, Private Bag 92170, Auckland Mail Centre, Auckland 1142, New Zealand (strans with prefix ICMP); IITA, PMB 5320, Ibadan, Nigeria (straisn with prefix IITA); The National Collections of Industrial and Marine Bacteria Ltd., Torry Research Station, P.O. Box 31 , 135 Abbey Road, Aberdeen, AB9 8DG, Scotland (strains with prefix NCIMB); ARS Cul- ture Collection of the National Center for Agricultural Utilization Research, Agricultural Research Service, U.S. Department of Agriculture, 1815 North University Street, Peoria, Illinois 61604, USA (strains with prefix NRRL); Department of Scientific and Industrial Research Culture Collection, Applied Biochemistry Division, Palmerston North, New Zealand (strains with prefix NZP); FEPAGRO-Fundagao Estadual de Pesquisa Agropecuaria, Rua Gongalves Dias, 570, Bairro Menino Deus, Porto Alegre/RS, Brazil (strains with prefix SEMIA); SARDI, Adelaide, South Australia (strains with prefix SRDI); U.S. Department of Agriculture, Agricultural Research Service, Soybean and Alfalfa Research Laboratory, BARC-West, 10300 Baltimore Boulevard, Building 011 , Room 19-9, Beltsville, MD 20705, USA (strains with prefix USDA: Beltsville Rhi- zobium Culture Collection Catalog March 1987 USDA-ARS ARS-30:
http://pdf.usaid.gov/pdf_docs/PNAAW891.pdf); and Murdoch University, Perth, Western Australia (strains with prefix WSM). Further strains may be found at the Global catalogue of Microorganisms: http://gcm.wfcc.info/ and
http://www.landcareresearch.co.nz/resources/collections/icmp and further references to strain collections and their prefixes at http://refs.wdcm.org/collections.htm.
Bacillus amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595) is deposited under accession number NRRL B-50595 with the strain designation Bacillus subtilis 1430 (and identical to NCIMB 1237). Recently, MBI 600 has been re-classified as Bacillus amyloliquefaciens subsp. plantarum based on polyphasic testing which combines classical microbiological methods relying on a mixture of traditional tools (such as culture-based methods) and molecular tools (such as genotyping and fatty acids analysis). Thus, Bacillus subtilis MBI600 (or MBI 600 or MBI-600) is identical to Bacillus amyloliquefaciens subsp. plantarum MBI600, formerly Bacillus subtilis MBI600. Bacillus amyloliquefaciens MBI600 is known as plant growth-promoting rice seed treatment from Int. J. Microbiol. Res. 3(2) (201 1 ), 120-130 and further described e.g. in US
2012/0149571 A1. This strain MBI600 is e.g. commercially available as liquid formulation product INTEGRAL® (Becker-Underwood Inc., USA).
Bacillus subtilis strain FB17 was originally isolated from red beet roots in North America (System Appl. Microbiol 27 (2004) 372-379). This B. subtilis strain promotes plant health (US 2010/0260735 A1 ; WO 201 1/109395 A2). B. subtilis FB17 has also been deposited at ATCC under number PTA-1 1857 on April 26, 201 1. Bacillus subtilis strain FB17 may be referred elsewhere to as UD1022 or UD10-22.
Bacillus amyloliquefaciens AP-136 (NRRL B-50614), B. amyloliquefaciens AP-188 (NRRL B- 50615), B. amyloliquefaciens AP-218 (NRRL B-50618), B. amyloliquefaciens AP-219 (NRRL B- 50619), B. amyloliquefaciens AP-295 (NRRL B-50620), B. japonicum SEMIA 5079 (e.g. Gelfix 5 or Adhere 60 from Nitral Urbana Laoboratories, Brazil, a BASF Company), B. japonicum SEMIA 5080 (e.g. GELFIX 5 or ADHERE 60 from Nitral Urbana Laoboratories, Brazil, a BASF Company), B. mojavensis AP-209 (NRRL B-50616), B. solisalsi AP-217 (NRRL B-50617), B. pumilus strain INR-7 (otherwise referred to as BU-F22 (NRRL B-50153) and BU-F33 (NRRL B-50185)), B. simplex ABU 288 (NRRL B-50340) and B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595) have been mentioned i.a. in US patent appl. 20120149571 , US 8,445,255, WO 2012/079073. Bradyrhizobium japonicum USDA 3 is known from US patent 7,262,151.
Jasmonic acid or salts (jasmonates) or derivatives include without limitation potassium jasmonate, sodium jasmonate, lithium jasmonate, ammonium jasmonate, dimethylammonium jasmonate, isopropylammonium jasmonate, diolammonium jasmonate, diethtriethanolammoni- um jasmonate, jasmonic acid methyl ester, jasmonic acid amide, jasmonic acid methylamide, jasmonic acid-L-amino acid (amide-linked) conjugates (e.g., conjugates with L-isoleucine, L- valine, L-leucine, or L-phenylalanine), 12-oxo-phytodienoic acid, coronatine, coronafacoyl-L- serine, coronafacoyl-L-threonine, methyl esters of 1-oxo-indanoyl-isoleucine, methyl esters of 1- oxo-indanoyl-leucine, coronalon (2-[(6-ethyl-l-oxo-indane-4-carbonyl) -amino]-3-methyl - pentanoic acid methyl ester), linoleic acid or derivatives thereof and cis-jasmone, or combina- tions of any of the above.
Humates are humic and fulvic acids extracted from a form of lignite coal and clay, known as leonardite. Humic acids are organic acids that occur in humus and other organically derived materials such as peat and certain soft coal. They have been shown to increase fertilizer efficiency in phosphate and micro-nutrient uptake by plants as well as aiding in the development of plant root systems.
According to one embodiment, the microbial pesticides selected from groups L1 ), L3) and L5) embrace not only the isolated, pure cultures of the respective micro-organism as defined herein, but also its cell-free extract, its suspensions in a whole broth culture or as a metabolite- containing supernatant or a purified metabolite obtained from a whole broth culture of the mi- croorganism or microorganism strain.
According to a further embodiment, the microbial pesticides selected from groups L1 ), L3 and L5) embraces not only the isolated, pure cultures of the respective micro-organism as defined herein, but also a cell-free extract thereof or at least one metabolite thereof, and/or a mutant of the respective micro-organism having all the identifying characteristics thereof and also a cell- free extract or at least one metabolite of the mutant.
"Whole broth culture" refers to a liquid culture containing both cells and media.
"Supernatant" refers to the liquid broth remaining when cells grown in broth are removed by centrifugation, filtration, sedimentation, or other means well known in the art.
The term "cell-free extract" refers to an extract of the vegetative cells, spores and/or the whole culture broth of a microorganism comprising cellular metabolites produced by the respective microorganism obtainable by cell disruption methods known in the art such as solvent-based (e.g. organic solvents such as alcohols sometimesin combination with suitable salts), temperature-based, application of shear forces, cell disrupotion with an ultrasonicator. The desired extract may be concentrated by conventional concentration techniques such as drying, evapora- tion, centrifugation or alike. Certain washing steps using organic solents and/or water-based media may also be applied to the crude extract preferably prior to use.
The term "metabolite" refers to any compound, substance or byproduct produced by a microorganism (such as fungi and bacteria) that has improves plant growth, water use efficiency of the plant, plant health, plant appearance, or the population of beneficial microorganisms in the soil around the plant activity.
The term "mutant" refers a microorganism obtained by direct mutant selection but also includes microorganisms that have been further mutagenized or otherwise manipulated (e.g., via the introduction of a plasmid). Accordingly, embodiments include mutants, variants, and or derivatives of the respective microorganism, both naturally occurring and artificially induced mutants. For example, mutants may be induced by subjecting the microorganism to known mutagens, such as N-methyl-nitrosoguanidine, using conventional methods.
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 hex- acyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacry- lates, biological or synthetic waxes, and cellulose ethers.
In the case of mixtures comprising microbial pesticides II selected from groups L1), L3) and L5), the microorganisms as used according to the invention can be cultivated continuously or discon- tinuously in the batch process or in the fed batch or repeated fed batch process. A review of known methods of cultivation will be found in the textbook by Chmiel (Bioprozesstechnik 1. Ein- fuhrung in die Bioverfahrenstechnik (Gustav Fischer Verlag, Stuttgart, 1991)) or in the textbook by Storhas (Bioreaktoren und periphere Einrichtungen (Vieweg Verlag, Braunschweig/Wiesbaden, 1994)).
When living microorganisms, such as pesticides II from groups L1 ), L3) and L5), form part of the compositions, such compositions can be prepared as compositions comprising besides the active ingredients at least one auxiliary (inert ingredient) by usual means (see e.g. H.D. Burges: Formulation of Micobial Biopestcides, Springer, 1998). Suitable customary types of such compositions are suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). Herein, it has to be taken into account that each formulation type or choice of auxiliary should not influence the viability of the microorganism during storage of thecomposition and when finally applied to the soil, plant or plant propagation material. Suitable formulations are e.g. mentioned in WO 2008/002371 , US 6955,912, US 5,422,107.
Examples for suitable auxiliaries are those mentioned earlier herein, wherein it must be taken care that choice and amounts of such auxiliaries should not influence the viability of the microbial pesticides in the composition. Especially for bactericides and solvents, compatibility with the respective microorganism of the respective microbial pesticide has to be taken into account. In addition, compositions with microbial pesticides may further contain stabilizers or nutrients and UV protectants. Suitable stabilzers or nutrients are e.g. alpha-tocopherol, trehalose, glutamate, potassium sorbate, various sugars like glucose, sucrose, lactose and maltodextrine (H.D.
Burges: Formulation of Micobial Biopestcides, Springer, 1998). Suitable UV protectants are e.g. inorganic compouns like titan dioxide, zinc oxide and iron oxide pigments or organic compounds like benzophenones, benzotriazoles and phenyltriazines. The compositions may in addition to auxiliaries mentioned for compositions comprising compounds I herein optionally comprise 0.1 - 80% stabilizers or nutrients and 0.1 -10% UV protectants. When mixtures comprising microbial pesticides are employed in crop protection, the application rates preferably range from about 1 x 106 to 5 x 1015 (or more) CFU/ha. Preferably, the spore concentration is about 1 x 107 to about 1 x 1011 CFU/ha. In the case of (entomopathogenic) nematodes as microbial pesticides (e.g. Steinernema feltiae), the application rates preferably range inform about 1 x 105 to 1 x 1012 (or more), more preferably from 1 x 108 to 1 x 1011, even more preferably from 5 x 108 to 1 x 1010 individuals (e.g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
When mixtures comprising microbial pesticides are employed in seed treatment, the application rates with respect to plant propagation material preferably range from about 1 x 106 to 1 x 1012 (or more) CFU/seed. Preferably, the concentration is about 1 x 106 to about 1 x 1011 CFU/seed. In the case of the microbial pesticides I I, the application rates with respect to plant propagation material also preferably range from about 1 x 107 to 1 x 1014 (or more) CFU per 100 kg of seed, preferably from 1 x 109 to about 1 x 1011 CFU per 100 kg of seed.
Accordingly, the present invention furthermore relates to compositions comprising one com- pound I (component 1 ) and one further active substance (component 2), which further active substance is selected from the column "Component 2" of the lines B-1 to B-398 of Table B.
A further embodiment relates to the compositions B-1 to B-398 listed in Table B, where a row oTable B corresponds in each case to a fungicidal composition comprising one of the in the present specification individualized compounds of formula I (component 1 ) and the respec- tive further active substance from groups A) to O) (component 2) stated in the row in question. According to a preferred embodiment, the "individualized compound I" is one of the compounds as individualized in Tables 1 a-l to 18a-l, 1 a-ll to 18a-ll, Tables 1 a-a to 18a-a, Tables 1 a-b to 18a-b and in Tables 1 a-l 11 to 10a-l ll, 1 a-IV to 10a-IV above or Table I below. Preferably, the compositions described comprise the active substances in synergistically ef- fective amounts.
Table B: Composition comprising one indiviualized compound I and one further active substance from groups A) to O)
ComComponent 1
Component 2
position
B-1 one individualized compound I Azoxystrobin
B-2 one individualized compound I Coumethoxystrobin
B-3 one individualized compound I Coumoxystrobin
B-4 one individualized compound I Dimoxystrobin
B-5 one individualized compound I Enestroburin
B-6 one individualized compound I Fenaminstrobin
B-7 one individualized compound I Fenoxystrobin/Flufenoxystrobin
B-8 one individualized compound I Fluoxastrobin
B-9 one individualized compound I Kresoxim-methyl
B-10 one individualized compound I Metominostrobin
B-1 1 one individualized compound I Orysastrobin
B-12 one individualized compound I Picoxystrobin ComComponent 1
Component 2
position
B-13 one individualized compound I Pyraclostrobin
B-14 one individualized compound I Pyrametostrobin
B-15 one individualized compound I Pyraoxystrobin
B-16 one individualized compound I Pyribencarb
B-17 one individualized compound I Trifloxystrobin
B-18 one individualized compound I Triclopyricarb/Chlorodincarb
2-[2-(2,5-dimethyl-phenoxymethyl)-
B-19 one individualized compound I phenyl]-3-methoxy-acrylic acid methyl ester
2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-
B-20 one individualized compound I allylideneaminooxymethyl)-phenyl)-
2-methoxyimino-N-methyl-acetamide
B-21 one individualized compound I Benalaxyl
B-22 one individualized compound I Benalaxyl-M
B-23 one individualized compound I Benodanil
B-24 one individualized compound I Benzovindiflupyr
B-25 one individualized compound I Bixafen
B-26 one individualized compound I Boscalid
B-27 one individualized compound I Carboxin
B-28 one individualized compound I Fenfuram
B-29 one individualized compound I Fenhexamid
B-30 one individualized compound I Flutolanil
B-31 one individualized compound I Fluxapyroxad
B-32 one individualized compound I Furametpyr
B-33 one individualized compound I Isopyrazam
B-34 one individualized compound I Isotianil
B-35 one individualized compound I Kiralaxyl
B-36 one individualized compound I Mepronil
B-37 one individualized compound I Metalaxyl
B-38 one individualized compound I Metalaxyl-M
B-39 one individualized compound I Ofurace
B-40 one individualized compound I Oxadixyl
B-41 one individualized compound I Oxycarboxin
B-42 one individualized compound I Penflufen
B-43 one individualized compound I Penthiopyrad
B-44 one individualized compound I Sedaxane
B-45 one individualized compound I Tecloftalam
B-46 one individualized compound I Thifluzamide
B-47 one individualized compound I Tiadinil ComComponent 1
Component 2
position
2-Amino-4-methyl-thiazole-5-carboxylic
B-48 one individualized compound I
acid anilide
N-(4'-trifluoromethylthiobiphenyl-2-yl)-
B-49 one individualized compound I 3- difluoromethyl-1 -methyl-1 H-pyrazole-
4- carboxamide
N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-
B-50 one individualized compound I 1 ,3-dimethyl-5-fluoro-1 H-pyrazole- 4-carboxamide
3-(difluoromethyl)-1 -methyl-N-(1 , 1 ,3-tri-
B-51 one individualized compound I methylindan-4-yl)pyrazole-4-carbox- amide
3-(trifluoromethyl)-1 -methyl-N-(1 , 1 ,3-tri-
B-52 one individualized compound I methylindan-4-yl)pyrazole-4-carbox- amide
1 ,3-dimethyl-N-(1 , 1 ,3-trimethylindan-
B-53 one individualized compound I
4-yl)pyrazole-4-carboxamide
3- (trifluoromethyl)-1 ,5-dimethyl-
B-54 one individualized compound I N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-
4- carboxamide
3- (difluoromethyl)-1 ,5-dimethyl-
B-55 one individualized compound I N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-
4- carboxamide
1 ,3,5-trimethyl-N-(1 , 1 ,3-trimethylindan-
B-56 one individualized compound I
4-yl)pyrazole-4-carboxamide
B-57 one individualized compound I Dimethomorph
B-58 one individualized compound I Flumorph
B-59 one individualized compound I Pyrimorph
B-60 one individualized compound I Flumetover
B-61 one individualized compound I Fluopicolide
B-62 one individualized compound I Fluopyram
B-63 one individualized compound I Zoxamide
B-64 one individualized compound I Carpropamid
B-65 one individualized compound I Diclocymet
B-66 one individualized compound I Mandipropamid
B-67 one individualized compound I Oxytetracyclin
B-68 one individualized compound I Silthiofam
N-(6-methoxy-pyridin-3-yl) cyclopro-
B-69 one individualized compound I
panecarboxylic acid amide
B-70 one individualized compound I Azaconazole
B-71 one individualized compound I Bitertanol ComComponent 1
Component 2
position
B-72 one individualized compound I Bromuconazole
B-73 one individualized compound I Cyproconazole
B-74 one individualized compound I Difenoconazole
B-75 one individualized compound I Diniconazole
B-76 one individualized compound I Diniconazole-M
B-77 one individualized compound I Epoxiconazole
B-78 one individualized compound I Fenbuconazole
B-79 one individualized compound I Fluquinconazole
B-80 one individualized compound I Flusilazole
B-81 one individualized compound I Flutriafol
B-82 one individualized compound I Hexaconazol
B-83 one individualized compound I Imibenconazole
B-84 one individualized compound I Ipconazole
B-85 one individualized compound I Metconazole
B-86 one individualized compound I Myclobutanil
B-87 one individualized compound I Oxpoconazol
B-88 one individualized compound I Paclobutrazol
B-89 one individualized compound I Penconazole
B-90 one individualized compound I Propiconazole
B-91 one individualized compound I Prothioconazole
B-92 one individualized compound I Simeconazole
B-93 one individualized compound I Tebuconazole
B-94 one individualized compound I Tetraconazole
B-95 one individualized compound I Triadimefon
B-96 one individualized compound I Triadimenol
B-97 one individualized compound I Triticonazole
B-98 one individualized compound I Uniconazole
1 - [re/-(2S;3R)-3-(2-chlorophenyl)-
B-99 one individualized compound I 2- (2,4-difluorophenyl)-oxiranylmethyl]- 5-thiocyanato-1 H-[1 ,2,4]triazole,
2-[re/-(2S;3R)-3-(2-chlorophenyl)-
B-100 one individualized compound I 2-(2,4-difluorophenyl)-oxiranylmethyl]-
2H-[1 ,2,4]triazole-3-thiol
B-101 one individualized compound I Cyazofamid
B-102 one individualized compound I Amisulbrom
B-103 one individualized compound I Imazalil
B-104 one individualized compound I Imazalil-sulfate
B-105 one individualized compound I Pefurazoate
B-106 one individualized compound I Prochloraz
B-107 one individualized compound I Triflumizole ComComponent 1
Component 2
position
B-108 one individualized compound I Benomyl
B-109 one individualized compound I Carbendazim
B-1 10 one individualized compound I Fuberidazole
B-1 1 1 one individualized compound I Thiabendazole
B-1 12 one individualized compound I Ethaboxam
B-1 13 one individualized compound I Etridiazole
B-1 14 one individualized compound I Hymexazole
2-(4-Chloro-phenyl)-N-[4-(3,4-dimeth-
B-1 15 one individualized compound I oxy-phenyl)-isoxazol-5-yl]-2-prop-2-yn- yloxy-acetamide
B-1 16 one individualized compound I Fluazinam
B-1 17 one individualized compound I Pyrifenox
3-[5-(4-Chloro-phenyl)-2,3-dimethyl-is-
B-1 18 one individualized compound I
oxazolidin-3-yl]-pyridine (Pyrisoxazole)
3-[5-(4-Methyl-phenyl)-2,3-dimethyl-
B-1 19 one individualized compound I
isoxazolidin-3-yl]-pyridine
B-120 one individualized compound I Bupirimate
B-121 one individualized compound I Cyprodinil
B-122 one individualized compound I 5-Fluorocytosine
5-Fluoro-2-(p-tolylmethoxy)pyrimidin-
B-123 one individualized compound I
4-amine
5-Fluoro-2-(4-fluorophenylmethoxy)-
B-124 one individualized compound I
pyrimidin-4-amine
B-125 one individualized compound I Diflumetorim
(5,8-Difluoroquinazolin-4-yl)-{2-[2-fluo-
B-126 one individualized compound I ro-4-(4-trifluoromethylpyridin-2-yloxy)- phenyl]-ethyl}-amine
B-127 one individualized compound I Fenarimol
B-128 one individualized compound I Ferimzone
B-129 one individualized compound I Mepanipyrim
B-130 one individualized compound I Nitrapyrin
B-131 one individualized compound I Nuarimol
B-132 one individualized compound I Pyrimethanil
B-133 one individualized compound I Triforine
B-134 one individualized compound I Fenpiclonil
B-135 one individualized compound I Fludioxonil
B-136 one individualized compound I Aldimorph
B-137 one individualized compound I Dodemorph
B-138 one individualized compound I Dodemorph-acetate
B-139 one individualized compound I Fenpropimorph ComComponent 1
Component 2
position
B-140 one individualized compound I Tridemorph
B-141 one individualized compound I Fenpropidin
B-142 one individualized compound I Fluoroimid
B-143 one individualized compound I I prod i one
B-144 one individualized compound I Procymidone
B-145 one individualized compound I Vinclozolin
B-146 one individualized compound I Famoxadone
B-147 one individualized compound I Fenamidone
B-148 one individualized compound I Flutianil
B-149 one individualized compound I Octhilinone
B-150 one individualized compound I Probenazole
B-151 one individualized compound I Fenpyrazamine
B-152 one individualized compound I Acibenzolar-S-methyl
B-153 one individualized compound I Ametoctradin
B-154 one individualized compound I Amisulbrom
[(3S,6S,7R,8R)-8-benzyl-3-[(3-isobuty- ryloxymethoxy-4-methoxypyridine-
B-155 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]-
B-156 one individualized compound I
6-methyl-4 ,9-di oxo-1 , 5-d ioxona n-7-yl] 2-methylpropanoate
[(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet- oxymethoxy)-4-methoxy-pyridine-
B-157 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-
B-158 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-
B-159 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]-
B-160 one individualized compound I
6-methyl-4,9-dioxo-8-(phenylmethyl)- 1 ,5-dioxonan-7-yl 2-methylpropanoate ComComponent 1
Component 2
position
B-161 one individualized compound I Anilazin
B-162 one individualized compound I Blasticidin-S
B-163 one individualized compound I Captafol
B-164 one individualized compound I Captan
B-165 one individualized compound I Chinomethionat
B-166 one individualized compound I Dazomet
B-167 one individualized compound I Debacarb
B-168 one individualized compound I Diclomezine
B-169 one individualized compound I Difenzoquat,
B-170 one individualized compound I Difenzoquat-methylsulfate
B-171 one individualized compound I Fenoxanil
B-172 one individualized compound I Folpet
B-173 one individualized compound I Oxolinsaure
B-174 one individualized compound I Piperalin
B-175 one individualized compound I Proquinazid
B-176 one individualized compound I Pyroquilon
B-177 one individualized compound I Quinoxyfen
B-178 one individualized compound I Triazoxid
B-179 one individualized compound I Tricyclazole
2-Butoxy-6-iodo-3-propyl-chromen-4-
B-180 one individualized compound I
one
5-Chloro-1 -(4,6-dimethoxy-pyrimidin-2-
B-181 one individualized compound I
yl)-2-methyl-1 H-benzoimidazole
5- Chloro-7-(4-methyl-piperidin-1 -yl)-
B-182 one individualized compound I 6- (2,4,6-trifluoro-phenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine
B-183 one individualized compound I Ferbam
B-184 one individualized compound I Mancozeb
B-185 one individualized compound I Maneb
B-186 one individualized compound I Metam
B-187 one individualized compound I Methasulphocarb
B-188 one individualized compound I Metiram
B-189 one individualized compound I Propineb
B-190 one individualized compound I Thiram
B-191 one individualized compound I Zineb
B-192 one individualized compound I Ziram
B-193 one individualized compound I Diethofencarb
B-194 one individualized compound I Benthiavalicarb
B-195 one individualized compound I Iprovalicarb
B-196 one individualized compound I Propamocarb ComComponent 1
Component 2
position
B-197 one individualized compound I Propamocarb hydrochlorid
B-198 one individualized compound I Valifenalate
N-(1 -(1 -(4-cyanophenyl)ethanesulfon-
B-199 one individualized compound I yl)-but-2-yl) carbamic acid-(4-fluoro- phenyl) ester
B-200 one individualized compound I Dodine
B-201 one individualized compound I Dodine free base
B-202 one individualized compound I Guazatine
B-203 one individualized compound I Guazatine-acetate
B-204 one individualized compound I Iminoctadine
B-205 one individualized compound I I m i n octa d i n e-tri acetate
B-206 one individualized compound I Iminoctadine-tris(albesilate)
B-207 one individualized compound I Kasugamycin
B-208 one individualized compound I Kasugamycin-hydrochloride-hydrate
B-209 one individualized compound I Polyoxine
B-210 one individualized compound I Streptomycin
B-21 1 one individualized compound I Validamycin A
B-212 one individualized compound I Binapacryl
B-213 one individualized compound I Dicloran
B-214 one individualized compound I Dinobuton
B-215 one individualized compound I Dinocap
B-216 one individualized compound I Nitrothal-isopropyl
B-217 one individualized compound I Tecnazen
B-218 one individualized compound I Fentin salts
B-219 one individualized compound I Dithianon
2,6-dimethyl-1 H,5H-[1 ,4]dithiino
B-220 one individualized compound I [2,3-c:5,6-c']dipyrrole-
1 ,3,5,7(2H ,6H)-tetraone
B-221 one individualized compound I Isoprothiolane
B-222 one individualized compound I Edifenphos
B-223 one individualized compound I Fosetyl, Fosetyl-aluminium
B-224 one individualized compound I Iprobenfos
Phosphorous acid (H3PO3) and deriva¬
B-225 one individualized compound I
tives
B-226 one individualized compound I Pyrazophos
B-227 one individualized compound I Tolclofos-methyl
B-228 one individualized compound I Chlorothalonil
B-229 one individualized compound I Dichlofluanid
B-230 one individualized compound I Dichlorophen
B-231 one individualized compound I Flusulfamide ComComponent 1
Component 2
position
B-232 one individualized compound I Hexachlorbenzene
B-233 one individualized compound I Pencycuron
B-234 one individualized compound I Pentachlorophenol and salts
B-235 one individualized compound I Phthalide
B-236 one individualized compound I Quintozene
B-237 one individualized compound I Thiophanate Methyl
B-238 one individualized compound I Tolylfluanid
N-(4-chloro-2-nitro- phenyl)-N-ethyl-
B-239 one individualized compound I
4-methyl- benzenesulfonamide
B-240 one individualized compound I Bordeaux composition
B-241 one individualized compound I Copper acetate
B-242 one individualized compound I Copper hydroxide
B-243 one individualized compound I Copper oxychlo ide
B-244 one individualized compound I basic Copper sulfate
B-245 one individualized compound I Sulfur
B-246 one individualized compound I Biphenyl
B-247 one individualized compound I Bronopol
B-248 one individualized compound I Cyflufenamid
B-249 one individualized compound I Cymoxanil
B-250 one individualized compound I Diphenylamin
B-251 one individualized compound I Metrafenone
B-252 one individualized compound I Pyriofenone
B-253 one individualized compound I Mildiomycin
B-254 one individualized compound I Oxin-copper
B-255 one individualized compound I Oxathiapiprolin
B-256 one individualized compound I Prohexadione calcium
B-257 one individualized compound I Spiroxamine
B-258 one individualized compound I Tebufloquin
B-259 one individualized compound I Tolylfluanid
N-(Cyclopropylmethoxyimino-(6-
B-260 one individualized compound I difluoromethoxy-2,3-difluoro-phenyl)- methyl)-2-phenyl acetamide
N'-(4-(4-chloro-3-trifluoromethyl-
B-261 one individualized compound I phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine
N'-(4-(4-fluoro-3-trifluoromethyl-
B-262 one individualized compound I phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine ComComponent 1
Component 2
position
N'-(2-methyl-5-trifluoromethyl-4-(3-tri-
B-263 one individualized compound I methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine
N'-(5-difluoromethyl-2-methyl-4-(3-tri-
B-264 one individualized compound I methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine
Methoxy-acetic acid 6-tert-butyl-8-
B-265 one individualized compound I
fluoro-2,3-dimethyl-quinolin-4-yl ester
B-266 one individualized compound I Bacillus subtilis NRRL No. B-21661
B-267 one individualized compound I Bacillus pumilus NRRL No. B-30087
B-268 one individualized compound I Ulocladium oudemansii
B-269 one individualized compound I Carbaryl
B-270 one individualized compound I Carbofuran
B-271 one individualized compound I Carbosulfan
B-272 one individualized compound I Methomylthiodicarb
B-273 one individualized compound I Bifenthrin
B-274 one individualized compound I Cyfluthrin
B-275 one individualized compound I Cypermethrin
B-276 one individualized compound I alpha-Cypermethrin
B-277 one individualized compound I zeta-Cypermethrin
B-278 one individualized compound I Deltamethrin
B-279 one individualized compound I Esfenvalerate
B-280 one individualized compound I Lambda-cyhalothrin
B-281 one individualized compound I Permethrin
B-282 one individualized compound I Tefluthrin
B-283 one individualized compound I Diflubenzuron
B-284 one individualized compound I Flufenoxuron
B-285 one individualized compound I Lufenuron
B-286 one individualized compound I Teflubenzuron
B-287 one individualized compound I Spirotetramate
B-288 one individualized compound I Clothianidin
B-289 one individualized compound I Dinotefuran
B-290 one individualized compound I Imidacloprid
B-291 one individualized compound I Thiamethoxam
B-292 one individualized compound I Flupyradifurone
B-293 one individualized compound I Acetamiprid
B-294 one individualized compound I Thiacloprid
B-295 one individualized compound I Endosulfan
B-296 one individualized compound I Fipronil
B-297 one individualized compound I Abamectin ComComponent 1
Component 2 position
B-298 one individualized compound I Emamectin
B-299 one individualized compound I Spinosad
B-300 one individualized compound I Spinetoram
B-301 one individualized compound I Hydramethylnon
B-302 one individualized compound I Chlorfenapyr
B-303 one individualized compound I Fenbutatin oxide
B-304 one individualized compound I Indoxacarb
B-305 one individualized compound I Metaflumizone
B-306 one individualized compound I Flonicamid
B-307 one individualized compound I Lubendiamide
B-308 one individualized compound I Chlorantraniliprole
B-309 one individualized compound I Cyazypyr (HGW86)
B-310 one individualized compound I Cyflumetofen
B-31 1 one individualized compound I Acetochlor
B-312 one individualized compound I Dimethenamid
B-313 one individualized compound I metolachlor
B-314 one individualized compound I Metazachlor
B-315 one individualized compound I Glyphosate
B-316 one individualized compound I Glufosinate
B-317 one individualized compound I Sulfosate
B-318 one individualized compound I Clodinafop
B-319 one individualized compound I Fenoxaprop
B-320 one individualized compound I Fluazifop
B-321 one individualized compound I Haloxyfop
B-322 one individualized compound I Paraquat
B-323 one individualized compound I Phenmedipham
B-324 one individualized compound I Clethodim
B-325 one individualized compound I Cycloxydim
B-326 one individualized compound I Profoxydim
B-327 one individualized compound I Sethoxydim
B-328 one individualized compound I Tepraloxydim
B-329 one individualized compound I Pendimethalin
B-330 one individualized compound I Prodiamine
B-331 one individualized compound I Trifluralin
B-332 one individualized compound I Acifluorfen
B-333 one individualized compound I Bromoxynil
B-334 one individualized compound I Imazamethabenz
B-335 one individualized compound I Imazamox
B-336 one individualized compound I Imazapic
B-337 one individualized compound I Imazapyr ComComponent 1
Component 2
position
B-338 one individualized compound I Imazaquin
B-339 one individualized compound I Imazethapyr
B-340 one individualized compound I 2,4-Dichlorophenoxyacetic acid (2,4-D)
B-341 one individualized compound I Chloridazon
B-342 one individualized compound I Clopyralid
B-343 one individualized compound I Fluroxypyr
B-344 one individualized compound I Picloram
B-345 one individualized compound I Picolinafen
B-346 one individualized compound I Bensulfuron
B-347 one individualized compound I Chlorimuron-ethyl
B-348 one individualized compound I Cyclosulfamuron
B-349 one individualized compound I lodosulfuron
B-350 one individualized compound I Mesosulfuron
B-351 one individualized compound I Metsulfuron-methyl
B-352 one individualized compound I Nicosulfuron
B-353 one individualized compound I imsulfuron
B-354 one individualized compound I Triflusulfuron
B-355 one individualized compound I Atrazine
B-356 one individualized compound I Hexazinone
B-357 one individualized compound I Diuron
B-358 one individualized compound I Florasulam
B-359 one individualized compound I Pyroxasulfone
B-360 one individualized compound I Bentazone
B-361 one individualized compound I Cinidon-ethyl
B-362 one individualized compound I Cinmethylin
B-363 one individualized compound I Dicamba
B-364 one individualized compound I Diflufenzopyr
B-365 one individualized compound I Quinclorac
B-366 one individualized compound I Quinmerac
B-367 one individualized compound I Mesotrione
B-368 one individualized compound I Saflufenacil
B-369 one individualized compound I 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-
B-370 one individualized compound I hyd ro-12-hyd roxy-4 ,6a, 12 b-tri methyl- 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 ComComponent 1
Component 2
position
one individualized compound I (3S,6S,7R,8R)-3-[[(3-hydroxy-4- methoxy-2-pyridinyl)carbonyl]amino]-
B-371
6-methyl-4,9-dioxo-8-(phenylmethyl)- 1 ,5-dioxonan-7-yl 2-methylpropanoate
B-372 one individualized compound I isofetamid
one individualized compound I N-(7-fluoro-1 , 1 ,3-trimethyl-indan-4-yl)-
B-373
1 ,3-dimethyl-pyrazole-4-carboxamide one individualized compound I N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -
B-374 methyl-ethyl]-3-(difluoromethyl)-1 - methyl-pyrazole-4-carboxamide one individualized compound I 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-
B-375
1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol one individualized compound I 1-[4-(4-chlorophenoxy)-2-(trifluoro-
B-376 methyl)phenyl]-1-cyclopropyl-2-(1 ,2,4- triazol-1-yl)ethanol
one individualized compound I 2-[4-(4-chlorophenoxy)-2-(trifluorometh-
B-377 yl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2- ol
one individualized compound I 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-
B-378
1 -(1 ,2,4-triazol-1 -yl)butan-2-ol one individualized compound I 2-[4-(4-chlorophenoxy)-2-
B-379 (trifluoromethyl)phenyl]-3-methyl-1- (1 ,2,4-triazol-1 -yl)butan-2-ol one individualized compound I 2-[4-(4-chlorophenoxy)-2-
B-380 (trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol- 1-yl)propan-2-ol
one individualized compound I 2- [2-chloro-4-(4-chlorophenoxy)phenyl]-
B-381
3- methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol one individualized compound I 2-[4-(4-chlorophenoxy)-2-
B-382 (trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol- 1-yl)pentan-2-ol
one individualized compound I 2-[4-(4-fluorophenoxy)-2-
B-383 (trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol- 1-yl)propan-2-ol
one individualized compound I 3-(4-chloro-2-fluoro-phenyl)-5-(2,4-
B-384 difluorophenyl)isoxazol-4-yl]-(3- pyridyl)methanol
one individualized compound I 2-{3-[2-(1 -{[3,5-bis(difluoromethyl-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-
B-385
thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5- yl}phenyl methanesulfonate ComComponent 1
Component 2
position
one individualized compound I 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl) 1 ,3-
B-386
thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol- 5-yl}-3-chlorophenyl methanesulfonate
B-387 one individualized compound I tolprocarb
one individualized compound I 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 - y|]-1 -[4-(4-{5-[2-(prop-2-yn-1 -
B-388 yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3- yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]etha- none
one individualized compound I 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 - y|]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 -yl-
B-389 oxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3- yl}-1 ,3-thiazol-2-yl)piperidin-1 - yl]ethanone
one individualized compound I 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 - y|]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -
B-390 yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3- yl}-1 ,3-thiazol-2-yl)piperidin-1 - yl]ethanone
one individualized compound I ethyl (Z)-3-am ino-2-cyano-3-phenyl-
B-391
prop-2-enoate ,
B-392 one individualized compound I picarbutrazox
one individualized compound I pentyl N-[6-[[(Z)-[(1 -methyltetrazol-5-
B-393 yl)-phenyl-methylene]amino]oxy- methyl]-2-pyridyl]carbamate, one individualized compound I 2-[2-[(7,8-difluoro-2-methyl-3-
B-394 quinolyl)oxy]-6-fluoro-phenyl]propan-2- ol
one individualized compound I 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-
B-395
quinolyl)oxy]phen-yl]propan-2-ol, one individualized compound I
3-(5-fluoro-3,3,4,4- tetramethyl-3,4-
B-396
dihydroisoquinolin-1 -yl)- quinoline
one individualized compound I
3-(4,4-difluoro-3,3- dimethyl-3,4-
B-397
dihydroisoquinolin-1 -yl)- quinoline ComComponent 1
Component 2
position
one individualized compound I
3-(4,4,5-trifluoro-3,3- dimethyl-3,4-
B-398
dihydroisoquinolin-1 - yl)quinoline;
The active substances referred to as component 2, their preparation and their activity e.g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by l UPAC nomenclature, their preparation and their fungicidal 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 13/024009and
WO 13/024010).
The compositions of active substances can be prepared as compositions comprising besides the active ingridients at least one inert ingredient by usual means, e. g. by the means given for the compositions of compounds I .
Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.
The compositions of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effective- ness against a broad spectrum of phytopathogenic fungi, especially from the classes of the As- comycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is refered to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I, respectively.
Synthesis examples
With due modification of the starting compounds, the procedures shown in the synthesis examples below were used to obtain further compounds I . The resulting compounds, together with physical data, are listed in Table I below.
Example 1 Synthesis of 1 -[[2-[2-chloro-4-(4-chlorophenoxy)phenyl]oxetan-2-yl]methyl]- 1 ,2,4-triazole. Compound 1-1 (Table I).
Figure imgf000185_0001
Step 1 -1 Synthesis of 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-4-en- 2-ol
Figure imgf000185_0002
The synthesis of the starting material 1-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-(1 ,2,4-triazol-1- yl)ethanone is described in WO 2013024083.
To a solution of 1-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-(1 ,2,4-triazol-1-yl)ethanone (1 g, 2.87 mmol) in 30 mL anhydrous THF was added allylmagnesium bromide (6.3 mL, 6.3 mmol) at 0°C under N2, then the reaction was stirred for 2 hrs at this temperature. NH4CI aq was added and extracted with EtOAc, combined the organic layers, dried, filtered and concentrated to give 2-[2- chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1-yl)pent-4-en-2-ol (0.17 g, 15%). 1H NMR: DMSO 400MHz: 6(ppm)= 8.322 (s, 1 H), 7.808 (s, 1 H), 7.499-7.423 (m, 3H), 7.023-7.000 (m, 3H), 6.842-6.819 (m, 1 H), 5.563-5.497 (m, 1 H), 5.000-4.889 (m, 1 H), 4.884-4.864 (m,1 H), 4.858-4.790 (m, 1 H), 4.755-4.577 (m, 1 H), 3.173-3.1 17 (m, 1 H), 2.491 -2.438 (m, 1 H).
Step 1-2: Synthesis of 3-[2-chloro-4-(4-chlorophenoxy)phenyl]-3-hydroxy-4-(1 , 2, 4-triazol-1 - l)butanal
Figure imgf000185_0003
An ozone-enriched steam of O3 was bubbled through a solution of 2-[2-chloro-4-(4- chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-4-en-2-ol (0.17 g) in CH2CI2 (30 mL) for 30 min. The solution was purged with argon for 10 min to remove the excess O3. DCM was removed in vacuo. 3-[2-chloro-4-(4-chlorophenoxy)phenyl]-3-hydroxy-4-(1 ,2,4-triazol-1-yl)butanal (0.17 g, crude) was used directly for next step.
Step 1 -3 Synthesis of 3-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-(1 ,2,4-triazol-1 -yl)butane-1 ,3- diol
Figure imgf000185_0004
To a solution of 3-[2-chloro-4-(4-chlorophenoxy)phenyl]-3-hydroxy-4-(1 ,2,4-triazol-1 -yl)butanal (1 g, 2.56 mmol) in 30 ml. anhydrous THF was added NaBH4 (0.19 g, 5.1 1 mmol) at 0°C under N2, then the reaction was stirred for 2 hrs at this temperature. NH4CI aq was added extracted with EtOAc, combined the organic layers, dried, filtered and concentrated to give 3-[2-chloro-4- (4-chlorophenoxy)phenyl]-4-(1 ,2,4-triazol-1 -yl)butane-1 ,3-diol (0.34 g, 34 %). 1H NMR: CDC 400MHz: 5(ppm)= 7.981 (s, 1 H), 7.765 (s, 1 H), 7.649-7.627 (d, 1 H), 7.273-7.251 (d, 2H), 6.887- 6.865 (m, 3H), 6.757-6.735 (m, 1 H), 5.219 (s, 1 H), 4.932-4.896 (d, J=14.4Hz, 1 H), 4.636-4.601 (d, J=14.4Hz, 1 H),3.71 1 -3.674 (m, 1 H), 3.537-3.505 (m, 1 H), 2.651 -2.607 (m, 1 H), 2.035-1 .972 (m, 1 H).
Step 1 -4: Synthesis of 1 -[[2-[2-chloro-4-(4-chlorophenoxy)phenyl]oxetan-2-yl]methyl]-1 ,2,4- triazole.
Figure imgf000186_0001
To a solution of 3-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-(1 ,2,4-triazol-1 -yl)butane-1 ,3-diol (0.34 g, 0.865 mmol) in 20 ml. anhydrous THF was added n-BuLi (0.34 ml_, 0.865mmol) at - 78°C under N2, then the reaction was stirred for 30min at this temperature. Tos-CI (0.16 g,
0.865mmol) in 5 ml_ anhydrous THF was added slowly at 0°C. The reaction was stirred for 30 min at this temperature, n-BuLi (0.34 ml_, 0.865 mmol) at -78°C was added. The reaction was stirred at 60°C for overnight. NH4CI aq was added and extracted with EtOAc, combined the organic layers, dried, filtered and concentrated. The residue purified by Pre-HPLC to give 1 -[[2- [2-chloro-4-(4-chlorophenoxy)phenyl]oxetan-2-yl]methyl]-1 ,2,4-triazole (0.06 g, 19%). 1H NMR: CDCI3400MHz: 5(ppm)= 8.231 (s, 1 H), 7.922 (s, 1 H), 7.485-7.464 (d, 1 H), 7.331 -7.308 (d, 2H), 6.998-6.969 (m, 3H), 6.947-6.886 (m, 1 H), 4.894-4.858 (d, J=14.4Hz, 1 H), 4.396-4.374 (m, 1 H), 4.346-4.308 (d, J=15.2Hz, 1 H), 4.129-4.3084(m, 1 H), 2.977-2.908 (m, 1 H), 2.866-2.818 (m, 1 H).
Example 2 Synthesis of 1 -[[2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]oxetan-2- -1 ,2,4-triazole. Compound xx (Table xx).
Figure imgf000186_0002
The synthesis of the title compound 1 -[[2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]oxetan- 2-yl]methyl]-1 ,2,4-triazole was made in an analogous fashion as the compound of Example 1 , 2- [2-chloro-4-(4-chlorophenoxy)phenyl]oxetan-2-yl]methyl]-1 ,2,4-triazole. The synthesis of the starting material 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-(1 ,2,4-triazol-1 -yl)ethanone is described in WO 2013007767. 1 -[[2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]oxetan-2- yl]methyl]-1 ,2,4-triazole: 1 H NMR: CDCb 400MHz: 5(ppm)= 8.237 (s, 1 H), 7.929 (s, 1 H), 7.591 - 7.346 (m, 1 H), 7.340-7.323 (m, 2H), 7.296-7.290 (m, 1 H), 7.097-6.975(m, 1 H), 6.970-6.953 (m, 2H), 4.752-4.715 (d, J=14.8Hz, 1H), 4.353-4.314 (m, 1H), 4.278-4.241 (d, J=14.8Hz, 1H), 4.033-4.011(m, 1H), 2.985-2.881 (m, 2H).
With due modification of the starting compounds, the procedures shown in the synthesis examples below were used to obtain further compounds I.
Figure imgf000187_0001
Table I:
com( 3)n (R)n R5 Rs 271 R72 HPLC * Rt 1H NMR (CDCI3l 400 MHz) pound (min)
S(ppm)
No.
1-1 2-CI 4-CI H H H H 1.243 8.231 (s, 1H), 7.922 (s,
1H), 7.485-7.464 (d, 1H), 7.331-7.308 (d, 2H), 6.998-6.969 (m, 3H), 6.947-6.886 (m, 1H), 4.894-4.858 (d, =14.4Hz, 1H), 4.396-4.374 (m, 1H), 4.346-4.308 (d,
J=15.2Hz,1H), 4.129- 4.3084(m, 1H), 2.977- 2.908 (m, 1H), 2.866- 2.818 (m, 1H)
I -2 2-CF3 4-CI H H H H 1.275
8.237 (s, 1H), 7.929 (s, 1H), 7.591-7.346 (m, 1H), 7.340-7.323 (m, 2H), 7.296-7.290 (m, 1H), 7.097- 6.975(m,
1H), 6.970- 6.953 (m, 2H), 4.752- 4.715 (d, J=14.8Hz, com(R3)n (R4)m R5 R71 R72 HPLC * Rt H NMR (CDCIs, 400 MHz) pound (min)
5(ppm)
No.
1 H), 4.353- 4.314 (m, 1 H), 4.278- 4.241 (d, J=14.8Hz,
1 H), 4.033- 4.01 1 (m,
1 H), 2.985- 2.881 (m, 2H)
* :HPLC method Data:
Mobile Phase: A: Wasser + 0.1 % T FA; B: acetonitrile; Gradient: 5% B to 100% B in 1 .5min; Temperature: 60 °C; MS-Method: ESI positive; mass area (m/z): 100-700; Flow: 0.8ml/min to
I , 0ml/min in 1.5min; Column: Kinetex XB C18 1.7μ 50 x 2.1 mm; Aparatus: Shimadzu Nexera LC-30 LCMS-2020.
I I. Examples of the action against harmful fungi
The fungicidal action of the compounds of the formula I was demonstrated by the following experiments:
Microtest
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
M 1 Activity against early blight caused by Alternaria solani (Alteso)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Alternaria solani in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The compound 1-1 showed a growth of 0 % at 31 ppm.
M2 Activity against the grey mold Botrytis cinerea in the microtiterplate test (Botrci) The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The compound I- 1 showed a growth of 0 % at 31 ppm.
M3 Activity against leaf blotch on wheat caused by Septoria tntici (Septtr) The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption pho- tometer, the MTPs were measured at 405 nm 7 days after the inoculation. The compound 1-1 showed a growth of 0 % at 31 ppm.
M4 Activity against the late blight pathogen Phytophthora infestans in the microtiter test (Phyt- in)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Phytophtora infestans containing a pea juice-based aqueous nutrient medium or DDC medium was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The compound 1-1 showed a growth of 1 % at 31 ppm.
The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.
Green House
The spray solutions were prepared in several steps:
The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml. This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.
G1 Preventative fungicidal control of early blight on tomatoes {Alternaria solani) (Alteso P1)
Young seedlings of tomato plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or mixture mentioned in the table below. The next day, the treated plants were inoculated with an aqueous suspension of Alternaria solani. Then the trial plants were immediately transferred to a humid chamber. After 5 days at 18 to 20° C and a relative humidity close to 100 %, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 150 ppm of the active substance I-2 showed an infection of 5 % whereas the untreated plants were 90% infected.
G2 Preventative fungicidal control of Botrytis cinerea on leaves of green pepper (Botrci P1 ) Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24°C and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 150 ppm of the active substance I-2 showed an infection of 1 % whereas the untreated plants were 90% infected.
G3 Protective control of soy bean rust on soy beans caused by Phakopsora pachyrhizi (Phakpa P1)
Leaves of pot-grown soy bean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 1 day in a greenhouse chamber at 23- 27°C and a relative humidity between 60 and 80 %.Then the plants were inoculated with spores of Phakopsora pachyrhizi. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24°C for 24 h. The trial plants were cultivated for fourteen days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80 %. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 150 ppm of the active substance I-2 showed an infection of 7 % whereas the untreated plants were 90% infected.

Claims

Compounds of formula I
Figure imgf000191_0001
wherein:
R is O or Chb;
Q is O or CH2;
wherein either R or Q is O;
A is CH or N;
D is H, halogen or SRD, wherein
RD is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6- alkynyl, C2-C6-haloalkynyl or CN;
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-C3-cycloalkyl), N(C3-C6-cycloalkyl)2, S(0)P(Ci-C4-alkyl),
Figure imgf000191_0002
C4-alkyl), C(=0)(OH),
Figure imgf000191_0003
alkyl)2), C(=0)(NH(C3-C3-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-C8-cycloalkyl, C3-Ce-halocycloalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy; n is 0, 1 , 2, 3 or 4;
Y is a direct bond or a divalent group selected from the group consisting of -0-, -S-, SO-, -SO2-; -NH-, -N(Ci-C4-alkyl)-, CR 5R8-, -CR9R10-CR R12-, -CR 3=CR1 and -C≡C-; wherein
R8,R9,R10,R11,R12,R13,R14,R15 are independently selected from hydrogen, halogen, CN, nitro, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and
Ci-C4-halogenalkoxy;
Z is five or six-membered heteroaryl, wherein the heteroaryl contains 1 , 2, 3 or 4 heteroa- toms selected from the group consisting of O, N and S, or phenyl, wherein the heteroaryl or phenyl is unsubstituted (m=0) or substituted by (R4)m, wherein
m is 0, 1 , 2, 3, 4 or 5;
R4 is independently selected from halogen, CN, NO2, OH, SH, Ci-C6-alkyl, C1-C6- alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C3-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), H), C(=0)(0-Ci-C4-alkyl),
C(=0)(NH(Ci-C4-al
Figure imgf000192_0001
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 , NO2, OH, Ci-C4-alkyl, Ci-C4- haloalkyl, C3-C8-cycloalkyl, Cs-Ce-halocycloalkyl, Ci-C4-alkoxy and Ci-C4- haloalkoxy;
p is 0, 1 or 2;
x is 0, 1 , 2, 3 or 4;
R5 is H , halogen, CN , N02, OH , SH , Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsul- finyl, Ci-C6-alkylsulfonyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8- cycloalkyloxy, C3-C8-cycloalkyl-Ci-C4-alkyl, N H2, N H(Ci-C4-alkyl), N(Ci-C4-alkyl)2, N H(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2,
Figure imgf000192_0002
alkyl, C(=0)-N H(Ci-C4-alkyl),C(=0)-N(Ci-C4-alkyl)2, C(=0)-NH(C3-C6-cycloalkyl), C(=0)- N(C3-C6-cycloalkyl)2, phenyl, heteroaryl, phenyl-Ci-C4-alkyl and heteroaryl-Ci-C4-alkyl, wherein the heteroaryl radical in the last-mentioned groups is 5- or 6-membered and wherein the aliphatic, alicyclic and aromatic moieties of R5 are unsubstituted or substituted by one, two, three or four or up to the maximum possible number of R5a; wherein
R5a is independently selected from halogen, CN, NO2, OH, SH , N H2, d-Ce-alkyl, Ci-C6- haloalkyl, C3-Ce-cycloalkyl, C3-Ce-halocycloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy,
Ci-C6-alkylthio, Ci-C6-haloalkylthio and Ci-C4-alkoxy-Ci-C4-alkyl;
R6 is H or is selected from the substituents defined for R5, wherein the aliphatic, alicyclic and aromatic moieties of R6 are unsubstituted or substituted by one, two, three or four or up to the maximum possible number of R6a, wherein R6a is defined as R5a;
or
R5 and R6 together with the carbon atom to which they are bound form a saturated or partially unsaturated three-, four-, five-, six- or seven-membered carbocycle or a saturated or partially unsaturated three-, four-, five-, six- or seven-membered heterocycle, wherein the heterocycle contains one, two, three or four heteroatoms selected from N , O and S, and wherein the carbo- or heterocycle is unsubstituted or carries one, two, three or four substituents independently selected from halogen, CN , N02, OH , SH , NH2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C4-alkoxy-Ci-C4-alkyl, phenyl and phenoxy; and wherein one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S);
or R5 and R6 together with the carbon atom to which they are bound (denominated C*) form a group (C*=CR55R66), wherein
R55, R56 are independently selected from hydrogen, halogen, CN , NO2, OH , SH, NH2,
Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio and Ci-C4-alkoxy-Ci-C4-alkyl; R7 is independently selected from Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ca-Ce-cycloalkyl, wherein each of R7 is unsubstituted or further substituted by one, two, three or four R7a; wherein
R7a is independently selected from halogen, OH and Ci-C6-alkoxy;
or
two substituents R7: R71 and R72 together with the carbon atom(s) to which they are bound form a saturated three-, four-, five-, six- or seven-membered carbocycle or heterocycle, wherein the heterocycle contains one, two, three or four O atoms.
o is 0, 1 , 2, 3 or 4;
and the N-oxides and the agricucturally acceptable salts thereof
with the proviso that
if R is O and Q is CH2 x is not 0.
2. The compounds according to claim 1 , wherein
A is N.
3. The compounds according to any of the claims 1 to 2, wherein
D is H.
4. The compounds according to any of the claims 1 to 3, wherein
R is O.
5. The compounds according to any of the claims 1 to 3, wherein
Q is O.
6. The compounds according to any of the claims 1 to 5, wherein
R3 is halogen, CN, N02, CrC6-alkoxy, CrC6-haloalkyl or S(0)2(CrC4-alkyl).
7. The compounds according to any of the claims 1 to 6, wherein
R5 and R6 are independently H, halogen, Ci-C4-alkyl, Ci-C4-alkoxy; or
R5 and R6 together with the carbon atom to which they are bound form a saturated three-, four-, five-, six- or seven-membered carbocycle; or
R5 and R6 together with the carbon atom to which they are bound (denominated C*) form a group C*=CH2.
8. The compound of claim 1 , wherein D is H, A is N, R is O, Q is CH2, R1 and R2 are H, (R3)n is 2-CI, (Z-Y)x is para-bound, Y is O and Z is 4-CI-phenyl; and the compound, wherein D is
H, A is N, R is O, Q is CH2, R1 and R2 are H, (R3)n is 2-CF3, (Z-Y)x is para-bound, Y is O and Z is 4-CI-phenyl.
8.
9. Agrochemical compositions, wherein said composition comprise an auxiliary and at least 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 compositions according to claim 9, comprising additionally a further active substance.
1 1. 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 to 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 9 to 10.
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 to 10, in an amount of from 0.1 to 10 kg per 100 kg of seed.
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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
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