Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• the present invention relates to fungicidal pyrimidine compounds, to their use and to methods for combating phytopathogenic fungi.
• the present invention also relates to seeds treated with at least one such compound.
• the invention relates to processes for preparing compounds of formula I and intermediates as well as processes for the preparation of such intermediates.
• WO 1998/003272 describes a process for the preparation of 4-amino-5-chloro-6-(1 -fluoro- ethyl)pyrimidine compounds, which are pest controlling agents for agricultural and horticultural use.
• WO 1997/028133 discloses acylated 4-amino and 4-hydrazinopyrimidines and their use as pesticides.
• EP 665225 A1 relates to 4-phenethylamino pyrimidine derivatives useful for chemical control of noxious organisms.
• WO 1995/018795 relates to N-(4 pyrimidinyl)amide pesticides with a carboxy moiety instead of a methylene group as in compounds I according to the present invention.
• the compounds according to the present invention differ from those described in the abovementioned publications by the specific substituent R a2 of the pyrimidyl moiety in position 2 and the specific ethylene linker between the phenyl ring and the amino function as defined herein.
• EP 264217 A2 relates to N-(4-pyrimidinyl)arylalkylamine pesticides, inter alia disclosing N- (4-pyrimidinyl)phenylethylamines, but does not mention specifically the combination of the ethylene linker between the phenyl ring and the amino function together with the group -O-Het as defined herein.
• the fungicidal activity of known fungicidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic fungi. This objective is achieved by the use of substituted pyrimidine compounds of formula I having good fungicidal activity against phytopathogenic harmful fungi.
• R a2 is halogen, CN, N0 2 , OH, SH, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy,
• R A , R B independently of one another are hydrogen, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, phenyl, benzyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkenyl or
• R' is hydrogen, OH, NH 2 , Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylamino or di(Ci-C4-alkyl)amino;
• R" is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl or
• R'" is hydrogen or Ci-C4-alkyl
• R is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy,
• Ci-C4-alkoxy-Ci-C4-alkyl Ci-C4-haloalkoxy-Ci-C4-alkyl, C2-C4-alkenyl,
• n indicates the number of substituents R b on the phenyl ring and n is 0, 1 , 2, 3 or 4;
• R b is halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy,
• n 2, 3 or 4 that R b are identical or different;
• Het is a 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl
• R c is halogen, CN, NO2, d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkoxy, d-Ce-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl,
• Ci-C6-alkylsulfonyl Ci-C6-haloalkylsulfonyl, Ci-Ce-alkoxy-Ci-d-alkyl,
• R d is halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; or two radicals R c that are bound to adjacent ring member atoms of the Het group form together with said ring member atoms a fused
• R e is halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; and the N-oxides and the agriculturally acceptable salts thereof.
• the present invention furthermore relates to processes for preparing the compounds I.
• the present invention furthermore relates to intermediates such as compounds of formulae II and III.
• the compounds of the present invention are useful for combating harmful fungi. Therefore the present invention furthermore relates to a method for combating harmful fungi, which process comprises 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 of an N- oxide or an agriculturally acceptable salt thereof.
• the present invention also relates to seed comprising a compound of formula I, or an N-oxide or an agriculturally acceptable salt thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed.
• the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.
• Agriculturally useful salts of the compounds I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I.
• Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably
• Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
• the compounds of formula I 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.
• inventive compounds I can be prepared by various routes in analogy to prior art processes and, advantageously, by the synthesis shown in the following schemes and in the experimental part of this application.
• a 4-halopyrimidine compound II, wherein Hal is halogen, preferably CI or F, can be reacted with a suitable phenethyl amine compound III as shown in Scheme 1 :
• this reaction is carried out at temperatures of from 0 to 200°C, preferably from 50 to 170°C, preferably in an inert organic solvent and preferably in presence of a base or a catalyst or a combination of a base and a catalyst (e.g. NaF, KF, LiF, NaBr, KBr, LiBr, Nal, Kl, Lil and ionic liquids, such as imidazolium catalysts).
• a base or a catalyst or a combination of a base and a catalyst e.g. NaF, KF, LiF, NaBr, KBr, LiBr, Nal, Kl, Lil and ionic liquids, such as imidazolium catalysts.
• Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene;
• halogenated hydro-carbons such as chlorobenzene, dichlorobenzene; ethers such as dioxane, anisole and tetra-hydrofuran (THF); nitriles such as acetonitrile and propionitrile; ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.
• -butyl methyl ketone alcohols such as ethanol, n-propanol, isopropanol, n-butanol and tert.-butanol; and also dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetamide, N-methyl-2-pyrrolidone (NMP), N- ethyl-2-pyrrolidone (NEP) and acetic acid ethyl ester, preferably DMSO, DMF, dimethyl acetamide, NMP, or NEP. Particular preference is given to NMP. It is also possible to use mixtures of the solvents mentioned.
• DMSO dimethylformamide
• NMP N-methyl-2-pyrrolidone
• NEP N- ethyl-2-pyrrolidone
• acetic acid ethyl ester preferably DMSO, DMF, dimethyl acetamide, NMP, or NEP.
• NMP N-butyl
• Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, potassium oxide and calcium oxide; alkali metal and alkaline earth metal phosphates such as lithium phosphate, sodium phosphate, potassium phosphate and calcium phosphate; alkali metal amides such as lithium amide, sodium amide and potassium amide; alkali metal and alkaline earth metal hydrides lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, caesium carbonate; moreover organic bases, for example tertiary amines such as trimethyl-amine (TMA), triethylamine (TEA), tributylamine (TBA), diisopropylethylamine
• the bases are generally employed in equimolar amounts, in excess or, if appropriate, as solvent.
• the amount of base is typically 1 .1 to 5.0 molar equivalents relative to 1 mole of compounds II.
• the starting materials are generally reacted with one another in equimolar amounts. In terms of yields, it may be advantageous to employ an excess of compounds III, based on 1 .1 to 2.5 equivalents, preferred 1 .1 to 1.5 equivalents of compounds II.
• the compounds II are known from the literature or are commercially available or they can be prepared for example in analogy to methods described in: Heterocycles (2009) 78(7), 1627- 1665; New J. Chem. (1994) 18(6), 701 -8; WO 2005/095357; Science of Synthesis (2004) 16, 379-572; WO 2008/156726; WO 2006/072831 ; Organic Reactions (Hoboken, NJ, United States) (2000), 56; or Targets in Heterocyclic Systems (2008) 12, 59-84.
• phenethyl amine compounds III are known from the literature or are commercially available or they can be prepared for example in analogy to methods described in:
• a carbonyl compound AD-1 can be transformed into its cyano hydrine (see e.g. Chemistry A Eur. J. (201 1 ), 17(44), 12276-12279; Eur. J. Org. Chem. (2002), (19), 3243-3249; Synlett (2003), (3), 353-356; Chirality (2009), 21 (9), 836-842; or J. Org. Chem. (2008), 73(18), 7373-7375). Reduction of the nitrile group provides compounds AD-3.
• the nitrile in AD-3 can be reduced and the hydroxyl group be removed in one step to furnish compounds III (see e.g. Justus Liebigs Annalen der Chemie (1949), 564, 49-54, Justus Liebigs Annalen der Chemie (1957), 605, 200-1 1 , J. Chem. Soc. (1959), 1780-2; or WO 2007/020381 ).
• Phenethylamine compounds III can also be prepared by reductive amination of aldehyde compounds AD-4 as described in Scheme 3.
• This conversion can be achieved using ammonia and a reducing agent or a metal organic compound or a cyanide source (see e.g. J. Am. Chem. Soc. (201 1 ), 133(33), 12914-12917; Acta Pharmaceutica Suecica (1976), 13(1 ), 65-74; J. Med. Chem. (1976), 19(6), 763-6; or J. Am. Chem. Soc. (1952), 74, 461 1 -15).
• substituted benzyl nitriles AD-9 which are available from benzyl halides AD-8, can be used as intermediates for the preparation of compounds III according to scheme 4 by way of reduction with an appropriate reducing agent (e.g. LiAII-U, PhSiH3 or hb and a catalyst) as shown in Scheme 4 (Tetrahedron (201 1 ), 67(42), 8183-8186; WO 201 1/088181 ; Eur. J. Inorg. Chem. (201 1 ), 201 1 (22), 3381 -3386; or WO 2008/124757):
• an appropriate reducing agent e.g. LiAII-U, PhSiH3 or hb and a catalyst
• Compounds I and intermediates, wherein R is hydrogen, can be converted to tertiary substituted amines by conventional processes such as alkylation.
• suitable alkylating agents include alkyl halides, such as alkyl chloride, alkyl bromide or alkyl iodide, examples being methyl chloride, methyl bromide or methyl iodide, or dialkyi sulfates such as dimethyl sulfate or diethyl sulfate.
• the reaction with the alkylating agent is carried out advantageously in the presence of a solvent.
• Solvents used for these reactions are - depending on the temperature range - aliphatic, cycloaliphatic or aromatic hydrocarbons such as hexane, cyclohexane, toluene, xylene, chlorinated aliphatic and aromatic hydrocarbons such as DCM, chlorobenzene, open-chain dialkyi ethers such as diethyl ether, di-n-propyl ether, MTBE, cyclic ethers such as THF, 1 ,4-dioxane, glycol ethers such as dimethyl glycol ether, and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester, preferably DMF, DMSO, NMP or NEP, or mixtures of these solvents.
• aliphatic, cycloaliphatic or aromatic hydrocarbons such as hexane, cyclohexane, toluene, xylene,
• the N-oxides may be prepared from the compounds I according to conventional oxidation methods, e. g. by treating compounds I with an organic peracid such as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem. 1995, 38(1 1 ), 1892-1903,); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 1981 , 18 (7), 1305-1308) or oxone (cf. J. Am. Chem. Soc. 2001 , 123 (25), 5962-5973).
• the oxidation may lead to pure mono-N- oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
• C n -C m indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
• halogen refers to fluorine, chlorine, bromine and iodine.
• Ci-C4-alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 4 carbon atoms, for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 - methylpropyl, 2-methylpropyl, and 1 ,1 -dimethylethyl.
• Ci-C6-alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms.
• Ci-C4-haloalkyl refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms (as defined above), wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl,
• Ci-C4-hydroxyalkyl refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms (as defined above), wherein one hydrogen atom in these groups may be replaced by one hydroxy group, for example hydroxym ethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl, or 4-hydroxy-n-butyl.
• Ci-C4-alkoxy refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms (as defined above) which is bonded via an oxygen, at any position in the alkyl group, for example methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1 -methyhpropoxy, 2- methylpropoxy or 1 ,1 -dimethylethoxy.
• Ci-C6-alkoxy refers to a straight- chain or branched alkyl group having 1 to 6 carbon atoms.
• Ci-C4-haloalkoxy refers to a Ci-C4-alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example, OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHCI 2 , OCCI 3 , chlorofluoromethoxy,
• dichlorofluoromethoxy chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2- difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2-fluoropropoxy, 3- fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3- dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3- trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1 -(CH 2 F)-2-fluoro
• Ci-C6-haloalkoxy refers to a Ci-C6-alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above.
• Ci-C4-alkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group (as defined above).
• Ci-C4-alkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C6-alkoxy group (as defined above).
• Ci-C4-alkoxy-Ci-C4-alkoxy refers to an alkoxy radical having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of this alkoxy radical is replaced by a
• Ci-C4-alkoxy group (as defined above).
• Ci-C6-alkoxy-Ci-C4-alkoxy refers to alkoxy having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C6-alkoxy group (as defined above).
• Ci-C4-haloalkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a
• Ci-C4-haloalkoxy group (as defined above).
• Ci-C6-haloalkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C6-alkoxy group (as defined above).
• Ci-C4-alkylthio refers to straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as defined above) bonded via a sulfur atom, at any position in the alkyl group, for example methylthio, ethylthio, propylthio, isopropylthio, and n butylthio.
• Ci-C6-alkylthio refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as defined above) bonded via a sulfur atom.
• Ci-C4-haloalkylthio and “Ci-C6-haloalkylthio” as used herein refer to straight-chain or branched haloalkyi groups having 1 to 4 or 1 to 6 carbon atoms (as defined above) bonded through a sulfur atom, at any position in the haloalkyi group.
• Ci-C4-alkylsulfonyl and “Ci-C6-alkylsulfonyl”, respectively, refer to straight-chain or branched alkyl groups having 1 to 4 and 1 to 6 carbon atoms (as defined above),
• Ci-C4-alkylamino refers to an amino radical carrying one Ci-C4-alkyl group (as defined above) as substituent, for example methylamino, ethylamino, propylamino, 1 - methylethylamino, butylamino, 1 -methylpropylamino, 2-methylpropylamino, 1 ,1 -di- methylethylamino and the like.
• Ci-C6-alkylamino refers to an amino radical carrying one Ci-C6-alkyl group (as defined above) as substituent.
• di(Ci-C4-alkyl)amino refers to an amino radical carrying two identical or different Ci-C4-alkyl groups (as defined above) as substituents, for example dimethylamino,
• di(Ci-C6-alkyl)amino refers to an amino radical carrying two identical or different Ci- C6-alkyl groups (as defined above) as substituents.
• (Ci-C4-alkoxy)carbonyl refers to a Ci-C4-alkoxy radical (as defined above) which is attached via a carbonyl group.
• di(Ci-C4-alkyl)aminocarbonyl refers to a di(Ci-C4)alkylamino radical as defined above which is attached via a carbonyl group.
• phenoxy and refers to a phenyl radical which is attached via an oxygen atom.
• phenoxy-Ci-C4-alkyl and refers to a phenoxy radical which is attached via a Ci-C4-alkyl group (as defined above).
• C2-C4-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and a double bond in any position, such as ethenyl, 1 - propenyl, 2-propenyl (allyl), 1 -methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 - propenyl, 2-methyl-1 -propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl.
• C2-C6-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.
• C2-C4-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond, such as ethynyl, 1 - propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl.
• C2-C6-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and at least one triple bond.
• Cs-Cs-cycloalkyl refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members, such as cyclopropyl (C3H5), cyclobutyl, cyclopentyl, cyclohexyl, cydoheptyl or cyclooctyl.
• C3-C8-cycloalkyl-Ci-C4-alkyl refers to an alkyl radical having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Cs-Cs- cycloalkyl group (as defined above).
• Cs-Cs-cycloalkyloxy refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above), which is bonded via an oxygen.
• saturated or partially unsaturated 3-, 4- 5-, 6- or 7-membered carbocycle is to be understood as meaning both saturated or partially unsaturated carbocycles having 3, 4, 5, 6 or 7 ring members.
• Examples include cyclopropyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cydoheptyl, cycloheptenyl, cycloheptadienyl, and the like.
• saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S is to be understood as meaning both saturated and partially unsaturated heterocycles, e.g.:
• - a 3- or 4-membered saturated heterocycle which contains 1 or 2 heteroatoms from the group consisting of N, O and S as ring members such as oxirane, aziridine, thiirane, oxetane, azetidine, thiethane, [1 ,2]dioxetane, [1 ,2]dithietane, [1 ,2]diazetidine; or
• - a 5- or 6-membered saturated or partially unsaturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of N, O and S as ring members such as 2- tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl,
• hexahydroazepinyl such as 2,3,4,5-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-,
• heteroaryl wherein the ring member atoms of the heteroaryl include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S
• ring member atoms of the heteroaryl include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S
• a 5-membered heteroaryl such as pyrrol-1 -yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1 -yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1 -yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-
• a 6-membered heteroaryl such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
• two radicals R c that are bound to adjacent ring member atoms form together with said ring member atoms a fused cycle refers to a condensed bicyclic ring system, wherein 5- or 6-membered heteroaryl carries a fused-on 5-, 6- or 7-membered carbocyclic or heterocyclic ring it being possible that these rings are saturated or partially saturated or aromatic.
• CH3 shall also be understood as Me
• CH2CH3 shall also be understood as Et
• OCH3 shall also be understood as OMe
• OCH2OCH3 shall also be understood as OMeOMe
• CH2OCH3 shall also be understood as MeOMe
• COOCH 3 shall also be understood as COOMe
• COOC2H5 shall also be understood as COOEt.
• R a2 is halogen, CN, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C2-C4-alkenyl, C2- C4-alkynyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkyloxy or (Ci-C4-alkoxy)carbonyl; preferably halogen, CN, Ci-C 2 -alkyl, Ci-C 2 -alkoxy, Ci-C 2 -alkoxy-Ci-C 2 -alkyl, Ci-C 2 -alkoxy-Ci-C 2 -alkoxy or (C1-C2- alkoxy)carbonyl; even more preferably F, CI, CH 3 , CH2CH3, CF 3
• R a2 is selected from CN, CH 3 , CF 3 , OCH 3 , COOCH3, OCH2CH3 and CH2OCH3, more preferably from CN and CH 3 .
• R a2 is C2-alkyl, C2-haloalkyl, C2-alkoxy, or C2-haloalkoxy.
• R a2 is selected from CN, CH 3 , CF 3 , OCH 3 , COOCH 3 , OCH2CH3 and CH2OCH3, more preferably from CN and CH 3 .
• R A , R B in radicals R a2 , R a5 and R a6 independently of one another preferably are hydrogen or Ci-C4-alkyl.
• R' in radicals R a2 , R a5 and R a6 which may the same or different, are hydrogen, NH2, Ci-C4-alkyl or Ci-C4-alkoxy.
• R" in radicals R a2 , R a5 and R a6 are hydrogen, Ci-C 4 -alkyl.
• R'" in radicals R a2 , R a5 and R a6 are hydrogen or Ci-C 4 -alkyl.
• R a5 and R a6 independently of each other are halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy,
• Ci-C4-alkylthio Ci-C4-haloalkylthio, C2-C4-alkenyl, C2-C4-alkynyl, Cs-Cs-cycloalkyl,
• C3-C8-cycloalkyloxy or (Ci-C4-alkoxy)carbonyl more preferably hydrogen, halogen, CN, C1-C2- alkyl, Ci-C2-alkoxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkoxy-Ci-C2-alkoxy or (C1-C2- alkoxy)carbonyl, it being possible that one of both, R a5 or R a6 , can in addition be hydrogen; even more preferably F, CI, CH 3 , CH2CH3, CF 3 , CHFCH3, CN, OCH 3 , OCH2OCH3, CH2OCH3,
• R a5 and R a6 independently of each other are halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkoxy or (Ci-C4-alkoxy)carbonyl, and it being possible that one of both, R a5 or R a6 , can in addition be hydrogen.
• R a2 , R a5 and R a6 independently of each other are in each case one of the following groups 1-1 to 1-12 in Table I, groups 11-1 to 11-13 in Table II and groups III-1 to 111-13 in Table III, respectively: Table I:
• R A , R B in radical R independently of one another preferably are hydrogen or Ci- C 4 -alkyl.
• R' in radical R is hydrogen, OH, NH 2 , Ci-C 4 -alkyl or Ci-C 4 -alkoxy.
• Another preferred embodiment relates to compounds I wherein R is CH3.
• n 0, R is hydrogen, the moiety O-Het is bound in para- position to the phenylring, which compounds are of formula I.A1 :
• n 0, R is CH3, the moiety O-Het is bound in para- position to the phenylring, which compounds are of formula I.A2:
• R A , R B in radicals R b and/or R c , independently of one another preferably are hydrogen or Ci-C 4 -alkyl.
• R' in radicalR c is hydrogen, NH 2 , Ci-C 4 -alkyl or Ci-C 4 -alkoxy.
• R" in radicals R b and/or R c are hydrogen, Ci-C 4 -alkyl.
• R'" in radicals R b and/or R c which may the same or different, are hydrogen or Ci-C 4 -alkyl.
• R b is preferably selected from the group consisting of halogen, CN, N0 2 , Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy and Ci-C 4 -alkoxy-Ci-C 4 -alkyl; more preferably R b is halogen, CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl or Ci-C4-alkoxy; most preferably R b is halogen, CN , CH3, CF3 or OCH3.
• n is 1 , 2, 3 or 4 and R b is selected from the group of halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and C1-C4- alkoxy-Ci-C4-alkyl.
• n is preferably 0. According to a further embodiment, n is preferably 1. According to a further embodiment, n is preferably 2. According to a further embodiment, n is preferably 3.
• Het is a 6-membered heteroaryl
• the ring member atoms of the heteroaryl include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherin the 6-membered heteroaryl is unsubstituted or carries 1 , 2, 3 or 4 identical or different groups R c .
• Het is a 6-membered heteroaryl
• Het carries at least one nitrogen as ring member atom.
• Het is a pyrimidinyl radical that is selected from pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl and pyrimidin-6-yl, and wherein the aformentioned pyrimidinyl radicals are unsubstituted or carry 1 , 2 or 3 identical or different substituents R c .
• Het is a 5-membered heteroaryl
• Het carries two heteroatoms as ring member atoms.
• Preferred embodiments of the invention relate to compounds I, in which the group Het is one of the following radicals H-1 to H-38:
• One embodiment of the invention relates to compounds I, wherein Het carries 1 , 2 or 3 radicals R c . Another embodiment relates to compounds I, wherein Het carries 1 or 2 radicals R c . A further embodiment relates to compounds I, wherein Het carries one radical R c . A further embodiment relates to compounds I, wherein Het carries two radicals R c . A further embodiment relates to compounds I, wherein Het is unsubstituted.
• two radicals R c that are bound to adjacent ring member atoms of the Het group do not form together with said ring member atoms any fused cycle.
• R c is halogen and selected from fluorine, chlorine, bromine and iodine and selected from fluorine and chlorine and in particular, R c is chlorine.
• R c is CN
• R c is Ci-C 4 -alkyl and selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, 1 -methyl-propyl, 2-methyl-propyl and 1 ,1 -dimethylethyl, and selected from methyl, ethyl, n-propyl and i-propyl, and in particular, R c is methyl.
• R c is Ci-C 4 -haloalkyl and selected from Ci-haloalkyl, d-haloalkyl, d-haloalkyl and C 4 -haloalkyl. More preferably, R c is Ci-haloalkyl and selected from fluormethyl, difluormethyl, trifluormethyl, chlormethyl, dichlormethyl and trichlormethyl, and in particular, R c is trifluormethyl.
• R c is Ci-C 4 -alkoxy and selected from methoxy, ethoxy, n-propyloxy, i-propyloxy, n-butyloxy, 1 -methyl-propyloxy, 2-methyl-propyloxy and 1 ,1 -dimethylethyloxy and in particular from methoxy and ethoxy.
• R c is Ci-C 4 -haloalkoxy and specifically halomethoxy, such as difluormethoxy, trifluormethoxy, dichlormethoxy and trichlormethoxy, and haloethoxy, such as 2,2-difluorethoxy, 2,2,2-trifluorethoxy, 2,2-dichlorethoxy and 2,2,2-trichlorethoxy, and halo-n- propoxy, halo-i-propoxy, halo-n-butoxy, halo-1 -methyl-propoxy, halo-2-methyl-propoxy or halo- 1 ,1 -dimethylethoxy.
• halomethoxy such as difluormethoxy, trifluormethoxy, dichlormethoxy and trichlormethoxy
• haloethoxy such as 2,2-difluorethoxy, 2,2,2-trifluorethoxy, 2,2-dichlorethoxy and 2,2,2-trichlorethoxy
• R c is Cs-Cs-cycloalkyl, and in particular, R c is cyclopropyl.
• R c is phenyl
• R c is phenoxy
• R c is phenoxy-Ci-C 4 -alkyl and selected from phenoxymethyl, 1 - phenoxy-ethyl and 2-phenoxyethyl.
• R c relates to compounds I, wherein R c carries 1 , 2, 3 or 4 radicals R d , preferably 1 , 2 or 3 radicals R d , and more preferably 1 or 2 radicals R d .
• R c carries one radical R d .
• R c carries two radicals R d .
• the group R c carries 3 radicals R d .
• R d is halogen and selected from fluorine, chlorine, bromine and iodine and specifically from fluorine and chlorine and in particular, R c is chlorine.
• R d is CN
• R d is Ci-C4-alkyl and selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, 1 -methyl-propyl, 2-methyl-propyl and 1 ,1 -dimethylethyl, and preferably selected from methyl, ethyl, n-propyl and i-propyl and in particular, R d is methyl.
• R d is Ci-C4-haloalkyl and selected from Ci-haloalkyl, C2-haloalkyl, C3-haloalkyl and C4-haloalkyl. More preferably, R c is Ci-haloalkyl and selected from fluormethyl, difluormethyl, trifluormethyl, chlormethyl, dichlormethyl and trichlormethyl, and in particular, R d is trifluormethyl.
• R d is Ci-C4-alkoxy and selected from methoxy, ethoxy, n-propyloxy, i-propyloxy, n-butyloxy, 1 -methyl-propyloxy, 2-methyl-propyloxy and 1 ,1 -dimethylethyloxy and in particular from methoxy and ethoxy.
• the present invention relates to compounds of formula I, wherein:
• R a2 is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio,
• R a5 , R a6 independently of each other are hydrogen, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-
• R is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylamino or di(Ci-C4-alkyl)amino;R is hydrogen; n indicates the number of substituents R b on the phenyl ring and n is 0 or 1 ;R b is
• Ci-C4-alkyl Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy;
• Het is a pyridinyl, which is unsubstituted or carries 1 or 2 identical or different groups R c :
• R c is halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy or Ci-C6-haloalkoxy;
• the compounds I and the compositions according to the invention are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
• the compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
• compounds I and compositions thereof are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
• plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g.
• potatoes which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
• These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
• treatment of plant propagation materials with compounds I and compositions thereof, respectively is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
• cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf.
• 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.
• the compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
• Albugo spp. white rust
• vegetables e. g. A. Candida
• sunflowers e. g. A. tragopogonis
• Alternaria spp. Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), 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. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e.g. B.
• 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
• corn C. carbonum
• cereals e. g. C. sativus, anamorph: B. sorokiniana
• rice e. g. C. miyabeanus, anamorph: H.
• gossypii corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C.
• coccodes black dot
• beans e. g. C. lindemuthianum
• soybeans e. g. C. truncatum or C. gloeosporioides
• Corticium spp. e. g. C. sasakii (sheath blight) on rice
• Corynespora cassiicola leaf spots
• Cycloconium spp. e. g. C. oleaginum on olive trees
• Cylindrocarpon spp. e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.
• Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum),
• 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.
• 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.
• soybeans e. g. P. gregata: stem rot
• Phoma lingam root and stem rot
• P. betae root rot, leaf spot and damping-off
• sugar beets e. g. P. viticola: can and leaf spot
• soybeans e. g. stem rot: P.
• phaseoli, teleomorph Diaporthe phaseolorum
• Physoderma maydis brown spots
• Phytophthora spp. wilt, root, leaf, fruit and stem root
• 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 yallundae
• cereals e. g. wheat or barley
• Pseudoperonospora downy mildew
• Pseudopezicula tracheiphila red fire disease or .rotbrenner', anamorph: Phialophora
• Puccinia spp. rusts
• striiformis stripe or yellow rust
• P. hordei dwarf rust
• P. graminis seed or black rust
• P. recondita brown or leaf rust
• cereals such as e. g. wheat, barley or rye
• P. kuehnii range rust
• Pyrenophora anamorph: Drechslera
• tritici-repentis tan spot
• P. teres net blotch
• 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, soy- beans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp.
• R. solani root and stem rot
• S. solani silk and stem rot
• S. solani silk and stem rot
• S. solani silk blight
• R. cerealis Rhizoctonia spring blight
• Rhizopus stolonifer black mold, soft rot
• Rhynchosporium secalis scald
• Sarocladium oryzae and S. attenuatum sheath rot) on rice
• Sclerotinia spp e. g.
• R. solani root and stem rot
• S. solani silk blight
• R. cerealis Rhizoctonia spring blight
• Rhizopus stolonifer black mold, soft rot
• Rhynchosporium secalis scald
• Sarocladium oryzae and S. attenuatum sheath rot
• Sclerotinia spp Sclerotinia spp.
• seed 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) nodorum (Stagonospora blotch) on cereals; Uncinula (syn.
• Erysiphe) necator pry mildew, anamorph: Oidium tuckeri
• 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:
• Leptosphaeria [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.
• the compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
• the term "protection of materials” is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, colling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
• Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
• 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 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 the formula (I) can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
• the compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances.
• the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
• Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
• the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
• An agrochemical composition comprises a fungicidally effective amount of a compound I.
• effective amount denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
• compositions e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
• composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
• compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical
• compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New
• 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 dimethyl sulfoxide (DMSO); ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids;
• phosphonates e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
• Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch;
• fertilizers e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas
• products of vegetable origin e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
• Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as 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 American Ed.).
• Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
• sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated
• tridecylbenzenes sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
• sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
• phosphates are phosphate esters.
• carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
• Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
• alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
• Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
• N-subsititued fatty acid amides are fatty acid glucamides or fatty acid
• esters are fatty acid esters, glycerol esters or monoglycerides.
• sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
• polymeric surfactants are home- or copolymers of vinylpyrrolidone, 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.
• polybases are polyvinylamines or polyethyleneamines.
• 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 alkyliso- thiazolinones and benzisothiazolinones.
• Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
• Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
• Suitable colorants are pigments of low water solubility and water- soluble dyes.
• examples are inorganic colorants (e.g. iron oxide, titan oxide, iron
• organic colorants e.g. alizarin-, azo- and phthalocyanine colorants.
• Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
• the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably 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).
• Water-soluble concentrates (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.
• Methods for applying or treating compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
• compound I or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
• the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
• amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
• the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
• Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
• the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
• the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
• 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
• composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
• strobilurins e.g. strobilurins: azoxystrobin, coumethoxy- strobin, 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/ch
• - inhibitors of complex II e. g. carboxamides: benodanil, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, 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, N-[9- (dichloromethylene)-l ,2,3,4-tetrahydro-1 ,4-methanonaphthalen-5-yl]-3-(
• respiration inhibitors e.g. complex I, uncouplers: diflumetorim, (5,8-difluoro- quinazolin-4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
• DMI fungicides triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole,
• tetraconazole triadimefon, triadimenol, triticonazole, uniconazole; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine;
• Delta14-reductase inhibitors aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
• phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
• hymexazole hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro- 2-(p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin- 4-amine;
• tubulin inhibitors such as benzimidazoles, thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro- 7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine
• cell division inhibitors diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
• - methionine synthesis inhibitors anilino-pyrimidines: cyprodinil, mepanipyrim, pyrimethanil;
• blasticidin-S blasticidin-S, kasugamycin, kasugamycin hydrochloride- hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
• MAP / histidine kinase inhibitors fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
• - 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, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1 -(4- cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
• organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2- nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
• organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles
• guanidine dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon;
• guanidine dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon;
• glucan synthesis validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
• phosphonates fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
• 4- thiazolecarboxamide 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,
• Antifungal biocontrol agents plant bioactivators: Ampelomyces quisqualis (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (e.g. AFLAGUARD® from Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR® from bio-ferm GmbH, Germany), Bacillus pumilus (e.g. NRRL Accession No. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA), Bacillus subtilis (e.g. isolate NRRL-Nr.
• Ampelomyces quisqualis e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany
• Aspergillus flavus e.g. AFLAGUARD® from Syngenta, CH
• Aureobasidium pullulans e.g. BOTECTOR® from bio-ferm GmbH, Germany
• Candida oleophila I-82 e.g. ASPIRE® from Ecogen Inc., USA
• Candida saitoana e.g. BIOCURE® (in mixture with lysozyme) and
• BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta
• Chitosan e.g.
• Clonostachys rosea f. catenulata also named Gliocladium catenulatum (e.g. isolate J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS® from Prophyta, Germany), Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g. YIELD PLUS® from Anchor Bio-Technologies, South Africa), Fusarium oxysporum (e.g.
• BIOFOX® from S.I.A.P.A., Italy, FUSACLEAN® from Natural Plant Protection, France
• Metschnikowia fructicola e.g. SHEMER® from Agrogreen, Israel
• Microdochium dimerum e.g. ANTIBOT® from Agrauxine, France
• Phlebiopsis gigantea e.g. ROTSOP® from Verdera, Finland
• Pseudozyma flocculosa e.g. SPORODEX® from Plant Products Co. Ltd., Canada
• Pythium oligandrum DV74 e.g.
• 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-22 e.g. PLANTSHIELD® der Firma BioWorks Inc., USA
• T. harzianum TH 35 e.g. ROOT PRO® from Mycontrol Ltd., Israel
• 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 (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), Ulocladium oudemansii HRU3 (e.g. BOTRY-ZEN® from Botry-Zen Ltd, NZ);
• T. viride TV1 e.g. T. viride TV
• 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-io
• acetochlor alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
• - aryloxyphenoxypropionates clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
• - (thio)carbamates asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb,
• acifluorfen acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen;
• - phenoxy acetic acids clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
• - 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,
• - triazines ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
• ureas chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
• acetolactate synthase inhibitors bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid,
• pyriminobac-methyl pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam; - others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin,
• fenoxasulfone fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon,
• oxaziclomefone pentoxazone, pinoxaden, pyraclonil, 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-
• organo(thio)phosphates acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
• - 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, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
• nicotinic receptor agonists/antagonists compounds clothianidin, dinotefuran, 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 I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
• oxidative phosphorylation inhibitors cyhexatin, diafenthiuron, fenbutatin oxide, propargite;
• cryomazine cryomazine
• the present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to L), as described above, and if desired one suitable solvent or solid carrier.
• agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to L), as described above, and if desired one suitable solvent or solid carrier.
• fungicide e. g. one or more fungicide from the groups A) to L
• combating harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to L), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to L).
• compounds I together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures).
• the order of application is not essential for working of the present invention.
• 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 .
• 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
• 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.
• mixtures 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, pyraclostrobin, trifloxystrobin; famoxadone, fenamidone; bixafen, boscalid, fluopyram, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid, fluazinam, fentin salts, such as fentin acetate.
• mixtures comprising a compound 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, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, fenarimol, triforine;
• mixtures comprising a compound I (component 1 ) and at least one active substance selected from group C) (component 2) and particularly selected from metalaxyl, (metalaxyl-M) mefenoxam, ofurace.
• mixtures comprising a compound 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.
• mixtures comprising a compound I (component 1 ) and at least one active substance selected from group E) (component 2) and particularly selected from cyprodinil, mepanipyrim, pyrimethanil.
• mixtures 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.
• mixtures comprising a compound I (component 1 ) and at least one active substance selected from group G) (component 2) and particularly selected from dimethomorph, flumorph, iprovalicarb, benthiavalicarb, mandipropamid, propamocarb.
• mixtures comprising a compound I (component 1 ) and at least one active substance selected from group H) (component 2) and particularly selected from copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, mancozeb, metiram, propineb, thiram, captafol, folpet, chlorothalonil, dichlofluanid, dithianon.
• mixtures comprising a compound I (component 1 ) and at least one active substance selected from group I) (component 2) and particularly selected from carpropamid and fenoxanil.
• mixtures 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.
• mixtures comprising a compound I (component 1 ) and at least one active substance selected from group K) (component 2) and particularly selected from cymoxanil, proquinazid and N-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.
• mixtures comprising a compound I (component 1 ) and at least one active substance selected from group L) (component 2) and particularly selected from Bacillus subtilis strain NRRL No. B-21661 , Bacillus pumilus strain NRRL No. B-30087 and Ulocladium oudemansii.
• the present invention furthermore relates to compositions comprising one compound I (component 1 ) and one further active substance (component 2), which further active substance is selected from the column "Component 2" of the lines D-1 to D-370 of Table D.
• a further embodiment relates to the compositions D-1 to D-370 listed in Table D, where a row of Table D 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 respective further active substance from groups A) to O) (component 2) stated in the row in question.
• the compositions described comprise the active substances in
• Table D Composition comprising one indiviualized compound I and one further active substance from groups A) to O)
• component 2 The active substances referred to as component 2, their preparation and their activity against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
• the compounds described by lUPAC nomenclature, their preparation and their 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,
• the mixtures 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.
• the mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn.
• the purified phenol was dissolved in dichloromethane (DCM, 1 .5 L) to which was added triethylamine (275 ml_), feri-butyloxycarbonyl anhydride (215 g, 990 mmol) in a solution of DCM (500 ml_), and was stirred for 30 min at room temperature.
• the reaction solution was washed with water, dried over Na2S0 4 , then concentrated in vacuo.
• the residue was purified by flash silica column chromatography (4:1 cyclohexane: MTBE) to afford 220 g (860 mmol, 92%) of the desired product.
• Example 2 Preparation of 2-[4-[[2-(trifluoromethyl)-4-pyridyl]oxy]phenyl]ethanamine hydrochloride To a solution of N-feri-butyloxycarbonyl-protected tyramine (130 g, 550 mmol), potassium carbonate (76 g, 550 mmol), and catalytic amounts of potassium iodide in N-methyl pyrrolidone (NMP, 400 ml.) that was stirred for 10 minutes at room temperature was added 4-chloro-2- trifluoromethylpyridine (100 g, 550 mmol).
• NMP N-methyl pyrrolidone
• 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.
• Use example 1 Preventative control of leaf blotch on wheat caused by Septoria tritici
• Leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension of the active compound or their mixture, prepared as described. The plants were allowed to air-dry. At the following day the plants were inoculated with an aqueous spore suspension of Septoria tritici. Then the trial plants were immediately transferred to a humid chamber at 18 to 22°C and a relative humidity close to 100%. After 4 days the plants were transferred to a chamber with 18 to 22°C and a relative humidity close to 70% and kept there for 4 weeks.
• 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 their mixture mentioned in the table below. The next day, the treated plants were inoculated with an aqueous suspension of sporangia of Phytophthora infestans. After inoculation, the trial plants were immediately transferred to a humid chamber and kept for 6 days at 18 to 20°C and a relative humidity close to 100%.
• Use example 3 Protective control of soy bean rust on soy beans caused by Phakopsora pachyrhizi Leaves of pot-grown soybean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 1 day in a greenhouse chamber at 23 to 27 ° C and a relative humidity between 60 and 80%.Then the plants were inoculated with spores of Phakopsora pachyrhizi. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 20 to 24°C for 24 h. The trial plants were cultivated for fourteen days in a greenhouse chamber at 23 to 27°C and a relative humidity between 60 and 80%.
• the first two developed leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below.
• the next day the plants were inoculated with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to
• the trial plants were cultivated for 6 days in a greenhouse chamber at 20 to 24° C and a relative humidity between 65 and 70 %.
• the first two developed leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. Seven days later the plants were inoculated with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to 24°C for 24 h. Then the trial plants were cultivated for 6 days in a greenhouse chamber at 20 to 24°C and a relative humidity between 65 and 70 %.
• Cucumber seedlings were grown in pots to the 2 leaf stage. The plants were sprayed to runoff with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the treated plants were inoculated with an aqueous spore suspension of cucumber powdery mildew (Sphaerotheca fuliginea). Then the trial plants were cultivated for 8 days in a greenhouse at temperatures between 20 and 24°C and a relative humidity between 60 and 80%.
• Use example 8 Fungicidal control of grape downy mildew caused by Plasmopara viticola
• Grape cuttings 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 plants were allowed to air-dry. The next day they were inoculated with an aqueous spore suspension of Plasmopara viticola by spraying it at the lower leaf-side. Then the trial plants were immediately transferred for 24 h to a humid chamber with 22 to 24°C and a relative humidity close to 100%. For a period of 5 days, cultivation followed in a greenhouse at 20 to 25°C and a relative humidity about 50 to 80%. To stimulate the outbreak of the disease symptoms, the plants were transferred to a humid chamber again for 24 hours. Then the extent of fungal attack on the lower leaf surface was visually assessed as % diseased leaf area.

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