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Fungicidal pyrimidine compounds

Imported: 13 Feb '17 | Published: 11 Oct '16

USPTO - Utility Patents

Abstract

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. Furthermore the invention relates to processes for preparing compounds of formula I.

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Description

This application is a National Stage application of International Application No. PCT/EP2013/054966, filed Mar. 12, 2013, which claims the benefit of U.S. Provisional Application No. 61/610,040, filed Mar. 13, 2012, the entire contents of which are hereby incorporated herein by reference. This application also claims priority under 35 U.S.C. §119 to EP Patent Application No. 12159313.1, filed Mar. 13, 2012, and EP Patent Application No. 12165108.7, filed Apr. 23, 2012, the entire contents of both are hereby incorporated herein by reference.

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. Furthermore the invention relates to processes for preparing compounds of formula I.

WO 2011007839 A1 describes 4-(3-butynyl)aminopyrimidine derivatives, which are pest controlling agents for agricultural and horticultural use.

EP 264217 A2 discloses certain aralkylaminopyrimidine derivatives, which are useful as insecticides, acaricides and fungicides.

The compounds according to the present invention differ from those described in the abovementioned publication in that the central phenyl ring is always substituted by a heteroaryloxy substituent and that the linker between said phenyl ring and the aminopyrimidine moiety is a butynyl derived group as described herein.

In many cases, in particular at low application rates, 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.

Accordingly, the present invention relates to compounds of the formula I

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wherein:

  • Ra2, Ra5, Ra6 independently of each other are hydrogen, halogen, CN, NO2, OH, SH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyloxy, C3-C8-cycloalkyl-C1-C4-alkyl, NRARB, C(═O)R′, C(═NOR″)R′″ or —C(═NH)—O—R′″;
    • RA, RB independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, phenyl, benzyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl or (C═O)—R′;
    • R′ is hydrogen, OH, NH2, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylamino or di(C1-C4-alkyl)amino;
    • R″ is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl or C1-C4-alkoxy-C1-C4-alkyl;
    • R′″ is hydrogen or C1-C4-alkyl; or
  • Ra5, Ra6 together with two ring member carbon atoms to which they are attached, form a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals selected from the group consisting of halogen, CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy;
  • R is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, CN, CH2CN, NRARB or CH2—O—C(═O)R′;
  • R1, R2 independently of each other are hydrogen, halogen, CN, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, C3-C8-cycloalkyloxy, NRARB, C(═O)R′, C(═NOR″)R′″, C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy)carbonyl and di(C1-C4-alkyl)aminocarbonyl;
    • or two radicals R1 and R2 that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated
    • 3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from halogen, CN, OH, SH, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio; and one or two CH2 groups of the abovementioned cycles may be respectively be replaced by one or two C(═O) or C(═S) groups;
  • X is a divalent group selected from —CR3R4—, —C(═O)—, —C(═S)—, —C(═NRD)— and —C(═NORD)—, wherein
    • RD is hydrogen or C1-C4-alkyl, and wherein
    • R3 and R4 independently of each other are hydrogen, CN, C1-C4-hydroxyalkyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, C3-C8-cycloalkyloxy, NRARB, C(═O)R′, C(═NOR″)R″′,—C(═NH)—O—R″′ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, (C1-C4-alkoxy)carbonyl and di(C1-C4-alkyl)aminocarbonyl, or
    • two radicals R3 and R4 that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated
    • 3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from halogen, CN, OH, SH, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio; and one or two CH2 groups of the abovementioned cycles may be respectively replaced by one or two C(═O) or C(═S) groups;
  • n indicates the number of substituents Rb on the phenyl ring and n is 0, 1, 2, 3 or 4;
  • Rb is halogen, CN, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, NRARB, C(═O)R′, C(═NOR″)R″′ or —C(═NH)—O—R″′,
    • it being possible for n=2, 3 or 4 that Rb are identical or different;
  • Het is a 5- or 6-membered 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 and wherein the heteroaryl is unsubstituted or carries 1, 2, 3 or 4 identical or different groups Rc:
    • Rc is halogen, CN, NO2, NH2, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylamino, di(C1-C6-alkyl)amino, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C1-C6-alkoxy-C1-C4-alkyl, C1-C6-haloalkoxy-C1-C4-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C(═O)R′, C(═NOR″)R″′, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenoxy, phenoxy C1-C4-alkyl or a 5- or 6-membered 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, and wherein the aforementioned cyclic radicals are unsubstituted or carry 1, 2, 3 or 4 identical or different substituents Rd:
      • Rd is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
      • or two radicals Rc that are bound to adjacent ring member atoms of the Het group form together with said ring member atoms a fused
      • 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals groups Re:
      • Re is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
        and the N-oxides and the agriculturally acceptable salts of the compounds of formula I.

The present invention furthermore relates to processes for preparing compounds of formula I. The present invention furthermore relates to intermediates such as compounds of formulae III, IIa and IIIa and to processes for preparing them. Accordingly a 4-halopyrimidine compound II, wherein Hal is halogen, preferably Cl or F, can be reacted with a suitable amine compound III, wherein X is —CR3R4—, to obtain a compound I according to the present invention, wherein X is —CR3R4—, as shown in scheme 1.

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Generally, 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.

Suitable catalysts are e.g. haldies such as NaF, KF, LiF, NaBr, KBr, LiBr, Nal, KI, LiI; ionic liquids, such as imidazolium catalysts; transition metal catalysts like palladium, rhodium, ruthenium, iron, copper in the form of halides, pseudohalides, alkoxides, carboxylates (precustom characterferred acetate), complexes with dibenzylidene acetone and ligands like phosphine, phoscustom characterphites, phosphoramidate ligands. Preferred ligands are bidentate and sterically demanding phosphorous ligands, even more preferably the catalysts are selected from 2,2′ bis(diphenylcustom characterphosphanyl)-1,1′-binaphthyl, 2,2′-Bis(diphenylphosphino)-1,1′-biphenyl, 2,4′,6′-diisopropyl-1,1′-biphenyl-2-yldicyclohexylphosphine, 2-(dicyclohexylphosphino)-2′,6′ dimethoxy-1,1′ bicustom characterphenyl, 1,1-bis(diphenylphosphino)ferrocene, 9,9-dimethyl-4,5 bis(diphenylphosphino)custom characterxancustom characterthene, 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-propanediylbis[diphenylphosphine], 1,4 butanediylbis[diphenylphosphine] and 1,1′-(1,2-ethanediyl)bis[1-(2-methoxyphenyl)-1 phenyl-diposphine.

Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene; halogenated hydro-carbons chlorobenzene, dichlorobenzene; ethers such as dioxane, anisole and 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 DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester, preferably THF, DMSO, DMF, dimethyl acetamide, NMP or NEP; even more preferably THF, DMF or NMP. It is also possible to use mixtures of the solvents mentioned.

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 (DIPEA) and N-methyl-2-pyrrolidone (NMP), pyridine, substituted pyridines such as collidine, lutidine and 4 dimethylaminopyridine (DMAP), and also bicyclic amines. Preference is given to sodium hydride, potassium hydride, lithium carbonate, potassium carbonate, caesium carbonate, TEA, TBA and DIPEA, in particular DIPEA. 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, N.J., United States) (2000), 56; or Targets in Heterocyclic Systems (2008) 12, 59-84.

The alkyne 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 WO 2011007839. The compounds III can also be prepared for example in analogy to methods described in scheme 2, wherein PG in compound AD-2 stands for a suitable protection group for an amine, for example tert-butoxycarbonyl, benzyloxy carbonyl, benzyl, 4-methoxy benzyl, acetyl or trichloro acetyl.

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According to scheme 2, butyne compounds can be synthesized via a palladium catalyzed crosscoupling of an aryl halide AD-1 with suitable alkynes AD-2 (US 20110105562 A1, Tetrahedron (1992), 48(15), 3239-50; WO 2004043458 A1); the heterocycle Het can be installed before or after the crosscoupling reaction.

Alkynes AD-2 are commercially available or they can be synthesized according to scheme 3.

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Ring opening of a substituted aziridine AD-3 with a metal acetylide, wherein M can be, for example, lithium, directly leads to the formation of AD-2 (Angewandte Chemie, International Edition (2011), 50(9), 2144-2147; Journal of the American Chemical Society (2010), 132(13), 4542-4543; Organic Letters (2007), 9(24), 5127-5130; WO 2006044412 A1). Nucleophilic addition of a propargyl metal, wherein AD-5, wherein M can be, for example, lithium, to an imine AD-4 is another way to prepare the amine compound AD-2 (European Journal of Organic Chemistry (2010), (8), 1587-1592; Synlett (2008), (4), 578-582; Journal of Organic Chemistry (1999), 64(7), 2406-2410; Synthetic Communications (1997), 27(15), 2601-2614).

Alkohols AD-7 can be used to synthesize amines AD-2. Alcohols AD-7 are commercially available or methods for their preparation are described in the literature.

Conversion of AD-7 to an amine can be achieved in a three step reaction sequence comprising a) mesylation with methyanesulfonic acid chloride (MsCl)) in the presence of a base such as triethylamine, b) treatment of the intermediate methylsulfonate with sodium azide, and c), subsequent reduction of the alkylazide with a suitable reductant (e.g. SnCl2; as described in Journal of Medicinal Chemistry (2011), 54(20), 7363-7374; WO 2011098603 A1, Bioorganic & Medicinal Chemistry (2011), 19(10), 3274-3279) followed by protection of the amino group. It is also possible to synthesize such compounds under Mitsunobu conditions as described in Journal of Organic Chemistry (2011), 76(14), 5661-5669 or Chemistry-A European Journal (2011), 17(6), 1764-1767 or by way of a Gabriel synthesis as described in European Journal of Medicinal Chemistry (2011), 46(8), 3227-3236, Chemistry-A European Journal (2010), 16(41), 12303-12306 or in WO 2010017047 A1.

Amide compounds AD-8 can be synthesized according to scheme 4. A suitably substituted acetamide can be formylated according to the synthesis described in Bulletin of the Chemical Society of Japan (1994), 67(9), 2514-21 or in Journal of Organic Chemistry (1983), 48(17), 2914-20.

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A subsequent Corey Fuchs cascade (formation of the dibromo alkene with tetrabromomethane and triphenylphosphine: U.S. Pat. No. 4,944,795 A, rearrangement induced with n-butyllithium furnishing the alkyne: Organic Letters (2011), 13(9), 2204-2207, Journal of the Chemical Society, Perkin Transactions 1 (2002), (9), 1199-1212) produces the alkyne amide AD-2.

An alternative way to prepare compounds AD-8 wherein PG is hydrogen is described in scheme 5. A propargyl halide is reacted with a metal cyanid, wherein the metal M can be, for example sodium or potassium, which is subsequently hydrolysed under basic aqueous conditions to give the alkyne.

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A 4-halopyrimidine compound II, wherein Hal is halogen, preferably Cl or F, can also be reacted with a suitable amide compound III, wherein X is —C(═O)— to obtain a compound I wherein X is —C(═O)— as shown in scheme 1.

Generally, this reaction is carried out at temperatures of from 0 to 200° C., preferably from 50 to 170° C., in an inert organic solvent preferably in the presence of a base or a catalyst or a combination of a base and a catalyst in a solvent.

Suitable catalysts are e.g. halides such as NaF, KF, LiF, NaBr, KBr, LiBr, Nal, KI, LiI; ionic liquids, such as imidazolium catalysts; transition metal catalysts like palladium, rhodium, ruthenium, iron, copper in the form of halides, pseudohalides, alkoxides, carboxylates (preferred acetate), complexes with dibenzylidene acetone and ligands like phosphine, phosphites, phosphoramidate ligands. Preferred ligands are bidentate and sterically demanding phosphorous ligands, even more preferably the catalysts are selected from 2,2′-bis(diphenyl-phosphanyl)-1,1′-binaphthyl, 2,2′-bis(diphenylphosphino)-1,1′-biphenyl, 2,4′,6′-diisopropyl-1,1′-biphenyl-2-yldicyclohexylphosphine, 2-(dicyclohexylphosphino)-2′,6′-dimethoxy-1,1′-biphenyl, 1,1-bis(diphenylphosphino)ferrocene, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-propanediylbis[diphenylphosphine], 1,4-butanediylbis[diphenylphosphine] and 1,1′-(1,2-ethanediyl)bis[1-(2-methoxyphenyl)-1-phenyl-diposphine.

Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene; ethers such as dioxane, anisole and 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 DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester. Preferably THF, DMSO, DMF, dimethyl acetamide, NMP or NEP are used; even more preferably THF, DMF or NMP are used. It is also possible to use mixtures of the solvents mentioned.

Suitable bases and their amounts are as described for the reaction with a phenethyl amine compound III, wherein X is —CR3R4—, as described above. 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.

Alternatively, amide compounds I, wherein X is —C(═O)—, can be synthesized by reacting 4-amino-pyrimidine compounds IIa [available by reaction of a chloropyrimidine II with excess of ammonia in analogy to methods described in WO 2011/147066, WO 2006/135719, US 2005/0245530 A1, J. Chem. Soc. (1951), 3439-44; Helv. Chim. Act. (1951), 34, 835-40] with compounds of the formula IIIa in which Z is hydrogen or C1-C4-alkyl, which are commercially available or which can be prepared as described above, preferably in the presence of Al(CH3)3 (1 to 3 equivalents) as stoichiometric reagent preferably in an inert organic solvent such as toluene (in analogy to US 2010/0063063 A1; WO 2005/011601; WO 2006/074884) as outlined in scheme 10.

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Compounds I, wherein X is —C(═S)—, can be prepared for example in analogy to methods described in US 20100022538 A1, J. Med. Chem. (2011), 54(9), 3241-3250, J. Org. Chem. (2011), 76(6), 1546-1553, Org. Lett. (2010), 12(23), 5570-5572.

Compounds I, wherein X is —C(═NRD)—, can be prepared from compounds I, wherein X is —C(═O)—, in analogy to Bioorg. Med. Chem. (2008) 16(8), 4600-4616, J. Med. Chem. (2004) 47(3), 663-672, Eur. J. Org. Chem. (2004) 5, 1025-1032, J. Med. Chem. (1987) 30(4), 720-1.

Compounds I, wherein X is —C(═NORD)—, can be prepared from compounds I, wherein X is —C(═O)—, in analogy to WO 2007/075598 or from compounds I, wherein X is —C(═S)—, according to WO 2008/039520 and O'zbekiston Kimyo Jurnali (2004) 4, 3-6.

Compounds I and intermediates, wherein R is hydrogen, can be converted by conventional processes such as alkylation. Examples of 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 dialkyl 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 temperature range—aliphatic, cycloaliphatic or aromatic hydrocarbons such as hexane, cyclohexane, toluene, xylene, chlorinated aliphatic and aromatic hydrocarbons such as DCM, chlorobenzene, open-chain dialkyl 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.

Compounds II, wherein Ra5 and Ra6 in each case constitute together with two ring member carbon atoms of the pyrimidine ring one of the following heterocyclic groups as defined in line 1 to line 26 in table A.2, wherein #5 and #6 indicate the point of attachment to the pyrimidine ring, each respectively corresponding to the positions of either substituent Ra5 or Ra6, can be prepared according to commonly known procedures such as those given below or in analogy to those cited references or are commercially available.

TABLE A.2 line Ra5/Ra6 A.2-1 #5-CH═CH—CH═CH-#6 A.2-2 #5-CH2—CH2—CH2—CH2-#6 A.2-3 #5-CH═CH—CH═N-#6 A.2-4 #5-N═CH—CH═CH-#6 A.2-5 #5-CH═N—CH═N-#6 A.2-6 #5-N═CH—N═CH-#6 A.2-7 #5-CH2—CH2—CH2-#6 A.2-8 #5-N═CH—CH═N-#6 A.2-9 #5-O—CH2—O-#6 A.2-10 #5-NH—CH═N-#6 A.2-11 #5-S—CH═N-#6 A.2-12 #5-N═CH—S-#6 A.2-13 #5-O—CH═N-#6 A.2-14 #5-N═CH—O-#6 A.2-15 #5-O—CH═CH-#6 A.2-16 #5-S—CH═CH-#6 A.2-17 #5-O—N═CH-#6 A.2-18 #5-S—N═CH-#6 A.2-19 #5-CH═N—O-#6 A.2-20 #5-CH═N—S-#6 A.2-21 #5-N(CH3)—CH═CH-#6 A.2-22 #5-CH═CH—N(CH3)-#6 A.2-23 #5=CH—N(NH2)—N=#6 A.2-24 #5-CH—N—N(CH3)-#6 A.2-25 #5=N—N(CH3) —CH=#6 A.2-26 #5-N(CH3) —N—CH-#6

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 1 of table A.2 can be prepared as described in EP 326329 A2, US 20050187231 A1, WO 2007071963 A2, Tetrahedron (2004), 60(25), 5373-5382, Bioorganic & Medicinal Chemistry Letters (2009), 19(6), 1715-1717 or in WO 2010025451 A2.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 3 of table A.2 can be prepared as described in European Journal of Medicinal Chemistry (2011), 46(9), 3887-3899, WO 2011104183 A1 or in Organic Process Research & Development (2011), 15(4), 918-924.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 4 of table A.2 can be prepared as described in WO 2011131741 A1, WO 2010101949 A1 or in Journal of Organic Chemistry (1979), 44(3), 435-40.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 5 or 20 of table A.2 can be prepared as described in Organic Process Research & Development (2011), 15(4), 918-924; or in Tetrahedron (1998), 54(33), 9903-9910.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 6 of table A.2 can be prepared as described in WO 2010026262 A1 or in WO 2007092681 A2.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 8 of table A.2 can be prepared as described in WO 2010038060 A1, Bioorganic & Medicinal Chemistry Letters (2010), 20(7), 2330-2334, CN 101544642 A or in Journal of the American Chemical Society (1956), 78, 225-8.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 11 of table A.2 can be prepared as described in US 20110028496 A1.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 12 of table A.2 can be prepared as described in WO 2010014930, US 20110028496 A1 or in WO 2008057402 A2.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 14 of table A.2 can be prepared as described in Australian Journal of Chemistry (1990), 43(1), 47-53 or in WO 2009013545 A2.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 24 of table A.2 can be prepared as described in US 20090005359 A1 or in US 20070281949 A1.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 25 of table A.2 can be prepared as described in WO 2007013964 A1.

Compounds II wherein the meaning of Ra5 and Ra6 corresponds to line 26 of table A.2 can be prepared as described in Journal of Medicinal Chemistry (1988), 31(2), 454-61 or in WO 2006046135 A2.

If individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I. 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(11), 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.

If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e.g. under the action of light, acids or bases). Such conversions may also take place after use, e.g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.

The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatic purification of the crude products. In some cases, the intermediates and end products are obtained in the form of colorless or slightly viscous oils which can be freed from volatile components or purified under reduced pressure and at moderately elevated temperatures. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

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.

Furthermore, 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.

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 C1-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-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.

Depending on the substitution pattern, the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.

Compounds I can be present in different crystal modifications whose biological activity may differ. They also form part of the subject matter of the present invention. 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.

In respect of the variables, the embodiments of the intermediates correspond to the embodiments of the compounds of formula I. The term “compounds I” refers to compounds of formula I. Likewise, the term “compounds IIa” refers to compounds of formula IIa.

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.

In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term “Cn-Cm” indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.

The term “halogen” refers to fluorine, chlorine, bromine and iodine.

The term “C1-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. Likewise, the term “C1-C6-alkyl” refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms.

The term “C1-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, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2—C2F5, CF2—C2F5, CF(CF3)2, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Likewise, the term “C1-C6-haloalkyl” refers to a straight-chained or branched alkyl group having 1 to 6 carbon atoms.

The term “C1-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-methylcustom characterpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy. Likewise, the term “C1-C6-alkoxy” refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

The term “C1-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 hydroxymethyl,

2-hydroxyethyl, 3-hydroxy-propyl, 4-hydroxy-butyl.

The term “C1-C4-haloalkoxy” refers to a C1-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, OCH2F, OCHF2, OCF3, OCH2Cl, OCHCl2, OCCl3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2—C2F5, OCF2—C2F5, 1-(CH2F)-2-fluoroethoxy, 1-(CH2Cl)-2-chloroethoxy, 1-(CH2Br)-2-bromocustom characterethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. Likewise, the term “C1-C6-haloalkoxy” refers to a C1-C6-alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above.

The term “C1-C4-alkoxy-C1-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 C1-C4-alkoxy group (as defined above). Likewise, the term “C1-C6-alkoxy C1-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 C1-C6-alkoxy group (as defined above).

The term “C1-C4-haloalkoxy C1-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 C1-C4-haloalkoxy group (as defined above). Likewise, the term “C1-C6-haloalkoxy-C1-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 C1-C6-alkoxy group (as defined above).

The term “C1-C4-alkylthio” as used herein 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. Likewise, the term “C1-C6-alkylthio” as used herein refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as defined above) bonded via a sulfur atom. Accordingly, the terms “C1-C4-haloalkylthio” and “C1-C6-haloalkylthio” as used herein refer to straight-chain or branched haloalkyl groups having 1 to 4 or 1 to 6 carbon atoms (as defined above) bonded through a sulfur atom, at any position in the haloalkyl group.

The terms “C1-C4-alkylsulfinyl” or “C1-C6-alkylsulfinyl” refer to straight-chain or branched alkyl groups having 1 to 4 or 1 to 6 carbon atoms (as defined above) bonded through a —S(═O)— moiety, at any position in the alkyl group, for example methylsulfinyl and ethylsulfinyl, and the like. Accordingly, the terms “C1-C4-haloalkylsulfinyl” and “C1-C6-haloalkylsulfinyl”, respectively, refer to straight-chain or branched haloalkyl groups having 1 to 4 and 1 to 6 carbon atoms (as defined above), respectively, bonded through a —S(═O)— moiety, at any position in the haloalkyl group.

The terms “C1-C4-alkylsulfonyl” and “C1-C6-alkylsulfonyl”, respectively, refer to straight-chain or branched alkyl groups having 1 to 4 and 1 to 6 carbon atoms (as defined above), respectively, bonded through a —S(═O)2— moiety, at any position in the alkyl group, for example methylsulfonyl. Accordingly, the terms “C1-C4-haloalkylsulfonyl” and “C1-C6-haloalkylsulfonyl”, respectively, refer to straight-chain or branched haloalkyl groups having 1 to 4 and 1 to 6 carbon atoms (as defined above), respectively, bonded through a —S(═O)2— moiety, at any position in the haloalkyl group.

The term “C1-C4-alkylamino” refers to an amino radical carrying one C1-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. Likewise, the term “C1-C6-alkylamino” refers to an amino radical carrying one C1-C6-alkyl group (as defined above) as substituent.

The term “di(C1-C4-alkyl)amino” refers to an amino radical carrying two identical or different C1-C4-alkyl groups (as defined above) as substituents, for example dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N methylamino, N-(n-butyl)-N-methylamino, N-(n-pentyl)-N-methylamino, N-(2-butyl)-N methylamino, N-(isobutyl)-N-methylamino, and the like. Likewise, the term “di(C1-C6-alkyl)amino” refers to an amino radical carrying two identical or different C1-C6-alkyl groups (as defined above) as substituents.

The term “C1-C4-alkoxy)carbonyl” refers to a C1-C4-alkoxy radical (as defined above) which is attached via a carbonyl group.

The term “di(C1-C4-alkyl)aminocarbonyl” refers to a di(C1-C4)alkylamino radical as defined above which is attached via a carbonyl group.

The term “phenoxy” and refers to a phenyl radical which is attached via an oxygen atom. Likewise, the term “phenoxy C1-C4-alkyl” and refers to a phenoxy radical which is attached via a C1-C4-alkyl group (as defined above).

The term “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. Likewise, the term “C2-C6-alkenyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.

The term “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. Likewise, the term “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.

The term “C3-C8-cycloalkyl” refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members, such as cyclopropyl(C3H5), cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The term “C3-C8-cycloalkyl-C1-C4-alkyl” refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above), which is bonded via a C1-C4-alkyl group (as defined above).

The term “C3-C8-cycloalkyloxy” refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above), which is bonded via an oxygen.

The term “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, cycloheptyl, cycloheptenyl, cycloheptadienyl, and the like.

The term “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, for example:

    • a 3- or 4-membered saturated heterocycle which contains 1 or 2 heteroatoms from the group consisting of N, O and S as ring members such as oxirane, aziridine, thiirane, oxetane, azetidine, thiethane, [1,2]dioxetane, [1,2]dithietane, [1,2]diazetidine; and
    • a 5- or 6-membered saturated or partially unsaturated heterocycle which contains 1, 2 or 3 heteroatoms from the group consisting of N, O and S as ring members such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl and also the corresponding -ylidene radicals; and
    • a 7-membered saturated or partially unsaturated heterocycle such as tetra- and hexahydroazepinyl, such as 2,3,4,5-tetrahydro[1H]azepin-1-,-2-,-3-,-4-,-5-,-6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-,-3-,-4-,-5-,-6- or -7-yl, 2,3,4,7-tetrahydro[1H]azepin-1-,-2-,-3-,-4-,-5-,-6- or -7-yl, 2,3,6,7-tetrahydro[1H]azepin-1-,-2-,-3-,-4-,-5-,-6- or -7-yl, hexahydroazepin-1-,-2-,-3- or -4-yl, tetra- and hexahydrooxepinyl such as 2,3,4,5-tetrahydro[1H]oxepin-2-,-3-,-4-,-5-,-6- or -7-yl, 2,3,4,7-tetrahydro[1H]oxepin-2-,-3-,-4-,-5-,-6- or -7-yl, 2,3,6,7-tetrahydro[1H]oxepin-2-,-3-,-4-,-5-,-6- or -7-yl, hexahydroazepin-1-,-2-,-3- or -4-yl, tetra- and hexahydro-1,3-diazepinyl, tetra- and hexahydro-1,4-diazepinyl, tetra- and hexahydro-1,3-oxazepinyl, tetra- and hexahydro-1,4-oxazepinyl, tetra- and hexahydro-1,3-dioxepinyl, tetra- and hexahydro-1,4-dioxepinyl and the corresponding -ylidene radicals; and

The term “5- or 6-membered 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”, refers to, for example,

    • a 5-membered heteroaryl such as pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2,4-triazolyl-1-yl, 1,2,4-triazol-3-yl 1,2,4-triazol-5-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl; or
    • a 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.

The term “two radicals Rc 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.

The term “one or two CH2 groups of the abovementioned cycles may be respectively replaced by one or two C(═O) or C(═S) groups” refers to an exchange of carbon atoms from a saturated or partially unsaturated 3-, 4-, 5-, 6- or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6- or 7-membered heterocycle, resulting in cycles such as cyclopropanone, cyclopentanone, cyclopropanethione, cyclopentanethione, 5-oxazolone, cyclohexane-1,4-dione, cyclohexane-1,4-dithione, cyclohex-2-ene-1,4-dione or cyclohex-2-ene-1,4-dithione.

As regards the fungicidal activity of the compounds I, preference is given to those compounds I wherein the substituents and variables (e.g. Ra2, Ra5, Ra6, R, X, R1, R2, R3, R4, Rb, Rc, R′, R″, R″′, RA, RB, n and Het) have independently of each other or more preferably in combination the following meanings and the groups mentioned herein for a substituent or for a combination of substituents are furthermore, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent or of the combination of substituents in question:

One embodiment of the present invention relates to compounds I wherein Ra2, Ra5 and Ra6 independently of each other are preferably selected from the group consisting of hydrogen, halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyloxy, (C1-C4-alkoxy)carbonyl.

A further embodiment relates to compounds I wherein Ra2, Ra5 and Ra6 independently of each other are preferably selected from the group consisting of hydrogen, halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy C1-C4-alkyl, C1-C4-alkoxy C1-C4-alkoxy and C1-C4-alkoxy)carbonyl.

A further embodiment relates to compounds I wherein Ra2, Ra5 and Ra6 independently of each other are halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy and (C1-C4-alkoxy)carbonyl, and it being possible that one or two of Ra2, Ra5 or Ra6 can in addition be hydrogen.

Further preferred embodiments relate to compounds I wherein Ra2, Ra5 and Ra6 independently of each other are preferably selected from the group consisting of hydrogen, Cl, F, CH3, CH2CH3, OCH3, OCF3, CH2OCH3, CN, OCH2OCH3, CF3, CHFCH3, COOCH3 and COOCH2CH3.

Further preferred embodiments relate to compounds I wherein Ra2, Ra5 and Ra6 independently of each other are preferably selected from the group consisting of Cl, F, CH3, CH2CH3, OCH3, OCF3, CH2OCH3, CN, OCH2OCH3, CF3, CHFCH3, COOCH3 and COOCH2CH3.

Further preferred embodiments relate to compounds I wherein Ra2, Ra5 and Ra6 independently of each other are hydrogen, Cl, CH3, OCH3, CN or COOCH3.

Further preferred embodiments relate to compounds I wherein Ra2, Ra5 and Ra6 independently of each other are Cl, CH3, OCH3, CN or COOCH3.

In another preferred embodiment of the invention Ra2 is hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.

In a further preferred embodiment Ra5 and Ra6 independently of each other are hydrogen, halogen, OH, CN, C1-C4-alkyl, C2-C4-alkenyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy)carbonyl; or Ra5 and R6 together with two ring member carbon atoms to which they are attached, form a fused 5- or 6-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2 or 3 heteroatoms selected from the group of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals selected from halogen, CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy.

In still another preferred embodiment Ra5 and Ra6 independently of each other are hydrogen, halogen, OH, CN, C1-C4-alkyl, C2-C4-alkenyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy)carbonyl; or Ra5 and R6 together with two ring member carbon atoms to which they are attached, form a fused 5- or 6-membered aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2 or 3 heteroatoms selected from the group of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals selected from halogen, CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy.

A particularly preferred embodiment relates to compounds I wherein Ra2 is Cl.

A particularly preferred embodiment relates to compounds I wherein Ra2 is F.

A particularly preferred embodiment relates to compounds I wherein Ra2 is CH3.

A particularly preferred embodiment relates to compounds I wherein Ra2 is OCH3.

A particularly preferred embodiment relates to compounds I wherein Ra2 is CO2CH3.

A particularly preferred embodiment relates to compounds I wherein Ra2 is CO2CH2CH3.

A particularly preferred embodiment relates to compounds I wherein Ra5 is Cl.

A particularly preferred embodiment relates to compounds I wherein Ra5 is F.

A particularly preferred embodiment relates to compounds I wherein Ra5 is CH3.

A particularly preferred embodiment relates to compounds I wherein Ra5 is OCH3.

A particularly preferred embodiment relates to compounds I wherein Ra5 is CO2CH3.

A particularly preferred embodiment relates to compounds I wherein Ra5 is CO2CH2CH3.

A particularly preferred embodiment relates to compounds I wherein Ra6 is Cl.

A particularly preferred embodiment relates to compounds I wherein Ra6 is F.

A particularly preferred embodiment relates to compounds I wherein Ra6 is CH3.

A particularly preferred embodiment relates to compounds I wherein Ra6 is OCH3.

A particularly preferred embodiment relates to compounds I wherein Ra6 is CO2CH3.

A particularly preferred embodiment relates to compounds I wherein Ra6 is CO2CH2CH3.

Further preferred embodiments relate to compounds I wherein Ra2, Ra5 and Ra6 in each case are one of the following combinations in line A.1-1 to line A.1-1190 in table A.1, wherein Me stands for CH3 and Et stands for CH2CH3.

TABLE A.1 Ra2 Ra5 Ra6 A.1-1 H H H A.1-2 Me H H A.1-3 Et H H A.1-4 OMe H H A.1-5 CH2OMe H H A.1-6 OCH2OMe H H A.1-7 CF3 H H A.1-8 CHFMe H H A.1-9 CN H H A.1-10 F H H A.1-11 Cl H H A.1-12 CO2Me H H A.1-13 CO2Et H H A.1-14 OCF3 H H A.1-15 H Me H A.1-16 Me Me H A.1-17 Et Me H A.1-18 OMe Me H A.1-19 CH2OMe Me H A.1-20 OCH2OMe Me H A.1-21 CF3 Me H A.1-22 CHFMe Me H A.1-23 CN Me H A.1-24 F Me H A.1-25 Cl Me H A.1-26 CO2Me Me H A.1-27 CO2Et Me H A.1-28 OCF3 Me H A.1-29 H Et H A.1-30 Me Et H A.1-31 Et Et H A.1-32 OMe Et H A.1-33 CH2OMe Et H A.1-34 OCH2OMe Et H A.1-35 CF3 Et H A.1-36 CHFMe Et H A.1-37 CN Et H A.1-38 F Et H A.1-39 Cl Et H A.1-40 CO2Me Et H A.1-41 CO2Et Et H A.1-42 OCF3 Et H A.1-43 H OMe H A.1-44 Me OMe H A.1-45 Et OMe H A.1-46 OMe OMe H A.1-47 CH2OMe OMe H A.1-48 OCH2OMe OMe H A.1-49 CF3 OMe H A.1-50 CHFMe OMe H A.1-51 CN OMe H A.1-52 F OMe H A.1-53 Cl OMe H A.1-54 CO2Me OMe H A.1-55 CO2Et OMe H A.1-56 OCF3 OMe H A.1-57 H CH2OMe H A.1-58 Me CH2OMe H A.1-59 Et CH2OMe H A.1-60 OMe CH2OMe H A.1-61 CH2OMe CH2OMe H A.1-62 OCH2OMe CH2OMe H A.1-63 CF3 CH2OMe H A.1-64 CHFMe CH2OMe H A.1-65 CN CH2OMe H A.1-66 F CH2OMe H A.1-67 Cl CH2OMe H A.1-68 CO2Me CH2OMe H A.1-69 CO2Et CH2OMe H A.1-70 OCF3 CH2OMe H A.1-71 H OCH2OMe H A.1-72 Me OCH2OMe H A.1-73 Et OCH2OMe H A.1-74 OMe OCH2OMe H A.1-75 CH2OMe OCH2OMe H A.1-76 OCH2OMe OCH2OMe H A.1-77 CF3 OCH2OMe H A.1-78 CHFMe OCH2OMe H A.1-79 CN OCH2OMe H A.1-80 F OCH2OMe H A.1-81 Cl OCH2OMe H A.1-82 CO2Me OCH2OMe H A.1-83 CO2Et OCH2OMe H A.1-84 OCF3 OCH2OMe H A.1-85 H CF3 H A.1-86 Me CF3 H A.1-87 Et CF3 H A.1-88 OMe CF3 H A.1-89 CH2OMe CF3 H A.1-90 OCH2OMe CF3 H A.1-91 CF3 CF3 H A.1-92 CHFMe CF3 H A.1-93 CN CF3 H A.1-94 F CF3 H A.1-95 Cl CF3 H A.1-96 CO2Me CF3 H A.1-97 CO2Et CF3 H A.1-98 OCF3 CF3 H A.1-99 H CHFMe H A.1-100 Me CHFMe H A.1-101 Et CHFMe H A.1-102 OMe CHFMe H A.1-103 CH2OMe CHFMe H A.1-104 OCH2OMe CHFMe H A.1-105 CF3 CHFMe H A.1-106 CHFMe CHFMe H A.1-107 CN CHFMe H A.1-108 F CHFMe H A.1-109 Cl CHFMe H A.1-110 CO2Me CHFMe H A.1-111 CO2Et CHFMe H A.1-112 OCF3 CHFMe H A.1-113 H CN H A.1-114 Me CN H A.1-115 Et CN H A.1-116 OMe CN H A.1-117 CH2OMe CN H A.1-118 OCH2OMe CN H A.1-119 CF3 CN H A.1-120 CHFMe CN H A.1-121 CN CN H A.1-122 F CN H A.1-123 Cl CN H A.1-124 CO2Me CN H A.1-125 CO2Et CN H A.1-126 OCF3 CN H A.1-127 H F H A.1-128 Me F H A.1-129 Et F H A.1-130 OMe F H A.1-131 CH2OMe F H A.1-132 OCH2OMe F H A.1-133 CF3 F H A.1-134 CHFMe F H A.1-135 CN F H A.1-136 F F H A.1-137 Cl F H A.1-138 CO2Me F H A.1-139 CO2Et F H A.1-140 OCF3 F H A.1-141 H Cl H A.1-142 Me Cl H A.1-143 Et Cl H A.1-144 OMe Cl H A.1-145 CH2OMe Cl H A.1-146 OCH2OMe Cl H A.1-147 CF3 Cl H A.1-148 CHFMe Cl H A.1-149 CN Cl H A.1-150 F Cl H A.1-151 Cl Cl H A.1-152 CO2Me Cl H A.1-153 CO2Et Cl H A.1-154 OCF3 Cl H A.1-155 H CO2Me H A.1-156 Me CO2Me H A.1-157 Et CO2Me H A.1-158 OMe CO2Me H A.1-159 CH2OMe CO2Me H A.1-160 OCH2OMe CO2Me H A.1-161 CF3 CO2Me H A.1-162 CHFMe CO2Me H A.1-163 CN CO2Me H A.1-164 F CO2Me H A.1-165 Cl CO2Me H A.1-166 CO2Me CO2Me H A.1-167 CO2Et CO2Me H A.1-168 OCF3 CO2Me H A.1-169 H CO2Et H A.1-170 Me CO2Et H A.1-171 Et CO2Et H A.1-172 OMe CO2Et H A.1-173 CH2OMe CO2Et H A.1-174 OCH2OMe CO2Et H A.1-175 CF3 CO2Et H A.1-176 CHFMe CO2Et H A.1-177 CN CO2Et H A.1-178 F CO2Et H A.1-179 Cl CO2Et H A.1-180 CO2Me CO2Et H A.1-181 CO2Et CO2Et H A.1-182 OCF3 CO2Et H A.1-183 H OCF3 H A.1-184 Me OCF3 H A.1-185 Et OCF3 H A.1-186 OMe OCF3 H A.1-187 CH2OMe OCF3 H A.1-188 OCH2OMe OCF3 H A.1-189 CF3 OCF3 H A.1-190 CHFMe OCF3 H A.1-191 CN OCF3 H A.1-192 F OCF3 H A.1-193 Cl OCF3 H A.1-194 CO2Me OCF3 H A.1-195 CO2Et OCF3 H A.1-196 OCF3 OCF3 H A.1-197 H CH(Me)2 H A.1-198 Me CH(Me)2 H A.1-199 Et CH(Me)2 H A.1-200 OMe CH(Me)2 H A.1-201 CH2OMe CH(Me)2 H A.1-202 OCH2OMe CH(Me)2 H A.1-203 CF3 CH(Me)2 H A.1-204 CHFMe CH(Me)2 H A.1-205 CN CH(Me)2 H A.1-206 F CH(Me)2 H A.1-207 Cl CH(Me)2 H A.1-208 CO2Me CH(Me)2 H A.1-209 CO2Et CH(Me)2 H A.1-210 OCF3 CH(Me)2 H A.1-211 H CH═CH2 H A.1-212 Me CH═CH2 H A.1-213 Et CH═CH2 H A.1-214 OMe CH═CH2 H A.1-215 CH2OMe CH═CH2 H A.1-216 OCH2OMe CH═CH2 H A.1-217 CF3 CH═CH2 H A.1-218 CHFMe CH═CH2 H A.1-219 CN CH═CH2 H A.1-220 F CH═CH2 H A.1-221 Cl CH═CH2 H A.1-222 CO2Me CH═CH2 H A.1-223 CO2Et CH═CH2 H A.1-224 OCF3 CH═CH2 H A.1-225 H C≡CH H A.1-226 Me C≡CH H A.1-227 Et C≡CH H A.1-228 OMe C≡CH H A.1-229 CH2OMe C≡CH H A.1-230 OCH2OMe C≡CH H A.1-231 CF3 C≡CH H A.1-232 CHFMe C≡CH H A.1-233 CN C≡CH H A.1-234 F C≡CH H A.1-235 Cl C≡CH H A.1-236 CO2Me C≡CH H A.1-237 CO2Et C≡CH H A.1-238 OCF3 C≡CH H A.1-239 H H F A.1-240 Me H F A.1-241 Et H F A.1-242 OMe H F A.1-243 CH2OMe H F A.1-244 OCH2OMe H F A.1-245 CF3 H F A.1-246 CHFMe H F A.1-247 CN H F A.1-248 F H F A.1-249 Cl H F A.1-250 CO2Me H F A.1-251 CO2Et H F A.1-252 OCF3 H F A.1-253 H Me F A.1-254 Me Me F A.1-255 Et Me F A.1-256 OMe Me F A.1-257 CH2OMe Me F A.1-258 OCH2OMe Me F A.1-259 CF3 Me F A.1-260 CHFMe Me F A.1-261 CN Me F A.1-262 F Me F A.1-263 Cl Me F A.1-264 CO2Me Me F A.1-265 CO2Et Me F A.1-266 OCF3 Me F A.1-267 H Et F A.1-268 Me Et F A.1-269 Et Et F A.1-270 OMe Et F A.1-271 CH2OMe Et F A.1-272 OCH2OMe Et F A.1-273 CF3 Et F A.1-274 CHFMe Et F A.1-275 CN Et F A.1-276 F Et F A.1-277 Cl Et F A.1-278 CO2Me Et F A.1-279 CO2Et Et F A.1-280 OCF3 Et F A.1-281 H OMe F A.1-282 Me OMe F A.1-283 Et OMe F A.1-284 OMe OMe F A.1-285 CH2OMe OMe F A.1-286 OCH2OMe OMe F A.1-287 CF3 OMe F A.1-288 CHFMe OMe F A.1-289 CN OMe F A.1-290 F OMe F A.1-291 Cl OMe F A.1-292 CO2Me OMe F A.1-293 CO2Et OMe F A.1-294 OCF3 OMe F A.1-295 H CH2OMe F A.1-296 Me CH2OMe F A.1-297 Et CH2OMe F A.1-298 OMe CH2OMe F A.1-299 CH2OMe CH2OMe F A.1-300 OCH2OMe CH2OMe F A.1-301 CF3 CH2OMe F A.1-302 CHFMe CH2OMe F A.1-303 CN CH2OMe F A.1-304 F CH2OMe F A.1-305 Cl CH2OMe F A.1-306 CO2Me CH2OMe F A.1-307 CO2Et CH2OMe F A.1-308 OCF3 CH2OMe F A.1-309 H OCH2OMe F A.1-310 Me OCH2OMe F A.1-311 Et OCH2OMe F A.1-312 OMe OCH2OMe F A.1-313 CH2OMe OCH2OMe F A.1-314 OCH2OMe OCH2OMe F A.1-315 CF3 OCH2OMe F A.1-316 CHFMe OCH2OMe F A.1-317 CN OCH2OMe F A.1-318 F OCH2OMe F A.1-319 Cl OCH2OMe F A.1-320 CO2Me OCH2OMe F A.1-321 CO2Et OCH2OMe F A.1-322 OCF3 OCH2OMe F A.1-323 H CF3 F A.1-324 Me CF3 F A.1-325 Et CF3 F A.1-326 OMe CF3 F A.1-327 CH2OMe CF3 F A.1-328 OCH2OMe CF3 F A.1-329 CF3 CF3 F A.1-330 CHFMe CF3 F A.1-331 CN CF3 F A.1-332 F CF3 F A.1-333 Cl CF3 F A.1-334 CO2Me CF3 F A.1-335 CO2Et CF3 F A.1-336 OCF3 CF3 F A.1-337 H CHFMe F A.1-338 Me CHFMe F A.1-339 Et CHFMe F A.1-340 OMe CHFMe F A.1-341 CH2OMe CHFMe F A.1-342 OCH2OMe CHFMe F A.1-343 CF3 CHFMe F A.1-344 CHFMe CHFMe F A.1-345 CN CHFMe F A.1-346 F CHFMe F A.1-347 Cl CHFMe F A.1-348 CO2Me CHFMe F A.1-349 CO2Et CHFMe F A.1-350 OCF3 CHFMe F A.1-351 H CN F A.1-352 Me CN F A.1-353 Et CN F A.1-354 OMe CN F A.1-355 CH2OMe CN F A.1-356 OCH2OMe CN F A.1-357 CF3 CN F A.1-358 CHFMe CN F A.1-359 CN CN F A.1-360 F CN F A.1-361 Cl CN F A.1-362 CO2Me CN F A.1-363 CO2Et CN F A.1-364 OCF3 CN F A.1-365 H F F A.1-366 Me F F A.1-367 Et F F A.1-368 OMe F F A.1-369 CH2OMe F F A.1-370 OCH2OMe F F A.1-371 CF3 F F A.1-372 CHFMe F F A.1-373 CN F F A.1-374 F F F A.1-375 Cl F F A.1-376 CO2Me F F A.1-377 CO2Et F F A.1-378 OCF3 F F A.1-379 H Cl F A.1-380 Me Cl F A.1-381 Et Cl F A.1-382 OMe Cl F A.1-383 CH2OMe Cl F A.1-384 OCH2OMe Cl F A.1-385 CF3 Cl F A.1-386 CHFMe Cl F A.1-387 CN Cl F A.1-388 F Cl F A.1-389 Cl Cl F A.1-390 CO2Me Cl F A.1-391 CO2Et Cl F A.1-392 OCF3 Cl F A.1-393 H CO2Me F A.1-394 Me CO2Me F A.1-395 Et CO2Me F A.1-396 OMe CO2Me F A.1-397 CH2OMe CO2Me F A.1-398 OCH2OMe CO2Me F A.1-399 CF3 CO2Me F A.1-400 CHFMe CO2Me F A.1-401 CN CO2Me F A.1-402 F CO2Me F A.1-403 Cl CO2Me F A.1-404 CO2Me CO2Me F A.1-405 CO2Et CO2Me F A.1-406 OCF3 CO2Me F A.1-407 H CO2Et F A.1-408 Me CO2Et F A.1-409 Et CO2Et F A.1-410 OMe CO2Et F A.1-411 CH2OMe CO2Et F A.1-412 OCH2OMe CO2Et F A.1-413 CF3 CO2Et F A.1-414 CHFMe CO2Et F A.1-415 CN CO2Et F A.1-416 F CO2Et F A.1-417 Cl CO2Et F A.1-418 CO2Me CO2Et F A.1-419 CO2Et CO2Et F A.1-420 OCF3 CO2Et F A.1-421 H OCF3 F A.1-422 Me OCF3 F A.1-423 Et OCF3 F A.1-424 OMe OCF3 F A.1-425 CH2OMe OCF3 F A.1-426 OCH2OMe OCF3 F A.1-427 CF3 OCF3 F A.1-428 CHFMe OCF3 F A.1-429 CN OCF3 F A.1-430 F OCF3 F A.1-431 Cl OCF3 F A.1-432 CO2Me OCF3 F A.1-433 CO2Et OCF3 F A.1-434 OCF3 OCF3 F A.1-435 H CH(Me)2 F A.1-436 Me CH(Me)2 F A.1-437 Et CH(Me)2 F A.1-438 OMe CH(Me)2 F A.1-439 CH2OMe CH(Me)2 F A.1-440 OCH2OMe CH(Me)2 F A.1-441 CF3 CH(Me)2 F A.1-442 CHFMe CH(Me)2 F A.1-443 CN CH(Me)2 F A.1-444 F CH(Me)2 F A.1-445 Cl CH(Me)2 F A.1-446 CO2Me CH(Me)2 F A.1-447 CO2Et CH(Me)2 F A.1-448 OCF3 CH(Me)2 F A.1-449 H CH═CH2 F A.1-450 Me CH═CH2 F A.1-451 Et CH═CH2 F A.1-452 OMe CH═CH2 F A.1-453 CH2OMe CH═CH2 F A.1-454 OCH2OMe CH═CH2 F A.1-455 CF3 CH═CH2 F A.1-456 CHFMe CH═CH2 F A.1-457 CN CH═CH2 F A.1-458 F CH═CH2 F A.1-459 Cl CH═CH2 F A.1-460 CO2Me CH═CH2 F A.1-461 CO2Et CH═CH2 F A.1-462 OCF3 CH═CH2 F A.1-463 H C≡CH F A.1-464 Me C≡CH F A.1-465 Et C≡CH F A.1-466 OMe C≡CH F A.1-467 CH2OMe C≡CH F A.1-468 OCH2OMe C≡CH F A.1-469 CF3 C≡CH F A.1-470 CHFMe C≡CH F A.1-471 CN C≡CH F A.1-472 F C≡CH F A.1-473 Cl C≡CH F A.1-474 CO2Me C≡CH F A.1-475 CO2Et C≡CH F A.1-476 OCF3 C≡CH F A.1-477 H H Cl A.1-478 Me H Cl A.1-479 Et H Cl A.1-480 OMe H Cl A.1-481 CH2OMe H Cl A.1-482 OCH2OMe H Cl A.1-483 CF3 H Cl A.1-484 CHFMe H Cl A.1-485 CN H Cl A.1-486 F H Cl A.1-487 Cl H Cl A.1-488 CO2Me H Cl A.1-489 CO2Et H Cl A.1-490 OCF3 H Cl A.1-491 H Me Cl A.1-492 Me Me Cl A.1-493 Et Me Cl A.1-494 OMe Me Cl A.1-495 CH2OMe Me Cl A.1-496 OCH2OMe Me Cl A.1-497 CF3 Me Cl A.1-498 CHFMe Me Cl A.1-499 CN Me Cl A.1-500 F Me Cl A.1-501 Cl Me Cl A.1-502 CO2Me Me Cl A.1-503 CO2Et Me Cl A.1-504 OCF3 Me Cl A.1-505 H Et Cl A.1-506 Me Et Cl A.1-507 Et Et Cl A.1-508 OMe Et Cl A.1-509 CH2OMe Et Cl A.1-510 OCH2OMe Et Cl A.1-511 CF3 Et Cl A.1-512 CHFMe Et Cl A.1-513 CN Et Cl A.1-514 F Et Cl A.1-515 Cl Et Cl A.1-516 CO2Me Et Cl A.1-517 CO2Et Et Cl A.1-518 OCF3 Et Cl A.1-519 H OMe Cl A.1-520 Me OMe Cl A.1-521 Et OMe Cl A.1-522 OMe OMe Cl A.1-523 CH2OMe OMe Cl A.1-524 OCH2OMe OMe Cl A.1-525 CF3 OMe Cl A.1-526 CHFMe OMe Cl A.1-527 CN OMe Cl A.1-528 F OMe Cl A.1-529 Cl OMe Cl A.1-530 CO2Me OMe Cl A.1-531 CO2Et OMe Cl A.1-532 OCF3 OMe Cl A.1-533 H CH2OMe Cl A.1-534 Me CH2OMe Cl A.1-535 Et CH2OMe Cl A.1-536 OMe CH2OMe Cl A.1-537 CH2OMe CH2OMe Cl A.1-538 OCH2OMe CH2OMe Cl A.1-539 CF3 CH2OMe Cl A.1-540 CHFMe CH2OMe Cl A.1-541 CN CH2OMe Cl A.1-542 F CH2OMe Cl A.1-543 Cl CH2OMe Cl A.1-544 CO2Me CH2OMe Cl A.1-545 CO2Et CH2OMe Cl A.1-546 OCF3 CH2OMe Cl A.1-547 H OCH2OMe Cl A.1-548 Me OCH2OMe Cl A.1-549 Et OCH2OMe Cl A.1-550 OMe OCH2OMe Cl A.1-551 CH2OMe OCH2OMe Cl A.1-552 OCH2OMe OCH2OMe Cl A.1-553 CF3 OCH2OMe Cl A.1-554 CHFMe OCH2OMe Cl A.1-555 CN OCH2OMe Cl A.1-556 F OCH2OMe Cl A.1-557 Cl OCH2OMe Cl A.1-558 CO2Me OCH2OMe Cl A.1-559 CO2Et OCH2OMe Cl A.1-560 OCF3 OCH2OMe Cl A.1-561 H CF3 Cl A.1-562 Me CF3 Cl A.1-563 Et CF3 Cl A.1-564 OMe CF3 Cl A.1-565 CH2OMe CF3 Cl A.1-566 OCH2OMe CF3 Cl A.1-567 CF3 CF3 Cl A.1-568 CHFMe CF3 Cl A.1-569 CN CF3 Cl A.1-570 F CF3 Cl A.1-571 Cl CF3 Cl A.1-572 CO2Me CF3 Cl A.1-573 CO2Et CF3 Cl A.1-574 OCF3 CF3 Cl A.1-575 H CHFMe Cl A.1-576 Me CHFMe Cl A.1-577 Et CHFMe Cl A.1-578 OMe CHFMe Cl A.1-579 CH2OMe CHFMe Cl A.1-580 OCH2OMe CHFMe Cl A.1-581 CF3 CHFMe Cl A.1-582 CHFMe CHFMe Cl A.1-583 CN CHFMe Cl A.1-584 F CHFMe Cl A.1-585 Cl CHFMe Cl A.1-586 CO2Me CHFMe Cl A.1-587 CO2Et CHFMe Cl A.1-588 OCF3 CHFMe Cl A.1-589 H CN Cl A.1-590 Me CN Cl A.1-591 Et CN Cl A.1-592 OMe CN Cl A.1-593 CH2OMe CN Cl A.1-594 OCH2OMe CN Cl A.1-595 CF3 CN Cl A.1-596 CHFMe CN Cl A.1-597 CN CN Cl A.1-598 F CN Cl A.1-599 Cl CN Cl A.1-600 CO2Me CN Cl A.1-601 CO2Et CN Cl A.1-602 OCF3 CN Cl A.1-603 H F Cl A.1-604 Me F Cl A.1-605 Et F Cl A.1-606 OMe F Cl A.1-607 CH2OMe F Cl A.1-608 OCH2OMe F Cl A.1-609 CF3 F Cl A.1-610 CHFMe F Cl A.1-611 CN F Cl A.1-612 F F Cl A.1-613 Cl F Cl A.1-614 CO2Me F Cl A.1-615 CO2Et F Cl A.1-616 OCF3 F Cl A.1-617 H Cl Cl A.1-618 Me Cl Cl A.1-619 Et Cl Cl A.1-620 OMe Cl Cl A.1-621 CH2OMe Cl Cl A.1-622 OCH2OMe Cl Cl A.1-623 CF3 Cl Cl A.1-624 CHFMe Cl Cl A.1-625 CN Cl Cl A.1-626 F Cl Cl A.1-627 Cl Cl Cl A.1-628 CO2Me Cl Cl A.1-629 CO2Et Cl Cl A.1-630 OCF3 Cl Cl A.1-631 H CO2Me Cl A.1-632 Me CO2Me Cl A.1-633 Et CO2Me Cl A.1-634 OMe CO2Me Cl A.1-635 CH2OMe CO2Me Cl A.1-636 OCH2OMe CO2Me Cl A.1-637 CF3 CO2Me Cl A.1-638 CHFMe CO2Me Cl A.1-639 CN CO2Me Cl A.1-640 F CO2Me Cl A.1-641 Cl CO2Me Cl A.1-642 CO2Me CO2Me Cl A.1-643 CO2Et CO2Me Cl A.1-644 OCF3 CO2Me Cl A.1-645 H CO2Et Cl A.1-646 Me CO2Et Cl A.1-647 Et CO2Et Cl A.1-648 OMe CO2Et Cl A.1-649 CH2OMe CO2Et Cl A.1-650 OCH2OMe CO2Et Cl A.1-651 CF3 CO2Et Cl A.1-652 CHFMe CO2Et Cl A.1-653 CN CO2Et Cl A.1-654 F CO2Et Cl A.1-655 Cl CO2Et Cl A.1-656 CO2Me CO2Et Cl A.1-657 CO2Et CO2Et Cl A.1-658 OCF3 CO2Et Cl A.1-659 H OCF3 Cl A.1-660 Me OCF3 Cl A.1-661 Et OCF3 Cl A.1-662 OMe OCF3 Cl A.1-663 CH2OMe OCF3 Cl A.1-664 OCH2OMe OCF3 Cl A.1-665 CF3 OCF3 Cl A.1-666 CHFMe OCF3 Cl A.1-667 CN OCF3 Cl A.1-668 F OCF3 Cl A.1-669 Cl OCF3 Cl A.1-670 CO2Me OCF3 Cl A.1-671 CO2Et OCF3 Cl A.1-672 OCF3 OCF3 Cl A.1-673 H CH(Me)2 Cl A.1-674 Me CH(Me)2 Cl A.1-675 Et CH(Me)2 Cl A.1-676 OMe CH(Me)2 Cl A.1-677 CH2OMe CH(Me)2 Cl A.1-678 OCH2OMe CH(Me)2 Cl A.1-679 CF3 CH(Me)2 Cl A.1-680 CHFMe CH(Me)2 Cl A.1-681 CN CH(Me)2 Cl A.1-682 F CH(Me)2 Cl A.1-683 Cl CH(Me)2 Cl A.1-684 CO2Me CH(Me)2 Cl A.1-685 CO2Et CH(Me)2 Cl A.1-686 OCF3 CH(Me)2 Cl A.1-687 H CH═CH2 Cl A.1-688 Me CH═CH2 Cl A.1-689 Et CH═CH2 Cl A.1-690 OMe CH═CH2 Cl A.1-691 CH2OMe CH═CH2 Cl A.1-692 OCH2OMe CH═CH2 Cl A.1-693 CF3 CH═CH2 Cl A.1-694 CHFMe CH═CH2 Cl A.1-695 CN CH═CH2 Cl A.1-696 F CH═CH2 Cl A.1-697 Cl CH═CH2 Cl A.1-698 CO2Me CH═CH2 Cl A.1-699 CO2Et CH═CH2 Cl A.1-700 OCF3 CH═CH2 Cl A.1-701 H C≡CH Cl A.1-702 Me C≡CH Cl A.1-703 Et C≡CH Cl A.1-704 OMe C≡CH Cl A.1-705 CH2OMe C≡CH Cl A.1-706 OCH2OMe C≡CH Cl A.1-707 CF3 C≡CH Cl A.1-708 CHFMe C≡CH Cl A.1-709 CN C≡CH Cl A.1-710 F C≡CH Cl A.1-711 Cl C≡CH Cl A.1-712 CO2Me C≡CH Cl A.1-713 CO2Et C≡CH Cl A.1-714 OCF3 C≡CH Cl A.1-715 H H CO2Me A.1-716 Me H CO2Me A.1-717 Et H CO2Me A.1-718 OMe H CO2Me A.1-719 CH2OMe H CO2Me A.1-720 OCH2OMe H CO2Me A.1-721 CF3 H CO2Me A.1-722 CHFMe H CO2Me A.1-723 CN H CO2Me A.1-724 F H CO2Me A.1-725 Cl H CO2Me A.1-726 CO2Me H CO2Me A.1-727 CO2Et H CO2Me A.1-728 OCF3 H CO2Me A.1-729 H Me CO2Me A.1-730 Me Me CO2Me A.1-731 Et Me CO2Me A.1-732 OMe Me CO2Me A.1-733 CH2OMe Me CO2Me A.1-734 OCH2OMe Me CO2Me A.1-735 CF3 Me CO2Me A.1-736 CHFMe Me CO2Me A.1-737 CN Me CO2Me A.1-738 F Me CO2Me A.1-739 Cl Me CO2Me A.1-740 CO2Me Me CO2Me A.1-741 CO2Et Me CO2Me A.1-742 OCF3 Me CO2Me A.1-743 H Et CO2Me A.1-744 Me Et CO2Me A.1-745 Et Et CO2Me A.1-746 OMe Et CO2Me A.1-747 CH2OMe Et CO2Me A.1-748 OCH2OMe Et CO2Me A.1-749 CF3 Et CO2Me A.1-750 CHFMe Et CO2Me A.1-751 CN Et CO2Me A.1-752 F Et CO2Me A.1-753 Cl Et CO2Me A.1-754 CO2Me Et CO2Me A.1-755 CO2Et Et CO2Me A.1-756 OCF3 Et CO2Me A.1-757 H OMe CO2Me A.1-758 Me OMe CO2Me A.1-759 Et OMe CO2Me A.1-760 OMe OMe CO2Me A.1-761 CH2OMe OMe CO2Me A.1-762 OCH2OMe OMe CO2Me A.1-763 CF3 OMe CO2Me A.1-764 CHFMe OMe CO2Me A.1-765 CN OMe CO2Me A.1-766 F OMe CO2Me A.1-767 Cl OMe CO2Me A.1-768 CO2Me OMe CO2Me A.1-769 CO2Et OMe CO2Me A.1-770 OCF3 OMe CO2Me A.1-771 H CH2OMe CO2Me A.1-772 Me CH2OMe CO2Me A.1-773 Et CH2OMe CO2Me A.1-774 OMe CH2OMe CO2Me A.1-775 CH2OMe CH2OMe CO2Me A.1-776 OCH2OMe CH2OMe CO2Me A.1-777 CF3 CH2OMe CO2Me A.1-778 CHFMe CH2OMe CO2Me A.1-779 CN CH2OMe CO2Me A.1-780 F CH2OMe CO2Me A.1-781 Cl CH2OMe CO2Me A.1-782 CO2Me CH2OMe CO2Me A.1-783 CO2Et CH2OMe CO2Me A.1-784 OCF3 CH2OMe CO2Me A.1-785 H OCH2OMe CO2Me A.1-786 Me OCH2OMe CO2Me A.1-787 Et OCH2OMe CO2Me A.1-788 OMe OCH2OMe CO2Me A.1-789 CH2OMe OCH2OMe CO2Me A.1-790 OCH2OMe OCH2OMe CO2Me A.1-791 CF3 OCH2OMe CO2Me A.1-792 CHFMe OCH2OMe CO2Me A.1-793 CN OCH2OMe CO2Me A.1-794 F OCH2OMe CO2Me A.1-795 Cl OCH2OMe CO2Me A.1-796 CO2Me OCH2OMe CO2Me A.1-797 CO2Et OCH2OMe CO2Me A.1-798 OCF3 OCH2OMe CO2Me A.1-799 H CF3 CO2Me A.1-800 Me CF3 CO2Me A.1-801 Et CF3 CO2Me A.1-802 OMe CF3 CO2Me A.1-803 CH2OMe CF3 CO2Me A.1-804 OCH2OMe CF3 CO2Me A.1-805 CF3 CF3 CO2Me A.1-806 CHFMe CF3 CO2Me A.1-807 CN CF3 CO2Me A.1-808 F CF3 CO2Me A.1-809 Cl CF3 CO2Me A.1-810 CO2Me CF3 CO2Me A.1-811 CO2Et CF3 CO2Me A.1-812 OCF3 CF3 CO2Me A.1-813 H CHFMe CO2Me A.1-814 Me CHFMe CO2Me A.1-815 Et CHFMe CO2Me A.1-816 OMe CHFMe CO2Me A.1-817 CH2OMe CHFMe CO2Me A.1-818 OCH2OMe CHFMe CO2Me A.1-819 CF3 CHFMe CO2Me A.1-820 CHFMe CHFMe CO2Me A.1-821 CN CHFMe CO2Me A.1-822 F CHFMe CO2Me A.1-823 Cl CHFMe CO2Me A.1-824 CO2Me CHFMe CO2Me A.1-825 CO2Et CHFMe CO2Me A.1-826 OCF3 CHFMe CO2Me A.1-827 H CN CO2Me A.1-828 Me CN CO2Me A.1-829 Et CN CO2Me A.1-830 OMe CN CO2Me A.1-831 CH2OMe CN CO2Me A.1-832 OCH2OMe CN CO2Me A.1-833 CF3 CN CO2Me A.1-834 CHFMe CN CO2Me A.1-835 CN CN CO2Me A.1-836 F CN CO2Me A.1-837 Cl CN CO2Me A.1-838 CO2Me CN CO2Me A.1-839 CO2Et CN CO2Me A.1-840 OCF3 CN CO2Me A.1-841 H F CO2Me A.1-842 Me F CO2Me A.1-843 Et F CO2Me A.1-844 OMe F CO2Me A.1-845 CH2OMe F CO2Me A.1-846 OCH2OMe F CO2Me A.1-847 CF3 F CO2Me A.1-848 CHFMe F CO2Me A.1-849 CN F CO2Me A.1-850 F F CO2Me A.1-851 Cl F CO2Me A.1-852 CO2Me F CO2Me A.1-853 CO2Et F CO2Me A.1-854 OCF3 F CO2Me A.1-855 H Cl CO2Me A.1-856 Me Cl CO2Me A.1-857 Et Cl CO2Me A.1-858 OMe Cl CO2Me A.1-859 CH2OMe Cl CO2Me A.1-860 OCH2OMe Cl CO2Me A.1-861 CF3 Cl CO2Me A.1-862 CHFMe Cl CO2Me A.1-863 CN Cl CO2Me A.1-864 F Cl CO2Me A.1-865 Cl Cl CO2Me A.1-866 CO2Me Cl CO2Me A.1-867 CO2Et Cl CO2Me A.1-868 OCF3 Cl CO2Me A.1-869 H CO2Me CO2Me A.1-870 Me CO2Me CO2Me A.1-871 Et CO2Me CO2Me A.1-872 OMe CO2Me CO2Me A.1-873 CH2OMe CO2Me CO2Me A.1-874 OCH2OMe CO2Me CO2Me A.1-875 CF3 CO2Me CO2Me A.1-876 CHFMe CO2Me CO2Me A.1-877 CN CO2Me CO2Me A.1-878 F CO2Me CO2Me A.1-879 Cl CO2Me CO2Me A.1-880 CO2Me CO2Me CO2Me A.1-881 CO2Et CO2Me CO2Me A.1-882 OCF3 CO2Me CO2Me A.1-883 H CO2Et CO2Me A.1-884 Me CO2Et CO2Me A.1-885 Et CO2Et CO2Me A.1-886 OMe CO2Et CO2Me A.1-887 CH2OMe CO2Et CO2Me A.1-888 OCH2OMe CO2Et CO2Me A.1-889 CF3 CO2Et CO2Me A.1-890 CHFMe CO2Et CO2Me A.1-891 CN CO2Et CO2Me A.1-892 F CO2Et CO2Me A.1-893 Cl CO2Et CO2Me A.1-894 CO2Me CO2Et CO2Me A.1-895 CO2Et CO2Et CO2Me A.1-896 OCF3 CO2Et CO2Me A.1-897 H OCF3 CO2Me A.1-898 Me OCF3 CO2Me A.1-899 Et OCF3 CO2Me A.1-900 OMe OCF3 CO2Me A.1-901 CH2OMe OCF3 CO2Me A.1-902 OCH2OMe OCF3 CO2Me A.1-903 CF3 OCF3 CO2Me A.1-904 CHFMe OCF3 CO2Me A.1-905 CN OCF3 CO2Me A.1-906 F OCF3 CO2Me A.1-907 Cl OCF3 CO2Me A.1-908 CO2Me OCF3 CO2Me A.1-909 CO2Et OCF3 CO2Me A.1-910 OCF3 OCF3 CO2Me A.1-911 H CH(Me)2 CO2Me A.1-912 Me CH(Me)2 CO2Me A.1-913 Et CH(Me)2 CO2Me A.1-914 OMe CH(Me)2 CO2Me A.1-915 CH2OMe CH(Me)2 CO2Me A.1-916 OCH2OMe CH(Me)2 CO2Me A.1-917 CF3 CH(Me)2 CO2Me A.1-918 CHFMe CH(Me)2 CO2Me A.1-919 CN CH(Me)2 CO2Me A.1-920 F CH(Me)2 CO2Me A.1-921 Cl CH(Me)2 CO2Me A.1-922 CO2Me CH(Me)2 CO2Me A.1-923 CO2Et CH(Me)2 CO2Me A.1-924 OCF3 CH(Me)2 CO2Me A.1-925 H CH═CH2 CO2Me A.1-926 Me CH═CH2 CO2Me A.1-927 Et CH═CH2 CO2Me A.1-928 OMe CH═CH2 CO2Me A.1-929 CH2OMe CH═CH2 CO2Me A.1-930 OCH2OMe CH═CH2 CO2Me A.1-931 CF3 CH═CH2 CO2Me A.1-932 CHFMe CH═CH2 CO2Me A.1-933 CN CH═CH2 CO2Me A.1-934 F CH═CH2 CO2Me A.1-935 Cl CH═CH2 CO2Me A.1-936 CO2Me CH═CH2 CO2Me A.1-937 CO2Et CH═CH2 CO2Me A.1-938 OCF3 CH═CH2 CO2Me A.1-939 H C≡CH CO2Me A.1-940 Me C≡CH CO2Me A.1-941 Et C≡CH CO2Me A.1-942 OMe C≡CH CO2Me A.1-943 CH2OMe C≡CH CO2Me A.1-944 OCH2OMe C≡CH CO2Me A.1-945 CF3 C≡CH CO2Me A.1-946 CHFMe C≡CH CO2Me A.1-947 CN C≡CH CO2Me A.1-948 F C≡CH CO2Me A.1-949 Cl C≡CH CO2Me A.1-950 CO2Me C≡CH CO2Me A.1-951 CO2Et C≡CH CO2Me A.1-952 OCF3 C≡CH CO2Me A.1-953 H H CO2Et A.1-954 Me H CO2Et A.1-955 Et H CO2Et A.1-956 OMe H CO2Et A.1-957 CH2OMe H CO2Et A.1-958 OCH2OMe H CO2Et A.1-959 CF3 H CO2Et A.1-960 CHFMe H CO2Et A.1-961 CN H CO2Et A.1-962 F H CO2Et A.1-963 Cl H CO2Et A.1-964 CO2Me H CO2Et A.1-965 CO2Et H CO2Et A.1-966 OCF3 H CO2Et A.1-967 H Me CO2Et A.1-968 Me Me CO2Et A.1-969 Et Me CO2Et A.1-970 OMe Me CO2Et A.1-971 CH2OMe Me CO2Et A.1-972 OCH2OMe Me CO2Et A.1-973 CF3 Me CO2Et A.1-974 CHFMe Me CO2Et A.1-975 CN Me CO2Et A.1-976 F Me CO2Et A.1-977 Cl Me CO2Et A.1-978 CO2Me Me CO2Et A.1-979 CO2Et Me CO2Et A.1-980 OCF3 Me CO2Et A.1-981 H Et CO2Et A.1-982 Me Et CO2Et A.1-983 Et Et CO2Et A.1-984 OMe Et CO2Et A.1-985 CH2OMe Et CO2Et A.1-986 OCH2OMe Et CO2Et A.1-987 CF3 Et CO2Et A.1-988 CHFMe Et CO2Et A.1-989 CN Et CO2Et A.1-990 F Et CO2Et A.1-991 Cl Et CO2Et A.1-992 CO2Me Et CO2Et A.1-993 CO2Et Et CO2Et A.1-994 OCF3 Et CO2Et A.1-995 H OMe CO2Et A.1-996 Me OMe CO2Et A.1-997 Et OMe CO2Et A.1-998 OMe OMe CO2Et A.1-999 CH2OMe OMe CO2Et A.1-1000 OCH2OMe OMe CO2Et A.1-1001 CF3 OMe CO2Et A.1-1002 CHFMe OMe CO2Et A.1-1003 CN OMe CO2Et A.1-1004 F OMe CO2Et A.1-1005 Cl OMe CO2Et A.1-1006 CO2Me OMe CO2Et A.1-1007 CO2Et OMe CO2Et A.1-1008 OCF3 OMe CO2Et A.1-1009 H CH2OMe CO2Et A.1-1010 Me CH2OMe CO2Et A.1-1011 Et CH2OMe CO2Et A.1-1012 OMe CH2OMe CO2Et A.1-1013 CH2OMe CH2OMe CO2Et A.1-1014 OCH2OMe CH2OMe CO2Et A.1-1015 CF3 CH2OMe CO2Et A.1-1016 CHFMe CH2OMe CO2Et A.1-1017 CN CH2OMe CO2Et A.1-1018 F CH2OMe CO2Et A.1-1019 Cl CH2OMe CO2Et A.1-1020 CO2Me CH2OMe CO2Et A.1-1021 CO2Et CH2OMe CO2Et A.1-1022 OCF3 CH2OMe CO2Et A.1-1023 H OCH2OMe CO2Et A.1-1024 Me OCH2OMe CO2Et A.1-1025 Et OCH2OMe CO2Et A.1-1026 OMe OCH2OMe CO2Et A.1-1027 CH2OMe OCH2OMe CO2Et A.1-1028 OCH2OMe OCH2OMe CO2Et A.1-1029 CF3 OCH2OMe CO2Et A.1-1030 CHFMe OCH2OMe CO2Et A.1-1031 CN OCH2OMe CO2Et A.1-1032 F OCH2OMe CO2Et A.1-1033 Cl OCH2OMe CO2Et A.1-1034 CO2Me OCH2OMe CO2Et A.1-1035 CO2Et OCH2OMe CO2Et A.1-1036 OCF3 OCH2OMe CO2Et A.1-1037 H CF3 CO2Et A.1-1038 Me CF3 CO2Et A.1-1039 Et CF3 CO2Et A.1-1040 OMe CF3 CO2Et A.1-1041 CH2OMe CF3 CO2Et A.1-1042 OCH2OMe CF3 CO2Et A.1-1043 CF3 CF3 CO2Et A.1-1044 CHFMe CF3 CO2Et A.1-1045 CN CF3 CO2Et A.1-1046 F CF3 CO2Et A.1-1047 Cl CF3 CO2Et A.1-1048 CO2Me CF3 CO2Et A.1-1049 CO2Et CF3 CO2Et A.1-1050 OCF3 CF3 CO2Et A.1-1051 H CHFMe CO2Et A.1-1052 Me CHFMe CO2Et A.1-1053 Et CHFMe CO2Et A.1-1054 OMe CHFMe CO2Et A.1-1055 CH2OMe CHFMe CO2Et A.1-1056 OCH2OMe CHFMe CO2Et A.1-1057 CF3 CHFMe CO2Et A.1-1058 CHFMe CHFMe CO2Et A.1-1059 CN CHFMe CO2Et A.1-1060 F CHFMe CO2Et A.1-1061 Cl CHFMe CO2Et A.1-1062 CO2Me CHFMe CO2Et A.1-1063 CO2Et CHFMe CO2Et A.1-1064 OCF3 CHFMe CO2Et A.1-1065 H CN CO2Et A.1-1066 Me CN CO2Et A.1-1067 Et CN CO2Et A.1-1068 OMe CN CO2Et A.1-1069 CH2OMe CN CO2Et A.1-1070 OCH2OMe CN CO2Et A.1-1071 CF3 CN CO2Et A.1-1072 CHFMe CN CO2Et A.1-1073 CN CN CO2Et A.1-1074 F CN CO2Et A.1-1075 Cl CN CO2Et A.1-1076 CO2Me CN CO2Et A.1-1077 CO2Et CN CO2Et A.1-1078 OCF3 CN CO2Et A.1-1079 H F CO2Et A.1-1080 Me F CO2Et A.1-1081 Et F CO2Et A.1-1082 OMe F CO2Et A.1-1083 CH2OMe F CO2Et A.1-1084 OCH2OMe F CO2Et A.1-1085 CF3 F CO2Et A.1-1086 CHFMe F CO2Et A.1-1087 CN F CO2Et A.1-1088 F F CO2Et A.1-1089 Cl F CO2Et A.1-1090 CO2Me F CO2Et A.1-1091 CO2Et F CO2Et A.1-1092 OCF3 F CO2Et A.1-1093 H Cl CO2Et A.1-1094 Me Cl CO2Et A.1-1095 Et Cl CO2Et A.1-1096 OMe Cl CO2Et A.1-1097 CH2OMe Cl CO2Et A.1-1098 OCH2OMe Cl CO2Et A.1-1099 CF3 Cl CO2Et A.1-1100 CHFMe Cl CO2Et A.1-1101 CN Cl CO2Et A.1-1102 F Cl CO2Et A.1-1103 Cl Cl CO2Et A.1-1104 CO2Me Cl CO2Et A.1-1105 CO2Et Cl CO2Et A.1-1106 OCF3 Cl CO2Et A.1-1107 H CO2Me CO2Et A.1-1108 Me CO2Me CO2Et A.1-1109 Et CO2Me CO2Et A.1-1110 OMe CO2Me CO2Et A.1-1111 CH2OMe CO2Me CO2Et A.1-1112 OCH2OMe CO2Me CO2Et A.1-1113 CF3 CO2Me CO2Et A.1-1114 CHFMe CO2Me CO2Et A.1-1115 CN CO2Me CO2Et A.1-1116 F CO2Me CO2Et A.1-1117 Cl CO2Me CO2Et A.1-1118 CO2Me CO2Me CO2Et A.1-1119 CO2Et CO2Me CO2Et A.1-1120 OCF3 CO2Me CO2Et A.1-1121 H CO2Et CO2Et A.1-1122 Me CO2Et CO2Et A.1-1123 Et CO2Et CO2Et A.1-1124 OMe CO2Et CO2Et A.1-1125 CH2OMe CO2Et CO2Et A.1-1126 OCH2OMe CO2Et CO2Et A.1-1127 CF3 CO2Et CO2Et A.1-1128 CHFMe CO2Et CO2Et A.1-1129 CN CO2Et CO2Et A.1-1130 F CO2Et CO2Et A.1-1131 Cl CO2Et CO2Et A.1-1132 CO2Me CO2Et CO2Et A.1-1133 CO2Et CO2Et CO2Et A.1-1134 OCF3 CO2Et CO2Et A.1-1135 H OCF3 CO2Et A.1-1136 Me OCF3 CO2Et A.1-1137 Et OCF3 CO2Et A.1-1138 OMe OCF3 CO2Et A.1-1139 CH2OMe OCF3 CO2Et A.1-1140 OCH2OMe OCF3 CO2Et A.1-1141 CF3 OCF3 CO2Et A.1-1142 CHFMe OCF3 CO2Et A.1-1143 CN OCF3 CO2Et A.1-1144 F OCF3 CO2Et A.1-1145 Cl OCF3 CO2Et A.1-1146 CO2Me OCF3 CO2Et A.1-1147 CO2Et OCF3 CO2Et A.1-1148 OCF3 OCF3 CO2Et A.1-1149 H CH(Me)2 CO2Et A.1-1150 Me CH(Me)2 CO2Et A.1-1151 Et CH(Me)2 CO2Et A.1-1152 OMe CH(Me)2 CO2Et A.1-1153 CH2OMe CH(Me)2 CO2Et A.1-1154 OCH2OMe CH(Me)2 CO2Et A.1-1155 CF3 CH(Me)2 CO2Et A.1-1156 CHFMe CH(Me)2 CO2Et A.1-1157 CN CH(Me)2 CO2Et A.1-1158 F CH(Me)2 CO2Et A.1-1159 Cl CH(Me)2 CO2Et A.1-1160 CO2Me CH(Me)2 CO2Et A.1-1161 CO2Et CH(Me)2 CO2Et A.1-1162 OCF3 CH(Me)2 CO2Et A.1-1163 H CH═CH2 CO2Et A.1-1164 Me CH═CH2 CO2Et A.1-1165 Et CH═CH2 CO2Et A.1-1166 OMe CH═CH2 CO2Et A.1-1167 CH2OMe CH═CH2 CO2Et A.1-1168 OCH2OMe CH═CH2 CO2Et A.1-1169 CF3 CH═CH2 CO2Et A.1-1170 CHFMe CH═CH2 CO2Et A.1-1171 CN CH═CH2 CO2Et A.1-1172 F CH═CH2 CO2Et A.1-1173 Cl CH═CH2 CO2Et A.1-1174 CO2Me CH═CH2 CO2Et A.1-1175 CO2Et CH═CH2 CO2Et A.1-1176 OCF3 CH═CH2 CO2Et A.1-1177 H C≡CH CO2Et A.1-1178 Me C≡CH CO2Et A.1-1179 Et C≡CH CO2Et A.1-1180 OMe C≡CH CO2Et A.1-1181 CH2OMe C≡CH CO2Et A.1-1182 OCH2OMe C≡CH CO2Et A.1-1183 CF3 C≡CH CO2Et A.1-1184 CHFMe C≡CH CO2Et A.1-1185 CN C≡CH CO2Et A.1-1186 F C≡CH CO2Et A.1-1187 Cl C≡CH CO2Et A.1-1188 CO2Me C≡CH CO2Et A.1-1189 CO2Et C≡CH CO2Et A.1-1190 OCF3 C≡CH CO2Et

Further preferred embodiments relate to compounds I wherein Ra5 and Ra6 in each case constitute together with two ring member carbon atoms of the pyrimidine ring one of the following heterocyclic groups as defined in line A.2-1 to line A.2-26 in table A, wherein #5 and #6 indicate the point of attachment to the pyrimidine ring, each respectively corresponding to the positions of either substituent Ra5 or Ra6.

TABLE A.2 line Ra5/Ra6 A.2-1 #5—CH═CH—CH═CH—#6 A.2-2 #5—CH2—CH2—CH2—CH2—#6 A.2-3 #5—CH═CH—CH═N—#6 A.2-4 #5—N═CH—CH═CH—#6 A.2-5 #5—CH═N—CH═N—#6 A.2-6 #5—N═CH—N═CH—#6 A.2-7 #5—CH2—CH2—CH2—#6 A.2-8 #5—N═CH—CH═N—#6 A.2-9 #5—O—CH2—O—#6 A.2-10 #5—NH—CH═N—#6 A.2-11 #5—S—CH═N—#6 A.2-12 #5—N═CH—S—#6 A.2-13 #5—O—CH═N—#6 A.2-14 #5—N═CH—O—#6 A.2-15 #5—O—CH═CH—#6 A.2-16 #5—S—CH═CH—#6 A.2-17 #5—O—N═CH—#6 A.2-18 #5—S—N═CH—#6 A.2-19 #5—CH═N—O—#6 A.2-20 #5—CH═N—S—#6 A.2-21 #5—N(CH3)—CH═CH—#6 A.2-22 #5—CH═CH—N(CH3)—#6 A.2-23 #5═CH—N(NH2)—N═#6 A.2-24 #5—CH═N—N(CH3)—#6 A.2-25 #5═N—N(CH3)—CH═#6 A.2-26 #5—N(CH3)—N═CH—#6

In the compounds I according to the invention, RA, RB in radical Ra2 preferably is hydrogen, C1-C4-alkyl.

In the compounds I according to the invention, RA, RB in radical Ra5 preferably is hydrogen, C1-C4-alkyl.

In the compounds I according to the invention, RA, RB in radical Ra6 preferably is hydrogen, C1-C4-alkyl.

In the compounds I according to the invention, R′ in radical Ra2 preferably is hydrogen, NH2, C1-C4-alkyl, C1-C4-alkoxy.

In the compounds I according to the invention, R′ in radical Ra5 preferably is hydrogen, NH2, C1-C4-alkyl, C1-C4-alkoxy.

In the compounds I according to the invention, R′ in radical Ra6 preferably is hydrogen, NH2, C1-C4-alkyl, C1-C4-alkoxy.

In the compounds I according to the invention, R″ in radical Ra2 preferably is hydrogen, C1-C4-alkyl.

In the compounds I according to the invention, R″ in radical Ra5 preferably is hydrogen, C1-C4-alkyl.

In the compounds I according to the invention, R″ in radical Ra6 preferably is hydrogen, C1-C4-alkyl.

In the compounds I according to the invention, R″′ in radical Ra2 preferably is hydrogen.

In the compounds I according to the invention, R″′ in radical Ra5 preferably is hydrogen.

In the compounds I according to the invention, R″′ in radical Ra6 preferably is hydrogen.

In the compounds I according to the invention, R is preferably selected from the group consisting of hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, CN, CH2CN or CH2—O—C(═O)R′, wherein R′ is hydrogen, C1-C4-alkyl, C1-C4-alkoxy; more preferably R is selected from the group consisting of hydrogen, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C2-C4-alkenyl and C2-C4-alkynyl; in another preferred embodiment R is hydrogen, C1-C4-alkyl, C2-C4-alkenyl or C2-C4-alkynyl; most preferably R is hydrogen or C1-C4-alkyl; more preferably R is hydrogen; a more preferred embodiment relates to compounds I wherein R is CH3.

In the compounds I according to the invention, X is preferably a divalent group —CR3R4—, wherein R3 and R4 independently of each other are hydrogen, CN, C1-C4-hydroxyalkyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl or C3-C8-cycloalkyl; in another preferred embodiment X is —CH2—, —CH(CH3), —CH(CH2CH3)—, —C(CH3)2—, —CHCN—, —C(═O)—, —C(═S)—, —CH(C(═O)—C1-C4-alkoxy), —CH(C(═O)NH2)—, —C(═O)N(C1-C4-alkyl)2-, and —CH(C(═O)OH)—. Another preferred embodiment of the invention relates to compounds I, wherein X is —CH2—, —C(═O)—, —CH(CH3), —C(CH3)2—, —CHCN—, —CH(C(═O)—OCH3) or —CH(C(═O)—OCH2CH3); more preferably X is —CH2— or —CH(CH3)—, in particular —CH2—; more preferably X is —C(═O)—.

In the compounds I according to the invention, R1 and R2 independently of each other are preferably selected from the group consisting of hydrogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and C3-C8-cycloalkyl; more preferably R1 and R2 independently of each other are hydrogen, CN, CH3, CH2CH3, F, Cl or OCH3; another more preferred embodiment relates to compounds I wherein R1 and R2 independently of each other are hydrogen or C1-C4-alkyl; another more preferred embodiment relates to compounds I wherein R1 and R2 independently of each other are hydrogen or CH3; more preferably R1 and R2 are hydrogen.

Further preferred embodiments relate to compounds I wherein R, X, R1 and R2 in each case are one of the following combinations B-1 to B-84 in table B:

TABLE B No. R R1 R2 X B-1 H H H —CH2 B-2 H CH3 H —CH2 B-3 H CN H —CH2 B-4 H F H —CH2 B-5 H Cl H —CH2 B-6 H OCH3 H —CH2 B-7 H CH3 CH3 —CH2 B-8 H H H —C(═O)— B-9 H CH3 H —C(═O)— B-10 H CN H —C(═O)— B-11 H F H —C(═O)— B-12 H Cl H —C(═O)— B-13 H OCH3 H —C(═O)— B-14 H CH3 CH3 —C(═O)— B-15 H H H —CH(CH3)— B-16 H CH3 H —CH(CH3)— B-17 H CN H —CH(CH3)— B-18 H F H —CH(CH3)— B-19 H Cl H —CH(CH3)— B-20 H OCH3 H —CH(CH3)— B-21 H CH3 CH3 —CH(CH3)— B-22 H H H —CH(CH3)— B-23 H CH3 H —CH(CH3)— B-24 H CN H —CH(CH3)— B-25 H F H —CH(CH3)— B-26 H Cl H —CH(CH3)— B-27 H OCH3 H —CH(CH3)— B-28 H CH3 CH3 —CH(CH3)— B-29 H H H —CH(C2H5)— B-30 H CH3 H —CH(C2H5)— B-31 H CN H —CH(C2H5)— B-32 H F H —CH(C2H5)— B-33 H Cl H —CH(C2H5)— B-34 H OCH3 H —CH(C2H5)— B-35 H CH3 CH3 —CH(C2H5)— B-36 H H H —CHCN— B-37 H CH3 H —CHCN— B-38 H CN H —CHCN— B-39 H F H —CHCN— B-40 H Cl H —CHCN— B-41 H OCH3 H —CHCN— B-42 H CH3 CH3 —CHCN— B-43 CH3 H H —CH2 B-44 CH3 CH3 H —CH2 B-45 CH3 CN H —CH2 B-46 CH3 F H —CH2 B-47 CH3 Cl H —CH2 B-48 CH3 OCH3 H —CH2 B-49 CH3 CH3 CH3 —CH2 B-50 CH3 H H —C(═O)— B-51 CH3 CH3 H —C(═O)— B-52 CH3 CN H —C(═O)— B-53 CH3 F H —C(═O)— B-54 CH3 Cl H —C(═O)— B-55 CH3 OCH3 H —C(═O)— B-56 CH3 CH3 CH3 —C(═O)— B-57 CH3 H H —CH(CH3)— B-58 CH3 CH3 H —CH(CH3)— B-59 CH3 CN H —CH(CH3)— B-60 CH3 F H —CH(CH3)— B-61 CH3 Cl H —CH(CH3)— B-62 CH3 OCH3 H —CH(CH3)— B-63 CH3 CH3 CH3 —CH(CH3)— B-64 CH3 H H —C(CH3)2 B-65 CH3 CH3 H —C(CH3)2 B-66 CH3 CN H —C(CH3)2 B-67 CH3 F H —C(CH3)2 B-68 CH3 Cl H —C(CH3)2 B-69 CH3 OCH3 H —C(CH3)2 B-70 CH3 CH3 CH3 —C(CH3)2 B-71 CH3 H H —CH(C2H5)— B-72 CH3 CH3 H —CH(C2H5)— B-73 CH3 CN H —CH(C2H5)— B-74 CH3 F H —CH(C2H5)— B-75 CH3 Cl H —CH(C2H5)— B-76 CH3 OCH3 H —CH(C2H5)— B-77 CH3 CH3 CH3 —CH(C2H5)— B-78 CH3 H H —CHCN— B-79 CH3 CH3 H —CHCN— B-80 CH3 CN H —CHCN— B-81 CH3 F H —CHCN— B-82 CH3 Cl H —CHCN— B-83 CH3 OCH3 H —CHCN— B-84 CH3 CH3 CH3 —CHCN—

In the compounds I according to the invention, Rb are independently selected from halogen, CN, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl and (C1-C4-alkoxy)carbonyl; more preferably Rb are independently selected from halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-alkoxy)carbonyl; in another preferred embodiment Rb are independently selected from halogen and C1-C4-alkoxy; most preferably Rb are independently selected from halogen, CN, CH3, CF3 and OCH3. A particularly preferred embodiment relates to compounds I wherein Rb is F. Another particularly preferred embodiment relates to compounds I wherein Rb is CH3. A further particularly preferred embodiment relates to compounds I wherein Rb is CF3. In yet another particularly preferred embodiment Rb is OCH3. In still a further embodiment Rb is attached to the phenyl ring adjacent (in ortho-position) to the alkyne group. A further embodiment relates to compounds I wherein Rb is attached in meta-position to the alkyne group.

In the compounds I according to the invention, n is preferably 0.

A further embodiment relates to compounds I wherein n is preferably 1.

A further embodiment relates to compounds I wherein n is preferably 0 or 1.

A further embodiment relates to compounds I wherein n is preferably 2.

A further embodiment relates to compounds I wherein n is preferably 0, 1 or 2.

A further embodiment relates to compounds I wherein n is preferably 3.

A further embodiment relates to compounds I wherein n is preferably 0, 1, 2 or 3.

A further embodiment relates to compounds I wherein n is preferably 4. In the compounds I according to the invention, Het is preferably 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; more preferably Het is selected from pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl; more preferably Het is selected from pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl; preferably Het is pyrimidin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl.

In a further preferred embodiment Het is a pyridinyl or pyrimidinyl ring, wherein the moiety O-Het is bound in para- or meta-position to the phenyl ring; and wherein the pyridinyl or pyrimidinyl are unsubstituted or carry 1 or 2 groups Rc; wherein Rc is halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy)carbonyl.

According to one embodiment Het is unsubstituted; a further preferred embodiment relates to compounds I wherein Het is unsubstituted or substituted by 1 radical Rc; another preferred embodiment relates to compounds I wherein Het is unsubstituted or substituted by 1 or 2 independently selected radicals Rc; yet another preferred embodiment relates to compounds I wherein Het is unsubstituted or substituted by 1, 2 or 3 independently selected radicals Rc; another preferred embodiment relates to compounds I wherein Het is unsubstituted or substituted by 1, 2, 3, or 4 independently selected radicals Rc.

In the compounds I according to the invention, Rc are preferably independently selected from halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C(═O)R′, C(═NOR″)R″′, C3-C8-cycloalkyl, phenyl and phenoxy. In another preferred embodiment Rc are independently selected from halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C4-alkoxy and (C1-C4-alkoxy)carbonyl. A further preferred embodiment relates to compounds I wherein Rc are independently selected from F, Cl, CN, CH3, OCH3, CF3, OCF3 and COOCH3; most preferably Rc are independently selected from Cl, CN and CF3.

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 in table H:

TABLE H No. Het H-1 embedded image H-2 embedded image H-3 embedded image H-4 embedded image H-5 embedded image H-6 embedded image H-7 embedded image H-8 embedded image H-9 embedded image H-10 embedded image H-11 embedded image H-12 embedded image H-13 embedded image H-14 embedded image H-15 embedded image H-16 embedded image H-17 embedded image H-18 embedded image H-19 embedded image H-20 embedded image H-21 embedded image H-22 embedded image H-23 embedded image H-24 embedded image H-25 embedded image H-26 embedded image H-27 embedded image H-28 embedded image H-29 embedded image H-30 embedded image H-31 embedded image H-32 embedded image H-33 embedded image H-34 embedded image H-35 embedded image H-36 embedded image H-37 embedded image H-38 embedded image in which # indicates the point of attachment.

With respect to their use, particular preference is given to the compounds I.A or I.B.

embedded image

A skilled person will readily understand that the preferences given in connection with compounds of formula I also apply for formulae I.A or I.B as defined herein.

According to a further embodiment, the present invention relates to compounds of the formula I wherein:

  • Ra2 is hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
  • Ra5, Ra6 independently of each other are hydrogen, halogen, OH, CN, C1-C4-alkyl, C2-C4-alkenyl, C1-C4-haloalkyl, C1-C4-alkoxy or (C1-C4-alkoxy)carbonyl; or
  • Ra5 and R6 together with two ring member carbon atoms to which they are attached, form a fused 5- or 6-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2 or 3 heteroatoms selected from the group of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals selected from the group consisting of halogen, CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy;
  • R is hydrogen, C1-C4-alkyl, C2-C4-alkenyl or C2-C4-alkynyl;
  • X is a divalent group —CR3R4—, wherein
    • R3 and R4 independently of each other are hydrogen, CN, C1-C4-hydroxyalkyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C8-cycloalkyl;
  • R1, R2 are independently selected from hydrogen and C1-C4-alkyl;
  • n is 0 or 1;
  • Rb is halogen or C1-C4-alkoxy;
  • Het is a pyridinyl or pyrimidinyl ring; wherein the moiety O-Het is bound in para- or meta-position to the phenyl ring; and wherein the pyridinyl or pyrimidinyl are unsubstituted or carry 1 or 2 groups Rc; wherein
    • Rc are independently selected from halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C4-alkoxy and (C1-C4-alkoxy)carbonyl;
      and the N-oxides and the agriculturally acceptable salts of the compounds of formula I.

The compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.

The compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e.g. wheat, rye, barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e.g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants. Preferably, compounds I and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

The term “plant propagation material” is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.

Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.

The term “cultivated plants” is to be understood as including plants which have been modified by 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 dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e.g. described in Pest Managem. Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1185; 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 available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cultivance® (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. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e.g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; 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, ecdysteroid-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 (Coeloptera), 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 Cry1Ab toxin), YieldGard® Plus (corn cultivars producing Cry1Ab and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1, Cry35Ab1 and the enzyme Phosphinothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1Ac toxin), Bollgard® I (cotton cultivars producing the Cry1Ac toxin), Bollgard® II (cotton cultivars producing Cry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e.g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the Cry1Ab toxin and PAT enzyme), 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 Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1F 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 Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e.g. in the publications mentioned above.

Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e.g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.

Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e.g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera® rape, DOW Agro Sciences, Canada).

Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e.g. potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).

The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. candida) and sunflowers (e.g. A. tragopogonis); 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. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.g. strawberries), vegetables (e.g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e.g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (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. lindemuthianum) and soybeans (e.g. C. truncatum or C. gloeosporioides); Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e.g. C. liriodendri, teleomorph: Neonectria liriodendri Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e.g. D. teres, net blotch) and wheat (e.g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e.g. E. pisi), such as cucurbits (e.g. E. cichoracearum), cabbages, rape (e.g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e.g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e.g. wheat or barley), F. oxysporum on tomatoes, F. solanion soybeans and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e.g. wheat or barley) and corn; Gibberella spp. on cereals (e.g. G. zeae) and rice (e.g. G. fujikuroi Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e.g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e.g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e.g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e.g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e.g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e.g. P. brassicae), rape (e.g. P. parasitica), onions (e.g. P. destructor), tobacco (P. tabacina) and soybeans (e.g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e.g. on vines (e.g. P. tracheiphila and P. tetraspora) and soybeans (e.g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e.g. P. viticola: can and leaf spot) and soybeans (e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e.g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e.g. P. infestans: late blight) and broad-leaved trees (e.g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e.g. P. viticola (grapevine 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) 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. 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. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e.g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer(black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on 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 (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. reliana: 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. (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. phaseoi) and sugar beets (e.g. U. betae); Ustilago spp. (loose smut) on cereals (e.g. U. nuda and U. avaenae), corn (e.g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e.g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e.g. V. dahliae on strawberries, rape, potatoes and tomatoes. The compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials. The term “protection of materials” is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, coiling 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., Penicillum 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, respectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.

The term “plant health” is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e.g. increased biomass and/or increased content of valuable ingredients), plant vigor (e.g. improved plant growth and/or greener leaves (“greening effect”)), quality (e.g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.

The compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.

The compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.

Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting. The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.

An agrochemical composition comprises a fungicidally effective amount of a compound I. The term “effective amount” denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.

The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of 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. Examples of 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 alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Examples for composition types and their preparation are:

i) Water-Soluble Concentrates (SL, LS)

10-60 wt % of a compound I and 5-15 wt % wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt %. The active substance dissolves upon dilution with water.

ii) Dispersible Concentrates (DC)

5-25 wt % of a compound I and 1-10 wt % dispersant (e.g. 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. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt % by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.

v) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt % of a compound I are comminuted with addition of 2-10 wt % dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt % thickener (e.g. xanthan gum) and water ad 100 wt % to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt % binder (e.g. 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 dimethylamide and cyclohexanone), 10-25 wt % surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100%. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.

x) Microcapsules (CS)

An oil phase comprising 5-50 wt % of a compound I, 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 dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 wt %. The wt % relate to the total CS composition.

xi) Dustable Powders (DP, DS)

1-10 wt % of a compound I are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt %.

xii) Granules (GR, FG)

0.5-30 wt % of a compound I is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt %. Granulation is achieved by extrusion, spray-drying or fluidized bed.

xiii) Ultra-Low Volume Liquids (UL)

1-50 wt % of a compound I are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %.

The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt % anti-freezing agents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt % colorants.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, 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) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

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 active substances, 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 Qo site (e.g. strobilurins): azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxy-methyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
    • inhibitors of complex III at Qi site: cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate; (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl 2-methylpropanoate
    • inhibitors of complex II (e.g. carboxamides): benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4′-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H-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, 3-(difluoromethyl)-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;
    • other respiration inhibitors (e.g. complex I, uncouplers): diflumetorim, (5,8-difluoro-quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam;
      B) Sterol Biosynthesis Inhibitors (SBI Fungicides)
    • C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, 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, 1-[rel-(2 S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1H-[1,2,4]triazole, 2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1,2,4]triazole-3-thiol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine;
    • Delta 14-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-fluorophenylmethoxyl)pyrimidin-4-amine;
      D) Inhibitors of Cell Division and Cytoskeleton
    • tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl, carbendazim, fuberidazole, 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, mandipropamid, 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, propamocarb-hydrochlorid
    • fatty acid amide hydrolase inhibitors: oxathiapiprolin;
      H) Inhibitors with Multi Site Action
    • inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
    • thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;
    • organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole 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-1H,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: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
      J) Plant Defense 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, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxathiapiprolin, 2-[3,5-bis(difluoromethyl)-1H-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)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N′-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N′-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N′-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N′-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole), N-(6-methoxy-pyridin-3-yl)cyclopropanecarboxylic acid amide, 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole, 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
      L) 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 pumillus (e.g. NRRL Accession No. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA), Bacillus subtilis (e.g. isolate NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc., USA), Bacillus subtilis var. amyloliquefaciens FZB24 (e.g. TAEGRO® from Novozyme Biologicals, Inc., USA), 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. ARMOUR-ZEN from BotriZen Ltd., NZ), 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. POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis (e.g. REGALIA® from Marrone BioInnovations, USA), Talaromyces flavus V117b (e.g. PROTUS® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL® from Agrimm Technologies Ltd, NZ), 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 (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);
      M) Growth Regulators

abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl and uniconazole;

N) Herbicides

    • acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
    • amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
    • aryloxyphenoxypropionates: 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, thiobencarb, triallate;
    • cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;
    • dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;
    • diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen;
    • hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;
    • imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
    • phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, 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, trifloxysulfuron, 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, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
    • others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlorthal, cinmethylin, 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 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-phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester.
      O) Insecticides
    • organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
    • carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;
    • pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin;
    • insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, 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, 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-1H-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, cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, pyrifluquinazon and 1,1′-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl]cyclopropaneacetic acid ester.

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. Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Furthermore, combating harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to L), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to L). By applying compounds I together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures).

This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e.g. as tank-mix) or separately, 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.

In binary mixtures, i.e. compositions according to the invention comprising one compound I (component 1) and one further active substance (component 2), e.g. one active substance from groups A) to O), the weight ratio of component 1 and component 2 generally depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:3 to 3:1. In ternary mixtures, i.e. compositions according to the invention comprising one compound I (component 1) and a first further active substance (component 2) and a second further active substance (component 3), e.g. two active substances from groups A) to O), the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1:50 to 50:1 and particularly in the range of from 1:10 to 10:1, and the weight ratio of component 1 and component 3 preferably is in the range of from 1:50 to 50:1 and particularly in the range of from 1:10 to 10:1.

Preference is also given to 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; benzovindiflupyr, bixafen, boscalid, fluopyram, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid, fluazinam, fentin salts, such as fentin acetate.

Preference is given to mixtures 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, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, fenarimol, triforine; dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine; fenhexamid.

Preference is given to mixtures 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 mixtures 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 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.

Preference is also given to 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.

Preference is also given to 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.

Preference is also given to 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.

Preference is also given to 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.

Preference is also given to 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.

Preference is also given to 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-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide.

Preference is also given to 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.

Accordingly, the present invention furthermore relates to compositions comprising one compound I (component 1) and one further active substance (component 2), which further active substance is selected from the column “Component 2” of the lines C-1 to C-381 of Table C.

A further embodiment relates to the compositions C-1 to C-381 listed in Table C, where a row of Table C 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. Preferably, the compositions described comprise the active substances in synergistically effective amounts.

TABLE C Composition comprising one indivivalized compound I and one further active substance from groups A) to O) Mixture Component 1 Component 2 C-1 one individualized compound I Azoxystrobin C-2 one individualized compound I Coumethoxystrobin C-3 one individualized compound I Coumoxystrobin C-4 one individualized compound I Dimoxystrobin C-5 one individualized compound I Enestroburin C-6 one individualized compound I Fenaminstrobin C-7 one individualized compound I Fenoxystrobin/Flufenoxystrobin C-8 one individualized compound I Fluoxastrobin C-9 one individualized compound I Kresoxim-methyl C-10 one individualized compound I Metominostrobin C-11 one individualized compound I Orysastrobin C-12 one individualized compound I Picoxystrobin C-13 one individualized compound I Pyraclostrobin C-14 one individualized compound I Pyrametostrobin C-15 one individualized compound I Pyraoxystrobin C-16 one individualized compound I Pyribencarb C-17 one individualized compound I Trifloxystrobin C-18 one individualized compound I Triclopyricarb/Chlorodincarb C-19 one individualized compound I 2-[2-(2,5-dimethyl-phenoxymethyl)- phenyl]-3-methoxy-acrylic acid methyl ester C-20 one individualized compound I 2-(2-(3-(2,6-dichlorophenyl)-1-methyl- allylideneaminooxymethyl)-phenyl)- 2-methoxyimino-N-methyl-acetamide C-21 one individualized compound I Benalaxyl C-22 one individualized compound I Benalaxyl-M C-23 one individualized compound I Benodanil C-24 one individualized compound I Benzovindiflupyr C-25 one individualized compound I Bixafen C-26 one individualized compound I Boscalid C-27 one individualized compound I Carboxin C-28 one individualized compound I Fenfuram C-29 one individualized compound I Fenhexamid C-30 one individualized compound I Flutolanil C-31 one individualized compound I Fluxapyroxad C-32 one individualized compound I Furametpyr C-33 one individualized compound I Isopyrazam C-34 one individualized compound I Isotianil C-35 one individualized compound I Kiralaxyl C-36 one individualized compound I Mepronil C-37 one individualized compound I Metalaxyl C-38 one individualized compound I Metalaxyl-M C-39 one individualized compound I Ofurace C-40 one individualized compound I Oxadixyl C-41 one individualized compound I Oxycarboxin C-42 one individualized compound I Penflufen C-43 one individualized compound I Penthiopyrad C-44 one individualized compound I Sedaxane C-45 one individualized compound I Tecloftalam C-46 one individualized compound I Thifluzamide C-47 one individualized compound I Tiadinil C-48 one individualized compound I 2-Amino-4-methyl-thiazole-5-carboxylic acid anilide C-49 one individualized compound I N-(4′-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1-methyl-1H-pyrazole- 4-carboxamide C-50 one individualized compound I N-(2-(1,3,3-trimethyl-butyl)-phenyl)- 1,3-dimethyl-5-fluoro-1H-pyrazole- 4-carboxamide C-51 one individualized compound I 3-(difluoromethyl)-1-methyl-N-(1,1,3-tri- methylindan-4-yl)pyrazole-4-carbox- amide C-52 one individualized compound I 3-(trifluoromethyl)-1-methyl-N-(1,1,3-tri- methylindan-4-yl)pyrazole-4-carbox- amide C-53 one individualized compound I 1,3-dimethyl-N-(1,1,3-trimethylindan- 4-yl)pyrazole-4-carboxamide C-54 one individualized compound I 3-(trifluoromethyl)-1,5-dimethyl- N-(1,1,3-trimethylindan-4-yl)pyrazole- 4-carboxamide C-55 one individualized compound I 3-(difluoromethyl)-1,5-dimethyl- N-(1,1,3-trimethylindan-4-yl)pyrazole- 4-carboxamide C-56 one individualized compound I 1,3,5-trimethyl-N-(1,1,3-trimethylindan- 4-yl)pyrazole-4-carboxamide C-57 one individualized compound I Dimethomorph C-58 one individualized compound I Flumorph C-59 one individualized compound I Pyrimorph C-60 one individualized compound I Flumetover C-61 one individualized compound I Fluopicolide C-62 one individualized compound I Fluopyram C-63 one individualized compound I Zoxamide C-64 one individualized compound I Carpropamid C-65 one individualized compound I Diclocymet C-66 one individualized compound I Mandipropamid C-67 one individualized compound I Oxytetracyclin C-68 one individualized compound I Silthiofam C-69 one individualized compound I N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide C-70 one individualized compound I Azaconazole C-71 one individualized compound I Bitertanol C-72 one individualized compound I Bromuconazole C-73 one individualized compound I Cyproconazole C-74 one individualized compound I Difenoconazole C-75 one individualized compound I Diniconazole C-76 one individualized compound I Diniconazole-M C-77 one individualized compound I Epoxiconazole C-78 one individualized compound I Fenbuconazole C-79 one individualized compound I Fluquinconazole C-80 one individualized compound I Flusilazole C-81 one individualized compound I Flutriafol C-82 one individualized compound I Hexaconazol C-83 one individualized compound I Imibenconazole C-84 one individualized compound I Ipconazole C-85 one individualized compound I Metconazole C-86 one individualized compound I Myclobutanil C-87 one individualized compound I Oxpoconazol C-88 one individualized compound I Paclobutrazol C-89 one individualized compound I Penconazole C-90 one individualized compound I Propiconazole C-91 one individualized compound I Prothioconazole C-92 one individualized compound I Simeconazole C-93 one individualized compound I Tebuconazole C-94 one individualized compound I Tetraconazole C-95 one individualized compound I Triadimefon C-96 one individualized compound I Triadimenol C-97 one individualized compound I Triticonazole C-98 one individualized compound I Uniconazole C-99 one individualized compound I 1[rel-(2S;3R)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)-oxiranylmethyl]- 5-thiocyanato-1H-[1,2,4]triazole, C-100 one individualized compound I 2-[rel(2S,3R)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)-oxiranylmethyl]- 2H-[1,2,4]triazole-3-thiol C-101 one individualized compound I Cyazofamid C-102 one individualized compound I Amisulbrom C-103 one individualized compound I Imazalil C-104 one individualized compound I Imazalil-sulfate C-105 one individualized compound I Pefurazoate C-106 one individualized compound I Prochloraz C-107 one individualized compound I Triflumizole C-108 one individualized compound I Benomyl C-109 one individualized compound I Carbendazim C-110 one individualized compound I Fuberidazole C-111 one individualized compound I Thiabendazole C-112 one individualized compound I Ethaboxam C-113 one individualized compound I Etridiazole C-114 one individualized compound I Hymexazole C-115 one individualized compound I 2-(4-Chloro-phenyl)-N-[4-(3,4-dimeth- oxy-phenyl)-isoxazol-5-yl]-2-prop-2-yn- yloxy-acetamide C-116 one individualized compound I Fluazinam C-117 one individualized compound I Pyrifenox C-118 one individualized compound I 3-[5-(4-Chloro-phenyl)-2,3-dimethyl-is- oxazolidin-3-yl]-pyridine (Pyrisoxazole) C-119 one individualized compound I 3-[5-(4-Methyl-phenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine C-120 one individualized compound I Bupirimate C-121 one individualized compound I Cyprodinil C-122 one individualized compound I 5-Fluorocytosine C-123 one individualized compound I 5-Fluoro-2-(p-tolylmethoxy)pyrimidin- 4-amine C-124 one individualized compound I 5-Fluoro-2-(4-fluorophenylmethoxy)- pyrimidin-4-amine C-125 one individualized compound I Diflumetorim C-126 one individualized compound I (5,8-Difluoroquinazolin-4-yl)-{2-[2-fluo- ro-4-(4-trifluoromethylpyridin-2-yloxy)- phenyl]ethyl}-amine C-127 one individualized compound I Fenarimol C-128 one individualized compound I Ferimzone C-129 one individualized compound I Mepanipyrim C-130 one individualized compound I Nitrapyrin C-131 one individualized compound I Nuarimol C-132 one individualized compound I Pyrimethanil C-133 one individualized compound I Triforine C-134 one individualized compound I Fenpiclonil C-135 one individualized compound I Fludioxonil C-136 one individualized compound I Aldimorph C-137 one individualized compound I Dodemorph C-138 one individualized compound I Dodemorph-acetate C-139 one individualized compound I Fenpropimorph C-140 one individualized compound I Tridemorph C-141 one individualized compound I Fenpropidin C-142 one individualized compound I Fluoroimid C-143 one individualized compound I Iprodione C-144 one individualized compound I Procymidone C-145 one individualized compound I Vinclozolin C-146 one individualized compound I Famoxadone C-147 one individualized compound I Fenamidone C-148 one individualized compound I Flutianil C-149 one individualized compound I Octhilinone C-150 one individualized compound I Probenazole C-151 one individualized compound I Fenpyrazamine C-152 one individualized compound I Acibenzolar-S-methyl C-153 one individualized compound I Ametoctradin C-154 one individualized compound I Amisulbrom C-155 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobuty- ryloxymethoxy-4-methoxypyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo- [1,5]dioxonan-7yl] 2-methylpropanoate C-156 one individualized compound I [(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 C-157 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet- oxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo- 1,5-dioxonan-7-yl] 2-methylpropanoate C-158 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobut- oxycarbonyloxy-4-methoxy-pyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo- 1,5-dioxonan-7-yl] 2-methylpropanoate C-159 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-ben- zodioxol-5-ylmethoxy)-4-methoxy-pyri- dine-2-carbonyl]amino]-6-methyl-4,9-di- oxo-1,5-dioxonan-7-yl] 2-methyl- propanoate C-160 one individualized compound I (3S,6S,7R,8R)-3-[[(3-hydroxy-4-meth- oxy-2-pyridinyl)carbonyl]amino]- 6-methyl-4,9-dioxo-8-(phenylmethyl)- 1,5-dioxonan-7-yl 2-methylpropanoate C-161 one individualized compound I Anilazin C-162 one individualized compound I Blasticidin-S C-163 one individualized compound I Captafol C-164 one individualized compound I Captan C-165 one individualized compound I Chinomethionat C-166 one individualized compound I Dazomet C-167 one individualized compound I Debacarb C-168 one individualized compound I Diclomezine C-169 one individualized compound I Difenzoquat, C-170 one individualized compound I Difenzoquat-methylsulfate C-171 one individualized compound I Fenoxanil C-172 one individualized compound I Folpet C-173 one individualized compound I Oxolinsäure C-174 one individualized compound I Piperalin C-175 one individualized compound I Proquinazid C-176 one individualized compound I Pyroquilon C-177 one individualized compound I Quinoxyfen C-178 one individualized compound I Triazoxid C-179 one individualized compound I Tricyclazole C-180 one individualized compound I 2-Butoxy-6-iodo-3-propyl-chromen-4- one C-181 one individualized compound I 5-Chloro-1-(4,6-dimethoxy-pyrimidin-2- yl)-2-methyl-1H-benzoimidazole C-182 one individualized compound I 5-Chloro-7-(4-methyl-piperidin-l-yl)- 6-(2,4,6-trifluoro-phenyl)-[1,2,4]tri- azolo[1,5-a]pyrimidine C-183 one individualized compound I Ferbam C-184 one individualized compound I Mancozeb C-185 one individualized compound I Maneb C-186 one individualized compound I Metam C-187 one individualized compound I Methasulphocarb C-188 one individualized compound I Metiram C-189 one individualized compound I Propineb C-190 one individualized compound I Thiram C-191 one individualized compound I Zineb C-192 one individualized compound I Ziram C-193 one individualized compound I Diethofencarb C-194 one individualized compound I Benthiavalicarb C-195 one individualized compound I Iprovalicarb C-196 one individualized compound I Propamocarb C-197 one individualized compound I Propamocarb hydrochlorid C-198 one individualized compound I Valifenalate C-199 one individualized compound I N-(1-(1-(4-cyanophenyl)ethanesulfon- yl)-but-2-yl) carbamic acid-(4-fluoro- phenyl) ester C-200 one individualized compound I Dodine C-201 one individualized compound I Dodine free base C-202 one individualized compound I Guazatine C-203 one individualized compound I Guazatine-acetate C-204 one individualized compound I Iminoctadine C-205 one individualized compound I Iminoctadine-triacetate C-206 one individualized compound I Iminoctadine-tris(albesilate) C-207 one individualized compound I Kasugamycin C-208 one individualized compound I Kasugamycin-hydrochloride-hydrate C-209 one individualized compound I Polyoxine C-210 one individualized compound I Streptomycin C-211 one individualized compound I Validamycin A C-212 one individualized compound I Binapacryl C-213 one individualized compound I Dicloran C-214 one individualized compound I Dinobuton C-215 one individualized compound I Dinocap C-216 one individualized compound I Nitrothal-isopropyl C-217 one individualized compound I Tecnazen C-218 one individualized compound I Fentin salts C-219 one individualized compound I Dithianon C-220 one individualized compound I 2,6-dimethyl-1H,5H-[1,4]dithiino [2,3-c:5,6-c′]ldipyrrole- 1,3,5,7(2H,6H)-tetraone C-221 one individualized compound I Isoprothiolane C-222 one individualized compound I Edifenphos C-223 one individualized compound I Fosetyl, Fosetyl-aluminium C-224 one individualized compound I Iprobenfos C-225 one individualized compound I Phosphorous acid (H3PO3) and derivatives C-226 one individualized compound I Pyrazophos C-227 one individualized compound I Tolclofos-methyl C-228 one individualized compound I Chlorothalonil C-229 one individualized compound I Dichlofluanid C-230 one individualized compound I Dichlorophen C-231 one individualized compound I Flusulfamide C-232 one individualized compound I Hexachlorbenzene C-233 one individualized compound I Pencycuron C-234 one individualized compound I Pentachlorophenol and salts C-235 one individualized compound I Phthalide C-236 one individualized compound I Quintozene C-237 one individualized compound I Thiophanate Methyl C-238 one individualized compound I Tolylfluanid C-239 one individualized compound I N-(4-chloro-2-nitro- phenyl)-N-ethyl- 4-methyl- benzenesulfonamide C-240 one individualized compound I Bordeaux mixture C-241 one individualized compound I Copper acetate C-242 one individualized compound I Copper hydroxide C-243 one individualized compound I Copper oxychloride C-244 one individualized compound I basic Copper sulfate C-245 one individualized compound I Sulfur C-246 one individualized compound I Biphenyl C-247 one individualized compound I Bronopol C-248 one individualized compound I Cyflufenamid C-249 one individualized compound I Cymoxanil C-250 one individualized compound I Diphenylamin C-251 one individualized compound I Metrafenone C-252 one individualized compound I Pyriofenone C-253 one individualized compound I Mildiomycin C-254 one individualized compound I Oxin-copper C-255 one individualized compound I Oxathiapiprolin C-256 one individualized compound I 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1- yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phe- nyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thi- azol-2-yl)piperidin-1-yl]ethanone C-257 one individualized compound I 2-[3,5-bis(difluoromethyl)-1H-pyrazol- 1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn- 1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol- 3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]- ethanone C-258 one individualized compound I 2-[3,5-bis(difluoromethyl)-1H-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 C-259 one individualized compound I Prohexadione calcium C-260 one individualized compound I Spiroxamine C-261 one individualized compound I Tebufloquin C-262 one individualized compound I Tolylfluanid C-263 one individualized compound I N-(Cyclopropylmethoxyimino-(6- difluoromethoxy-2,3-difluoro-phenyl)- methyl)-2-phenyl acetamide C-264 one individualized compound I N′-(4-(4-chloro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine C-265 one individualized compound I N′-(4-(4-fluoro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine C-266 one individualized compound I N′-(2-methyl-5-trifluoromethyl-4-(3-tri- methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine C-267 one individualized compound I N′-(5-difluoromethyl-2-methyl-4-(3-tri- methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine C-268 one individualized compound I Methoxy-acetic acid 6-tert-butyl-8- fluoro-2,3-dimethyl-quinolin-4-yl ester C-269 one individualized compound I Bacillus subtilis NRRL No. B-21661 C-270 one individualized compound I Bacillus purndus NRRL No. B-30087 C-271 one individualized compound I Ulocladium oudemansii C-272 one individualized compound I Carbaryl C-273 one individualized compound I Carbofuran C-274 one individualized compound I Carbosulfan C-275 one individualized compound I Methomylthiodicarb C-276 one individualized compound I Bifenthrin C-277 one individualized compound I Cyfluthrin C-278 one individualized compound I Cypermethrin C-279 one individualized compound I alpha-Cypermethrin C-280 one individualized compound I zeta-Cypermethrin C-281 one individualized compound I Deltamethrin C-282 one individualized compound I Esfenvalerate C-283 one individualized compound I Lambda-cyhalothrin C-284 one individualized compound I Permethrin C-285 one individualized compound I Tefluthrin C-286 one individualized compound I Diflubenzuron C-287 one individualized compound I Flufenoxuron C-288 one individualized compound I Lufenuron C-289 one individualized compound I Teflubenzuron C-290 one individualized compound I Spirotetramate C-291 one individualized compound I Clothianidin C-292 one individualized compound I Dinotefuran C-293 one individualized compound I Imidacloprid C-294 one individualized compound I Thiamethoxam C-295 one individualized compound I Flupyradifurone C-296 one individualized compound I Acetamiprid C-297 one individualized compound I Thiacloprid C-298 one individualized compound I Endosulfan C-299 one individualized compound I Fipronil C-300 one individualized compound I Abamectin C-301 one individualized compound I Emamectin C-302 one individualized compound I Spinosad C-303 one individualized compound I Spinetoram C-304 one individualized compound I Hydramethylnon C-305 one individualized compound I Chlorfenapyr C-306 one individualized compound I Fenbutatin oxide C-307 one individualized compound I Indoxacarb C-308 one individualized compound I Metaflumizone C-309 one individualized compound I Flonicamid C-310 one individualized compound I Flubendiamide C-311 one individualized compound I Chlorantraniliprole C-312 one individualized compound I Cyantraniliprole C-313 one individualized compound I N-[4,6-dichloro-2-[(diethyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluorometh- yl)pyrazole-3-carboxamide C-314 one individualized compound I N-[4-chloro-2-[(diethyl-lambda-4-sul- fanylidene)carbamoyl]-6-methyl-phe- nyl]-2-(3-chloro-2-pyridyl)-5-(trifluoro- methyl)pyrazole-3-carboxamide C-315 one individualized compound I N-[4-chloro-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-6-methyl- phenyl]-2-(3-chloro-2-pyridyl)-5-(tri- fluoromethyl)pyrazole-3-carboxamide C-316 one individualized compound I N-[4,6-dichloro-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoro- methyl)pyrazole-3-carboxamide C-317 one individualized compound I N-[4,6-dichloro-2-[(diethyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(difluoro- methyl)pyrazole-3-carboxamide C-318 one individualized compound I N-[4,6-dibromo-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-2- (3-chloro-2-pyridyl)-5-(trifluoromethyl)- pyrazole-3-carboxamide C-319 one individualized compound I N-[4-chloro-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-6-cyano- phenyl]-2-(3-chloro-2-pyridyl)-5-(tri- fluoromethyl)pyrazole-3-carboxamide C-320 one individualized compound I N-[4,6-dibromo-2-[(diethyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluorometh- yl)pyrazole-3-carboxamide C-321 one individualized compound I Cyflumetofen C-322 one individualized compound I Acetochlor C-323 one individualized compound I Dimethenamid C-324 one individualized compound I metolachlor C-325 one individualized compound I Metazachlor C-326 one individualized compound I Glyphosate C-327 one individualized compound I Glufosinate C-328 one individualized compound I Sulfosate C-329 one individualized compound I Clodinafop C-330 one individualized compound I Fenoxaprop C-331 one individualized compound I Fluazifop C-332 one individualized compound I Haloxyfop C-333 one individualized compound I Paraquat C-334 one individualized compound I Phenmedipham C-335 one individualized compound I Clethodim C-336 one individualized compound I Cycloxydim C-337 one individualized compound I Profoxydim C-338 one individualized compound I Sethoxydim C-339 one individualized compound I Tepraloxydim C-340 one individualized compound I Pendimethalin C-341 one individualized compound I Prodiamine C-342 one individualized compound I Trifluralin C-343 one individualized compound I Acifluorfen C-344 one individualized compound I Bromoxynil C-345 one individualized compound I Imazamethabenz C-346 one individualized compound I Imazamox C-347 one individualized compound I Imazapic C-348 one individualized compound I Imazapyr C-349 one individualized compound I Imazaquin C-350 one individualized compound I Imazethapyr C-351 one individualized compound I 2,4-Dichlorophenoxyacetic acid (2,4-D) C-352 one individualized compound I Chloridazon C-353 one individualized compound I Clopyralid C-354 one individualized compound I Fluroxypyr C-355 one individualized compound I Picloram C-356 one individualized compound I Picolinafen C-357 one individualized compound I Bensulfuron C-358 one individualized compound I Chlorimuron-ethyl C-359 one individualized compound I Cyclosulfamuron C-360 one individualized compound I lodosulfuron C-361 one individualized compound I Mesosulfuron C-362 one individualized compound I Metsulfuron-methyl C-363 one individualized compound I Nicosulfuron C-364 one individualized compound I Rimsulfuron C-365 one individualized compound I Triflusulfuron C-366 one individualized compound I Atrazine C-367 one individualized compound I Hexazinone C-368 one individualized compound I Diuron C-369 one individualized compound I Florasulam C-370 one individualized compound I Pyroxasulfone C-371 one individualized compound I Bentazone C-372 one individualized compound I Cinidon-ethyl C-373 one individualized compound I Cinmethylin C-374 one individualized compound I Dicamba C-375 one individualized compound I Diflufenzopyr C-376 one individualized compound I Quinclorac C-377 one individualized compound I Quinmerac C-378 one individualized compound I Mesotrione C-379 one individualized compound I Saflufenacil C-380 one individualized compound I Topramezone C-381 one individualized compound I 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- hydro-12-hydroxy-4,6a,12b-trimethyl- 11-oxo-9-(3-pyridinyl)-2H,11H-naph- tho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester

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 IUPAC 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; U.S. Pat. No. 3,296,272; U.S. Pat. No. 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 11/028657, WO2012/168188, WO 2007/006670, PCT/EP2012/065650 and PCT/EP2012/065651).

The mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient by usual means, e.g. by the means given for the compositions of compounds I.

Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.

The mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is referred to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I, respectively.

I. Synthesis Examples

With appropriate modification of the starting materials, the procedures given in the synthesis examples below were used to obtain further compounds I. The compounds produced in this manner are listed in Table I below including corresponding physical data. 4-Chloro-6-ethyl-5-pyrimidinecarboxylic acid ethyl ester was synthesized according to a procedure given in U.S. Pat. No. 5,439,911 A. 4-Chloro-6-methyl-5-pyrimidinecarboxylic acid methyl ester was prepared as described in EP 606011 A1.

Example 1

Preparation of 2-(4-iodophenoxy)-4-(trifluoromethyl)pyridine

To a solution of 4-iodophenol (200 g, 910 mmol) in N,N-dimethylformamide (1 L) was slowly added sodium hydride (47 g, 1.2 mol). The reaction was stirred for 30 min at room temperature, then 2-chloro-4-trifluoromethylpyridine (165 g, 910 mmol) was added and the solution was stirred at 110° C. for 4 h and 12 h at room temperature. The reaction solution was poured into water and extracted with methyl tert-butylether (3×). The combined organic layers were washed successively with water, lithium chloride solution and 10% sodium hydroxide solution. The combined organic phases were then dried over sodium sulfate and the solvent was removed in vacuo to afford 91% (303 g, 830 mmol) yield of 2-(4-iodophenoxy)-4-(trifluoromethyl)pyridine.

Example 2

Preparation of 5-[4-[[4-(trifluoromethyl)-2-pyridyl]oxy]phenyl]pent-4-yn-2-amine

To a solution of 2-(4-iodophenoxy)-4-(trifluoromethyl)pyridine (102 g, 279 mmol) in tetrahydrofuran (500 mL) was added triethylamine (84 g, 838 mmol), copper(I) iodide (0.53 g, 3 mmol) and Pd(PPh3)2Cl2 (2 g, 3 mmol), followed by pent-4-yn-2-ol (28 g, 335 mmol). The reaction was stirred at room temperature for 1 h and was then filtered over celite, followed by rinsing with methyl tert-butylether. Water and methyl tert-butylether were then added to the filtrate. The organic layer was separated and concentrated in vacuo to provide 93 g of crude 5-[4-[[4-(trifluoromethyl)-2-pyridyl]oxy]phenyl]pent-4-yn-2-ol. This material was redissolved in dichloromethane (1 L) and triethylamine (58 g, 576 mmol). The reaction solution was cooled to 5° C. and methyanesulfonyl chloride (42 g, 288 mmol) was added. The solution was allowed to warm to room temperature overnight. The reaction solution was poured into water and extracted with dichloromethane. The combined organic layers were dried over sodium sulfate and the solvent was then removed in vacuo to afford 121 g of the crude mesylate. The crude product was redissolved in N,N-dimethylformamide (600 mL) to which sodium azide was added (94 g, 1.4 mol). The reaction solution was heated to 80° C. for 2 h then cooled to room temperature. Water and methyl tert-butylether were added, the organic layers were combined and concentrated in vacuo to provide 91 g of the crude azide product. The azide was dissolved in methanol (700 mL) to which was added tin(II) chloride-H2O (118 g, 523 mmol). The reaction was stirred at room temperature overnight and was then concentrated. To the residue was added 10% sodium hydroxide solution and the crude product was extracted with dichloromethane before it was dried over sodium sulfate and concentrated in vacuo. The residue was filtered over a silica gel plug to provide 96% of the desired product.

Example 3

Preparation of 6-chloro-5-methoxy-N-[1-methyl-4-[4-[[4-(trifluoromethyl)-2-pyridyl]oxy]phenyl]but-3-ynyl]pyrimidin-4-amine (I-27)

To a solution of 5-[4-[[4-(trifluoromethyl)-2-pyridyl]oxy]phenyl]pent-4-yn-2-amine (268 mg, 0.84 mmol) in N,N-dimethylformamide (5 mL) was added diisopropylethylamine (216 mg, 1.7 mmol). The solution was stirred for 5 min at room temperature at which time 4,6-dichloro-5-methoxypyrimidine (150 mg, 0.84 mmol) was added. The reaction mixture was stirred at 80° C. overnight, then allowed to cool to room temperature. It was concentrated in vacuo and filtered over a plug of silica gel to provide 215 mg (0.47 mmol, 55%) of the brown oily product.

The compounds listed in Table I have been prepared in an analogous manner.

TABLE I Compounds I-1 to I-82 of formula I as defined herein and wherein R, R1 and R2 in each case are hydrogen. Pos. HPLC Rt m.p. Ex. no Ra2 Ra5 Ra6 Het O-Het X (Rb)n (min) (° C.) I-1 H Cl Cl H-1 p- —CH2 n = 0 4.327 127 I-2 H Cl Me H-1 p- —CH2 n = 0 3.196 135 I-3 H Cl Et H-1 p- —CH2 n = 0 3.301 81 I-4 H Cl Me H-1 p- —CH(CH3)— n = 0 1.126 92 I-5 H Cl Et H-1 p- —CH(CH3)— n = 0 1.177 I-6 H Cl Cl H-1 p- —CH(CH3)— n = 0 1.504 I-7 H #5—CF═CCl—CH═CF—#6 H-1 p- —CH2 n = 0 1.263 160 I-8 H #5—CF═CH—CH═CF—#6 H-1 p- —CH2 n = 0 1.122 157 I-9 H #5—CF═CH—CH═CF—#6 H-1 p- —CH(CH3)— n = 0 1.181 147 I-10 H #5—CF═CF—CH═CF—#6 H-1 p- —CH(CH3)— n = 0 1.318 144 I-11 H Cl CHFCH3 H-1 p- —CH2 n = 0 1.28 79 I-12 H Cl CHFCH3 H-1 p- —CH(CH3)— n = 0 3.915 I-13 H #5—N(CH3)—N═CH—#6 H-1 p- —CH(CH3)— n = 0 1.07 205 I-14 H #5—CH═CH—CH═CF—#6 H-1 p- —CH(CH3)— n = 0 1.084 126 I-15 H #5—C(CH3)═CH—CH═CH—#6 H-1 p- —CH(CH3)— n = 0 1.107 I-16 H Me Cl H-1 p- —CH(CH3)— n = 0 1.381 I-17 Me Cl Me H-1 p- —CH(CH3)— n = 0 1.082 I-18 H #5—N═CH—S—#6 H-1 p- —CH2 n = 0 1.239 155 I-19 H #5—N═CH—S—#6 H-1 p- —CH(CH3)— n = 0 1.299 I-20 H OMe H H-1 p- —CH(CH3)— n = 0 1.034 I-21 Me Cl Cl H-1 p- —CH(CH3)— n = 0 1.519 I-22 H Cl COOMe H-1 p- —CH(CH3)— n = 0 1.36 109 I-23 H Cl CHFCH3 H-1 p- —CH(CH3)— o-F; n = 1 1.36 I-24 H Cl Cl H-1 p- —CH(CH3)— o-F; n = 1 1.48 I-25 H Cl CHFCH3 H-1 p- —CH2 o-F; n = 1 1.29 I-26 H Cl Cl H-1 p- —CH2 o-F; n = 1 1.41 I-27 H OMe Cl H-1 p- —CH(CH3)— n = 0 1.387 I-28 H #5—N═CH—S—#6 H-1 p- —CH2 o-F; n = 1 1.25 119 I-29 H #5—N(CH2CH3)—N═CH—#6 H-1 p- —CH2 n = 0 1.036 I-30 H F Cl 5-trifluoromethyl-pyridin-3-yl p- —CH(CH3)— n = 0 1.423 112 I-31 Cl Cl Cl H-1 p- —CH(CH3)— n = 0 1.523 I-32 H COOEt Et H-1 p- —CH(CH3)— n = 0 1.193 91 I-33 H #5—N═CH—CH═CH—#6 H-1 p- —CH2 n = 0 1.025 124 I-34 H #5—N═CH—CH═CH—#6 H-1 p- —CH(CH3)— n = 0 1.065 I-35 H OMe COOMe H-1 p- —CH(CH3)— n = 0 1.173 I-36 H COOMe Me H-1 p- —CH(CH3)— n = 0 1.135 I-37 H Br Cl H-1 p- —CH(CH3)— n = 0 1.503 I-38 OMe F H H-1 p- —CH(CH3)— n = 0 1.143 I-39 H Et COOMe H-1 p- —CH(CH3)— n = 0 1.127 I-40 H Br F H-1 p- —CH(CH3)— n = 0 1.473 I-41 H Br OH H-1 p- —CH(CH3)— n = 0 1.245 I-42 H #5—CF═CH—CH═CF—#6 H-4 p- —CH(CH3)— n = 0 1.193 I-43 H #5—CF═CH—CH═CF—#6 H-2 p- —CH(CH3)— n = 0 1.174 I-44 H #5—CF═CH—CH═CF—#6 H-3 p- —CH(CH3)— n = 0 1.186 97 I-45 Me Me Cl H-1 p- —CH(CH3)— n = 0 1.307 113 I-46 H F F H-1 p- —CH(CH3)— n = 0 1.393 I-47 H Cl CHFCH3 H-2 p- —CH(CH3)— n = 0 1.297 I-48 H Cl CHFCH3 H-3 p- —CH(CH3)— n = 0 1.329 I-49 H Cl CHFCH3 H-4 p- —CH(CH3)— n = 0 1.314 I-50 H Cl CHFCH3 3,5-dichloro-pyridin-2-yl p- —CH(CH3)— n = 0 1.39 I-51 H Cl Cl H-2 p- —CH(CH3)— n = 0 1.419 I-52 H Cl Cl H-3 p- —CH(CH3)— n = 0 1.447 I-53 H Cl Cl H-4 p- —CH(CH3)— n = 0 1.434 I-54 H Cl Cl 3,5-dichloro-pyridin-2-yl p- —CH(CH3)— n = 0 1.519 I-55 H Me Cl H-2 p- —CH(CH3)— n = 0 1.321 I-56 H Me Cl H-3 p- —CH(CH3)— n = 0 1.35 I-57 H Me Cl H-4 p- —CH(CH3)— n = 0 1.344 I-58 H OMe Cl H-2 p- —CH(CH3)— n = 0 1.336 I-59 H OMe Cl H-3 p- —CH(CH3)— n = 0 1.361 I-60 H OMe Cl H-4 p- —CH(CH3)— n = 0 1.358 I-61 H OMe Cl 3,5-dichloro-pyridin-2-yl p- —CH(CH3)— n = 0 1.434 I-62 Cl Cl Me H-1 p- —CH(CH3)— n = 0 1.486 I-63 OMe Cl Me H-1 p- —CH(CH3)— n = 0 1.17 I-64 H CN Cl H-1 p- —CH(CH3)— n = 0 1.42 I-65 H Cl CHFCH3 H-16 p- —CH(CH3)— n = 0 1.299 I-66 H Me Cl H-16 p- —CH(CH3)— n = 0 1.324 I-67 H OMe Cl H-16 p- —CH(CH3)— n = 0 1.338 I-68 Me H Cl H-1 p- —CH(CH3)— n = 0 1.302 I-69 H Et Cl H-1 p- —CH(CH3)— n = 0 1.43 I-70 H OMe CH2OCH3 H-1 p- —CH(CH3)— n = 0 1.07 I-71 H #5—CF═CH—CH═CF—#6 H-16 p- —CH(CH3)— n = 0 1.16 97 I-72 H #5—N═N—S—#6 H-1 p- —CH(CH3)— n = 0 1.372 116 I-73 H CN Me H-1 p- —CH(CH3)— n = 0 1.247 I-74 H #5—CF═CH—CH═CF—#6 3,5-dichloro-pyridin-2-yl p- —CH(CH3)— n = 0 1.242 97 I-75 H Cl Cl H-2 m- —CH(CH3)— n = 0 1.427 I-76 OMe H Cl H-1 p- —CH(CH3)— n = 0 1.372 I-77 H Cl CHFCH3 H-2 p- —CH(CH3)— n = 0 1.270 I-78 H Cl Cl H-16 p- —CH(CH3)— n = 0 1.428 I-79 H CH═CH2 Cl H-1 p- —CH(CH3)— n = 0 1.460 I-80 H Me Cl H-30 p- —CH(CH3)— n = 0 1.351 I-81 H OMe Cl H-28 p- —CH(CH3)— n = 0 1.308 I-82 H Me COOMe 4-carboxymethyl-5-methyl- p- —CH(CH3)— n = 0 0.976 122 pyrimidin-6-yl * The position of Rb or the group —O-Het on the phenyl ring is defined relative to the alkyne-moiety bound to the phenyl ring as being in ortho (o-), para (p-) or meta (m-) position; n = 0 indicates that no substituent Rb is present on the phenyl ring. m.p. = melting point (° C.); in cases where Ra5 and Ra6 together with two ring member carbon atoms of the pyrimidine ring constitute a fused ring system #5 and #6 indicate the point of attachment to the pyrimidine ring, each respectively corresponding to the positions of either substituent Ra5 or Ra6. HPLC: HPLC-column Kinetex XB C18 1.7μ (50 × 2.1 mm); eluent: acetonitrile/water + 0.1% TFA (gradient from 5:95 to 100:0 in 1.5 min at 60° C., flow gradient from 0.8 to 1.0 ml/min in 1.5 min). MS: Quadrupol Electrospray Ionisation, 80 V (positive mode).

II. Biological Examples for Fungicidal Activity

The fungicidal action of the compounds I was demonstrated by the following experiments:

A. Glass House Trials

The spray solutions were prepared in several steps: The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml.

This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.

After the final cultivation period, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

Use Example 1

Control of Late Blight on Tomatoes Caused by Phytophthora infestans

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. After 6 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 250 ppm of the active compound I-5, I-11, I-14, I-20, I-23, I-27, I-31, I-34, I-35, I-37, I-44, I-47, I-48, I-50, I-56, I-59, I-65, I-66, I-67, I-70, I-71, I-79, I-81 or I-82 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 84% diseased leaf area.

Use Example 2

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%. After 4 weeks 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 250 ppm of the active compound I-1, I-3, I-4, I-5, I-7, I-8, I-9, I-10, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-25, I-26, I-27, I-28, I-29, I-30, I-31, I-32, I-33, I-34, I-35, I-36, I-37, I-38, I-40, I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-49, I-50, I-51, I-52, I-53, I-54, I-55, I-56, I-57, I-58, I-59, I-60, I-61, I-62, I-63, I- 64, I-69, I-72, I-74, I-75 or I-76 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 92% diseased leaf area.

Use Example 3

Preventative Control of Brown Rust on Wheat Caused by Puccinia recondita

The first two developed leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The next day the plants were inoculated with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to 24° C. for 24 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%. 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 250 ppm of the active compound I-1, I-3, I-4, I-5, I-6, I-8, I-9, I-11, I-12, I-13, I-14, I-15, I-17, I-19, I-20, I-21, I-23, I-24, I-25, I-26, I-27, I-28, I-29, I-34, I-45, I-46, I-47, I-48, I-49, I-50, I-51, I-52, I-54, I-56, I-57, I-58, I-59, I-60, I-62, I-64, I-69 or I-73 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 86% diseased leaf area.

Use Example 4

Protective Control of Soy Bean Rust on Soy Beans Caused by Phakopsora pachyrhizi

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 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 extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

In this test, the plants which had been treated with 250 ppm of the active compound I-2, I-4, I-9, I-10, I-18, I-20, I-22, I-27, I-29, I-30, I-31, I-31, I-33, I-36, I-37, I-39, I-42, I-43, I-46, I-48, I-49, I-50, I-51, I-52, I-55, I-56, I-58, I-59, I-62, I-64, I-65, I-66, I-67, I-68, I-69, I-71, I-73, I-77, I-80 or I-82 showed a diseased leaf area of at most 15%, whereas the untreated plants showed 94% diseased leaf area.

Use Example 5

Preventative Fungicidal Control of Botrytis cinerea on Leaves of Green Pepper

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 a aqueous biomalt solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber and kept for 5 days at 22 to 24° C. and a relative humidity close to 100%.

In this test, the plants which had been treated with 250 ppm of the active compound I-2, I-18, I-22, I-27, I-29, I-33, I-35, I-36, I-39, I-41, I-42, I-43, I-60 or I-74 showed a diseased leaf area of at most 15%, whereas the untreated plants showed 95% diseased leaf area.

Use Example 6

Control of Late Blight on Tomatoes Caused by Phytophthora infestans

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. After seven days 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%.

In this test, the plants which had been treated with 250 ppm of the active compound I-27, I-29, I-35, I-37, I-44, I-45, I-47, I-48, I-49, I-50, I-56, I-59, I-65, I-66, I-67, I-70 or I-78 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 67% diseased leaf area.

Claims

1. A compound of formula I
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wherein:
Ra2, Ra5, Ra6 independently of each other are hydrogen, halogen, CN, NO2, OH, SH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyloxy, C3-C8-cycloalkyl-C1-C4-alkyl, NRARB, C(═O)R′, C(═NOR″)R′″ or —C(═NH)—O—R′″;
RA, RB independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, phenyl, benzyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl or —(C═O)—R′;
R′ is hydrogen, OH, NH2, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylamino or di(C1-C4-alkyl)amino;
R″ is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl or C1-C4-alkoxy-C1-C4-alkyl;
R′″ is hydrogen or C1-C4-alkyl;
R is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, CN, CH2CN, NRARB or CH2—O—C(═O)R′;
R1, R2 independently of each other are hydrogen, halogen, CN, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-halo-alkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, C3-C8-cycloalkyloxy, NRARB, C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, (C1-C4-alkoxy)carbonyl and di(C1-C4-alkyl)aminocarbonyl;
or two radicals R1 and R2 that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated
3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from the group consisting of halogen, CN, OH, SH, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio; and one or two CH2 groups of the abovementioned cycles may respectively be replaced by one or two C(═O) or C(═S) groups;
X is a divalent group selected from the group consisting of —CR3R4—, —C(═O)—, —C(═S)—, —C(═NRD)— and —C(═NORD)—, wherein
RD is hydrogen or C1-C4-alkyl, and wherein
R3, R4 independently of each other are hydrogen, CN, C1-C4-hydroxyalkyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, C3-C8-cycloalkyloxy, NRARB, C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, (C1-C4-alkoxy)carbonyl and di(C1-C4-alkyl)aminocarbonyl, or
two radicals R3 and R4 that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from the group consisting of halogen, CN, OH, SH, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio; and one or two CH2 groups of the abovementioned cycles may be respectively replaced by one or two C(═O) or C(═S) groups;
n indicates the number of substituents Rb on the phenyl ring and n is 0, 1, 2, 3 or 4;
Rb is halogen, CN, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, NRARB, C(═O)R′, C(═NOR″)R′″ or —C(═NH)—O—R′″,
it being possible for n=2, 3 or 4 that Rb are identical or different;
Het is a 5- or 6-membered 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 and wherein the heteroaryl is unsubstituted or carries 1, 2, 3 or 4 identical or different groups Rc:
Rc is halogen, CN, NO2, NH2, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylamino, di(C1-C6-alkyl)amino, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C1-C6-alkoxy-C1-C4-alkyl, C1-C6-haloalkoxy-C1-C4-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C(═O)R′, C(═NOR″)R′″, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenoxy, phenoxy-C1-C4-alkyl or a 5- or 6-membered 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, and wherein the aforementioned cyclic radicals are unsubstituted or carry 1, 2, 3 or 4 identical or different substituents Rd:
Rd is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
or two radicals Rc that are bound to adjacent ring member atoms of the Het group form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals groups Re:
Re is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
or an N-oxide or an agriculturally acceptable salt of the compounds of formula I.
wherein:
Ra2, Ra5, Ra6 independently of each other are hydrogen, halogen, CN, NO2, OH, SH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyloxy, C3-C8-cycloalkyl-C1-C4-alkyl, NRARB, C(═O)R′, C(═NOR″)R′″ or —C(═NH)—O—R′″;
RA, RB independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, phenyl, benzyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl or —(C═O)—R′;
R′ is hydrogen, OH, NH2, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylamino or di(C1-C4-alkyl)amino;
R″ is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl or C1-C4-alkoxy-C1-C4-alkyl;
R′″ is hydrogen or C1-C4-alkyl;
R is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, CN, CH2CN, NRARB or CH2—O—C(═O)R′;
R1, R2 independently of each other are hydrogen, halogen, CN, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-halo-alkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, C3-C8-cycloalkyloxy, NRARB, C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, (C1-C4-alkoxy)carbonyl and di(C1-C4-alkyl)aminocarbonyl;
or two radicals R1 and R2 that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated
3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from the group consisting of halogen, CN, OH, SH, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio; and one or two CH2 groups of the abovementioned cycles may respectively be replaced by one or two C(═O) or C(═S) groups;
X is a divalent group selected from the group consisting of —CR3R4—, —C(═O)—, —C(═S)—, —C(═NRD)— and —C(═NORD)—, wherein
RD is hydrogen or C1-C4-alkyl, and wherein
R3, R4 independently of each other are hydrogen, CN, C1-C4-hydroxyalkyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, C3-C8-cycloalkyloxy, NRARB, C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, (C1-C4-alkoxy)carbonyl and di(C1-C4-alkyl)aminocarbonyl, or
two radicals R3 and R4 that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from the group consisting of halogen, CN, OH, SH, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio; and one or two CH2 groups of the abovementioned cycles may be respectively replaced by one or two C(═O) or C(═S) groups;
n indicates the number of substituents Rb on the phenyl ring and n is 0, 1, 2, 3 or 4;
Rb is halogen, CN, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, NRARB, C(═O)R′, C(═NOR″)R′″ or —C(═NH)—O—R′″,
it being possible for n=2, 3 or 4 that Rb are identical or different;
Het is a 5- or 6-membered 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 and wherein the heteroaryl is unsubstituted or carries 1, 2, 3 or 4 identical or different groups Rc:
Rc is halogen, CN, NO2, NH2, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylamino, di(C1-C6-alkyl)amino, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C1-C6-alkoxy-C1-C4-alkyl, C1-C6-haloalkoxy-C1-C4-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C(═O)R′, C(═NOR″)R′″, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenoxy, phenoxy-C1-C4-alkyl or a 5- or 6-membered 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, and wherein the aforementioned cyclic radicals are unsubstituted or carry 1, 2, 3 or 4 identical or different substituents Rd:
Rd is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
or two radicals Rc that are bound to adjacent ring member atoms of the Het group form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals groups Re:
Re is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
or an N-oxide or an agriculturally acceptable salt of the compounds of formula I.
RA, RB independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, phenyl, benzyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl or —(C═O)—R′;
R′ is hydrogen, OH, NH2, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylamino or di(C1-C4-alkyl)amino;
R″ is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl or C1-C4-alkoxy-C1-C4-alkyl;
R′″ is hydrogen or C1-C4-alkyl;
3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from the group consisting of halogen, CN, OH, SH, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio; and one or two CH2 groups of the abovementioned cycles may respectively be replaced by one or two C(═O) or C(═S) groups;
RD is hydrogen or C1-C4-alkyl, and wherein
R3, R4 independently of each other are hydrogen, CN, C1-C4-hydroxyalkyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, C3-C8-cycloalkyloxy, NRARB, C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, (C1-C4-alkoxy)carbonyl and di(C1-C4-alkyl)aminocarbonyl, or
two radicals R3 and R4 that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from the group consisting of halogen, CN, OH, SH, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio; and one or two CH2 groups of the abovementioned cycles may be respectively replaced by one or two C(═O) or C(═S) groups;
it being possible for n=2, 3 or 4 that Rb are identical or different;
Rc is halogen, CN, NO2, NH2, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylamino, di(C1-C6-alkyl)amino, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C1-C6-alkoxy-C1-C4-alkyl, C1-C6-haloalkoxy-C1-C4-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C(═O)R′, C(═NOR″)R′″, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenoxy, phenoxy-C1-C4-alkyl or a 5- or 6-membered 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, and wherein the aforementioned cyclic radicals are unsubstituted or carry 1, 2, 3 or 4 identical or different substituents Rd:
Rd is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
or two radicals Rc that are bound to adjacent ring member atoms of the Het group form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals groups Re:
Re is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
Rd is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
Re is halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
2. A The compound according to claim 1, wherein Ra2, Ra5 and Ra6 independently of each other are halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy or (C1-C4-alkoxy)carbonyl, and it being possible that one or two of Ra2, Ra5 or Ra6 can in addition be hydrogen.
3. The compound according to claim 1, wherein X is —CH2—, —C(═O)—, —CH(CH3), —C(CH3)2—, —CHCN—, —CH(C(═O)—OCH3), or CH(C(═O)—OCH2CH3).
4. The compound according to claim 1, wherein X is —CH2—.
5. The compound according to claim 1, wherein X is —C(═O)—.
6. The compound according to claim 1, wherein Het is pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, or 1,2,4-triazin-3-yl.
7. The compound according to claim 1, wherein Het carries 1 or 2 radicals Rc which are selected from the group consisting of F, Cl, Br, CN, C1-C2-alkylsulfonyl, C1-C2-alkoxycarbonyl, aminocarbonyl, C1-C2-alkylaminocarbonyl, di(C1-C2-alkyl)aminocarbonyl, C1-C2-alkoxy, CF3, CHF2, OCF3 and OCHF2.
8. A process for preparing the compound of claim 1, wherein X is —CR3R4— or —C(═O)—, which comprises reacting a compound of formula II
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wherein Ra2, Ra5 and Ra6 are as defined in claim 1, Hal is fluorine, chlorine or bromine, with a compound of formula III
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wherein R, R1, R2, Rb, n and Het are as defined in claim 1 and X is —CR3R4— or —C(═O)— as defined in claim 1 in the presence of a base or a catalyst or a combination of a base and a catalyst in a solvent.
wherein Ra2, Ra5 and Ra6 are as defined in claim 1, Hal is fluorine, chlorine or bromine, with a compound of formula III
wherein R, R1, R2, Rb, n and Het are as defined in claim 1 and X is —CR3R4— or —C(═O)— as defined in claim 1 in the presence of a base or a catalyst or a combination of a base and a catalyst in a solvent.
9. An agrochemical composition which comprises an auxiliary and at least one compound of claim 1.
10. The agrochemical composition according to claim 9 comprising at least one further active substance.
11. A method for combating phytopathogenic 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 claim 1.
12. Seed treated with a compound of claim 1, in an amount of from 0.1 g to 10 kg per 100 kg of seed.
13. The method of claim 11, wherein, in the compound of formula (I), Ra2, Ra5 and Ra6 independently of each other are halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy or (C1-C4-alkoxy)carbonyl, and it being possible that one or two of Ra2, Ra5 or Ra6 can in addition be hydrogen.
14. The method of claim 11, wherein, in the compound of formula (I), X is —CH2—, —C(═O)—, —CH(CH3), —C(CH3)2—, —CHCN—, —CH(C(═O)—OCH3), or —CH(C(═O)—OCH2CH3).
15. The method of claim 11, wherein, in the compound of formula (I), X is —CH2—.
16. The method of claim 11, wherein, in the compound of formula (I), X is —C(═O)—.
17. The method of claim 11, wherein, in the compound of formula (I), Het is pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, or 1,2,4-triazin-3-yl.
18. The method of claim 11, wherein, in the compound of formula (I), Het carries 1 or 2 radicals Rc which are selected from the group consisting of F, Cl, Br, CN, C1-C2-alkylsulfonyl, C1-C2-alkoxycarbonyl, aminocarbonyl, C1-C2-alkylaminocarbonyl, di(C1-C2-alkyl)aminocarbonyl, C1-C2-alkoxy, CF3, CHF2, OCF3 and OCHF2.