# Patent

## Title
Fungicidal pyrimidine compounds

## 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.

## Background
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




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.




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 (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(diphenylphosphanyl)-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 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.




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.




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.




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.




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.




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-methylpropoxy, 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-bromoethoxy, 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







 



H-2







 



H-3







 



H-4







 



H-5







 



H-6







 



H-7







 



H-8







 



H-9







 



H-10







 



H-11







 



H-12







 



H-13







 



H-14







 



H-15







 



H-16







 



H-17







 



H-18







 



H-19







 



H-20







 



H-21







 



H-22







 



H-23







 



H-24







 



H-25







 



H-26







 



H-27







 



H-28







 



H-29







 



H-30







 



H-31







 



H-32







 



H-33







 



H-34







 



H-35







 



H-36







 



H-37







 



H-38











in which # indicates the point of attachment.






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




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



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.

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



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.