# Patent

## Title
2-Substituted pyrimidines

## Abstract

The invention relates to 2-substituted pyrimidines of the formula I




in which the index n and these substituents R1, R2 and R3 are as defined in the description and R4 is as defined below:

    
    
        R4 corresponds to one of the formulae
    
    






where

    
    
        Ra is hydrogen, C1-C6-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C6-cycloalkyl or C1-C4-alkoxy and
        R5 is hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C4-alkyloxy-C1-C2-alkyl, phenyl-C1-C2-alkyl or phenyloxy-C1-C2-alkyl,

to processes for preparing these compounds, to compositions comprising these compounds and to their use as pesticides.

## Background
The invention relates to 2-substituted pyrimidines of the formula I




in which the index and the substituents are as defined below:

    n is an integer from 1 to 5;
    L is halogen, cyano, cyanato (OCN), C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C6-alkoxy, C2-C8-alkenyloxy, C2-C8-alkynyloxy, C3-C6-cycloalkyl, C4-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C4-C6-cycloalkenyloxy, nitro, —C(═O)-A, —C(═O)—O-A, -C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A, N(A′)-C(═O)-A, N(A′′)—C(═O)—N(A′)A, S(═O)m-A, S(═O)m—O-A or S(═O)m—N(A′)A,
    
        m is 0, 1 or 2;
        A, A′, A′′ independently of one another are hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl, phenyl, where the organic radicals may be partially or fully halogenated or may be substituted by nitro, cyanato, cyano or C1-C4-alkoxy; or A and A′ together with the atoms to which they are attached are a five- or six-membered saturated, partially unsaturated or aromatic hetero cycle which contains one to four heteroatoms from the group consisting of O, N and S;
        where the aliphatic groups of the radical definitions of L for their part may be partially or fully halogenated or may carry one to four groups Ru:
        Ru is cyano, C1-C6-alkoxy, C3-C6cycloalkyl, C2-C8-alkenyloxy, C2-C8-alkynyloxy, C4-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C4-C6-cycloalkenyloxy, —C(═O)-A, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A, N(A′)-C(═O)-A, N(A′′)-C(═O)—N(A′)A, S(═O)m-A,
        R1, R2 independently of one another are C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, where the aliphatic groups of the radical definitions of R1 and R2 may for their part be partially or fully halogenated or may carry one to four groups Rv:
        
            Rv is cyano, C3-C6-cycloalkyl, C4-C6-cycloalkenyl, hydroxyl, C1-C6-alkoxy, C2-C8-alkenyloxy, C2-C8-alkynyloxy, C3-C6-cycloalkyloxy, C4-C6-cycloalkenyloxy, C1-C6-alkylthio, —C(═O)-A, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A, N(A′)-C(═O)-A, N(A′′)-C(═O)—N(A′)A, S(═O)m-A, S(═O)m—O-A or S(═O)m—N(A′)A or phenyl, where the phenyl moiety may carry one to three radicals selected from the group consisting of halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, cyano, nitro, —C(═O)-A, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A;
        
        
        R2 may additionally be hydrogen;
        R1 and R2 may also, together with the nitrogen atom to which they are attached, form a saturated or unsaturated five- or six-membered ring which may be interrupted by an ether (—O—), carbonyl (C═O—), thio (—S—), sulfoxyl (—S[═O]—) or sulfenyl (—SO2—) or a further amino —(—N(Ra)— group where Ra is hydrogen or C1-C6-alkyl and/or may contain one or more substituents from the group consisting of halogen, C1-C6-alkyl, C1-C6-haloalkyl and oxy-C1-C3-alkylenoxy;
        R3 is halogen, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6cycloalkyl, C1-C4-alkoxy, C3-C4-alkenyloxy, C3-C4-alkynyloxy, C1C6-alkylthio, di-(C1-C6-alkyl)amino or C1-C6-alkylamino, where the alkyl, alkenyl and alkynyl radicals of R3 may be substituted by halogen, cyano, nitro, C1-C2-alkoxy or C1-C4-alkoxycarbonyl;
        R4 corresponds to one of the formulae
    
    






    
    
        
        
            where
            X is a direct bond, —(C═O)—, —(C═O)—NH, —(C═O)—O—, —O—, —NRc—, where the molecule moiety to the left in each case is attached to the nitrogen atom;
            Ra is hydrogen, methyl, benzyl, trofluoromethyl, allyl, propargyl or methoxymethyl;
            Rb is hydrogen, C1-C6-alkyl, C2-C6-alkynyl;
            Rc is hydrogen, methyl or C1-C4acyl and
            Z is S or NRb;
        
        
        where the aliphatic groups of the radical definitions of Ra, Rb and/or Rc for their part may carry one or two groups Rw:
        Rw is halogen, ORx, NHRx, C1-C6-alkyl, C1-C4-alkoxycarbonyl, C1-C4-acylamino, [1,3]dioxolane-C1-C4-alkyl, [1,3]dioxane-C1-C4-alkyl, where
        Rx is hydrogen, methyl, allyl or propargyl.
    
    


Moreover, the invention relates to a process for preparing these compounds, to compositions comprising them and to their use for controlling phytopathogenic harmful fungi.
Fungicidal pyrimidines carrying a cyanamino substituent in the 2-position are known from WO-A 01/96314. Furthermore, fungicidal pyrimidines carrying, inter alia, an amide radical in the 2-position are known from WO-A 03/43993.
However, in many cases the activity of the abovementioned pyrimidines is unsatisfactory.
It is an object of the present invention to provide compounds having improved activity.
We have found that this object is achieved by the pyrimidines of the formula I defined at the outset. Moreover, we have found processes for their preparation and compositions comprising them for controlling harmful fungi.
The compounds I can be obtained by different routes.
It is possible, for example, to use sulfones of the formula II whose preparation is described in detail in WO-A 02/074753 or DE 10156279.9 and where R′ is an unsubstituted or substituted C1-C6-alkyl radical or an unsubstituted or substituted phenyl radical as starting materials. Reaction of the sulfones II with metal cyanides III (Me+CN−) yields the nitrites IV. Metal cyanides are to be understood as meaning primarily alkali metal cyanides or alkaline earth metal cyanides or else covalent cyanides, such as tin tetracyanides.




The exchange of the sulfonate group for the nitrile group is carried out by methods known from the literature, as described, for example, in WO-A 03/043993.
The further synthesis can be carried out as shown in Scheme 1:




Using hydrogen sulfide, preferably under acidic conditions, the nitrile compound IV can be thiolyzed to give thioamide IA. The thiolysis is carried out under the conditions of the Pinner reaction (see Preparation Examples). Alkylation with Rb—X, where Rb is as defined above and X is a leaving group, such as halide, sulfate or sulfonate, affords compounds of type IB. A further alkylation step with Ra—X, where Ra is, for example, C1-C6-alkyl and X is a leaving group, such as halide, sulfate or sulfonate, yields compounds of type IC. The two alkylations mentioned above can also be carried out using Meerwein salts of the formula (Rb)3OBF4, analogously to the procedures given in Synth. Commun. 13, (1983), 753 or Helv. Chim. Acta 69, (1986), 1224.
Compounds IC′ according to the invention in which Ra is a C1-C6-alkoxy substituent can be obtained as shown in Scheme 2.




Starting with nitrile IV and using a C1-C6-alkoxyamine, the hydroxamic acid derivative V is obtained under acidic conditions. Conversion into the thione compound ID can be realized using, for example, phosphorus pentasulfide or Lawesson's reagent. Compounds IC according to the invention can be obtained by alkylation with Rb—X, where Rb is as defined above and X is a leaving group, such as halide, sulfonate or sulfate.
An alternative synthesis of the compounds IC′ and ID according to the invention is shown in Scheme 3.




In the synthesis, shown in Scheme 3, of compounds IC′ and ID, the starting material used is the ester of the formula VIII. Reaction of VIII with hydroxylamines to give hydroxamic acids V can be carried out as described in Org. Lett. 3 (2001), 1053-56 or in J. Org. Chem. 85 (2000), 8415-20. The subsequent sulfurization can be carried out analogously to Aust. J. Chem. 41 (1988), 37. The iminohalides of the formula IX where Hal is halogen and in particular chlorine and bromine can be obtained analogously to Synthesis 9 (1991), 750-752. In an Appel reaction using, for example, carbon tetrabromide and triphenylphosphine, the corresponding bromine compounds are prepared. The latter can finally be reacted with mercaptans of the formula RbSH and bases to give the compounds IC′ according to the invention.
The radical R3 (in particular alkyl) in the 6-position on the pyrimidine ring can be introduced by reaction with transition metal catalysis, such as Ni or Pd catalysis. In some cases it may be advisable to change the order and to introduce substituent R3 first and then substituent NR1R2.




In the formula (R3)y-wXw-My, M is a metal ion of valency Y, such as, for example, B, Zn, Mg, Cu or Sn, X chlorine, bromine, iodine or hydroxy, R3 is preferably C1-C4-alkyl and w is a number from 0 to 3. This reaction can be carried out, for example, analogously to the following methods: J. Chem. Soc., Perkin Trans. 1 (1994), 1187, ibid. 1 (1996), 2345; WO-A 99/41255; Aust. J. Chem. 43 (1990); 733; J. Org. Chem. 43 (1978), 358; J. Chem. Soc., Chem. Commun. (1979), 866; Tetrahedron Lett. 34 (1993), 8267; ibid. 33 (1992), 413. In the formulae mentioned above, R′ is in particular unsubstituted or substituted C1-C6-alkyl or unsubstituted or substituted phenyl.
Pyrimidines which carry a radical R4 in the 2-position:




where Ra is alkyl, alkenyl, alkynyl or cycloalkyl can also be prepared, for example, by the synthesis routes below.





As shown in Scheme 5, the nitriles IV described above can be reacted under acidic conditions with mercaptans RbSH, where Rb is as defined above (see Chem. Ber. 113 (1980), 1898). In a subsequent reaction with azides, it is possible to introduce the radical Ra—N, where Ra is as defined above (see Pol. J. Chem. 75 (2001), 975-82).




Scheme 6 shows an alternative synthesis route to the compounds IC according to the invention. Starting with the nitrites of the formula IV, the amides of the formula X are obtained in a modified Ritter reaction using alcohols of the formula Ra—OH and trifluoroacetic anhydride (see Tetrahedron Lett. 30 (1989), 581-82). The sulfurization with Lawesson's reagent can be carried out using the method described in J. Labelled Compd. Rad. 25 (1988), 335-343. The alkylation with Rb—X finally is carried out according to customary methods known from the literature, as described, for example, in Heterocycles 23 (1985), 2213-15.
What was said above refers in particular to the preparation of compounds in which R3 is an alkyl group. If R3 is a cyano group or an alkoxy substituent, the radical R3 can be introduced by reaction with alkali metal cyanides and alkali metal alkoxides, respectively.
In the definitions of the symbols given in the formulae above, collective terms were used which are generally representative for the following substituents:

    halogen: fluorine, chlorine, bromine and iodine;
    alkyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for example C1-C6-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
    haloalkyl: straight-chain or branched alkyl groups having 1 to 8 carbon atoms (as mentioned above), where in these groups some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example C1-C2-haloalkyl, such as 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, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;
    alkenyl: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 or 8 carbon atoms and a double bond in any position, for example C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
    alkadienyl: unsaturated straight-chain or branched hydrocarbon radicals having 4, 6 or 8 carbon atoms and two double bonds in any position;
    haloalkenyl: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position (as mentioned above), where in these groups some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular by fluorine, chlorine and bromine;
    alkynyl: straight-chain or branched hydrocarbon groups having 2 to 6 carbon atoms and a triple bond in any position, for example C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
    cycloalkyl: mono- or bicyclic saturated hydrocarbon groups having 3 to 6 carbon ring members, for example C3-C6-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;
    five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S:
    5- or 6-membered heterocyclyl which contains one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for example 2-tetrahydrofuryl, 3-tetrahydrofuryl, 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 -isothiazo -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;
    5-membered heteroaryl which contains one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5 -isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and 1,3,4-triazol-2-yl;
    6-membered heteroaryl which contains one to three or one to four nitrogen atoms: 6-membered heteroaryl groups which, in addition to carbon atoms, may contain one to three and one to four nitrogen atoms, respectively, as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.


The scope of the present invention includes the (R) and (S) isomers and the racemates of compounds of the formula I having chiral centers.
Hereinbelow, the embodiments of the invention are described in more detail.
With a view to the intended use of the pyrimidines of the formula I, particular preference is given to the following meanings of the substituents, in each case on their own or in combination:
Preference is given to compounds I in which R1 is C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl or C3-C6-cycloalkyl and R2 is hydrogen.
Especially preferred are compounds I in which R1 is C1-C6-alkyl, C2-C6-alkenyl or C1-C6-haloalkyl branched in the α-position.
In addition, preference is given to compounds I in which R1 is C1-C4-haloalkyl and R2 is hydrogen.
Moreover, preference is given to compounds I in which R1 and R2 together with the nitrogen to which they are attached form a five- or six-membered ring which may be interrupted by an oxygen atom and may carry one or two C1-C6-alkyl substituents.
Especially preferred are groups NR1R2 such as—in particular in the α-position—methylated pyrrolidines or piperidines. 4-Methylpiperidine is furthermore preferred.
Moreover, particular preference is given to pyrimidines I in which the index n and the substituents L1 to L5 are as defined below:

    n is 1 to 3;
    L is halogen, cyano, C1-C8-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C2-C10-alkenyloxy, C2-C10-alkynyloxy, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A, N(A′)-C(═O)-A or S(═O)m-A;
    
        m is 0, 1 or 2;
        A, A′, A′′ independently of one another are hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the organic radicals may be partially or fully halogenated or may be substituted by cyano or C1-C4-alkoxy, or A and A′ together with the atoms to which they are attached are a five- or six-membered saturated heterocycle which contains one to four heteroatoms from the group consisting of O, N and S.
    
    


Especially preferred are pyrimidines I where the substituents L1 to L5 are as defined below:

    L is halogen, cyano, C1-C8-alkyl, C1-C6-alkoxy, —C(═O)—O-A, —C(═O)—N(A′)A,
    
        A, A′, A′′ independently of one another are hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl.
    
    


Particular preference is given to compounds I in which Ru is halogen, cyano, C1-C8-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C2-C10-alkenyloxy, C2-C10-alkynyloxy, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), where the aliphatic or alicyclic groups for their part may be partially or fully halogenated.
Especially preferred are compounds I in which Ru is halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy.
Moreover, preference is given to pyrimidines I where the phenyl group substituted by Ln is the group B




where # is the point of attachment to the pyrimidine skeleton and

    
    
        L1 is fluorine, chlorine, CH3 or CF3;
        L2,L4 independently of one another are hydrogen, CH3 or fluorine;
        L3 is hydrogen, fluorine, chlorine, bromine, cyano, CH3, SCH3, OCH3, SO2CH3, CO—NH2, CO—NHCH3, CO—NHC2H5, CO—N(CH3)2, NH—C(═O)CH3, N(CH3)—C(═O)CH3 or COOCH3 and
        L5 is hydrogen, fluorine, chlorine or CH3.
    
    


Particular preference is also given to compounds I in which R3 is C1-C4-alkyl which may be substituted by halogen.
Moreover, particular preference is given to compounds I in which R3 is halogen, cyano, C1-C4-alkyl or C1-C4-alkoxy.
Especially preferred are compounds I in which R3 is methyl, cyano, methoxy or in particular chlorine.
Suitable with a view to their fungicidal action are pyrimidines of the formula I in which R4 is




Preference is furthermore given to pyrimidines of the formula I in which R4 is




Especially preferred are pyrimidines of the formula I in which R4 is




Finally, R4 may preferably have the following meanings, which may also be understood as prodrug radical definitions (see Medicinal Research Reviews 2003, 23, 763-793, or J. of Pharmaceutical Sciences 1997, 86, 765-767):




The index n in the alkenyl radicals of the above formulae is an integer from 1 to 3.
Particular preference is given to the radical definition R4:




The bridge member X is preferably a direct bond and —(C═O)—.
The substituent Ra is preferably hydrogen, methyl, allyl or propargyl and particularly preferably hydrogen.
The substituent Rb is preferably hydrogen, C1-C6-alkyl or C2-C6-alkenyl and with particular preference methyl, allyl or propargyl.
The substituent Rc is preferably hydrogen or methyl.




Table 1

Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,6-chloro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 2
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 3
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-dichloro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 4
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,6-methyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 5
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,6-trifluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 6
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-fluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 7
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methoxycarbonyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 8
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-CN, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 9
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,5-trifluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 10
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-dichloro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 11
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 12
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 13
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-difluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 14
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro, 4-chloro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 15
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro, 4-fluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 16
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,3-difluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 17
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-difluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 18
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,3,4-trifluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 19
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 20
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-dimethyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 21
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-chloro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 22
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 23
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-dimethyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 24
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,6-trimethyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 25
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-cyano, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 26
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 27
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methoxycarbonyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 28
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methoxy, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 29
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 30
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methoxycarbonyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 31
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-bromo, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 32
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-cyano, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 33
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methoxy, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 34
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,3-methyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 35
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-dimethyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 36
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-cyano, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 37
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-bromo, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 38
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,5-fluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 39
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-methoxy, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 40
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl, 4-methoxycarbonyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 41
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-dimethyl,4-bromo, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 42
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-bromo, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 43
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methoxy, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 44
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,5-methyl, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 45
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is pentafluoro, R3 is methyl and R1, R2 for each compound corresponds to one row of Table A
Table 46
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluor,6-chloro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 47
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 48
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-dichloro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 49
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,6-methyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 50
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,6-trifluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 51
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-fluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 52
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methoxycarbonyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 53
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-CN, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 54
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,5-trifluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 55
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-dichloro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 56
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 57
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 58
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-difluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 59
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-chloro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 60
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-fluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 61
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,3-difluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 62
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-difluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 63
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,3,4-trifluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 64
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 65
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-dimethyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 66
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-chloro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 67
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 68
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-dimethyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 69
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,6-trimethyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 70
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-cyano, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 71
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 72
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methoxycarbonyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 73
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methoxy, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 74
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 75
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methoxycarbonyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 76
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-bromo, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 77
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-cyano, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 78
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methoxy, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 79
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,3-methyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 80
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-dimethyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 81
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-cyano, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 82
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-bromo, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 83
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,5-fluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 84
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-methoxy, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 85
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-methoxycarbonyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 86
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-dimethyl,4-bromo, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 87
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-bromo, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 88
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methoxy, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 89
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,5-methyl, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 90
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is pentafluoro, R3 is chloro and R1, R2 for each compound corresponds to one row of Table A
Table 91
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,6-chloro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 92
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 93
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-dichloro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 94
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,6-methyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 95
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,6-trifluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 96
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-fluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 97
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methoxycarbonyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 98
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-CN, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 99
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,5-trifluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 100
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-dichloro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 101
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 102
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 103
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-difluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 104
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-chloro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 105
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-fluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 106
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,3-difluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 107
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-difluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 108
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,3,4-trifluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 109
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 110
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-dimethyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 111
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-chloro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 112
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 113
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-dimethyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 114
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If, in which Ln is 2,4,6-trimethyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 115
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-cyano, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 116
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 117
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methoxycarbonyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 118
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methoxy, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 119
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 120
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methoxycarbonyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 121
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methoxy, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 122
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-cyano, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 123
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methoxy, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 124
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,3-methyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 125
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-dimethyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 126
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-cyano, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 127
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-bromo, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 128
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,5-fluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 129
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-methoxy, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 130
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If, in which Ln is 2-methyl,4-methoxycarbonyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 131
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-dimethyl,4-bromo, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 132
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-bromo, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 133
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methoxy, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 134
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,5-methyl, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 135
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is pentafluoro, R3 is methoxy and R1, R2 for each compound corresponds to one row of Table A
Table 136
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,6-chloro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 137
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 138
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 139
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,6-methyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 140
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,6-trifluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 141
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-fluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 142
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methoxycarbonyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 143
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-CN, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 144
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,5-trifluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 145
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-dichloro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 146
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If, in which Ln is 2-chloro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 147
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 148
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-difluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 149
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-chloro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 150
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-fluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 151
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,3-difluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 152
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-difluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 153
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,3,4-trifluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 154
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 155
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4-dimethyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 156
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-chloro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 157
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 158
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-dimethyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 159
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,4,6-trimethyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 160
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-cyano, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 161
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 162
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methoxycarbonyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 163
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methoxy, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 164
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 165
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-methoxycarbonyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 166
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-bromo, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 167
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-chloro,4-cyano, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 168
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,6-difluoro,4-methoxy, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 169
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,3-methyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 170
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-dimethyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 171
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-cyano, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 172
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-bromo, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 173
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,5-fluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 174
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-methoxy, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 175
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-methyl,4-methoxycarbonyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 176
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2,5-dimethyl,4-bromo, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 177
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-bromo, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 178
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,4-methoxy, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 179
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is 2-fluoro,5-methyl, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A
Table 180
Compounds of the formulae Ia, Ib, Ic, Id, Ie and If in which Ln is pentafluoro, R3 is cyano and R1, R2 for each compound corresponds to one row of Table A











TABLE A







No.
R1
R2









A-1.
CH2CH3
H



A-2.
CH2CH3
CH3



A-3.
CH2CH3
CH2CH3



A-4.
CH2CH2CH3
H



A-5.
CH2CH2CH3
CH3



A-6.
CH2CH2CH3
CH2CH3



A-7.
CH2CH2CH3
CH2CH2CH3



A-8.
CH2CH2F
H



A-9.
CH2CH2F
CH3



A-10.
CH2CH2F
CH2CH3



A-11.
CH2CF3
H



A-12.
CH2CF3
CH3



A-13.
CH2CF3
CH2CH3



A-14.
CH2CF3
CH2CH2CH3



A-15.
CH2CCl3
H



A-16.
CH2CCl3
CH3



A-17.
CH2CCl3
CH2CH3



A-18.
CH2CCl3
CH2CH2CH3



A-19.
CH(CH3)2
H



A-20.
CH(CH3)2
CH3



A-21.
CH(CH3)2
CH2CH3



A-22.
CH(CH3)2
CH2CH2CH3



A-23.
CH2C(CH3)3
H



A-24.
CH2C(CH3)3
CH3



A-25.
CH2C(CH3)3
CH2CH3



A-26.
CH2CH(CH3)2
H



A-27.
CH2CH(CH3)2
CH3



A-28.
CH2CH(CH3)2
CH2CH3



A-29.
(±) CH(CH2CH3)CH3
H



A-30.
(±) CH(CH2CH3)CH3
CH3



A-31.
(±) CH(CH2CH3)CH3
CH2CH3



A-32.
(R) CH(CH2CH3)CH3
H



A-33.
(R) CH(CH2CH3)CH3
CH3



A-34.
(R) CH(CH2CH3)CH3
CH2CH3



A-35.
(S) CH(CH2CH3)CH3
H



A-36.
(S) CH(CH2CH3)CH3
CH3



A-37.
(S) CH(CH2CH3)CH3
CH2CH3



A-38.
(±) CH(CH3)—CH(CH3)2
H



A-39.
(±) CH(CH3)—CH(CH3)2
CH3



A-40.
(±) CH(CH3)—CH(CH3)2
CH2CH3



A-41.
(R) CH(CH3)—CH(CH3)2
H



A-42.
(R) CH(CH3)—CH(CH3)2
CH3



A-43.
(R) CH(CH3)—CH(CH3)2
CH2CH3



A-44.
(S) CH(CH3)—CH(CH3)2
H



A-45.
(S) CH(CH3)—CH(CH3)2
CH3



A-46.
(S) CH(CH3)—CH(CH3)2
CH2CH3



A-47.
(±) CH(CH3)—C(CH3)3
H



A-48.
(±) CH(CH3)—C(CH3)3
CH3



A-49.
(±) CH(CH3)—C(CH3)3
CH2CH3



A-50.
(R) CH(CH3)—C(CH3)3
H



A-51.
(R) CH(CH3)—C(CH3)3
CH3



A-52.
(R) CH(CH3)—C(CH3)3
CH2CH3



A-53.
(S) CH(CH3)—C(CH3)3
H



A-54.
(S) CH(CH3)—C(CH3)3
CH3



A-55.
(S) CH(CH3)—C(CH3)3
CH2CH3



A-56.
(±) CH(CH3)—CF3
H



A-57.
(±) CH(CH3)—CF3
CH3



A-58.
(±) CH(CH3)—CF3
CH2CH3



A-59.
(R) CH(CH3)—CF3
H



A-60.
(R) CH(CH3)—CF3
CH3



A-61.
(R) CH(CH3)—CF3
CH2CH3



A-62.
(S) CH(CH3)—CF3
H



A-63.
(S) CH(CH3)—CF3
CH3



A-64.
(S) CH(CH3)—CF3
CH2CH3



A-65.
(±) CH(CH3)—CCl3
H



A-66.
(±) CH(CH3)—CCl3
CH3



A-67.
(±) CH(CH3)—CCl3
CH2CH3



A-68.
(R) CH(CH3)—CCl3
H



A-69.
(R) CH(CH3)—CCl3
CH3



A-70.
(R) CH(CH3)—CCl3
CH2CH3



A-71.
(S) CH(CH3)—CCl3
H



A-72.
(S) CH(CH3)—CCl3
CH3



A-73.
(S) CH(CH3)—CCl3
CH2CH3



A-74.
CH2C(CH3)═CH2
H



A-75.
CH2C(CH3)═CH2
CH3



A-76.
CH2C(CH3)═CH2
CH2CH3



A-77.
Cyclopentyl
H



A-78.
Cyclopentyl
CH3



A-79.
Cyclopentyl
CH2CH3



A-80.
Cyclohexyl
H



A-81.
Cyclohexyl
CH3



A-82.
Cyclohexyl
CH2CH3










A-83.
—(CH2)4—



A-84.
(±) —(CH2)2—CH(CH3)—CH2—



A-85.
(R) —(CH2)2—CH(CH3)—CH2—



A-86.
(S) —(CH2)2—CH(CH3)—CH2—



A-87.
—(CH2)2—CH(OCH3)—CH2—



A-88.
—(CH2)2—CH(CH2CH3)—CH2—



A-89.
—(CH2)2—CH[CH(CH3)2]—CH2—



A-90.
(±) —(CH2)3—CH(CH3)—



A-91.
(±) —CH(CH3)—(CH2)2—CH(CH3)—



A-92.
—CH2—CH═CH—CH2—



A-93.
—(CH2)5—



A-94.
(±) —(CH2)4—CH(CH3)—



A-95.
—(CH2)2—CH(CH3)—(CH2)2—



A-96.
(±) —(CH2)3—CH(CH3)—CH2—



A-97.
(R) —(CH2)3—CH(CH3)—CH2—



A-98.
(S) —(CH2)3—CH(CH3)—CH2—



A-99.
—(CH2)2—C(O[CH2]2O)—(CH2)2—



 



A-100.







 



A-101.
—(CH2)2—C(O[CH2]3O)—(CH2)2—



A-102.
—(CH2)2—CH═CH—CH2—










The compounds I are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some are systemically effective and they can be used in plant protection as foliar and soil fungicides.
They are particularly important in the control of a multitude of fungi on various cultivated plants, such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soy-bean, coffee, sugar cane, vines, fruits and ornamental plants, and vegetables, such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.
They are especially suitable for controlling the following plant diseases:

    Alternaria species on fruit and vegetables,
    Bipolaris and Drechslera species on cereals, rice and lawns,
    Blumeria graminis (powdery mildew) on cereals,
    Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and grapevines,
    Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
    Fusarium and Verticillium species on various plants,
    Mycosphaerella species on cereals, bananas and peanuts,
    Phytophthora infestans on potatoes and tomatoes,
    Plasmopara viticola on grapevines,
    Podosphaera leucotricha on apples,
    Pseudocercosporella herpotrichoides on wheat and barley,
    Pseudoperonospora species on hops and cucumbers,
    Puccinia species on cereals,
    Pyricularia oryzae on rice,
    Rhizoctonia species on cotton, rice and lawns,
    Septoria tritici and Stagonospora nodorum on wheat,
    Uncinula necator on grapevines,
    Ustilago species on cereals and sugar cane, and
    Venturia species (scab) on apples and pears.


The compounds I are also suitable for controlling harmful fungi, such as Paecilomyces variotii, in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
The compounds I are employed by treating the fungi or the plants, seeds, materials or soil to be protected from fungal attack with a fungicidally effective amount of the active compounds. The application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
The fungicidal compositions generally comprise between 0.1 and 95%, preferably between 0.5 and 90%, by weight of active compound.
When employed in plant protection, the amounts applied are, depending on the kind of effect desired, between 0.01 and 2.0 kg of active compound per ha.
In seed treatment, amounts of active compound of 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kilogram of seed are generally necessary.
When used in the protection of materials or stored products, the amount of active compound applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of treated material.
The compounds I can be converted to the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the particular intended use; it should in any case ensure a fine and uniform distribution of the compound according to the invention.
The formulations are prepared in a known manner, for example by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants. Solvents/auxiliaries which are suitable are essentially:

    
    
        water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.
        carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.
    
    


Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compounds. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The following are examples of formulations: 1. Products for dilution with water
A) Water-soluble Concentrates (SL)


    
    
        10 parts by weight of a compound according to the invention are dissolved in water or in a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound dissolves upon dilution with water.

B) Dispersible Concentrates (DC)

        20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.

C) Emulsifiable Concentrates (EC)

        15 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). Dilution with water gives an emulsion.

D) Emulsions (EW, EO)

        40 parts by weight of a compound according to the invention are dissolved in xlene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). This mixture is introduced into water by means of an emulsifier (Ultratursax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.

E) Suspensions (SC, OD)

        In an agitated ball mill, 20 parts by weight of a compound according to the invention are comminuted with addition of dispersants, wetters and water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound.

F) Water-dispersible Granules and Water-soluble Granules (WG, SG)

        50 parts by weight of a compound according to the invention are ground finely with addition of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP)

        75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with addition of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound.

2. Products to be Applied Undiluted

H) Dusts (DP)

        5 parts by weight of a compound according to the invention are ground finely and mixed intimately with 95% of finely divided kaolin. This gives a dustable product.

I) Granules (GR, FG, GG, MG)

        0.5 part by weight of a compound according to the invention is ground finely and associated with 95.5% carriers. Customary methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted.

J) ULV Solutions (UL)

        10 parts by weight of a compound according to the invention are dissolved in an organic solvent, for example xylene. This gives a product to be applied undiluted.
    
    


The active compounds can be used as such, in the form of their formulations or of the application forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, preparations for broadcasting or granules, by spraying, atomizing, dusting, broadcasting or watering. The application forms depend entirely on the intended uses; they should always ensure the finest possible dispersion of the active compounds according to the invention.
Aqueous application forms can be prepared from emulsifiable concentrates, pastes or wettable powders (spray powders, oil dispersions) by addition of water. To prepare emulsions, pastes or oil dispersions, the substances can be homogenized in water, as such or dissolved in an oil or solvent, by means of wetting agents, tackifiers, dispersants or emulsifiers. However, it is also possible to prepare concentrates comprising active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil which are suitable for dilution with water.
The concentrations of active compound in the ready-for-use preparations can be varied within relatively wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
The active compounds can also be used with great success in the ultra-low volume (ULV) process, it being possible to apply formulations with more than 95% by weight of active compound or even the active compound without additives.
Oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, if need be also not until immediately before use (tank mix). These agents can be added to the preparations according to the invention in a weight ratio of 1:10 to 10:1.
The preparations according to the invention can, in the application form as fungicides, also be present together with other active compounds, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. On mixing the compounds I or the preparations comprising them in the application form as fungicides with other fungicides, in many cases an expansion of the fungicidal spectrum of activity is obtained.
The following list of fungicides, with which the compounds according to the invention can be used in conjunction, is intended to illustrate the possible combinations but does not limit them:

    acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl,
    amine derivatives, such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine or tridemorph,
    anilinopyrimidine, such as pyrimethanil, mepanipyrim or cyprodinyl,
    antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,
    azoles, such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, tebuconazole, triadimefon, triadimenol, triflumizole or triticonazole,
    dicarboximides, such as iprodione, myclozolin, procymidone or vinclozolin,
    dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram or zineb,
    heterocyclic compounds, such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole or triforine,
    copper fungicides, such as Bordeaux mixture, copper acetate, copper oxychloride or basic copper sulfate,
    nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton or nitrophthal-isopropyl,
    phenylpyrroles, such as fenpiclonil or fludioxonil,
    sulfur,
    other fungicides, such as acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid, cymoxanil, dazomet, diclomezine, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toiclofos-methyl, quintozene or zoxamide,
    strobilurins, such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,
    sulfenic acid derivatives, such as captafol, captan, dichlofluanid, folpet or tolylfluanid,
    cinnamides and analogous compounds, such as dimethomorph, flumetover or flumorph.




SYNTHESIS EXAMPLES
Example 1
Synthesis of (S)-4-chloro-6-(2,2,2-trifluoro-1-methylethylamino)-5-(2,4,6-trifluorophenyl)pyrimidine-2-thiocarbamide




At room temperature, hydrogen sulfide was introduced for 5 minutes into a solution of 0.5 g (1.35 mmol) of (S)-4-chloro-6-(2,2,2-trifluoro-1-methylethylamino)-5-(2,4,6-trifluorophenyl)pyrimidine-2-carbonitrile, prepared according to WO 03/043993, in 0.16 g of triethylamine and 6 ml of N-methylpyrrolidone. After the reaction had ended, 20 ml of water were added, the mixture was neutralized with acetic acid and extracted with methyl tert-butyl ether and the organic phase was washed with water, dried over magnesium sulfate and concentrated.
Yield: 0.44 g (81% of theory) M.p.: 101-103° C.
Example 2
Synthesis of 4-sec-butylamino-6-chloro-5-(2-chloro-6-fluorophenyl)-pyrimidine-2-thiocarbamide




At room temperature, hydrogen sulfide was introduced for 5 minutes into a solution of 1.0 g (2.9 mmol) of 4-sec-butylamino-6-chloro-5-(2-chloro-6-fluorophenyl)pyrimidine-2-carbonitrile in 0.36 g of triethylamine and 12 ml of N-methylpyrrolidone. After the reaction had ended, 20 ml of water were added, the mixture was neutralized with acetic acid and extracted with methyl tert-butyl ether and the organic phase was washed with water, dried over magnesium sulfate and concentrated.
Yield: 0.57 g (53% of theory) M.p.: 147-150° C.
The compounds listed in the table below were synthesized analogously to the procedures given above.
















 














No.
R1
R2
R3
R4
Ar
m.p.: [° C.]
1H-NMR [ppm, CHCl3]





I-1
CH2CH2CH(CH3)
CH2CH2
Cl
H
2-chloro-6-fluorophenyl
170-172



I-2
(S)-CH(CH3)CF3
H
Cl
H
2,4,6-trifluorophenyl
101-103


I-3
CH(CH3)2
H
Cl
H
2-chloro-6-fluorophenyl

1.21 (d, 6H); 4.42 (m, br, 2H); 7.21 (t,









1H); 7.36 (m, 2H); 8.03 (s, br, 1H); 9.12









(s, br, 1H)


I-4
CH(CH3)2
H
Cl
H
2,4,6-trifluorophenyl
145-149


I-5
CH(CH3)CH2CH3
H
Cl
H
2,4,6-trifluorophenyl
110-113


I-6
CH2CH2CH2CH

Cl
H
2,4,6-trifluorophenyl

1.27 (d, 3H); 1.6 (m, 4H); 3.92 (m, 2H);









4.48 (m, 1H); 6.76 (m, 2H); 7.80 (s, br,









1H); 9.04 (s, br, 1H)


I-7
CH2C(CH3)═CH2
CH2CH3
Cl
H
2,4,6-trifluorophenyl
130-132


I-8
CH(CH3)CH2CH3
H
Cl
H
2-chloro-6-fluorophenyl
147-150


I-9
CH2C(CH3)═CH2
CH2CH3
Cl
H
2-chloro-6-fluorophenyl

1.03 (m, 3H); 1.45 (s, 3H); 3.24 (m, 1H);









3.50 (m, 1H); 3.83 (m, 2H); 4.79 (s, 2H);









7.10 (m, 1H); 7.36 (m, 2H); 8.00 (s, br,









1H); 9.05 (s, br, 1H)


I-10
(S)-CH(CH3)CH(CH3)2
H
Cl
H
2-chloro-6-fluorophenyl

0.88 (dd, 6H); 1.20 (dd, 3H); 1.79 (m,









1H); 4.45 (m, br, 2H); 7.20 (m, 1H); 7.43









(m, 2H); 7.70 (s, br, 1H); 9.06 (s, br, 1H)


I-11
(S)-CH(CH3)CH(CH3)2
H
Cl
H
2-chloro-4-fluorophenyl

0.85 (dd, 6H); 1.15 (dd, 3H); 1.75 (m,









1H); 4.40 (m, br, 2H); 7.19 (m, 1H); 7.33









(m, 2H); 8.03 (s, br, 1H); 9.11 (s, br, 1H)


I-12
(S)-CH(CH3)CH(CH3)2
H


2,4-difluorophenyl

0.84 (dd, 6H); 1.16 (dd, 3H); 1.78 (m,









1H); 4.30 (m, br, 2H); 7.00 (m, 1H); 7.08









(m, 1H); 7.38 (m, 1H); 8.0 (s, br, 1H); 9.0









(s, br, 1H)


I-13
CH2CH═CH2
CH2CH═CH2
Cl
H
2,4,6-trifluorophenyl
54-60


I-14
(S)-CH(CH3)CH(CH3)2

Cl
H
2-chloro-6-fluorophenyl
120-123


I-15
(S)-CH(CH3)CH(CH3)2
H
Cl
H
2,4,6-trifluorophenyl
142-145


I-16
CH2CH2CH(CH3)CH2CH2

Cl
H
2,4,6-trifluorphenyl
66-69


I-17
(S)-CH(CH3)CF3
H
Cl
COCH3
2,4,6-trifluorophenyl
55-58


I-18
(S)-CH(CH3)CF3
H
Cl
H
2-chloro-4-fluorophenyl

1.34 (m, 3H), 4.4 (d, 1H); 4.94 (m, 1H);









7.19 (m, 1H); 7.31 (m, 2H); 8.31 (s, 1H);









8.92 (s, 1H); 11.61 (s, 1H)


I-19
CH2CH3
CH2CH3
Cl
H
2,4,6-trifluorophenyl
55-58
1.03 (m, 6H); 3.37 (m, 4H); 6.8 (m, 2H);









8.03 (m, 1H); 9.02 (m, 1H)


I-20
(S)-CH(CH3)CH(CH3)2
H
Cl
H
2-chloro-4-fluorophenyl

0.85 (m, 6H); 1.1 (m, 3H); 1.7 (m, 1H);









4.03 (s, 1H); 4.35 (d, 1H); 7.17 (m, 1H);









7.33 (m, 2H); 7.7 (s, 1H); 8.86 (s, 1H);









11.39 (s, 1H)


I-21
CH2CH3
CH2CH3
Cl
COCH3
2,4,6-trifluorophenyl

1.07 (m, 6H); 2.65 (s, 3H); 3.37 (m, 4H);









6.83 (t, 2H); 11.62 (s, 1H)


I-22
CH(CH3)CH2CH3
H
Cl
H
2-chloro-4-fluorophenyl
172-175


I-23
CH(CH3)2
H
Me
H
2,4,6-trifluorophenyl
158


I-24
CH(CH3)CH2CH3
H
Me
H
2,4,6-trifluorophenyl
114-117


I-25
CH2CH2CH(CH3)CH2CH2

Me
H
2,4,6-trifluorophenyl
149-151









Examples of the Action Against Harmful Fungi

The fungicidal action of the compounds of the formula I was demonstrated by the following experiments:
The active compounds were prepared separately as a stock solution with 0.25% by weight of active compound in acetone or DMSO. 1% by weight of the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkyl-phenols) was added to this solution. The stock solutions of the active compounds were diluted with water to the desired concentration.
Use Examples
1) Activity Against Gray Mold on Bell Pepper Leaves Caused by Botrytis cinerea, Protective Application
Bell pepper seedlings of the cultivar “Neusiedler Ideal Elite” were, after 4-5 leaves were well developed, sprayed to runoff point with an aqueous suspension having a concentration of active compound of 250 ppm. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea, this contained 1.7×106 spores/ml in a 2% strength aqueous biomalt solution. The test plants were then placed in a climate-chamber at 22-24° C. and high atmospheric humidity. After 5 days, the extent of the fungal infection on the leaves was determined visually in %.
In this test, the plants which had been treated with compounds I-2, I-3, I-4, I-6, I-7, I-8, I-10 and I-11 were not infected, whereas the untreated plants were 90% infected.
2) Activity Against Mildew on Cucumber Leaves Caused by Sphaerotheca fuliginea, Protective Application
The leaves of potted cucumber seedlings of the cultivar “Chinese snake” were, at the cutyledon stage, sprayed to runoff point with an aqueous suspension having a concentration of active compound of 250 ppm. 20 hours after the spray coating had dried, the plants were inoculated with an aqueous spore suspension of mildew of cucumber (Sphaerotheca fuliginea). The plants were then cultivated in a greenhouse at 20-24° C. and 60-80% relative atmospheric humidity for 7 days. The extent of the mildew development was then determined visually in % infection of the cotyledon area.
In this test, the plants which had been treated with compounds I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10 and I-11 showed no infection or infection of less than 10%, whereas the untreated plants were 100% infected.
3) Activity Against Early Blight of Tomatoes Caused by Altemaria solani 
Leaves of potted plants of the cultivar “Goldene Prinzessin” were sprayed to runoff point with an aqueous suspension having an active compound concentration of 250 ppm. The next day, the leaves were infected with an aqueous spore suspension of Altemaria solani in a 2% biomalt solution having a density of 0.17×106 spores/ml. The plants were then placed in a water-vapor-saturated chamber at 20-22° C. After 5 days, the early blight on the untreated, but infected control plants had developed to such an extent that the infection could be determined visually in %.
In this test, the plants which had been treated with compounds I-13, I-14, I-15, I-16, I-17 and I-19 had an infection of <5%, while the untreated plants were 80% infected.
4) Activity Against Net Blotch of Barley Caused by Pyrenophora teres 
Leaves of pot-grown barley seedlings of the cultivar “Hanna” were sprayed to runoff point with an aqueous suspension having an active compound concentration of 250 ppm. 24 hours after the spray coating had dried on, the test plants were inoculated with an aqueous suspension of spores of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch. The test plants were subsequently placed in a greenhouse at temperatures of between 20 and 24° C. and a relative atmospheric humidity of 95 to 100%. After 6 days, the extent of development of the disease was determined visually in % of infection of the total leaf area.
In this test, the plants treated with compounds I-13, I-14, I-15, I-16, I-17 and I-19 had an infection of 10%, while the untreated plants were 80% infected.

## Claims

1. A 2-substituted pyrimidine of the formula I



in which the index and the substituents are as defined below:
n is an integer from 1 to 5;
L is halogen, cyano, cyanato (OCN), C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C6-alkoxy, C2-C8-alkyenyloxy, C2-C8-alkynyloxy, C3-C6-cycloalkyl, C4-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C4-C6-cycloalkenyloxy, nitro, —C(═O)-A, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A, N(A′)—C(═O)-A, N(A′′)—C(═O)—N(A′)A, S(═O)m-A, S(═O)m—O-A or S(═O)m—N(A′)A,
m is 0, 1 or 2;
A, A′, A′′ independently of one another are hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl, phenyl, where the organic radicals may be partially or fully halogenated or may be substituted by nitro, cyanato, cyano or C1-C4-alkoxy; or A and A′ together with the atoms to which they are attached are a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S;
where the aliphatic groups of the radical definitions of L for their part may be partially or fully halogenated or may carry one to four groups Ru:
Ru is cyano, C1-C6-alkoxy, C3-C6-cycloalkyl, C2-C8-alkenyloxy, C2-C8-alkynyloxy, C4-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C4-C6-cycloalkenyloxy, —C(═O)-A, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A, N(A′)-C(═O)-A, N(A′′)-C(═O)—N(A′)A, S(═O)m-A, S(═O)m—O-A or S(═O)m—N(A′)A;

R1, R2 independently of one another are C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, where the aliphatic groups of the radical definitions of R1 and R2 may for their part be partially or fully halogenated or may carry one to four groups Rv:
Rv is cyano, C3-C6-cycloalkyl, C4-C6-cycloalkenyl, hydroxyl, C1-C6-alkoxy, C2-C8-alkenyloxy, C2-C8-alkynyloxy, C3-C6-cycloalkyloxy, C4-C6-cycloalkenyloxy, C1-C6-alkylthio, —C(═O)-A, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A, N(A′)—C(═O)-A, N(A′′)—C(═O)—N(A′)A, S(═O)m-A, S(═O)m—O-A or S(═O)m—N(A′)A or phenyl, where the phenyl moiety may carry one to three radicals selected from the group consisting of halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, cyano, nitro, —C(═O)-A, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A;
R2 may additionally be hydrogen;
R1 and R2 may also, together with the nitrogen atom to which they are attached, form a saturated or unsaturated five- or six-membered ring which may be interrupted by an ether (—O—), carbonyl (C═O—), thio (—S—), sulfoxyl (—S[═O]—) or sulfenyl (—SO2—) or a further amino —(—N(Ra) group where Ra is hydrogen or C1-C6 alkyl and/or may contain one or more substituents from the group consisting of halogen, C1-C6-alkyl, C1-C6-haloalkyl and oxy-C1-C3-alkylenoxy;

R3 is halogen, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C3-C4-alkenyloxy, C3-C4-alkynyloxy, C1-C6-alkylthio, di-(C1-C6-alkyl)amino or C1-C6-alkylamino, where the alkyl, alkenyl and alkynyl radicals of R3 may be substituted by halogen, cyano, nitro, C1-C2-alkoxy or C1-C4-alkoxycarbonyl;

R4 corresponds to one of the formulae





where
x is a direct bond, —(C═O)—, —(C═O)—NH, —(C═O)—O—, —O—, —NRc—, where the molecule moiety to the left in each case is attached to the nitrogen atom;
Ra is hydrogen, methyl, benzyl, trifluoromethyl, allyl, propargyl or methoxymethyl;
Rb is hydrogen, C1-C6-alkyl; C2-C6-alkynyl;
Rc is hydrogen, methyl or C1-C4-acyl and
Z is S or NRb;

where the aliphatic groups of the radical definitions of Ra, Rb and/or Rc for their part may carry one or two groups Rw:
Rw is halogen, ORx, NHRx, C1-C6-alkyl, C1-C4-alkoxycarbonyl, C1-C4-acyl-amino, [1,3]dioxolane-C1-C4-alkyl, [1,3]dioxane-C1-C4-alkyl, where [Rx is hydrogen, methyl, allyl or propargyl.

2. A 2-substituted pyrimidine as claimed in claim 1, where R3 is chlorine, cyano, methyl or methoxy.

3. A 2-substituted pyrimidine as claimed in claim 1, where Ra is hydrogen and Rb is hydrogen, C1-C6-alkyl or C2-C6-alkenyl.

4. A 2-substituted pyrimidine as claimed in claim 1, in which the phenyl group substituted by Ln is the group B



where # is the point of attachment to the pyrimidine skeleton and
L1 is fluorine, chlorine, CH3 or CF3;
L2, L4 independently of one another are hydrogen, CH3 or fluorine;
L3 is hydrogen, fluorine, chlorine, cyano, CH3, SCH3, OCH3, SO2CH3, NH—C(═O)CH3, N(CH3)—C(═O)CH3 or COOCH3 and
L5 is hydrogen, fluorine, chlorine or CH3.

5. A process for preparing 2-substituted pyrimidines of the formula I as claimed in claim 1, where R4 is a thioamide, which comprises reacting a compound of the formula II




in which the substituents L, R1, R2 and R3 are as defined in claim 1 and R′ is an unsubstituted or substituted C1-C6-alkyl radical or an unsubstituted or substituted phenyl radical with an alkali metal cyanide, alkaline earth metal cyanide or tin cyanide of the formula (III) and then reacting the resulting compound IV




with hydrogen sulfide to give IA

6. A process for preparing compounds of the formula IC, where the substituents Ln, R1, R2, R3, Ra and Rb are as defined in claim 1




starting from nitrile IV by reaction with mercaptans of the formula RbSH under acidic conditions and further reaction of the dithiocarboxylic ester of the formula VII which is obtained, with azides of the formula RaN3.

7. A compound of the formula VII




where the substituents R1, R2, R3, Rb and Ln have the meaning in claim 1.

8. A composition suitable for controlling harmful fungi, which composition comprises a solid or liquid carrier and a compound of the formula I as claimed in claim 1.

9. A method for controlling phytopathogenic harmful fungi, which comprises treating the fungi or the materials, plants, the soil or the seeds to be protected against fungal attack with an effective amount of a compound of the formula I as claimed in claim 1.

10. A 2-substituted pyrimidine as claimed in claim 2, in which the phenyl group substituted by Ln is the group B



where # is the point of attachment to the pyrimidine skeleton and
L1 fluorine, chlorine, CH3 or CH3;
L2, L4 independently of one another are hydrogen, CH3 or fluorine;
L3 is hydrogen, fluorine, chlorine, cyano, CH3, SCH3, OCH3, SO2CH3, NH—C(═O)CH3, N(CH3)—C(═O)CH3 or COOCH3 and
L5 is hydrogen, fluorine, chlorine or CH3.

11. A 2-substituted pyrimidine as claimed in claim 3, in which the phenyl group substituted by Ln is the group B



where # is the point of attachment to the pyrimidine skeleton and
L1 fluorine, chlorine, CH3 or CH3;
L2, L4 independently of one another are hydrogen, CH3 or fluorine;
L3 is hydrogen, fluorine, chlorine, cyano, CH3, SCH3, OCH3, SO2CH3, NH—C(═O)CH3, N(CH3)—C(═O)CH3 or COOCH3 and
L5 is hydrogen, fluorine, chlorine or CH3.