DE3436380A1 - Selective fungicidal agents based on a pyrimidine derivative - Google Patents

Abstract

The invention relates to the use of pyrimidine derivatives, some of which are known, of the formula (I) <IMAGE> in which R represents halogen, haloalkyl, alkyl, alkoxy, alkylthio or <IMAGE> in which R<4> represents hydrogen, alkyl or alkenyl, R<5> represents hydrogen, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, aryl, or aralkyl; or R<4> and R<5>, together with the nitrogen atom to which they are attached, form a saturated, optionally substituted heterocycle which can contain further heteroatoms, R<1> represents alkyl, haloalkyl, alkoxy, alkylthio, halogen or phenylthio, R<2> represents alkoxy or halogen and R<3> represents hydrogen, alkyl, alkoxy, alkylthio, phenylthio or <IMAGE> where R<4> and R<5> have the abovementioned meaning, with the proviso that one of the radicals R or R<3> represents <IMAGE> for combating BCM-resistant fungal strains, in particular in combination with BCM, BCM analogues or BCM-forming compounds.

Description

Selective fungicidal agents based on pyrimidine derivatives

The present invention relates to the use of some known Pyrimidine derivatives as fungicides against BCM-resistant fungal strains.

It is known that pyrimidine derivatives such as 4,6-dichloro-2-dimethylaminopyrimidine and 5-allyl-4-chloro-2-dimethylamino-6-methyl-pyrimidine, fungicidal properties own (cf. DE-OS 1 800 708).

It is also known that benzimidazole carbamates such as methylbenzimidazol-2-yl carbamate (BCM for short), and phenylenediamine thiourea carbamates, such as 1,2-bis- (3-ethoxyearbonyl-2-thioureido) -benzene, show an excellent effect against a wide variety of phytopathogenic fungi. They have been used as plant fungicides for over a decade. However the use of these highly active fungicides over a long period of time has problems brought with it; resistance has been observed in a wide variety of microorganisms. Furthermore, a distinction was made between benzimidazole carbamates and phenylenediamine thiourea carbamates extensive cross-resistance demonstrated /see. e.g. M.C. Brown et al. "Plant. Pathol., 33 (1), 101-111 = C.A. 100 (23): 187.178n; CA. 100 (7): 46.896h and C.A. 100 (1): 2.204b7.

It is also known that certain N-phenylcarbamates, such as .B. Ethyl-N- e.g. ethyl-N- (3,5-diisopropoxyphenyl) -carbamate, a fungicidal effect have fungal strains resistant to benzimidazole carbamate derivatives (cf. EP-OS 0 051 871 and EP-OS 0 063 905).

It has been found that the partially known pyrimidine derivatives of the formula (I) in which R stands for halogen, haloalkyl, alkyl, alkoxy, alkylthio or for where R4 is hydrogen, alkyl or alkenyl, R5 is hydrogen, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, aryl or aralkyl, or R4 and R5 are saturated with the nitrogen atom on which they are attached , optionally substituted heterocycle which may contain further heteroatoms, R1 is alkyl, haloalkyl, alkoxy, alkylthio, halogen or phenylthio, R2 is alkoxy or halogen and R3 is hydrogen, alkyl, alkoxy, alkylthio, phenylthio, or above specified stands, where R4 and R5 have the meaning, with the proviso that one of the radicals R or R3 is have a strong fungicidal effect against BCM-resistant fungal strains.

By BCM-resistant strains of fungi we mean strains of fungi that are against BCM itself, BCM analogs, such as methyl-BCM, and against compounds that are before, during or form BCM after application, such as methyl 1- (butylcarbamoyl) benzimidazol-2-yl carbamate, or phenylenediamine thiourea carbamates, are resistant.

Surprisingly, the pyrimidine derivatives used according to the invention show an excellent, very specific action against fungal isolates with resistance against BCM; BCM as defined above.

The pyrimidine derivatives to be used according to the invention are through the formula (I) is precisely defined.

Preference is given to compounds of the formula (I) in which R represents fluorine, chlorine, straight-chain or branched haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine and chlorine, straight-chain or branched alkyl, alkoxy or alkylthio each 1 to 4 carbon atoms or for where R4 is hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms or straight-chain or branched alkenyl having 3 to 6 carbon atoms, R5 is hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine and chlorine, for straight-chain or branched alkenyl with 3 to 6 carbon atoms, for cycloalkyl with 3 to 6 carbon atoms, for straight-chain or branched alkoxyalkyl, alkoxycarbonyl or alkoxycarbonylalkyl with 1 each up to 4 carbon atoms per alkoxy and alkyl part, stands for phenyl or phenylalkyl with 1 to 4 carbon atoms in the straight-chain or branched alkyl part or R4 and R5 with the nitrogen atom on which they are attached are saturated, optionally by alkyl with 1 to 4 carbon atoms or phenyl substituted 5- or 6-membered H eterocycle, which can contain other heteroatoms, identical or different, such as nitrogen and oxygen, form, R1 for straight-chain or branched alkyl with 1 to 4 carbon atoms, for straight-chain or branched haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms , such as fluorine and chlorine, for straight-chain or branched alkoxy or alkylthio with 1 to 4 carbon atoms per alkyl part, for fluorine, chlorine or phenylthio, R2 for straight-chain or branched alkoxy with 1 to 6 carbon atoms, for fluorine or chlorine, R3 for hydrogen , for straight-chain or branched alkyl with 1 to 4 carbon atoms, for straight-chain or branched alkoxy or alkylthio with 1 to 4 carbon atoms per alkyl part, for phenylthio or for -NR4R5, where R4 and R5 have the meaning given above, with the proviso that one of the radicals R or R3 for stands.

Particularly preferred are compounds of the formula (I) in which R stands for fluorine, for haloalkyl with 1 or 2 carbon atoms and 1 to 5 identical or different fluorine and chlorine atoms, preferably trichloromethyl or dichlorofluoromethyl, for straight-chain or branched alkyl with 1 to 3 carbon atoms , such as methyl, ethyl, n-propyl and iso-propyl, alkoxy or alkylthio each with 1 or 2 carbon atoms, such as methoxy 'ethoxy, methylthio and ethylthio, or for where R is hydrogen, methyl, ethyl or allyl, R5 is hydrogen, straight-chain or branched alkyl with 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl and hexyl, for straight-chain or branched alkenyl with 3 or 4 carbon atoms, such as allyl, buten-1-yl and buten-2-yl, for cyclopentyl, cyclohexyl, for straight-chain or branched alkoxyalkyl With 1 to 3 carbon atoms per alkoxy and alkyl part, such as 3-methoxyn-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxy-ethyl, 2-ethoxy-ethyl, 2-n-propoxy-ethyl and 2-iso-propoxy-ethyl, for alkoxycarbonyl with 1 to 3 carbon atoms in the alkoxy part, such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl and iso-propoxycarbonyl, for alkoxycarbonylalkyl with 1 to 3 carbon atoms in the alkoxy part and 1 or 2 carbon atoms in the alkyl part, such as methoxycarbonylmethyl, ethoxycarbonylmethyl, nP ropoxycarbonylmethyl, iso-propoxycarbonylmethyl, 2-methoxycarbonyl-ethyl, 2-ethoxycarbonyl-ethyl, 2-n-propoxycarbonyl-ethyl and 2-iso-propoxycarbonyl-ethyl, for phenyl or phenylalkyl with 1 or 2 carbon atoms in the alkyl part, such as phenylmethyl, 2 -Phenylethyl and 1-phenylethyl, or R4 and R5 together with the nitrogen atom on which they are attached form a pyrrolidine, piperidine, piperazine or morpholine radical, optionally mono- to trisubstituted, identically or differently by methyl, ethyl or phenyl, R1 for methyl , Ethyl, trichloromethyl, dichlorofluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, n-, sec-, tert- or iso-butylthio, fluorine or phenylthio , R2 stands for methoxy, ethoxy, n-propoxy, iso-propoxy, fluorine or chlorine, R³ for hydrogen, methyl, ethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, methylthio, ethylthio, n-propylthio, iso- Propylthio, n-, sec-, tert- or iso-butylthio, phenylthi o or represents —NR4R5, in which R4 and R5 have the meaning given above, with the proviso that one of the radicals R or R3 represents —NR4R5.

Examples of the active ingredients used according to the invention are in addition to those mentioned in the preparation examples: 2-allylamino-4,6-bisethylthio-5-chloro-pyrimidine; 2-allylamino-4,6-bis-n-propylthio-5-chloro-pyrimidine; 2-allylamino-4,6-bis-iso-propylthio-5-chloro-pyrymidine; 2-allylamino-4,6-bis-tert-butylthio-5-chloro-pyrimidine; 2-allylamino-4,6-bis-methoxy-5-chloro-pyrimidine; 2-allylamino-4, 6-bis-ethoxy-5-chloro-pyrimidine; 2-allylamino-4, 6-bis-n-propoxy-5-chloro-pyrimidine; 2-allylamino-4,6-bis-methyl-5-chloro-pyrimidine; 2-allylamino-4, 6-bis-ethyl-5-chloro-pyrimidine; 2-allylamino-4,6-bis-n-propyl-5-chloro-pyrimidine; 2-allylamino-4-methyl-6-methylthio-5-chloro-pyrimidine; 2-allylamino-4-ethyl-6-methylthio-5-chloro-pyrimidine; 2-allylamino-4-n-propyl-6-methylthio-5-chloro-pyrimidine; 2-allylamino-4-methyl-6-methoxy-5-chloro-pyrimidine; 2-allylamino-4-methyl-6-ethoxy-5-chloro-pyrimidine; 2-allylamino-4-methyl-6-n-propoxy-5-chloro-pyrimidine; 2-allylamino-4-ethyl-6-ethoxy-5-chloro-pyrimidine; 2-allylamino-4-n-propyl-6-iso-propoxy-5-chloro-pyrimidine; 2-allylamino-4-fluoro-6-methyl-5-chloro-pyrimidine; 2-allylamino-4-fluoro-6-ethyl-5-chloro-pyrimidine; 2-allylamino-4-fluoro-6-methylthio-5-chloro-pyrimidine; 2-allylamino-4-fluoro-6-ethylthio-5-chloro-pyrimidine; 2-allylamino-4-fluoro-6-methoxy-5-chloro-pyrimidine; 2-allylamino-4-fluoro-6-ethoxy-5-chloro-pyrimidine; 2-allylamino-4,6-bis-ethylthio-5-methoxy-pyrymidine; 2-allylamino-4,6-bis-n-propylthio-5-methoxypyrimidine; 2-allylamino-4,6-bis-isopropylthio-5-methoxy-pyrimidine; 2-allylamino-4,6-bis-tert-buthylthio-5-methoxypyrimidine; 2-allylamino-4,6-bis-methoxy-5-methoxypyrimidine; 2-allylamino-4,6-bis-ethoxy-5-methoxypyrimidine; 2-allylamino-4,6-bis-n-propoxy-5-methoxy-pyrimidine; 2-allylamino-4,6-bis-methyl-5-methoxypyrimidine; 2-allylamino-4, 6-bis-ethyl-5-methoxypyrimidine; 2-allylamino-4,6-bis-n-propyl-methoxypyrimidine; 2-allylamino-4-methyl-6-methylthio-5-methoxypyrimidine; 2-allylamino-4-ethyl-6-methylthio-5-methoxypyrimidine; 2-allylamino-4-n-propyl-6-methylthio-5-methoxypyrimidine; 2-allylamino-4-methyl-6-methoxypyrimidine; 2-allylamino-4-methyl-6-ethoxy-5-methoxy-pyrimidine; 2-allylamino-4-methyl-6-n-propoxy-5-methoxy-pyrimidine; 2-allylamino-4-ethyl-6-ethoxy-5-methoxy-pyrimidine; 2-allylamino-4-n-propyl-6-iso-propoxy-5-methoxypyrimidine; 2-allylamino-4-fluoro-6-methyl-5-methoxypyrimidine; 2-allylamino-4-fluoro-6-ethyl-5-methoxypyrimidine; 2-allylamino-4-fluoro-6-methylthio-5-metoxy-pyrymidine; 2-allylamino-4-fluoro-6-ethylthio-5-methoxy-pyrimidine; 2-allylamino-4-fluoro-6-methoxy-5-methoxy-pyrimidine; 2-allylamino-4-fluoro-6-ethoxy-5-methoxy-pyrimidine; 2-allylamino-4,6-bisethylthio5ethoxypyrimidine; 2-allylamino-4,6-bis-n-prophylthio-5-ethoxy-pyrimidine; 2-allylamino-4,6-bis-iso-propylthio-5-ethoxypyrimydine; 2-allylamino-4,6-bis-tert-buthylthio-5-ethoxypyrimidine; 2-allylamino-4,6-bis-methoxy-5-ethoxy-pyrymydine; 2-allylamino-4, 6-bis-ethoxy-5-ethoxy-pyrimidine; 2-allylamino-4,6-bis-n-propoxy-5-ethoxy-pyrymidine; 2-allylamino-4, 6-bis-methyl-5-ethoxypyrimidine; 2-allylamino-4, 6-bis-ethyl-5-ethoxypyrimidine; 2-allylamino-4,6-bis-n-propyl-5-ethoxypyrimidine; 2-allylamino-4-methyl-6-methylthio-5-ethoxypyrimidine; 2-allylamino-4-ethyl-6-methylthio-5-ethoxy-pyrimidine; 2-allylamino-4-n-propyl-6-methylthio-5-ethoxypyrimidine; 2-allylamino-4-methyl-6-methoxy-5-ethoxy-pyrimidine; 2-allylamino-4-methyl-6-ethoxy-5-ethoxy-pyrimidine; 2-allylamino-4-methyl-6-n-propoxy-5-ethoxy-pyrimidine; 2-allylamino-4-ethyl-6-ethoxy-5-ethoxy-pyrimidine; 2-allylamino-4-n-propyl-6-iso-propoxy-5-ethoxypyrimidine; 2-allylamino-4-fluoro-6-methyl-5-ethoxypyrimidine; 2-allylamino-4-fluoro-6-ethyl-5-ethoxypyrimidine; 2-allylamino-4-fluoro-6-methylthio-5-ethoxypyrimidine; 2-allylamino-4-fluoro-6-ethylthio-5-ethoxy-pyrimidine; 2-allylamino-4-fluoro-6-methoxy-5-ethoxy-pyrimidine; 2-allylamino-4-fluoro-6-ethoxy-5-ethoxy-pyrimidine; 2-allylamino-4,6-bis-ethylthio-5-iso-propoxy-pyrimidine; 2-allylamino-4, 6-bis-n-propylthio-5-iso-propoxypyrimidine; 2-allylamino-4, 6-bis-iso-propylthio-5-iso-propoxypyrimidine; 2-allylamino-4,6-bis-tert-butylthio-5-iso-prop-oxypyrimidine; 2-allylamino-4,6-bis-methoxy-5-iso-propoxy-pyrimidine; 2-allylamino-4,6-bis-ethoxy-5-iso-propoxy-pyrymidine; 2-allylamino-4,6-bis-n-propoxy-5-iso-propoxy-pyrimidine; 2-allylamino-4,6-bis-methyl-5-iso-propoxypyrimidine; 2-allylamino-4,6-bis-ethyl-5-iso-propoxy-pyrimidine; 2-allylamino-4,6-bis-n-propyl-5-iso-propoxypyrimidine; 2-allylamino-4-methyl-6-methylthio-5-iso-prop-oxypyrimidine; 2-allylamino-4-ethyl-6-methylthio-5-iso-propoxypyrimidine; 2-allylamino-4-n-propyl-6-methylthio-5-iso-propoxypyrimidine; 2-allylamino-4-methyl-6-methoxy-5-iso-propoxy-pyrimidine; 2-allylamino-4-methyl-6-ethoxy-5-iso-propoxy-pyrimidine; 2-allylamino-4-methyl-6-n-propoxy-5-iso-propoxy-pyrimidine; 2-allylamino-4-ethyl-6-ethorxy-5-iso-propoxypyrimidine; 2-allylamino-4-n-propyl-6-iso-propoxy-5-iso-propoxypyrimidine; 2-allylamino-4-fluoro-6-methyl-5-iso-propoxypyrimidine; 2-allylamino-4-fluoro-6-ethyl-5-iso-propoxy-pyrimidine; 2-allylamino-4-fluoro-6-methylthio-5-iso-propoxypyrimidine; 2-allylamino-4-fluoro-6-ethylthio-5-iso-propoxypyrimidine; 2-allylamino-4-fluoro-6-methoxy-5-iso-propoxy-pyrimidine; 2-allylamino-4-fluoro-6-ethoxy-5-iso-propoxy-pyridimine; 2-allylamino-4, 6-bisethylthio-5-fluoro-pyrimidine; 2-allylamino-4,6-bis-n-prophylthio-5-fluoro-pyrimidine; 2-allylamino-4,6-bis-iso-prophylthio-5-fluoro-pyridimine; 2-allylamino-4,6-bis-tert-butylthio-5-fluoro-pyrimidine; 2-allylamino-4, 6-bis-methoxy-5-fluoro-pyrimidine; 2-allylamino-4, 6-bis-ethoxy-5-fluoro-pyrimidine; 2-allylamino-4,6-bis-n-propoxy-5-flor-pyrimidine; 2-allylamino-4, 6-bis-methyl-5-fluoro-pyrimidine; 2-allylamino-4, 6-bis-ethyl-5-fluoro-pyrimidine; 2-allylamino-4,6-bis-n-propyl-5-fluoro-pyrimidine; 2-allylamino-4-methyl-6-methylthio-5-fluoro-pyrimidine; 2-allylamino-4-ethyl-6-methylthio-5-fluoro-pyrimidine; 2-allylamino-4-n-propyl-6-methylthio-5-fluoro-pyrimidine; 2-allylamino-4-methyl-6 methoxy-5-fluoro-pyrimidine; 2-allylamino-4-methyl-6-ethoxy-5-fluoro-pyrimidine; 2-allylamino-4-methyl-6-n-propoxy-5-fluoro-pyrimidine; 2-allylamino-4-ethyl-6-ethoxy-5-fluoro-pyrimidine; 2-allylamino-4-n-propyl-6-iso-propoxy-5-fluoro-pyrimidine; 2-allylamino-4-fluoro-6-methyl-5-fluoro-pyrimidine; 2-allylamino-4-fluoro-6-ethyl-5-fluoro-pyrimidine; 2-allylamino-4-fluoro-6-methylthio-5-fluoro-pyrimidine; 2-allylamino-4-fluoro-6-ethylthio-5-fluoro-pyrimidine; 2-allylamino-4-fluoro-6-methoxy-5-fluoro-pyrimidine; 2-Allylamino-4-fluoro-6-ethoxy-5-fluoro-pyrimidine.

Some of the active ingredients used according to the invention are new. The known compounds can be prepared by processes known from the literature, as can the still new pyrimidine derivatives of the formula (Ia) in which R 'stands for -NR4, R5, in which R stands for hydrogen, R5 stands for alkyl, cycloalkyl, alkenyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, aryl or stands for aralkyl or R and R together with the nitrogen atom on which they stand , form a pyrrolidine radical, piperidine radical, piperazine radical or morpholine radical, which is optionally substituted one to three times, identically or differently by alkyl having 1 to 4 carbon atoms or phenyl, R¹ 'represents alkyl, haloalkyl, alcohol or alkylthio, R represents fluorine, chlorine or alkoxy and 3 'is hydrogen, alkoxy or alkylthio or R' is alkoxy or alkylthio, R¹ 'is halogen, alkyl, alcohol or alkylthio, R²' is fluorine, chlorine or alkoxy and R³ 'is -NR4' R5 ', where R4' and R5 'have the meaning given above, by a) for the case that one of the radicals R' or R31 is -NR4'R5 ', 2- or 4-halopyrimidine derivatives of Formulas (II) and (IIa) in which R ', R¹', R² 'and are as defined above and Hal is a halogen atom, preferably fluorine or chlorine, with amines of the formula (III) HNR4'R5' in which R4 'and the meaning given above h optionally in the presence of a solvent or diluent and optionally in the presence of an acid binder, or b) in the event that the radical R is -NR R, the 4-amino-pyrimidine derivatives of the formula (IV) in which Hal represents halogen, preferably chlorine or fluorine, and R1, R21, R4 and R5 have the meaning given above, with compounds of the formula (V) R'H (V) in which R 'has the meaning given above, optionally in the presence of a solvent or diluent and optionally in the presence of an acid binder, or c) in the event that R5 is alkoxycarbonyl, 2-amino- or 4-amino-pyrimidines of the formulas (VII) or (VIIa) in which R ', R1, R2 and R³' have the meaning given above, with the proviso that only one of the radicals R 'and R³' stands for -NR4'R5 ', with halocarbonic acid esters of the formula (VIII) in which Hal "stands for a halogen atom, preferably chlorine and R6 stands for alkyl, optionally in the presence of a solvent or diluent and in the presence of an acid-binding agent.

Preferably, the substituents in the formula (Ia) have the following Meaning: R 'stands for -NR R, in which R4 stands for hydrogen, R5 for alkyl with 1 to 6 carbon atoms, such as methyl, ethyl, n- or iso-propyl, n-, sec.-, tert.- or iso-butyl, pentyl or hexyl, for alkenyl with 3 or 4 carbon atoms, such as Allyl, buten-1-yl and buten-2-yl, for alkoxyalkyl with 1 to 3 carbon atoms per alkyl part, such as methoxymethyl, ethoxymethyl, iso-propoxymethyl, 2-methoxy-ethyl, 2-ethoxyethyl, 2-iso-propoxy-ethyl, 3-methoxy-n-propyl and 3-ethoxy-n-propyl, for Phenyl, for alkoxycarbonyl with 1 to 3 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl and iso-propoxycarbonyl, for ethoxycarbonylmethyl, for phenylalkyl with 1 or 2 carbon atoms in the alkyl part, such as phenylmethyl, 1-phenyl-ethyl and 2-phenyl-ethyl, or R4 and R5, together with the nitrogen atom, on which they stand, one optionally substituted by methyl, ethyl or phenyl Form piperidine residue, piperazine residue or morpholine residue, R11 for methyl, methoxy, Ethoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, n-, se.-, tert.- or iso-butylthio, R is fluorine, chlorine, methoxy or ethoxy, R3 is hydrogen, Methylthio, ethylthio, n-propylthio, iso-propylthio, n-, se-, tert- or iso-butylthio, Methoxy or ethoxy or R 'stands for methylthio, methoxy or ethoxy, R1 for fluorine, chlorine, methyl, methoxy, ethoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, n-, sec-, tert- or iso-butylthio, R2 'stands for fluorine, chlorine, Is methoxy or ethoxy and R3 is -NR4 R5, in which R4 and R5 are as indicated above Have meaning.

The starting materials for carrying out the process according to the invention 2- or 4-halopyrimidine derivatives required are represented by the formulas (II) or (IIa) Are defined. In them the substituents already have at the meaning mentioned in the description of the compounds of the formula (Ia) according to the invention. Some of the compounds are new, but analogy techniques can be used are replaced by halogen atoms in the corresponding pyrimidines successively by others Residues, e.g. when reacting with methanol or ethanol in the presence of alkali metal carbonates, be exchanged / cf. Manufacture of the starting products "and" E. Klauke et al. " J. Fluorine Chem. 21, 495 (1982) 7. The polyhalopyrimidines required for this are e.g. known from DE-OS 2 187 780; D. Chambers, Mac Bride and Musgrave "Chem. And Ind. "1966", 1721; RE. Banks et al. "J. Chem.

Soc. C (9) ", 1280 (1970) 7.

The amines still required as starting compounds are through the formula (III) defines. In it the substituents have the meaning they already have was given at the corresponding substituents of the compounds of formula (Ia), The amines are generally known compounds in organic chemistry and also in available for purchase on a technical scale.

The 4-aminopyrimidine derivatives are also used as starting compounds required, which are defined by the formula (1V). The substituents have the Meaning, those already included for the corresponding substituents the compounds of formula (Ia) were given. The connections are partial new, but can be produced by analogy processes. For example, the 4-alkylamino-5-chloro-2,6-difluoropyrimidine from the known 5-chloro-2,4,6-trifluoropyrimidine (known from D. Chembers et.al. "Chem. And Ind." 1966, 1721) by reaction with equimolar amounts of alkylamine in Presence of triethylamine at -400C in tetrahydrofuran can be obtained. The follow-up reaction e.g. with sodium methyl mercaptide leads to the desired end products.

The connections of the Formula (V) as well as the halocarbonic acid esters defined by the formula (VIII) are well-known, easily accessible connections. The substituents in these Formulas have the meanings already related to these substituents with the compounds of formula (Ia) was given.

In addition, the 2- and 4-aminopyrimidines are used as starting materials required, which are defined by formulas (VII) and (VIIa). The substituents in these formulas have the meanings already related to these substituents given with the corresponding substituents in the compounds of formula (Ia) became. Some of these compounds are known, but so are the new compounds can be prepared by analogy processes, as already described from the corresponding halogen compounds (II) or (IIa) with ammonia.

The process can be carried out in the presence of solvents or diluents be performed.

As a diluent for carrying out the process variants according to the invention a) and b) are inert organic solvents.

These include, in particular, aliphatic or aromatic, if appropriate halogenated hydrocarbons, such as gasoline, benzene, toluene, xylene, Chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone or butanone; Nitriles such as acetonitrile or propionitrile; Amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide or esters, such as ethyl acetate.

Process variants a) and b) according to the invention are optionally used carried out in the presence of an acid binder.

All common inorganic or organic bases come as such in question. These include, for example, alkali metal hydroxides, amides and alcoholates or hydrides, such as sodium hydroxide or potassium hydroxide, sodium methylate or potassium t-butylate, Sodium hydride or sodium amide; Alkali metal carbonates, such as sodium carbonate, potassium carbonate nat or sodium hydrogen carbonate, as well as tertiary amines such as triethylamine, N, N-dimethylaniline, Pyridine or N, N-dimethylaminopyridine.

The reaction temperatures can when carrying out the invention Process a) and b) can be varied within a larger range. Generally works one at temperatures between -0 ° C and +200 "C, preferably at temperatures between 500C to 1200C.

As a diluent for carrying out the process variant according to the invention c) inert organic solvents or aqueous systems are suitable.

These include, in particular, aliphatic or aromatic, if appropriate halogenated hydrocarbons, such as gasoline, benzene, toluene, xylene, Chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone or butanone; Nitriles such as acetonitrile or propionitrile; Amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters, such as ethyl acetate, or heteroaromatics, like pyridine or quinoline.

Process variant c) according to the invention is optionally used in Carried out in the presence of an acid binder.

All common inorganic or organic bases come as such in question. These include, for example, alkali metal hydroxides, amides and alcoholates or hydrides, such as sodium hydroxide or potassium hydroxide, sodium methylate or potassium t-butylate, Sodium hydride or sodium amide; Alkali metal carbonates such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, as well as tertiary amines such as triethylamine, N, N-dimethylaniline, Pyridine or N, N-dimethylaminopyridine.

The reaction temperatures can when carrying out the invention Process variant c) can be varied over a wide range. In general one works at temperatures between -200C and 1500C, preferably at temperatures between 0 ° C and 500C.

The active ingredients which can be used according to the invention have a strong, specific nature Effect against BCM-resistant fungal strains. You can therefore fight against unwanted microorganisms are used. The active ingredients are for use only suitable as fungicides.

The active ingredients can mainly be used against all BCM-resistant strains, which are preferred for powdery mildew, scab, Cerospa species, Mycosphaerelia species, Botrytis species, Pseudocercosporella species, Penicillium species, Fusarium species, Sclerotinia species, Monilia species, Cladosporium species, Colletotrichum species or Verticillium species can be observed.

The good plant tolerance of the active ingredients in the control Concentrations necessary for plant diseases allow the treatment of above-ground parts of plants, of plant material and seeds, and of the soil.

Some of the active ingredients used according to the invention also have also a root systemic effect against leaf insects, also worth mentioning fungicidal effect against Pyricularia oryzae on rice (protective and systemic).

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, Finest encapsulation in polymeric substances and in coating compounds for seeds, as well as ULV formulations.

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents.

In the case of using water as an extender, e.g. organic solvents can be used as auxiliary solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or Paraffins, e.g. petroleum fractions, alcohols such as butanol or Glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water. With liquefied gaseous extenders or carriers are such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g.

Aerosol propellants such as halogenated hydrocarbons as well as butane, propane, Nitrogen and carbon dioxide. The following can be used as solid carriers: e.g. natural Ground rock, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as highly dispersed silica, Alumina and silicates. The following can be used as solid carriers for granulates: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules made from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks. Possible emulsifiers and / or foam-generating agents are: e.g. non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g.

Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates as well as protein hydrolysates. Possible dispersants are: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex shaped Polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Further additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active ingredients to be used according to the invention can be used in the formulations present in a mixture with other known active ingredients, such as fungicides, insecticides, Acaricides and herbicides, as well as in mixtures with fertilizers and growth regulators.

The active ingredients to be used can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable Concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, Dusts and granules. The application happens in the usual Way, e.g. by pouring, spraying, atomizing, scattering, dusting, spilling men, Brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume method to apply or to prepare the active ingredient or the active ingredient itself in the soil to inject. The seeds of the 5 plants can also be treated.

When treating parts of plants, the drug concentrations can be varied in the application forms over a wide range. You are in generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

In the treatment of seeds, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are required.

When treating the soil, the active ingredient concentrations are 0.00001 up to 0.1% by weight, preferably from 0.0001 to 0.02%, required at the site of action.

In practice one usually proceeds in such a way that d e according to the invention Active ingredients to be used with BCM, BCM analogues or with before, during or after the application of BCM-forming compounds together, i.e. preferably in a mixture with them, can be used to detect the sensitive and resistant fungal strains.

The BCM analogs include, for example, methyl-BCM and the BCM-forming ones Compounds e.g. methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate, 2- (2-furyl) -benzimide- azole, 2- (4-thiazolyl) -benzimidazole, 1,2-bis- (3-methoxycarbonyl-2-thioureido) -phenyl, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -phenyl, 2- (O, S-dimethylphosphorylamino) -1- (3'-methoxycarbonyl-2'-thioureido) -phenyl or 2- (O, O-dimethylthiophosphorylamino) -1- (3'-methoxycarbonyl-2'-thioureido) phenyl.

Usage examples In the following usage examples, the compound given below is used as a reference substance: Methyl benzimidazol-2-yl-carbamate (BCM) Example A Botrytis test (bean) / protective / Botrytis cinerea BCM-resistant Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkyl aryl polyglycol ether For the preparation of an appropriate Preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the active ingredient preparation to runoff. After the spray coating has dried on 2 small pieces of agar overgrown with Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened, humid chamber at 20 "C set up. 3 days after the inoculation, the size of the infestation spots on the Scroll evaluated.

In this test, for example, the compounds according to the following examples show a clear superiority in effectiveness compared to the prior art: Table A Botrytis test (bean) / protective / Botrytis cinerea BCM-resistant Active ingredient infestation in% in one Active ingredient concentration of 100 ppm H NNO -NH-CO-CH3 100 (known) C1 CH J NH-CH2-CH = CH 2 : 3 rJ o C1 t 5-NH-Co-C3H7-iso 13 C 2H50 Example B Botrytis cinerea / radial mycelial growth. Compounds according to the invention are each incorporated in graduated concentrations into an agar which is prepared from glucose, malt extract and peptone.

To produce an appropriate preparation of the active ingredient, the active ingredient dissolved in acetone. The ratio of acetone to nutrient medium is 0.2: 99.8.

After the agar has solidified, the inoculation of the agar thus produced takes place Agar samples with fresh mycelium of Botrytis cinerea - pure cultures based on benzimidazole fungicides react either sensitively or resistively.

After three days of incubation at 250C the radial mycelial growth evaluated. In the table, the ED50 value is that concentration of the active ingredient indicated, in which the mycelial growth is inhibited by 50%.

Compounds according to the following examples, for example, show in this test a clear superiority in effectiveness over the prior art, based on fungal isolates with resistance to benzimidazole fungicides: Table B Botrytis cinerea / radial mycelial growth Active ingredient ED value er ED50 value er means to means to a sensitive len isolate constant iso- (ppm) lat (ppm) H i½i ;; / NH0C "OCH3 0.06 100 (known) C1 n c3 7 12 2.0 JI H 3 9 N. C1I-NH- (CH,), - CH, 0.6 CH3S =: / L ~ CH3S H 3CN C1- C \) - NH- (CH2) 3-OCH3 25 2.4 N CH3 5 Table B (continued) Botrytis cinerea / radial mycelial growth Active ingredient ED50 value er ED value er means to means to a sensitive len isolate constant iso- (ppm) lat (ppm) H3CSN Cl NH-CH2-CH = CH2> 100 0.2 CH3 5 H3C -LT Cl g -NH-CH2-CH = CH2 90 5.5 CH3O Table B (continued) Botrytis cinerea / radial mycelial growth Active ingredient ED50 value er ED50 value er means to means to a sensitive len isolate constant iso- (ppm) lat (ppm) CH3O N r \ T CH3S K, C -NH-CH2-CH2-CH3 10 0.3 C 2H5 H3C C1-NH-CH, -CH = CH2 12 0.9 C 2H5 FC12C ; -N Cl - /) - NH-CH2-CH = CH2 100 0.8 C 2H5 Table B (continued) Botrytis cinerea / radial mycelial growth Active ingredient ED50 value er ED value er means to means to a sensitive len isolate constant iso- (ppm) lat (ppm) C2H5O N Cl- t} -NH-CH2-CH = CH2 11 5.5 H3C 0 Cl <N) NH C-OC3H7-iso> 100 1.2 C2H50 H3C Cl 4NH-CH-CH = CH2 100 30 N / tNH-CH2-CH = CH2 100 30 N F. C2 5 Cl Table B (continued) Botrytis cinerea / radial mycelial growth Active ingredient ED50 value er ED50 value er means to means to a sensitive len isolate constant iso- (ppm) lat (ppm) H3 U Q NH-CH2-CH = CH2 1.3 CH3 5 H3C Cl N $) / NNHCH2CH = CH2 100 20 C2H50 ffi Cl NNH-CH2-CH = CH2 10 2.4 Cl3C Example C Pseudocercosporella herpotrichoides / radial mycelial growth. Compounds according to the invention are each incorporated in graduated concentrations into an agar which is produced from glucose, malt extract and peptone.

To produce an appropriate preparation of the active ingredient, the active ingredient dissolved in acetone. The ratio of acetone to nutrient medium is 0.2: 99.8. After the agar has solidified, the agar samples produced in this way are inoculated with spores of Pseudocercosporella herpotrichoides - pure cultures sensitive to benzimidazole fungicides react either sensitively or resistively.

After three weeks of incubation at 250C, the radial growth is evaluated. In the table, that concentration of the active ingredient is given as the ED50 value, where growth is 50% inhibited.

Compounds according to the following examples, for example, show in this test a clear superiority in effectiveness over the prior art, based on fungal isolates with resistance to benzimidazole fungicides: Table C Pseudocercosporella herpotrichoides / radial mycelial growth Active ingredient ED50 value er ED50 value er means to means to a sensitive len isolate constant iso- (ppm) lat (ppm) Ii 0 S> NH-C-OCH3 0.1> 100 (known) CH, SN. C1NH-CH2-CH = CH,> 100 0.2 CH 3 H, C J \ 0 C2Hgo)> 100 0.4 CHO Preparation examples Example 1 15.4 g (0.08 mol) of 5-chloro-2-fluoro-4-methyl-6-methylthiopyrimidine are dissolved in 400 ml of dioxane, and 9.1 g (0.16 mol) of allylamine are added at 80.degree. After refluxing for 6 hours, the cooled reaction mixture is poured into 2 l of ice water and the product which has precipitated is filtered off with suction. After recrystallization from petroleum ether, 13.5 g (73% of theory) of 2-allylamino-5-chloro-4-methyl-6-methylthiopyrimidine with a melting point of 950 ° C. are obtained.

Example 2 To 10 g (0.05 mol) of 4-allylamino-5-chloro-2-fluoro-6-methylpyrimidine dissolved in 300 ml of dioxane, 25 ml (0.05 mol) of 2N sodium methyl mercaptide solution are added dropwise. After stirring for 6 hours at room temperature, the reaction mixture is diluted with 1 liter of water and extracted with methylene chloride. After drying over magnesium sulfate and removing the solvent, 4.8 g (48.2% of theory) of 4-allylamino-5-chloro-6-methyl-2-methylthiopyrimidine are obtained as a colorless oil, which solidifies and increases after prolonged standing 40 - 420C melts.

The compounds of the formula (I) are prepared analogously to one of the examples described above: Ex - R R¹ R² R³ Physical. Constants No. #Melting point: ° C; 20 # Refractive index: nD # 3 -NH2 -CH3 Cl -SCH3 112 4 -NH-CH3 -CH3 Cl -SCH3 157-159 5 -N (CH3) 2 -CH3 Cl -SCH3 62 6 -NH-C3H7-n -CH3 Cl -SCH3 98 7 -NH-C3H7-iso -CH3 Cl -SCH3 53 8 -NH- (CH2) 3-OCH3 -CH3 Cl -SCH3 67-69 9 -NH- # -CH3 Cl -SCH3 82 10 -NH-CH2-CH = CH2 -CH3 Cl -OCH3 75-77 11 -NH-CH2-CH = CH2 -CH3 Cl -OC2H5 50-52 12 -NH-C3H7-n -CH3 Cl -OC3H5 45 -47 13 -NH2 -CH3 CL -OC2H5 123 14 -NH2 -CH3 Cl -SCH3 130-132 15 -NH-CH2-CH = CH2 -CH3 Cl -SCH§ 40-42 Ex - R R¹ R² R³ Physical. Constants No. # Melting point: ° C; 20 # Refractive index: nD # 16 -NH-CH3 - ## -SCH3 CL - SCH3 1.6135 # CH3 17 -NH-CH2-CH = CH2 -OC2H5 CL -OC2H5 in the mix with -OC2H5 OC2H5 CL -NH-CH2-CH = CH2 18 -NH-CH2-CH = CH2 -OC2H5 CL H 82-84 19 -NH-CH2-CH = CH2 -OC2H5 -OC2H5 H 73-75 (analogous to example 1, but under pressure for 6 h at 160 ° c) 20 -NH-CH2-CH = CH2 -CCl2 CL -OC2H5 1.5490 21 -CCl3 CL CL -NH-CH2-CH = CH2 bp 20 ° C / 0.2 mm Hg 22 F -CH3 CL -NH-CH2-CH = CH2 43-45 23 -NH-CH2-CH = CH2 -OCH3 CL -SCH3 1.5940 24 -NH-CH2-CH = CH2 F CL -OC2H5 mixture F -OC2H5 Cl -NH-CH2-CH = CH2 40:60% (with equivalent amounts of amine and triethylamine) 25 -OC2H5 -CH3 CL -NH-CH2-CH = CH2 bp .: 230 ° C / 1 mm Hg 26 -SCH3 -SCH3 CL -NH-CH2-CH = CH2 mixed with -NH-CH2-CH = CH2 -SCH3 CL -SCH3 27 -OC2H5 -OC2H5 CL -NH-CH2-CH = CH2 1.5349 28 -NH-CH2-COOC2-H5 -SCH3 CL -SCH3 142 - 146 CH3 # 29 -NH-CH-C6H5 SCH3 CL -SCH3 1: 6315 Ex - R R¹ R² R³ Physical. Constants No. # Melting point: ° C; 20 # Refractive index: nD- # 30 -NH- (CH2) 3-CH3 -SCH3 CL -SCH3 43 - 46 31 -NH- (CH2) 3-CH3 -SCH3 CL -SCH3 bp 220 ° C / 0.1 mm Hg 32 -N ## O -SCH3 CL -SCH3 130 33 -N ## N-CH3 -SCH3 CL -SCH3 95 34 -N ## N-C6H5 -SCH3 CL -SCH3 140 - 143 Example 35 7.5 g (0.04 mol) of 2-amino-5-chloro-4-methyl-6-methylthiopyrimidine are dissolved in 100 ml of pyridine with the addition of 10 mg of 4-dimethylaminopyridine. 9.8 g (0.04 mol) of isopropyl chlorocarbonate are added dropwise at OOC and the mixture is stirred at room temperature for 10 h. After dilution with 800 ml of water, extraction with toluene, drying of the organic phase over sodium sulfate and removal of the solvent, the resulting residue is chromatographed on silica gel with ethyl acetate / petroleum ether = 1/5. 4 g (37% of theory) of N- (5-chloro-4-methyl-6-methylthiopyrimidin-2-yl) -carbamic acid isopropyl ester with a melting point of 960 ° C. are obtained.

The following are prepared analogously to Example 35: Example- R R¹ R² R³ Physical. Constants # Melting point: ° C # 36 -NH-COOC3H7-iso -CH3 CL -OC2H5 106 - 108 37 -NH-COOC3H7-iso -SCH3 CL -SCH3 124 38 -NH-COOC3H7-iso -OC2H5 CL H 166 - 168 Production of the starting products Example a: 16.5 g (1 mol) of 5-chloro-2,6-difluoro-4-methylpyrimidine (prepared according to the instructions from DE-PS 2 187 780) are dissolved in 200 ml of methanol at -200.degree. 50 ml (0.1 mol) of aqueous 2N NaSCH3 solution are added dropwise to this, the mixture is stirred for 30 minutes at −200 ° C., the reaction mixture is brought to room temperature and it is stirred into 1 liter of ice water. After suctioning off and drying, 18 g (93.5% of theory) of 5-chloro-2-fluoro-4-methyl-6-methylthiopyrimidine with a melting point of 68-71 ° C. are obtained.

Example b: 135 g (0.8 mol) of 5-chloro-2,4,6-trifluoropyrimidine are added dropwise at 0 ° C. to a mixture of 700 ml of ethanol and 800 ml of aqueous 2N NaSCH3 solution, the mixture is stirred for 4 hours at room temperature and the reaction mixture is added to 2 1 ice water. The resulting precipitate is filtered off with suction and dried. 175 g (97% of theory) of 5-chloro-4,6-bismethylthio-2-fluoropyrimidine with a melting point of 1350 ° C. are obtained.

Analogously or according to E. Klauke et al. "J. Fluorine Chem." 21, 495 (1982) can be produced: Melting point: 56-570C Boiling point: 1040C / 30 mm Hg Boiling point: 34 ° c / 0.7 mm Hg 20 refractive index: nD = 1.4663; Boiling point: 840C / 20 mm Hg Melting point: 134-136 ° C Boiling point: 90-920C / made from see DE-OS 2 920 9497 Melting point: 49-51 # made # from produced analogously to JHChesterfield et.al.

"J. Chem. Soc.", 4590 (1969) m.p. 50OC7 Refractive index: nD ° = 1.5030 Refractive index: nD [made from known from E. Klauke et.al.

"J. Fluorine Chem." 21, 495 (1982) #

Claims (10)

Claims 1. Selective fungicidal agents, characterized in that they contain at least one pyrimidine derivative of the formula (I) in which R stands for halogen, haloalkyl, alkyl, alkoxy, alkylthio or for where R4 is hydrogen, alkyl or alkenyl, R5 is hydrogen, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, aryl or aralkyl; or R4 and R5 with the nitrogen atom on which they are attached form a saturated, optionally substituted heterocycle which may contain further heteroatoms, R1 is alkyl, haloalkyl, alkoxy, alkylthio, halogen or phenylthio, R2 is alkoxy or halogen and R3 stands for hydrogen, alkyl, alkoxy, alkylthio, phenylthio, or for stands, where R4 and R5 have the same meaning as given above, with the proviso that one of the radicals R or R3 is stands. 2. Selective fungicidal agent according to claim 1, wherein R is fluorine, chlorine, straight-chain or branched haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkyl, alkoxy or alkylthio each with 1 to 4 carbon atoms or for what R4 stands for hydrogen, for straight-chain or branched alkyl with 1 to 6 carbon atoms or for straight-chain or branched alkenyl with 3 to 6 carbon atoms, R5 for hydrogen, for straight-chain or branched alkyl with 1 to 8 carbon atoms, for straight-chain or branched haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, for straight-chain or branched alkenyl with 3 to 6 carbon atoms, for cycloalkyl with 3 to 6 carbon atoms, for straight-chain or branched alkoxyalkyl, alkoxycarbonyl or alkoxycarbonylalkyl with 1 to 4 carbon atoms per alkoxy and alkyl part, for phenyl or phenylalkyl with 1 to 4 carbon atoms in the straight-chain or branched alkyl part, or R4 and R5 with the nitrogen atom on which they stand, a saturated 5- or 6 optionally substituted by alkyl with 1 to 4 carbon atoms or phenyl -linked heterocycle, the further hete roatoms, identical or different, can contain, form, R1 for straight-chain or branched alkyl with 1 to 4 carbon atoms, for straight-chain or branched haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, for straight-chain or branched alkoxy or alkylthio with 1 to 4 carbon atoms per alkyl part, stands for fluorine, chlorine or phenylthio, R2 stands for straight-chain or branched alkoxy with 1 to 6 carbon atoms, for fluorine or chlorine R³ stands for hydrogen, for straight-chain or branched alkyl with 1 to 4 carbon atoms, for straight-chain or branched alkoxy or alkylthio with 1 to 4 carbon atoms per alkyl part, for phenyltio or for -NR4R5, where R4 and R5 have the meaning given above, with the measure that one of the radicals R ader R3 for stands. 3. Selective fungicidal agent according to claim 1, wherein R for Fluor1 for haloalkyl with 1 or 2 carbon atoms and 1 to 5 identical or different fluorine and chlorine atoms, for straight-chain or branched alkyl with 1 to 3 carbon atoms, alkoxy or alkylthio with 1 each or 2 carbon atoms or represents wherein R4 represents hydrogen, methyl, ethyl or allyl, R5 represents hydrogen, for straight-chain or branched alkyl with 1 to 6 carbon atoms, for straight-chain or branched alkenyl with 3 or 4 carbon atoms, for cyclopentyl, cyclohexyl, for straight-chain or branched alkoxyalkyl with 1 to 3 carbon atoms per alkoxy and alkyl part, for alkoxycarbonyl with 1 to 3 carbon atoms in the alkoxy part, for alkoxycarbonylalkyl with 1 to 3 carbon atoms in the alkoxy part and 1 or 2 carbon atoms in the alkyl part, for phenyl or phenylalkyl with 1 or 2 carbon atoms in the alkyl part, or R4 and R5 together with the nitrogen atom on which they are attached form a pyrrolidine radical, piperidine radical, piperazine radical or morpholine radical, optionally mono- to three-fold, identically or differently substituted by methyl, ethyl or phenyl, R1 for methyl, ethyl, trichloromethyl, dichlorofluoromethyl, methoxy, ethoxy , n-propoxy, iso-propoxy, methylthio, ethylthio, n-propylthio, iso-propylth io, n-, sec-, tert- or iso-butylthio, fluorine or phenylthio, R2 stands for methoxy, ethoxy, n-propoxy, iso-propoxy, fluorine or chlorine, R³ stands for hydrogen, methyl, ethyl, methoxy , Ethoxy, n-propoxy, iso-propoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, n-, sec-, tert- or iso-butylthio, phenylthio or -NR4R5, in which R4 and R5 represent the Have the meaning given above, with the proviso that one of the radicals R or R3 stands for -NR4R5. 4. Method of combating BCM-resistant fungal strains, thereby characterized in that pyrimidine derivatives of the formula (I) according to claim 1 are BCM-resistant Allows fungus strains and / or their habitat to act. 5. Use of pyrimidine derivatives of the formula (I) according to claim 1 for combating BCM-resistant fungal strains. 6. Process for the preparation of selective fungicidal agents, thereby characterized in that pyrimidine derivatives of the formula (I) according to Claim 1 are mixed with extenders and / or surfactants mixed together. 7. Process for the preparation of fungicidal agents according to the claims 1 and 6, characterized in that pyrimidine derivatives of the formula (I) with BCM and / or BCM-forming compounds and with extenders and / or surface-active Means mixed up. 8. Pyrimidine derivatives of the formula (Ia) in which R 'stands for -NR4'R5', in which 4, R @ stands for hydrogen, R5 'for alkyl, cycloalkyl, alkenyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, aryl or for aralkyl or R4' and R5 'together with the Nitrogen atom in which they stand form a pyrrolidine, piperidine, piperazine or morpholine radical, which is optionally substituted one to three times, identically or differently, by alkyl having 1 to 4 carbon atoms or phenyl, R¹ 'is alkyl, haloalkyl, alkoxy or alkylthio , R2 'stands for fluorine, chlorine or alkoxy and R³' stands for hydrogen, alkoxy or alkylthio or R 'stands for alkoxy or alkylthio, R11 stands for halogen, alkyl, alkoxy or alkylthio, R²' stands for fluorine, chlorine or alkoxy and R³ 'stands for -NR4 R5, where R4 and R5 have the meanings given above. 9. pyrimidine derivatives of the formula (Ia) according to claim 8, wherein R 'is -NR4, R5, where 4 'R is hydrogen, R5 is alkyl having 1 to 6 carbon atoms, for alkenyl with 3 or 4 carbon atoms, for alkoxyalkyl with 1 to 3 carbon atoms per alkyl part, for phenyl, for alkoxycarbonyl with 1 to 3 carbon atoms, for Ethoxycarbonylmethyl, for phenylalkyl with 1 or 2 carbon atoms in the alkyl part, or R4 and R5 together with the nitrogen atom on which they are attached, one optionally substituted by methyl, ethyl or phenyl piperidine radical, piperazine radical or form morpholine radical, R1 for methyl, methoxy, ethoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, n-, sec.-, tert. - Or iso-butylthio, R2 is Stands for fluorine, chlorine, methoxy or ethoxy, 3 'R for hydrogen, methylthio, ethylthio, n-propylthio, iso-propylthio, n-, sec.-, tert. - or iso-butylthio, methoxy or Is ethoxy or R 'is methylthio, methoxy or ethoxy, R¹ ' for fluorine, chlorine, methyl, methoxy, ethoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, n-, sec-, tert- or iso-butylthio, R2 'stands for fluorine, chlorine, Methoxy or ethoxy and R3 is -NR4, R5, in which R4 and R5 are as indicated above Have meaning. 10. Process for the preparation of pyrimidine derivatives of the formula (Ia) in which R 'stands for -NR4'NR5', in which R4 'stands for hydrogen, 5' for alkyl, cycloalkyl, alkenyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, aryl or for aralkyl or R4 and R5 together with the nitrogen atom on which they are, form a pyrrolidine, piperidine, piperazine or morpholine radical, which is optionally substituted one to three times, identically or differently by alkyl with 1 to 4 carbon atoms or phenyl, R11 stands for alkyl, haloalkyl, alkoxy or alkylthio, R2 for fluorine, Is chlorine or alkoxy and R³ 'is hydrogen, alkoxy or alkylthio or R' is alkoxy or alkylthio, R¹ 'is halogen, alkyl, alkoxy or alkylthio, R2' is fluorine, chlorine or alkoxy and R3 is -NR4 R5 where R4 and R5 have the meaning given above, characterized in that a) if one of the radicals R 'or R31 is -NR4, R5, 2- or 4-halopyrimidine derivatives of the formulas ( II) or (IIa) in which R ', R11, R²' and R³ 'have the meaning given above and Hal stands for a halogen atom, with amines of the formula (III) HNR4'R5' (III) in which R4 'and R5' have the meaning given above , if appropriate in the presence of a solvent or diluent and if appropriate in the presence of an acid binder, or b) in the event that the radical R31 is -NR4, R5 ', the 4-aminopyrimidine derivatives of the formula (IV) in which Hal stands for a halogen atom and R1 ', R²', R4 and R5 have the meaning given above, with compounds of the formula (V) R'H (V) in which R has the meaning given above, optionally in the presence of a solution - or diluent and optionally reacts in the presence of an acid binder, or c) in the event that R5 is alkoxycarbonyl, 2-amino- or 4-amino-pyrimidines of the formulas (VII) or (VIIa) in which R ', R11, r²' and R3 have the meaning given above, with the proviso that only one of the radicals R 'and R31 is -NR41R5, with halocarbonic acid esters of the formula (VIII) in which Hal "stands for a halogen atom and R6 stands for alkyl, optionally in the presence of a solvent or diluent and in the presence of an acid-binding agent.