DE4029649A1 - New 2-pyridyl-pyrimidine derivs. - useful as fungicides - Google Patents

Abstract

2-Pyridylpyrimidine derivs. of formula (I) are new: R1 = H, alkyl, alkoxyalkyl, alkylthioalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, phenoxyalkyl, phenylthioalkyl or phenylalkyl, where cycloalkyl is opt. substd. by alkyl and phenyl is opt. substd. by halogen, alkyl, alkoxy, alkylthio, haloalkyl, NO2 or CN; R2 and R4 = H, alkyl or phenyl opt. substd. by halogen, (halo)alkyl, (halo)alkoxy, alkylthio or NO2; or R1+R2 forms a 3- to 8-membered ring; R3 = alkyl, cycloalkylalkyl, cycloalkyl, haloalkyl or phenylalkyl or phenoxyalkyl opt. substd. by halogen, (halo)alkyl, (halo)alkoxy, alkylthio or NO2; R5 = H, alkyl, alkoxyalkyl, alkylthioalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, haloalkyl, halogen, phenyl or phenylalkyl, where cycloalkyl is opt. substd. by alkyl and phenyl is opt. substd. by halogen, (halo)alkyl, (halo)alkoxy, alkylthio or NO2; R6 = H, alkyl, haloalkyl, alkoxy, thialkyl (sic), alkenylalkoxy, alkynylalkoxy, halogen or phenyl, phenylalkyl or phenoxyalkyl opt. substd. as in R3; R7 = H, alkyl, alkoxyalkyl, alkylthioalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, haloalkyl, alkoxy, alkylthio, halogen, phenyl, phenoxy, phenylthio, phenylalkyl, phenoxyalkyl, phenylthioalkyl, phenylalkoxy, phenylalkylthio, alkenylalkoxy, alkylnylalkoxy, haloalkoxy, alkoxyalkoxy, phenylalkoxyalkoxy, hydroxyalkoxy, alkylthioalkylthio, NR8R9 or NHNR8R9, where cycloalkyl is opt. substd. by alkyl and phenyl is opt. substd. by COOH, halogen (halo)alkyl, (halo)alkoxy, alkylthio or NO2; R8 and R9 = H, alkyl, hydroxyalkyl, heterocyclylalkyl, alkenylalkyl, alkynylalkyl, cycloalkyl, cycloalkylalkyl, CHO, phenyl or phenylalkyl, where cycloalkyl is opt. substd. by alkyl and phenyl is opt. substd. by halogen, alkyl, COOH, alkoxy, CF3 or CCl3; or NR8R9 is an opt. substd. 5- to 7-membered ring contg. 1 or 2 heteroatoms.

Description

The present invention relates to alkoxypyridyl-pyrimidine derivatives, processes for their Manufacture, compositions containing them and their use as fungicides.

Pyrimidine derivatives are already known as effective components in fungicidal compositions (see EP-A-270 362, EP-A-259 139, EP-A-234 104). The effect of this However, pyrimidine derivatives are not always available, especially when low application rates are involved satisfying.

New pyrimidine derivatives have been found which have advantageous effects in the Control of a wide range of phytopathogenic fungi, especially at low levels Have dosages.

The present invention therefore relates to compounds of the formula I.

wherein
R¹ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) alkoxy- (C₁-C₄-) alkyl, (C₁-C₄) alkylthio- (C₁-C₄) alkyl, (C₂-C₆) alkenyl, (C₂- C₆) alkynyl, (C₃-C₇) cycloalkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, where the latter two radicals in the cycloalkyl part can be substituted up to three times by (C₁-C₄) alkyl, phenyl, phenoxy- (C₁-C₄) alkyl, phenylmercapto- (C₁-C₄) alkyl, phenyl- (C₁-C₄) alkyl, the four last-mentioned radicals in the phenyl part being up to threefold by halogen, (C₁-C₄) alkyl, (C₁-C₄) Alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) haloalkyl, or can simply be substituted by nitro or cyano, and halo can be substituted one or more times by halogen atoms,
R², R⁴ = independently of one another hydrogen, (C₁-C₆) alkyl, phenyl, the phenyl radical being up to threefold by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁- C₄) haloalkyl, (C₁-C₄) haloalkoxy or simply substituted by nitro, and halo can be substituted one or more times by halogen atoms,
R¹ and R² together form part of a maximally saturated 3- to 8-membered ring,
R³ = (C₁-C₆) alkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) haloalkyl, phenyl- (C₁-C₄) alkyl, phenoxy- (C₁ -C₄) alkyl, the latter two radicals in the phenyl part up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) haloalkyl, (C₁-C₄ ) Haloalkoxy or can be substituted simply by nitro, and can mean halo substituted one or more times by halogen atoms,
R⁵ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₄) alkylthio- (C₁-C₄) alkyl, (C₂-C₆) alkenyl, (C₂-C₆ ) Alkynyl, (C₃-C₇) cycloalkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, where the latter two radicals in the cycloalkyl part can be substituted up to three times by (C₁-C₄) alkyl, (C₁-C₄) Haloalkyl, halogen, phenyl or phenyl- (C₁-C₄) alkyl, the latter two radicals in the phenyl part being up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁ -C₄) haloalkyl, (C₁-C₄) haloalkoxy or simply substituted by nitro, and halo can be mono- or polysubstituted by halogen atoms,
R⁶ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) thioalkyl, (C₂-C₄) alkenyl- (C₁-C₄) alkoxy, (C₂-C₄ ) Alkynyl- (C₁-C₄) alkoxy, halogen, phenyl, phenyl- (C₁-C₄) alkyl, phenoxy- (C₁-C₄) alkyl, the three last-mentioned radicals in the phenyl part being up to three times by halogen, (C₁-C₄) Alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) haloalkyl, (C₁-C₄) haloalkoxy or can be substituted simply by nitro, and can mean halo substituted one or more times by halogen atoms,
R⁷ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₄) alkylthio- (C₁-C₄) alkyl, (C₂-C₆) alkenyl, (C₂-C₆ ) Alkynyl, (C₃-C₇) cycloalkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, where the latter two radicals in the cycloalkyl part can be substituted up to three times by (C₁-C₄) alkyl, (C₁-C₄) Haloalkyl, (C₁-C₁₈) alkoxy, (C₁-C₆) alkylthio, halogen, phenyl, phenoxy, phenylthio, phenyl- (C₁-C₄) alkyl, phenoxy- (C₁-C₄) alkyl, phenylthio- (C₁-C₄) alkyl , Phenyl- (C₁-C₄) alkoxy, phenyl- (C₁-C₄) alkylthio, the eight last-mentioned radicals in the phenyl part up to three times by carboxyl, halogen, (C₁-C₁) alkyl, (C₁-C₄) alkoxy, (C₁ -C₄) alkylthio, (C₁-C₄) haloalkyl, (C₁-C₄) haloalkoxy or simply substituted by nitro, (C₂-C₄) alkenyl- (C₁-C₄) alkoxy, (C₂-C₄) alkynyl- (C₁- C₄) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkoxy, phenyl- (C₁-C₄) alkoxy- (C₁-C₄) alkox y, (C₁-C₆) hydroxyalkoxy, (C₁-C₄) alkylthio- (C₁-C₄) alkylthio, amines of the formula NR⁸R⁹ or hydrazines of the formula NH-NR⁸R⁹, and halo can be substituted one or more times by halogen atoms,
R⁸, R⁹ independently of one another hydrogen, (C₁-C₆) alkyl, (C₁-C₆) hydroxyalkyl, (C₃-C₇) heterocyclyl- (C₁-C₆) alkyl, (C₂-C₄) alkenyl- (C₁-C₂) alkyl, ( C₂-C₄) alkynyl- (C₁-C₂) alkyl, (C₃-C₇) cycloalkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, the latter two radicals in the cycloalkyl part being up to twice by (C₁-C₄) Alkyl may be substituted, formyl, phenyl, phenyl- (C₁-C₄) alkyl, the latter two radicals in the phenyl part being substituted up to twice by halogen, (C₁-C₄) alkyl, carboxyl, (C₁-C₄) alkoxy, trifluoromethyl or trichloromethyl can be substituted,
R⁸ and R⁹ together with the nitrogen atom to which they are attached mean an unsubstituted or up to doubly substituted 5- to 7-membered saturated or unsaturated heterocycle with 1 or 2 identical or different heteroatoms,
as well as their acid addition salts.

Preferred among the compounds of formula I are those in which
R¹ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) alkoxy- (C₁-C₂) alkyl, phenyl, phenoxy- (C₁-C₂) alkyl or phenyl- (C₁-C₄) alkyl, the latter three Residues in the phenyl moiety can be substituted up to three times by halogen, (C₁-C₄) alkoxy.

R² preferably denotes hydrogen, (C₁-C₄) alkyl, phenyl, which can be substituted up to three times by halogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy,
R¹ and R² together form part of a maximally saturated 5- to 7-membered ring, and
R³ preferably denotes (C₁-C₆) alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) haloalkyl, phenyl- (C₁-C₂) alkyl, phenoxy- (C₁-C₂) alkyl, the latter two radicals in the phenyl part bis can be substituted three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) haloalkyl.

R⁴ preferably denotes hydrogen or (C₁-C₄) alkyl,
R⁵ is preferably hydrogen, (C₁-C₆) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₃) alkyl, (C₁-C₄) haloalkyl, halogen, phenyl, phenyl- (C₁-C₂ ) alkyl, where the latter two radicals in the phenyl moiety can be substituted up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₂) haloalkyl, and
R⁶ preferably denotes hydrogen, (C₁-C₆) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₂-C₄) alkenyl- (C₁-C₄) alkoxy, (C₂- C₄) alkynyl- (C₁-C₄) alkoxy, halogen, phenyl, phenyl- (C₁-C₄) alkyl, phenoxy- (C₁-C₄) alkyl, the last three radicals in the phenyl part being up to three times by halogen, (C₁-C₄ ) Alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) haloalkyl, (C₁-C₄) haloalkoxy or simply substituted by nitro or cyano.

R⁷ preferably denotes hydrogen, (C₁-C₆) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₃) alkyl, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₄) alkylthio- (C₁-C₄) alkyl, (C₂-C₆) alkenyl, (C₂-C₆) alkynyl, (C₁-C₁₈) alkoxy, (C₁-C₄) alkylthio, (C₂-C₆) alkenyl- (C₁-C₄) alkoxy, (C₂-C₆) alkynyl- (C₁-C₄) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkoxy, (C₁-C₄) hydroxyalkoxy, Phenyl- (C₁-C₂) alkoxy- (C₁-C₄) alkoxy, (C₁-C₄) alkylthio- (C₁-C₄) alkylthio, halogen, Phenyl, phenoxy, phenylthio, phenyl- (C₁-C₂) alkyl, phenyl- (C₁-C₂) alkoxy, Phenyl- (C₁-C₂) alkylthio, the six latter radicals in the phenyl part up to triple by carboxyl, halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₂) haloalkyl or (C₁-C₃) haloalkoxy may be substituted, amines of the formula NR⁸R⁹ or hydrazines of the formula NH-NR⁸N⁹.  

R⁸, R⁹ preferably independently represent hydrogen, (C₁-C₄) alkyl, (C₁-C₄) hydroxyalkyl, (C₅-C₆) heterocyclyl- (C₁-C₄) alkyl, (C₂-C₃) alkenyl- (C₁-C₂) alkyl , (C₂-C₃) alkynyl- (C₁-C₂) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₂) alkyl, the latter two radicals in the cycloalkyl part being up to twice by (C₁- C₄) alkyl can be substituted, formyl, phenyl, phenyl- (C₁-C₂) alkyl, the latter two radicals in the phenyl part being substituted up to twice by halogen, (C₁-C₃) alkyl, carboxyl, (C₁-C₃) alkoxy, trifluoromethyl or trichloromethyl may be substituted, or
R⁸ and R⁹ together with the nitrogen atom to which they are attached form an unsubstituted or up to twice substituted 5- to 7-membered saturated or unsaturated heterocycle with 1 or 2 identical or different heteroatoms.

In formula I mean
R¹ in particular hydrogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy-methyl, phenyl, phenoxy-methyl, phenyl (C₁-C₄) alkyl, the three last-mentioned radicals in the phenyl part being up to three times by halogen, (C₁- C₄) alkyl or (C₁-C₄) alkoxy may be substituted.

R² is especially hydrogen, (C₁-C₄) alkyl, phenyl, with phenyl part up to can be substituted three times by halogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy, or together with R¹ part of a maximally unsaturated 5- to 7-membered ring forms.

R³ means in particular (C₁-C₆) alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) haloalkyl, phenyl- (C₁-C₂) alkyl, phenoxy- (C₁-C₂) alkyl, the phenyl radical of the last two examples bis can be substituted three times with halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, or (C₁-C₄) haloalkyl, and
R⁴ means in particular hydrogen or (C₁-C₂) alkyl.

R⁵ means in particular hydrogen, (C₁-C₆) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₃) alkyl, (C₁-C₄) haloalkyl, halogen, phenyl, phenyl-methyl, the the latter two radicals in the phenyl moiety can be substituted up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₂) haloalkyl,
R⁶ means in particular hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, halogen, phenyl, phenyl-methyl, the phenyl radical of the last two examples up to can be substituted three times with halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) haloalkyl, and
R⁷ means in particular hydrogen, (C₁-C₄) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl-methyl, (C₂-C₆) alkenyl, (C₂-C₆) alkynyl, (C₁-C₁₈) alkoxy, ( C₁-C₄) alkylthio, (C₂-C₆) alkenyl- (C₁-C₂) alkoxy, (C₂-C₆) alkynyl (C₁-C₃) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁- C₂) alkoxy, (C₁-C₄) hydroxyalkoxy, halogen, phenyl-methoxy- (C₁-C₄) alkoxy, phenyl, phenoxy, phenylmercapto, phenyl (C₁-C₂) alkyl, phenyl (C₁-C₂) alkoxy, phenyl-methylthio, where the latter seven radicals in the phenyl moiety can be substituted up to three times by carboxyl, halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₂) haloalkyl or (C₁-C₃) haloalkoxy, amines of the form NR⁸R⁹ or hydrazines of the form NH-NR⁸N⁹.

R⁸, R⁹ mean in particular independently of one another hydrogen, (C₁-C₄) alkyl, (C₁-C₂) hydroxyalkyl, (C₅-C₅) heterocyclyl- (C₁-C₄) alkyl, (C₂-C₃) alkenyl-methyl, (C₂- C₃) alkynyl-methyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl-methyl, where the latter two radicals in the cycloalkyl part can be substituted up to twice by (C₁-C₄) alkyl, formyl, phenyl, phenyl-methyl , where the latter two radicals in the phenyl moiety can be substituted up to twice by halogen, (C₁-C₃) alkyl, (C₁-C₃) alkoxy, carboxyl, trifluoromethyl or trichloromethyl, or
R⁸, R⁹ together with the nitrogen atom to which they are attached represent an up to doubly substituted 5- or 6-membered saturated or unsaturated heterocycle with 1 or 2 identical or different heteroatoms, particularly preferably with the heteroatoms nitrogen and / or oxygen and the Substituents (C₁-C₂) alkyl.

The alkyl, alkenyl or alkynyl radicals can be either straight-chain or branched be. Halogen means F, Cl, Br, J, preferably F, Cl, Br. The prefix "Halo" in the Designation of a substituent means that this substituent is single or multiple can occur with the same or different meaning. The prefix "Halo" includes Fluorine, chlorine,  Bromine or iodine, preferably fluorine, chlorine or bromine. As examples of haloalkanes may be mentioned: CF₃, CF₂CHF₂, CCl₃, CCl₂F, CF₂CF₂CF₃, CF₂CHFCF₃, CH₂CF₃ and (CH₂) ₃CF₃.

The following are used to prepare the acid addition salts of the compounds of the formula I. Acids in question:

Hydrohalic acids such as hydrochloric acid or hydrobromic acid, further Phosphoric acid, nitric acid, sulfuric acid, mono- or bifunctional carboxylic acids and hydroxycarboxylic acids such as acetic acids, succinic acid, fumaric acid, tartaric acid, Citric acid, salicylic acid, sorbic acid or lactic acid, and sulfonic acids such as p-toluenesulfonic acid or 1,5-naphthalenedisulfonic acid. The acid addition salts of Compounds of the formula I can be prepared in a simple manner by customary methods Salt formation methods, e.g. B. by dissolving in an organic solvent and Add the acid obtained and in a known manner, e.g. B. by filtering, isolated and optionally cleaned by washing with an inert solvent will.

The present invention also relates to a method for producing the Compounds of formula I.

The alkoxypyridyl pyrimidine derivatives of formula I can be according to the following Methods are made:

a) Pyrimidine derivatives of formula I with R⁷ = H can be according to the following Reaction equation through reductive dehalogenation of corresponding Halopyrimidines, in which Hal stands for halogen (Cl, Br, J) and the rest Substituents as defined in formula I can be obtained. Dehalogenation can with hydrogen in the presence of catalysts (e.g. palladium / carbon) in an inert Solvent z. B. water, lower alcohol (such as methanol and ethanol), ethyl acetate or toluene or mixtures thereof. The addition is advantageous of bases such as alkali or alkaline earth metal hydroxides or carbonates. The reaction is preferably in the range from 15 ° C. to 60 ° C. under a hydrogen pressure of 1 to 5 carried out in cash.  

b) pyrimidine derivatives of the formula I, in which R⁷ = (C₁-C₁₈) alkoxy, (C₁-C₃) alkylthio, (C₂-C₆) alkenyl- (C₁-C₄) alkoxy, (C₂-C₆) alkynyl- (C₁-C₄) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkoxy, phenyl- (C₁-C₂) alkoxy- (C₁-C₄) alkoxy, (C₁-C₄) alkylthio- (C₁-C₄) alkylthio, phenoxy, phenylmercapto, phenyl- (C₁-C₂) alkoxy, Phenyl- (C₁-C₂) alkylthio, the four latter radicals in the phenyl part up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₂) haloalkyl or (C₁-C₃) haloalkoxy may be substituted means by reaction of corresponding ones Halopyrimidines with an alkali metal compound of the formula R⁷-Y (II), in which R⁷ is like is defined above and Y = an alkali metal. Examples for alkali metals are sodium, potassium and lithium.

The reaction can take place between 0 ° C and 130 ° C within 0.5 to 72 hours be performed. The alkali metal compound R⁷-Y can be used in amounts of 1 to 2 Molar equivalents, based on 1 equivalent of halopyrimidine, are used. The Reactions are carried out in the presence of a solvent.

In cases where an alkali metal compound R⁷-Y is used, in which R⁷ = (C₁-C₁₈) alkoxy, (C₂-C₆) alkenyl- (C₁-C₄) alkoxy, (C₂-C₆) alkynyl- (C₁-C₄) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkoxy, phenyl- (C₁-C₂) alkoxy- (C₁-C₄) alkoxy, or phenyl- (C₁-C₂) alkoxy means, the corresponding one is expediently  Alcohol R⁷ or an ether (e.g. diethyl ether, dioxane or tetrahydrofuran) or a Mixture of the same used as a solvent. In cases where one Alkali metal compound R⁷-Y is used, in which R⁷ = (C₁-C₃) alkylthio, (C₁-C₄) alkylthio- (C₁-C₄) alkylthio, phenoxy, phenylmercapto, phenyl- (C₁-C₂) alkylthio means an ether (e.g. diethyl ether, dioxane or tetrahydrofuran), a nitrile (e.g. Acetonitrile), an aromatic hydrocarbon (e.g. toluene or xylene) or one Mixture of the same used as a solvent.

c) pyrimidine derivatives of the formula I, in which R⁷ = (C₁-C₆) alkyl, phenyl- (C₁-C₂) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₃) alkyl, (C₂-C₆) alkenyl, (C₂-C₆) alkynyl or Phenyl means, the latter radical up to three times by (C₁-C₄) alkyl or (C₁-C₄) alkoxy can be substituted by reacting corresponding Halopyrimidines with Grignard compounds R⁷-MgX (III), where R⁷ as indicated above and X is halogen (Cl, Br, J) in the presence of a catalyst, for example 1,2-bis (diphenylphosphino) ethane nickel (II) chloride or 1,2-bis (diphenylphosphino) propane nickel (II) chloride can be obtained (cf. Chem. Pharm. Bull 26, 2160 (1978) and Pure & Appl. Chem. 52, 669 (1980)). The reaction can between 0 ° C and 80 ° C or at the boiling point of the solvent. The Grignard compound R⁷-MgX can be used in amounts of 1 to 2.5 molar equivalents, based on 1 equivalent of halopyrimidine. Suitable as a solvent ethers, for example diethyl ether, dioxane, tetrahydrofuran or dimethoxyethane.

d) pyrimidine derivatives of the formula I, in which the radical R⁷ = NR⁸R⁹ and as above in of the general formula I are defined, can be achieved by the reaction of corresponding halopyrimidines with primary or secondary amines of the formula HNR⁸R⁹ (IV), where R⁸ and R⁹ are as defined above and X for halogen (Cl, Br, J) is obtained.

The reaction is preferably carried out in the amine of the formula IV itself, or in inert  aprotic solvents such as B. acetonitrile, dichloromethane, toluene, xylene, Tetrahydrofuren, dioxane, dialkyl ether or DMF at temperatures between -10 ° C and the boiling point of the solvent within 0.5 to 72 hours in the presence of a Base. The bases which are customary for this type of reaction, such as carbonates, are suitable as bases and bicarbonates of alkali and alkaline earth metals, alkali hydroxides, tertiary amines, Pyridine or substituted pyridine base (e.g. 4-dimethylaminopyridine). A second too The function of the base can be equivalent to the compounds of the formula HNR⁸R⁹ take over.

The halopyrimidines can by reacting the corresponding hydroxypyrimidines Formula V, wherein the radicals R¹-R⁶ are as defined in the general formula I, with Halogenation reagents can be obtained. As a halogenating reagent such. B. Thionyl chloride, phosgene, phosphorus oxychloride, phosphorus pentachloride, phosphorus oxybromide or phosphorus tribromide can be used. The reactions can be in one Solvent, but also be carried out without solvent.

The halogenating reagent can be used in amounts of 1 to 4 equivalents based on 1 Equivalent of the hydroxypyrimidine (V) can be used. The reactions can take place in in a temperature range from 25 ° C to 160 ° C. As a solvent z. B. aromatic hydrocarbons (z. B. benzene or toluene, etc.) or halogenated hydrocarbons (e.g. chlorobenzene, dichloromethane or 1,2-dichloroethane) used.

The hydroxypyrimidines (V) can be condensed with the amidine derivatives (VI) β-oxocarboxylates of the formula VII are represented,  

wherein the radicals R¹-R⁶ are as defined in formula I, X for halogen (chlorine, bromine, iodine) and R⁹ for lower alkyl radicals, for. As methyl, ethyl or propyl.

The reactions are in the temperature range of 20-110 ° C or at the boiling point of Solvent carried out within 2 to 72 hours. The β-oxocarboxylate can in amounts of 1-1.5 equivalents, based on one equivalent of amidine derivative (VI), be used. The reaction is carried out in the presence of a base and a solvent carried out. Inorganic bases such as alkali metal hydroxides and carbonates, or organic bases such as sodium alkoxides, trialkylamines and N, N-dialkylanilines can be used. Lower alcohols are suitable as solvents (such as methanol and ethanol), cyclic ethers (such as dioxane and THF), pyridine, N, N-dimethylformamide, water or mixtures thereof.

The amidine derivatives of the formula VI and the β-oxocarboxylates of the formula VII can can be prepared by known processes (cf. J. Org. Chem. 32, 1591 (1967) or Synthesis 1982, 451 and Organikum 1986, 516 ff.).

The compounds of formula I according to the invention are characterized by a excellent fungicidal activity. Already penetrated into the plant tissue fungal pathogens can be successfully combated curatively. This is special important and advantageous for those fungal diseases that develop after infection the usual fungicides can no longer be effectively combated. The The spectrum of activity of the claimed compounds covers a large number of different ones economically important phytopathogenic fungi, such as. B. Piricularia oryzae, Leptosphaeria nodorum, Pyrenophora teres, powdery mildew species, Phytophthora infestans, various rust fungi and botrytis cinerea. Benzimidazole and Dicarboximide sensitive and resistant Botrytis cinerea strains detected.  

The compounds of the invention are also suitable for use in technical areas, for example as a wood preservative, as a preservative in Paints, in cooling lubricants for metalworking or as Preservative in drilling and cutting oils.

The invention also relates to agents which in addition to the compounds of the formula I. contain suitable formulating agents. The agents according to the invention contain the active compounds of the formula I in general from 1 to 95% by weight.

They can be formulated in different ways, depending on how it is done by the biological and / or chemical-physical parameters is specified. As Formulation options are therefore possible: wettable powder (WP), emulsifiable Concentrates (EC), aqueous dispersions based on oil or water (SC), suspo emulsions (SC), dusts (DP), mordants, granules in the form of water-dispersible Granules (WG), ULV formulations, microcapsules, waxes or baits.

These individual types of formulation are known in principle and are described, for example, in:
Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker NY, 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in:
Watkins, "Handbook of Insecticide Dust Diluents and Carrier," 2nd Ed., Darland Book, Caldwell NJ; Olphen, "Introduction to Clay Colloid Chemistry, 2nd Ed., J. Wiley & Sons, NY; Marschen," Solvents Guide ", 2nd Ed., Interscience, NY 1950; McCutcheon's" Detergents and Emulsifiers Annual ", MC Publ. Corp. Ridgewood NJ, Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "Interface-active Ethylene Oxide Adducts", Scientific Publishing Company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology" , Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

On the basis of these formulations, combinations with other pesticides can also be made produce effective substances, fertilizers and / or growth regulators, e.g. B. in Form of a finished formulation or as a tank mix.

Spray powders are preparations which are uniformly dispersible in water Active ingredient in addition to a diluent or inert substance, also wetting agent, e.g. B. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or Alkylphenol sulfonates and dispersants, e.g. B. sodium lignosulfonic acid, 2,2′-dinaphthylmethane-6,6′-disulfonic acid sodium, dibutylnaphthalenesulfonic acid Contain sodium or oleylmethyl tauric acid sodium. Emulsifiable concentrates are by dissolving the active ingredient in an organic solvent, e.g. B. Butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers

The following can be used as emulsifiers: Alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or non-ionic Emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, Fatty alcohol polyglycol ether, propylene oxide-ethylene oxide-sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester or polyoxethylene sorbitol ester.

Dusts are obtained by grinding the active ingredient with finely divided solid Fabrics, e.g. B. talc, natural clays such as kaolin, bentonite, poryphillite or Diatomaceous earth. Granules can either by spraying the active ingredient adsorbable, granulated inert material can be produced or by application of active ingredient concentrates by means of adhesives, e.g. B. polyvinyl alcohol, polyacrylic acid Sodium or mineral oils on the surface of carriers such as sand, kaolinite or of granulated inert material. Suitable active ingredients in the for Production of fertilizer granules in the usual way - if desired in a mixture with fertilizers - be granulated.

The active ingredient concentration in wettable powders is e.g. B. about 10 to 90 wt .-%, the rest 100% by weight consists of conventional formulation components. With emulsifiable Concentrates can have an active ingredient concentration of about 5 to 80% by weight. Dust-like formulations usually contain 5 to 20% by weight. Hangs on granules the active ingredient content partly depends on whether the active compound is liquid or solid  is present and which compound is liquid or solid and which granulating aids, fillers etc. are used.

In addition, the active ingredient formulations mentioned may each contain usual adhesives, wetting agents, dispersing agents, emulsifying agents, penetrating agents, solvents, fillers or Carriers.

The concentrates available in commercial form are used optionally diluted in a conventional manner, e.g. B. with wettable powders, emulsifiable Concentrates, dispersions and sometimes also in the case of microgranules using water.

Dusty and granular preparations as well as sprayable solutions are used before Application usually no longer diluted with other inert substances.

With the external conditions such as temperature, humidity and. a. varies the required Application rate. It can fluctuate within wide limits. It is between 0.005 and 10.0 kg / ha of active ingredient, but preferably between 0.01 and 5 kg / ha of active ingredient.

The active compounds according to the invention can be in their commercially available formulations either alone or in combination with other fungicides known from the literature be applied.

As fungicides known in the literature which, according to the invention, with the compounds of the formula I can be combined, e.g. B. to name the following products:

Imazalil, Prochloraz, Fenapanil, SSF 105, Triflumizol, PP 969 Flutriafol, BAY-MEB 6401, propiconazole, etaconazole, tebuconazole, diclobutrazole, bitertanol, triadimphone, Triadimenol, fluotrimazole, dimethomorph, tridemorph, dodemorph, fenpropimorph, Falimorph, S-32165, Chlobenzthiazone, Parinol, Buthiobat, Fenpropidin, Triforine, Fenarimol, Nuarimol, Triarimol, Ethirimol, Dimethirimol, Bupirimate, Rabenzazole, Tricyclazole, fluobenzimine, pyroxyfur, NK-483, PP-389, pyroquilon hymexazole, Fenitropan, UHF-8227, Cymoxanil, Dichlofunanid, Captafol, Captan, Folpet, Tolyfluanid, Chlorothalonil, etridiazole, iprodione (formula II), procymidone, vinclozole, metomeclan, Myclozolin, dichlozolinate, fluorimide, drazoxolan, quinomethionate, Nitrothalisopropyl, Dithianon, Dinocap, Binapacryl, Fentinacetate, Fentinhydroxide,  Carboxin, Oxycarboxin, Pyracarolid, Methfuroxam, Fenfura, Furmecyclos, Benodanil, Mebenil, Mepronil, Flutalanil, Fuberidazole, Thiabendazole, Carbendazim, Benomyl, Thiofante, Thiofanatemethyl, CGD-95340 F, IKF-1216, Mancozeb, Maneb, Zineb, Nabam, Thiram, Probineb, Prothiocarb, Propamocarb, Dodine, Guazatine, Dicloran, Quintozene, Chloroneb, Tecnazene, Biphenyl, Anilazine, 2-Phenylphenol, Copper compounds such as Cu-oxychloride, Oxine-Cu, Cu-Oxide, sulfur, Fosethyl aluminum, Sodium dodecylbenzenesulfonate, sodium dodecylsulfate, Sodium C13 / C15 alcohol ether sulfonate, sodium cetostearyl phosphate ester, Dioctyl sodium sulfosuccinate, sodium isopropylnaphthalenesulfonate, Sodium methylene bisnaphthalene sulfonate, cetyl trimethyl ammonium chloride, Salts of long-chain primary, secondary or tertiary amines, Alkyl propylene amines, lauryl pyridinium bromide, ethoxylated quaternized fatty amines, Alkyl-dimethyl-benzylammonium chloride and 1-hydroxyethyl-2-alkyl-imidazoline.

The above-mentioned combination partners are well-known active ingredients that are great Part in CH. R. Worthing, U.S.B. Walker and The Pesticide Manual, 7th ed. (1983), British Crop Protection Council.

In addition, the active ingredients according to the invention in their commercially available Formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, Acaricides, nematicides, fungicides, growth regulators or herbicides are available. Insecticides include, for example, phosphoric acid esters, carbamates, Carboxylic acid esters, formamidines, tin compounds, produced by microorganisms Fabrics and a.

Preferred mix partners are:

1. from the group of the phosphoric acid esters azinphos-ethyl, azinphosmethyl, 1- (4-chlorophenyl) -4- (O-ethyl, s-propyl) phosphoryloxypyrazole (TIA-230), chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoat, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophos, Parathion, Parathion-methyl, Phosalon, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprofos,  Triazophos, trichlorphone.

2. from the group of carbamates
Aldicarb, Bendiocarb, BPMC (2- (1-methylpropyl) phenylmethyl carbamate), Butocarboxim, Butoxicarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Primicarb, Promecarb, Propoxur, Thiodicarb.

3. from the group of carboxylic acid esters
Allethrin, Alphamethrin, Bioallethrin, Bioresmethrin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Deltamethrin, 2,2-Dimethyl-3- (2-chloro-2-trifluoromethylvinyl) -cyclopropanecarboxylic acid- (alpha cyano-3-phenyl-2-methyl- benzyl) ester (FMC 54800), fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin, tralomethrin.

4. from the group of formamidines
Amitraz, chlorordime form

5. from the group of tin compounds
Azocyclotin, Cyhexatin, Fenbutatinoxid

6. Other
Abamectin, Bacillus thuringiensis, Bensultap, Binapacyl, Bromopropylate, Buprofecin, Camphechlor, Cartap, Chlorbenzialate, Chlorfluazuron, 2- (4-Chlorphenyl) - 4,5-diphenylthiophene (UBI-T 930), Chlofentezine, Cyclopropanecarboxylic acid (2-naphthylmethyl) ester Ro 12-0470) cyromacin, DDT, dicofol, N- (3,5-dichloro-4- (1,1,2,2-tetrafluoroethoxy) phenylamino) carbonyl) -2,6-difluorobenzamide (XRD 473), diflubenzuron , N- (2,3-Dihydro-3-methyl-1,2-thiazol-2-ylidenes) 2,4-xylidines, dinobutone, dinocap, endosulfan, fenoxycarb, fenthiocarb, flubenzimine, flufenoxuron, gamma-HCH hexythiazox, hydramethylnon (AC 217 300) ivermectin, 2-nitromethyl-4,5-dihydro-6H-thiazine (SD 52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1,3-thiazinane-3 -yl-carbamaldehyde (WL 108 477), propargite, teflubenzuron, tetradifone, tetrasul, thicyclam, triflumarone core polyhedron and granulosic viruses.

The active substance content of those prepared from the commercially available formulations Forms of use can vary widely, the active ingredient concentration Use forms can be from 0.0001 to 100% by weight of active compound, preferably from 0.001 to 1 wt .-% lie. The application takes place in one of the application forms adapted usual way.

The following examples serve to explain the invention.

A. Examples of formulation

a) A dusting agent is obtained by adding 10 parts by weight of active ingredient and 90 Mixes parts by weight of talc as an inert substance and crushed them in a hammer mill.

b) A wettable powder which is readily dispersible in water is obtained by 25 Parts by weight of active ingredient, 65 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight Potassium lignosulfonate and 1 part by weight sodium oleoylmethyl taurine as wetting and dispersant mixes and grinds in a pin mill.

c) A dispersion concentrate which is easily dispersible in water is prepared by 40 parts by weight of active ingredient with 7 parts by weight of a sulfosuccinic acid half-ester, 2 parts by weight Mix parts of a lignosulfonic acid sodium salt and 51 parts by weight of water and in grinded to a fineness of less than 5 micro.

d) An emulsifiable concentrate can be prepared from 15 parts by weight of active ingredient, 75 Parts by weight of cyclohexane as a solvent and 10 parts by weight of ethoxylated Nonylphenol (10 AeO) as an emulsifier.

e) Granules can be produced from 2 to 15 parts by weight of active ingredient and an inert one Granulate carrier material such as attapulgite, pumice granulate and / or quartz sand. A suspension of the wettable powder from example b) is expediently used a solids content of 30% and sprayed this onto the surface of a Attapulgite granules, dry and mix intimately. The weight percentage is Spray powder approx. 5% and that of the inert carrier material approx. 95% of the finished granulate.  

B. Chemical examples Example 1 2- (4-ethoxypyrid-2-yl) -4-methylpyrimidine

To a solution of 3.0 g (0.012 mol) 4-Chloro-2- (4-ethoxypyrid-2-yl) -6-methylpyrimidine in 50 ml of methanol became 0.2 g Palladium / coal added. Under a pressure of 3 bar and a temperature of 60 ° C this mixture became in contact with hydrogen with vigorous stirring for 6 hours brought. The catalyst was then filtered off and the filtrate in vacuo constricted. The residue was chromatographed on silica gel with ethyl acetate, concentrated and dried. 1.2 g (46.5%) of a beige powder were obtained with the Melting point 168 ° C.

Example 2 2- (4-ethoxy-6-methylpyrid-2-yl) -4-methoxy-6-methylpyrimidine

To a solution of 1.6 g (0.0061 mol) 4-chloro-2- (4-ethoxy-6-methyl-pyrid-2-yl) -6-methylpyrimidine in 20 ml of absolute Methanol was made under argon 1.6 g (0.009 mol) of a 30% solution of Sodium methylate placed in methanol. The mixture was stirred at room temperature for 30 hours, the solvent was distilled off, taken up in water and extracted with ethyl acetate. The organic phase was dried over Na₂SO₄ and concentrated. There were 1.5 g Obtained (96.7%) of a brown oil.

Example 3 5-methoxy-2- (4-methoxy-6-methyl-pyrid-2-yl) -4-propynyl- aminopyrimidine

To a solution of 1.24 g (0.005 mol) 4-chloro-5-methoxy-2- (4-methoxy-6-methyl-pyrid-2-yl) pyrimidine and 0.549 g (0.005 mmol) N-methylmorpholine in 20 ml abs. THF became 0.342 g (0.005 mol) of propargylamine added and heated under reflux for 18 hours. It was then concentrated to Added water and extracted with ethyl acetate. The organic phase was dried (MgSO₄) and concentrated. Flash chromatography with silica gel and ethyl acetate / methanol  (98/2) provided 1.0 g (70.4%) of yellowish crystals, which decomposed at 146-148 ° C melted.

Example 4 4-butylthio-2- (4-ethoxy-6-methyl-pyrid-2-yl) -6-propyl- pyrimidine

To a solution of 1.07 ml (0.01 mol) of butyl mercaptan in 20 ml abs. THF was 0.3 g (0.01 mol) of an 80% at room temperature under argon Suspended suspension of sodium hydride in paraffin and stirred for 2 hours. Then were 1.45 g (0.005 mol) of 4-chloro-2- (4-ethoxy-6-methyl-pyrid-2-yl) -6-propylpyrimidine was added and stirred at room temperature for 6 hours. The mixture was then concentrated added to water, extracted with ethyl acetate, the organic phase over MgSO₄ dried, concentrated and dried. 0.7 g (81.4%) of a yellowish oil was obtained.

Example 5 2- (4-ethoxy-6-methyl-pyrid-2-yl) -6-methyl-4-propylpyrimidine

To a suspension of 50 mg (0.00009 mol) 1,3-bis (diphenylphosphino-propane-nickel (II) chloride and 1.0 g (0.003 mol) 4-chloro-2- (4-ethoxy-6-methyl-pyrid-2-yl) -6-propylpyrimidine in 20 ml abs. Diethyl ether were under argon at 0 ° C 2 ml of a 3 molar solution (0.006 mol) of Methylmagnesium bromide in diethyl ether was added dropwise with vigorous stirring. It was 8th Heated under reflux for hours and then stirred at room temperature for 18 hours. It was poured into dilute hydrochloric acid, stirred for 30 minutes and with NaCO₃ neutralized. The organic phase was dried and concentrated. The residue was Flash chromatographed (silica gel, ethyl acetate)

Example 6 4-chloro-5-methoxy-2- (4-methoxy-6-methyl-pyrid-2-yl) pyrimidine

To a solution of 49.4 g (0.20 mol) 5-methoxy-2- (4-methoxy-6-methyl-pyrid-2-yl) pyrimid-4-one in 500 ml abs. Dichloroethane  61 g (0.4 mol) of phosphorus oxychloride were added at 0 ° C. and 6 hours at 40 ° C. touched. The solvent was then largely removed, with intensive Stir poured onto 10% sodium carbonate solution and the basic solution with Extracted dichloromethane. The organic phase was dried (MgSO₄), concentrated and dried. 46.4 g (87%) of a white powder of melting point were obtained 145-146 ° C.

The compounds of Table 1 can be prepared analogously to these examples.

The hydrogen position of the 1 H-NMR spectra are shown as below busy:

C. Biological examples Example 1

Rice plants of the "Ballilia" variety, about 5 weeks old, were given the ones listed below Concentrations of the compounds of the invention treated. After the The plants were sprayed with a spore suspension of Pircularia oryzae evenly inoculated and 48 h in a dark climate chamber with a Temperature of 25 ° C and 100% rel. Humidity set. After that, the Rice plants in a greenhouse with a temperature of 25 ° C and 80% rel. Humidity continued to be cultivated. The infestation was evaluated after 5 days. The Degree of infestation was in% affected leaf area compared to untreated, infected Control plants expressed. The results are summarized in Table 2.  

Table 2

Example 2

Wheat plants of the "jubilar" variety were watered at the 2-leaf stage Suspensions of the preparations listed in Table 3 treated to runoff.

After the spray coating had dried on, the plants were washed with an aqueous Pycnospore suspension of Leptosphaeria nodorum and inoculated for several hours 100% rel. Humidity incubated in a climatic chamber. Up to the level of symptoms the plants were further cultivated in the greenhouse at about 90% atmospheric humidity.

The degree of infestation was in% affected leaf area compared to untreated,  infected control plants and is shown in Table 3.

Table 3

Example 3

Barley plants of the "Igri" variety were grown in the 2-leaf stage with an aqueous Suspension of the claimed compounds treated to runoff.

After the spray coating had dried on, the plants were washed with an aqueous Spore suspension of Pyrenophora teres inoculated and for 16 h in a climatic chamber at 100% rel. Humidity incubated. The infected plants were then in the Greenhouse at 25 ° C and 80% rel. Humidity continued to be cultivated.

Approx. The infestation was evaluated 1 week after incubation. The degree of infestation was in% infected leaf area in comparison to the untreated, infected control. The Results are shown in Table 4.

Table 4

Example 4

Approx. 14 day old beans of the "Herz Freya" or "Frank′s Ackerperle" variety were grown treated to runoff with aqueous suspensions of the claimed compounds.

After the spray coating had dried on, the plants were spore-suspended (1.5 Million spores / ml) of Botrytis cinerea. The plants were in a Climatic chamber at 20-22 ° C and approx. 99% rel. Humidity continued to be cultivated. The infection of the plants manifests itself in the formation of black spots on leaves and stems. The The tests were evaluated approximately 1 week after inoculation.

The efficiency of the test substances was a percentage of the untreated, infected Control is rated and is shown in Table 5.

Table 5

Example 5

Barley plants were cultivated in the 2-leaf stage with conidia of barley mildew (Erysiphe graminis hordei) strongly inoculated and in a greenhouse at 20 ° C and a relative Humidity of approx. 50% cultivated further. The plants were grown 1 day after inoculation with the compounds listed in Table 5 in the specified Active substance concentrations evenly wetted. After an incubation period of 7-9 days the plants were examined for infestation with barley mildew. The degree of infestation will expressed in% affected leaf area, based on untreated, infected Control plants (= 100% infestation). The result is summarized in Table 6.

Table 6

Example 6

Tomato plants of the "Rheinland Ruhm" variety were in the 3-4 leaf stage with aqueous Suspensions of the claimed compounds wetted evenly to the point of dripping wet.

After drying, the plants were treated with a zoosporangia suspension of Phytophthora infestans inoculated and for 2 days under optimal infection conditions kept in a climatic chamber. Then the plants were up to Symptoms continued to be cultivated in the greenhouse.

The infection was assessed approximately 1 week after inoculation. The degree of infestation of the plants was in% infested leaf area, based on untreated, infected plants expressed and is shown in Table 7.

Table 7

Claims (7)

1. Compounds of formula I. wherein
R¹ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) alkoxy- (C₁-C₄-) alkyl, (C₁-C₄) alkylthio- (C₁-C₄) alkyl, (C₂-C₆) alkenyl, (C₂- C₆) alkynyl, (C₃-C₇) cycloalkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, where the latter two radicals in the cycloalkyl part can be substituted up to three times by (C₁-C₄) alkyl, phenyl, phenoxy- (C₁-C₄) alkyl, phenylmercapto- (C₁-C₄) alkyl, phenyl- (C₁-C₄) alkyl, the four last-mentioned radicals in the phenyl part being up to threefold by halogen, (C₁-C₄) alkyl, (C₁-C₄) Alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) haloalkyl, or can simply be substituted by nitro or cyano, and halo can be substituted one or more times by halogen atoms,
R², R⁴ = independently of one another hydrogen, (C₁-C₆) alkyl, phenyl, the phenyl radical being up to threefold by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁-C₄ ) Haloalkyl, (C₁-C₄) haloalkoxy or can be substituted simply by nitro, and halo can be substituted one or more times by halogen atoms,
R¹ and R² together form part of a maximally saturated 3- to 8-membered ring,
R³ = (C₁-C₆) alkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) haloalkyl, phenyl- (C₁-C₄) alkyl, phenoxy- (C₁ -C₄) alkyl, the latter two radicals in the phenyl part up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) haloalkyl, (C₁-C₄ ) Haloalkoxy or can be substituted simply by nitro, and can mean halo substituted one or more times by halogen atoms,
R⁵ = hydrogen, (C₁-C₆) alkyl, (C₁-C₆) alkoxy- (C₁-C₄) alkyl, (C₁-C₄) alkylthio- (C₁-C₄) alkyl, (C₂-C₆) alkenyl, (C₂-C₆ ) Alkynyl, (C₃-C₇) cycloalkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, where the latter two radicals in the cycloalkyl part can be substituted up to three times by (C₁-C₄) alkyl, (C₁-C₄) Haloalkyl, halogen, phenyl or phenyl- (C₁-C₄) alkyl, the latter two radicals in the phenyl part being up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁ -C₄) haloalkyl, (C₁-C₄) haloalkoxy or simply substituted by nitro, and halo can be substituted one or more times by halogen atoms,
R⁶ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) thioalkyl, (C₂-C₄) alkenyl- (C₁-C₄) alkoxy, (C₂-C₄ ) Alkynyl- (C₁-C₄) alkoxy, halogen, phenyl, phenyl- (C₁-C₄) alkyl, phenoxy- (C₁-C₄) alkyl, the three last-mentioned radicals in the phenyl part being up to three times by halogen, (C₁-C₄) Alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) haloalkyl, (C₁-C₄) haloalkoxy or can be substituted simply by nitro, and can mean halo substituted one or more times by halogen atoms,
R⁷ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₄) alkylthio, (C₁-C₄) alkyl, (C₂-C₆) alkenyl, (C₂-C₆ ) Alkynyl, (C₃-C₇) cycloalkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, where the latter two radicals in the cycloalkyl part can be substituted up to three times by (C₁-C₄) alkyl, (C₁-C₄) Haloalkyl, (C₁-C₁₈) alkoxy, (C₁-C₆) alkylthio, halogen, phenyl, phenoxy, phenylthio, phenyl- (C₁-C₄) alkyl, phenoxy- (C₁-C₄) alkyl, phenylthio- (C₁-C₄) alkyl , Phenyl- (C₁-C₄) alkoxy, phenyl- (C₁-C₄) alkylthio, the eight last-mentioned radicals in the phenyl part up to three times by carboxyl, halogen, (C₁-C₁) alkyl, (C₁-C₄) alkoxy, (C₁ -C₄) alkylthio, (C₁-C₄) haloalkyl, (C₁-C₄) haloalkoxy or simply substituted by nitro, (C₂-C₄) alkenyl- (C₁-C₄) alkoxy, (C₂-C₄) alkynyl- (C₁- C₄) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkoxy, phenyl- (C₁-C₄) alkoxy- (C₁-C₄) alko xy, (C₁-C₆) hydroxyalkoxy, (C₁-C₄) alkylthio- (C₁-C₄) alkylthio, amines of the formula NR⁸R⁹ or hydrazines of the formula NH-NR⁸R⁹, and halo can be substituted one or more times by halogen atoms,
R⁸, R⁹ independently of one another hydrogen, (C₁-C₆) alkyl, (C₁-C₆) hydroxyalkyl, (C₃-C₇) heterocyclyl- (C₁-C₆) alkyl, (C₂-C₄) alkenyl- (C₁-C₂) alkyl, (C₂-C₄) alkynyl- (C₁-C₂) alkyl, (C₃-C₇) cycloalkyl, (C₃-C₇) cycloalkyl- (C₁-C₄) alkyl, the latter two radicals in the cycloalkyl part being up to twice by (C₁- C₄) alkyl can be substituted, formyl, phenyl, phenyl- (C₁-C₄) alkyl, the latter two radicals in the phenyl part up to twice by halogen, (C₁-C₄) alkyl, carboxyl, (C₁-C₄) alkoxy, trifluoromethyl or can be substituted by trichloromethyl,
R⁸ and R⁹ together with the nitrogen atom to which they are attached mean an unsubstituted or up to doubly substituted 5- to 7-membered saturated or unsaturated heterocycle with 1 or 2 identical or different heteroatoms,
as well as their acid addition salts. 2. Compounds of formula I according to claim 1, characterized in that
R¹ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) alkoxy- (C₁-C₂) alkyl, phenyl, phenoxy- (C₁-C₂) alkyl, phenyl- (C₁-C₄) alkyl, the latter three radicals can be substituted up to three times in the phenyl part by halogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy,
R² = hydrogen, (C₁-C₄) alkyl, phenyl, which can be substituted up to three times by halogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy,
R¹ and R² together form part of a maximally saturated 5- to 7-membered ring,
R³ = (C₁-C₆) alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) haloalkyl, phenyl- (C₁-C₂) alkyl, phenoxy- (C₁-C₂) alkyl, the latter two radicals in the phenyl part up to can be substituted three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, or (C₁-C₄) haloalkyl, and can mean halo substituted one or more times by halogen atoms,
R⁴ = hydrogen or (C₁-C₄) alkyl,
R⁵ = hydrogen, (C₁-C₆) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₃) alkyl, (C₁-C₄) haloalkyl, halogen, phenyl, phenyl- (C₁-C₂) alkyl, where the latter two radicals in the phenyl moiety can be substituted up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₂) haloalkyl, and halo can be substituted one or more times by halogen atoms ,
R⁶ = hydrogen, (C₁-C₆) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₂-C₄) alkenyl- (C₁-C₄) alkoxy, (C₂- C₄) alkynyl- (C₁-C₄) -alkoxy, halogen, phenyl, phenyl- (C₁-C₄) alkyl, phenoxy- (C₁-C₄) alkyl, the three last-mentioned radicals in the phenyl part being up to threefold by halogen, (C₁- C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) haloalkyl, (C₁-C₄) haloalkoxy or simply substituted by nitro or cyano, and halo is substituted one or more times by halogen atoms can mean
R⁷ = hydrogen, (C₁-C₆) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₃) alkyl, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₄ ) Alkylthio- (C₁-C₄) alkyl, (C₂-C₆) alkenyl, (C₂-C₆) alkynyl, (C₁-C₁₈) alkoxy, (C₁-C₄) alkylthio, (C₂-C₆) alkenyl- (C₁-C₄) -alkoxy, (C₂-C₆) alkynyl- (C₁-C₄) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkoxy, (C₁-C₄) hydroxyalkoxy, phenyl- (C₁ -C₂) alkoxy- (C₁-C₄) alkoxy, (C₁-C₄) alkylthio- (C₁-C₄) alkylthio, halogen, phenyl, phenoxy, phenylthio, phenyl- (C₁-C₂) alkyl, phenyl- (C₁-C₂) alkoxy, phenyl- (C₁-C₂) alkylthio, the six last-mentioned radicals in the phenyl part being up to triple by carboxyl, halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₂) haloalkyl or (C₁- C₃) Haloalkoxy can be substituted, amines of the formula NR⁸R⁹ or hydrazines of the formula NH-NR⁸N⁹, and halo can be substituted one or more times by halogen atoms,
R⁸, R⁹ = independently of one another hydrogen, (C₁-C₄) alkyl, (C₁-C₄) hydroxyalkyl, (C₅-C₆) heterocyclyl- (C₁-C₄) alkyl, (C₂-C₃) alkenyl- (C₁-C₂) alkyl, (C₂-C₃) alkynyl- (C₁-C₂) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₂) alkyl, the latter two radicals in the cycloalkyl part being up to twice by (C₁-C₄ ) Alkyl can be substituted, formyl, phenyl, phenyl- (C₁-C₂) alkyl, the latter two radicals in the phenyl part up to twice by halogen, (C₁-C₃) alkyl, carboxyl, (C₁-C₃) alkoxy, trifluoromethyl or Trichloromethyl may be substituted,
R⁸ and R⁹ together with the nitrogen atom to which they are attached represent an unsubstituted or up to twice substituted 5- to 7-membered saturated or unsaturated heterocycle with 1 or 2 identical or different heteroatoms,
as well as their acid addition salts. 3. Compounds of formula I according to claim 1 or 2, characterized in that
R¹ = hydrogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy-methyl, phenyl, phenoxy-methyl, phenyl (C₁-C₄) alkyl, the three latter radicals in the phenyl part being up to three times by halogen, (C₁- C₄) alkyl, (C₁-C₄) alkoxy may be substituted,
R² = hydrogen, (C₁-C₄) alkyl, phenyl, where phenyl part can be substituted up to three times by halogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy,
R¹ and R² together form part of a maximally unsaturated 5- to 7-membered ring,
R³ = (C₁-C₆) alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) haloalkyl, phenyl- (C₁-C₂) alkyl, phenoxy- (C₁-C₂) alkyl, the phenyl radical of the last two examples up to can be substituted three times with halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, or (C₁-C₄) haloalkyl,
R⁴ = hydrogen or (C₁-C₂) alkyl,
R⁵ = hydrogen, (C₁-C₆) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₃) alkyl, (C₁-C₄) haloalkyl, halogen, phenyl, phenyl-methyl, the two the latter radicals in the phenyl part may be unsubstituted or substituted up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₂) haloalkyl,
R⁶ = hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, halogen, phenyl, phenyl-methyl, the phenyl radical of the last two examples up to three times can be substituted with halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) haloalkyl,
R⁷ = hydrogen, (C₁-C₄) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl-methyl, (C₂-C₆) alkenyl, (C₂-C₆) alkynyl, (C₁-C₁₈) alkoxy, (C₁ -C₄) alkylthio, (C₂-C₆) alkenyl- (C₁-C₂) alkoxy, (C₂-C₆) alkynyl (C₁-C₃) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₂ ) alkoxy, (C₁-C₄) hydroxyalkoxy, halogen, phenyl-methoxy- (C₁-C₄) alkoxy, phenyl, phenoxy, phenylmercapto, phenyl (C₁-C₂) alkyl, phenyl (C₁-C₂) alkoxy, phenyl-methylthio, where the seven latter radicals in the phenyl part can be substituted up to three times by carboxyl, halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₂) haloalkyl or (C₁-C₃) haloalkoxy, amines of the form NR⁸R⁹ or Hydrazines of the form NH-NR⁸N⁹,
R⁸, R⁹ are each independently hydrogen, (C₁-C₄) alkyl, (C₁-C₂) hydroxyalkyl, (C₅-C₆) heterocyclyl- (C₁-C₄) alkyl, (C₂-C₃) alkenyl-methyl, (C₂-C₃) Alkynyl-methyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl-methyl, where the latter two radicals in the cycloalkyl part can be substituted up to twice by (C₁-C₄) alkyl, formyl, phenyl, phenyl-methyl, where the latter two radicals in the phenyl moiety can be substituted up to twice by halogen, (C₁-C₃) alkyl, (C₁-C₃) alkoxy, carboxyl, trifluoromethyl or trichloromethyl, and
R⁸ and R⁹ together with the nitrogen atom to which they are attached represent an unsubstituted or up to twice substituted 5- to 6-membered saturated or unsaturated heterocycle with 1 or 2 identical or different heteroatoms,
as well as their acid addition salts. 4. A process for the preparation of compounds of formula I according to one or more of claims 1 to 3, characterized in that

• a) for compounds with R⁷ = hydrogen, a corresponding halopyrimidine of the formula I with R⁷ = halogen and all other substituents in the meanings mentioned reductively dehalogenated or
• b) for compounds of formula I, wherein R⁷ for (C₁-C₁₈) alkoxy, (C₁-C₃) alkylthio, (C₂-C₆) alkenyl- (C₁-C₄) alkoxy, (C₂-C₆) alkynyl- (C₁-C₄ ) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkoxy, phenyl- (C₁-C₂) alkoxy- (C₁-C₄) alkoxy, (C₁-C₄) alkylthio- (C₁- C₄) alkylthio, phenoxy, phenylmercapto, phenyl- (C₁-C₂) alkoxy, phenyl- (C₁-C₂) alkylthio, the four last-mentioned radicals in the phenyl part being up to three times by halogen, (C₁-C₄) alkyl, (C₁-C₄ ) Alkoxy, (C₁-C₂) haloalkyl or (C₁-C₃) haloalkoxy may be substituted, a corresponding halopyrimidine of the formula I with R⁷ = halogen with an alkali metal compound of the formula II R⁷-Y (II), in which R⁷ has the abovementioned meaning possesses and Y stands for an alkali metal, converts, or
• c) for compounds of the formula I in which R⁷ is (C₁-C₆) alkyl, phenyl- (C₁-C₂) alkyl, (C₃-C₆) cycloalkyl, (C₅-C₆) cycloalkyl- (C₁-C₃) alkyl, (C₂ -C₆) alkenyl, (C₂-C₆) alkynyl or phenyl, where the latter radical can be substituted up to three times by (C₁-C₄) alkyl or (C₁-C₄) alkoxy, a corresponding halopyrimidine of the formula I with R⁷ = halogen with a Grignard compound of the formula III, R⁷-MgX (III), in which R⁷ has the abovementioned meaning and X = halogen, in the presence of nickel-phosphine complexes or
• d) for compounds of the formula I in which R⁷ is NR⁸R⁹, and R⁸, R⁹ have the meaning given under formula I, a corresponding halopyrimidine of the formula I with R⁷ = halogen with a primary or secondary amine of the formula IV HNR⁸R⁹ (IV) .

5. Fungicidal compositions, characterized in that they are an effective amount of a Contain compound of formula I according to one or more of claims 1 to 3. 6. Use of compounds of the formula I according to one or more of the Claims 1 to 3 for combating harmful fungi. 7. A method of combating harmful fungi, characterized in that one this or the plants, surfaces or substrates affected by them an effective one Amount of a compound of formula I according to one or more of claims 1 to 3 applied.