EP1638400A2 - Triazolopyrimidines - Google Patents

Abstract

The invention relates to novel triazolopyrimidines of formula (I), in which R<1>, R<2>, R<3> and X are defined as cited in the description, to a method for producing said substances and to their use for controlling undesirable micro-organisms. The invention also relates to novel intermediate products of the formulae (II), (VI), (VII-a) and (VII-b), in addition to methods for producing said substances.

Description

triazolopyrimidines

The present invention relates to new triazolopyrimides, a process for their preparation and their use for controlling unwanted microorganisms. The invention also relates to new intermediates and processes for their production.

It has already become known that certain triazolopyrimides have fungicidal properties (cf. WO 99-41 255, WO 02-02 563, JP-A 2002-308 878, WO 03-04465 and WO 03-08 417). The effectiveness of these substances is good, but leaves something to be desired in some cases at low application rates.

There have now been new triazolopyrimidines of the formula

in which

B.1 represents optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl or for optionally substituted carbon-linked heterocyclyl,

R.2 represents hydrogen, halogen, optionally substituted alkyl or optionally substituted cycloalkyl,

R3 represents optionally substituted heterocyclyl and

X represents halogen, cyano, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulfonyl or optionally substituted alkylsulfonyl,

found.

It was also found that triazolopyrimidines of the formula (I) can be prepared by

(a) Dihalotriazolopyrimidines of the formula

in which

R2 and R ^ have the meanings given above,

X 1 represents halogen and

γ represents halogen,

with metal compounds of the formula

Rl -Me (oil)

in which

Rl has the meaning given above and

Me for lithium, dihydroxyboranyl or a radical of the formula

or MgHal

stands in what

Shark represents chlorine or bromine,

if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, and if appropriate the triazolopyrimidines of the formula thus obtained

in which

R, R ^, R3 and X have the meanings given above,

either

α) with compounds of the formula

R ⁴ - Me! (IV)

in which

R ^{4 represents} optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl or cyano and

Me 1 stands for sodium or potassium,

if appropriate in the presence of a diluent,

or

β) with Grignard compounds of the formula

R ⁵ - Mg Shark ¹ (V)

in which

R-> represents optionally substituted alkyl and

Shark ^{1 represents} chlorine or bromine,

in the presence of a diluent.

Finally, it was found that the triazolopyrimidines of the formula (I) are very suitable for controlling unwanted microorganisms. Above all, they show a strong fungicidal activity and can be used both in crop protection and in material protection.

Surprisingly, the triazolopyrimidines of the formula (I) according to the invention have a substantially better microbicidal activity than the constitutionally most similar, previously known substances with the same direction of action. The compounds of the formula (I) according to the invention can, if appropriate, as mixtures of various possible isomeric forms, in particular of stereoisomers, such as E and Z, threo- and eiythro, and optical isomers, such as R and S isomers or atropisomers, but if appropriate also of tautomers.

Both the pure stereoisomers and any mixtures of these isomers are the subject of this invention, even if only the compounds of the formula (I) are mentioned here in general.

Depending on the nature of the substituents defined above, the compounds of the formula (I) have acidic or basic properties and can form salts. If the compounds of the formula (T) carry hydroxyl, carboxy or other groups which induce acidic properties, these compounds can be reacted with bases to form salts. Suitable bases are, for example, hydroxides, carbonates, bicarbonates of the alkali and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines with (Cj-C ^ -alkyl radicals and mono-, di- and trialkanolamines ^ of (C _j -C alkanols. wearing the compounds of formula (I) amino, alkylamino or other groups inducing basic properties, these compounds can be with acids converted to salts. Suitable acids are for example mineral acids, such as salt, Sulfuric and phosphoric acid, organic acids such as acetic acid or oxalic acid and acidic salts such as aHS04 and KHSO4 The salts thus obtainable also have fungicidal and microbicidal properties.

The invention also relates to the salt-like derivatives formed from compounds of the formula (I) by reaction with basic or acidic compounds, and to the N-oxides which can be prepared by customary oxygenation methods.

In the present case, heterocyclyl stands for saturated or unsaturated aromatic or non-aromatic, ring-shaped compounds with 3 to 8 ring members, in which at least one ring member is a hetero atom, that is to say represents an atom other than carbon. If the ring contains several heteroatoms, these can be the same or different. Heteroatoms are preferably oxygen, nitrogen or sulfur. If the ring contains several oxygen atoms, these are not directly adjacent. If appropriate, the ring-shaped compounds together with further carbocyclic or heterocyclic fused or bridged rings together form a polycyclic ring system. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic, aromatic or non-aromatic ring systems.

The triazolopyrimidines according to the invention are generally defined by the formula (I). Preferred substances of the formula (I) are those in which R stands for alkyl with 1 to 6 carbon atoms, which can be substituted one to five times, in the same way or differently, by halogen, cyano, alkoxy with 1 to 4 carbon atoms, tri (C 1 -C 4 -alkyl) silyl and / or cycloalkyl with 3 to 6 Carbon atoms which can be monosubstituted to trisubstituted, identical or different, by halogen, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or alkyl having 1 to 4 carbon atoms, or

R ^{1 represents} alkenyl having 2 to 6 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by halogen, cyano, hydroxyl, alkoxy having 1 to 4 carbon atoms, tri (-CC4-alkyl) silyl and / or cycloalkyl 3 to 6 carbon atoms, which can be substituted by up to three, identical or different

Halogen, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or alkyl having 1 to 4 carbon atoms, or

R represents alkynyl having 3 to 6 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by halogen, cyano, alkoxy having 1 to 4 carbon atoms, tri (C 1 -C 4 -alkyl) silyl and / or cycloalkyl having 3 up to 6 carbon atoms, which can be substituted once to three times, in the same way or differently, by halogen, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or alkyl having 1 to 4 carbon atoms, or

R stands for cycloalkyl having 3 to 6 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by halogen, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or alkyl having 1 to 4 carbon atoms, or

R ^{1 stands} for cycloalkenyl with 3 to 6 carbon atoms, which can be monosubstituted to trisubstituted, identical or different, by halogen and / or alkyl having 1 to 4 carbon atoms, or

R ^{1 represents} saturated or unsaturated, carbon-linked heterocyclyl having 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, where the heterocyclyl can be mono- or disubstituted by halogen, alkyl having 1 to 4 carbon atoms, cyano, nitro, alkoxy with 1 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 9 halogen atoms and / or haloalkoxy with 1 to 4 carbon atoms and 1 to 9 halogen atoms, R ^{2 represents} hydrogen, fluorine, chlorine, bromine, iodine, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms or cycloalkyl having 3 to 6 carbon atoms,

R3 represents saturated or unsaturated heterocyclyl with 5 or 6 ring members and 1 to 4 heteroatoms, such as nitrogen, oxygen and / or sulfur, it being possible for the heterocyclyl to be monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, bromine, cyano, nitro

Alkyl, alkoxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 3 carbon atoms per alkyl part,

Haloalkyl or haloalkoxy each having 1 to 3 carbon atoms and 1 to 7 halogen atoms,

and

X for fluorine, chlorine, bromine, cyano, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4

Carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylsulfinyl with 1 to 4 carbon atoms or alkylsulfonyl with 1 to 4 carbon atoms.

Those triazolopyrimidines of the formula (I) in which

R for a residue of the formula

_{oc he} stands,

or

R for a residue of the formula

stands,

or

R ¹ for a radical of the formula

where # marks the point of attachment,

R ^{2 represents} hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, l-trifluoromethyl-2,2,2-trifluoroethyl or heptafluoroisopropyl,

R ^ stands for pyridyl which is linked in the 2- or 4-position and can be mono- to tetrasubstituted, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro,

Methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl, or

^ stands for pyrimidyl, which is linked in the 2- or 4-position and can be mono- to trisubstituted, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl,

Methoximinomethyl, methoximinoethyl and / or trifluoromethyl, or

R3 represents thienyl which is linked in the 2- or 3-position and can be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl , Methoximinoethyl and / or trifluoromethyl, or R ^ stands for thiazolyl which is linked in the 2-, 4- or 5-position and can be mono- or disubstituted, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl , Hydroximinoethyl, methoxyiminomethyl, methoximinoethyl and / or trifluoromethyl and

X represents fluorine, chlorine, bromine, cyano, methyl, methoxy or methylthio.

The aforementioned radical definitions can be combined with one another in any way. In addition, individual definitions can be omitted.

If 5,7-dichloro-6- (5-chloropyrimidin-4-yl) [l, 2,4] triazolo [l, 5-a] pyrimidine and 4-methylcyclohexyl-magnesium bromide are used as starting materials, the course of the first Stage of process (a) according to the invention can be illustrated by the following formula.

If the above-mentioned compound prepared according to the first stage of process (a) according to the invention is used as the starting substance and sodium methylate as the reaction component, the course of the second stage of process (a) according to variant α can be illustrated by the following formula.

If the above-mentioned compound prepared according to the first stage of process (a) according to the invention is used as the starting substance and methylmagnesium bromide as the reaction component, the course of the second stage of process (a) according to variant β can be illustrated by the following formula ,

BrMgCH

-MgBrCI

Formula (II) provides a general definition of the dihalotriazolopyrimidines required as starting materials when carrying out process (a) according to the invention. In this formula, R ² and R-3 preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention. X ¹ preferably represents fluorine, chlorine or bromine.

Y preferably represents fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.

The dihalotriazolopyrimidines of the formula (II) are new. These substances are also suitable for controlling unwanted microorganisms.

The dihalotriazolopyrimidines of the formula (H) can be prepared by

(b) Dihydroxy-triazolopyrimidines of the formula

in which

R- and R3 have the meanings given above,

with halogenating agents, optionally in the presence of a diluent. If 6- (5-chloropyrir ^ in-4-yl) - [l, 2,4] triazolo [l, 5-a] pyrimidine-5,7-diol is used as the starting material and phosphorus oxychloride in a mixture with phosphorus pentachloride as the halogenating agent, the course of process (b) according to the invention can be illustrated by the following formula.

Formula (VI) provides a general definition of the dihydroxytriazolopyrimidines required as starting materials when carrying out process (b). In this formula, R ² and R ^ preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The dihydroxy-triazolopyrimidines of the formula (VT) are also not yet known. They can be made by

(c) Heterocyclylmalonic esters of the formula

in which

R- has the meaning given above and

R ^ represents alkyl having 1 to 4 carbon atoms,

with aminotriazoles of the formula

in which

R ^{2 has} the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

If dimethyl 2- (5-chloropyrimidin-4-yl) malonate and 3-aminotriazole are used as starting materials, the course of process (c) according to the invention can be illustrated by the following formula.

The heterocyclylmalonic esters required as starting materials for carrying out the process (c) according to the invention are generally defined by the formula (VH); this formula preferably has those meanings which are already those in connection with the description of the substances of the formula (I) according to the invention this rest were mentioned as preferred. R> is preferably methyl or ethyl.

The heterocyclylmalonic esters of the formula (VΗ) are known in some cases (cf. DE 3820538-A, WO 01-11 965 and WO 99-32 464).

Pyridylmalonic esters of the formula are new

in which

R6 has the meaning given above and

R ^ represents halogen or haloalkyl.

Pyrimidylmalonic esters of the formula are also new

in which

R6 has the meaning given above,

R ^ represents halogen or haloalkyl, and

R ^ and R ¹ ^ are independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy.

The pyridylmalonic esters of the formula (VIII-a) can be prepared by

(d) Halopyridines of the formula

in which

R7 has the meaning given above and

Y ^ represents halogen,

with malon esters of the formula

in which

R ^{Ö has} the meaning given above,

if appropriate in the presence of a diluent, if appropriate in the presence of a copper salt and if appropriate in the presence of an acid acceptor. If 2-chloro-3-trifluoromethylpyridine and dimethyl malonate are used as starting materials, the course of process (d) according to the invention can be illustrated by the following formula.

Formula (IX) provides a general definition of the halopyridines required as starting materials for carrying out process (d) according to the invention. In this formula, R7 preferably represents fluorine, chlorine or trifluoromethyl. Y ^ preferably represents chlorine or bromine.

The halopyridines of the formula (IX) are known synthetic chemicals.

The malonic esters of the formula (X) which are also required as starting materials for carrying out the process (d) according to the invention are likewise known synthetic chemicals.

The pyrimidylmalonic esters of the formula (VIII-b) can be prepared by

(e) Halogenopyrimidines of the formula

in which

R ^§ , R ^ and R ¹ ^ have the meanings given above and

γ3 represents halogen,

with malon esters of the formula

in which

R6 has the meaning given above,

if appropriate in the presence of a diluent, if appropriate in the presence of a copper salt and if appropriate in the presence of an acid acceptor.

If 4,5-dichloropyrimidine and dimethyl malonate are used as starting materials, the course of process (e) according to the invention can be illustrated by the following formula.

Formula (XI) provides a general definition of the halopyrirnidines required as starting materials for carrying out process (e) according to the invention. In this formula, R ° preferably represents fluorine, chlorine or trifluoromethyl. R "and R ^ are also preferably independently of one another hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy. Y ^ is preferably chlorine or bromine.

The halopyrirnidines of the formula (XI) are known and can be prepared by known methods (cf. J. Chem. Soc. 1955, 3478-3481).

Formula (VIII) provides a general definition of the aminotriazoles required as reaction components for carrying out process (c) according to the invention. In this formula, R ^ preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention.

The aminotriazoles of the formula (VIII) are known or can be prepared by known methods (cf. DE-A 10 121 162).

Suitable halogenating agents for carrying out process (b) are all components customary for the replacement of hydroxyl groups by halogen. Phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, thionyl bromide or mixtures thereof are preferably usable. The corresponding fluorine compounds of the Formula (II) can be prepared from the chlorine or bromine compounds by reaction with potassium fluoride.

The halogenating agents mentioned are known.

Formula (HI) provides a general definition of the compounds which are required as reaction components when carrying out process (a) according to the invention. In this formula, R preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention. Me also preferably represents lithium, dihydroxyboranyl, a radical of the formula

wherein

Shark represents chlorine or bromine,

The metal compounds of the formula (DI) are known or can be prepared by known methods.

Formula (Ia) generally defines the triazolopyrimidines required as starting materials when carrying out the second stage of process (a) according to the invention. In this formula, R ¹ , ^ and R ^ preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these radicals. X preferably represents fluorine, chlorine or bromine.

Formula (IV) provides a general definition of the compounds required as reaction components when carrying out the second stage of process (a, variant α). In this formula, R ^ preferably represents cyano, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, alkylsulfinyl having 1 to 4 carbon atoms or alkylsulfonyl having 1 to 4 carbon atoms. Me is also preferably sodium or potassium.

In the formula (TV), R ^ is particularly preferably cyano, methoxy or methylthio. Me ¹ also particularly preferably stands for sodium or potassium.

The compounds of formula (IV) are known. Formula (V) provides a general definition of the Grignard compounds required as reaction components when carrying out the second stage of the process (a, variant β). In this formula, R-> preferably represents alkyl having 1 to 4 carbon atoms, particularly preferably methyl. Shark ¹ is both preferably and particularly preferably chlorine or bromine.

The Grignard compounds of the formula (V) are known or can be prepared by known methods, advantageously immediately before they are used for further synthesis.

Suitable diluents for carrying out the first step of process (a) according to the invention are all inert organic solvents which are customary for such reactions. Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole can preferably be used; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide.

Suitable acid acceptors for carrying out the first step of process (a) according to the invention are all inorganic and organic bases customary for such reactions. Alkaline earth metal or alkali metal hydroxides, acetates, carbonates, hydrogen carbonates or phosphates, such as, for example, sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, cesium carbonate or silver phosphate, are preferably usable.

Suitable catalysts for carrying out the first stage of process (a) according to the invention are all reaction accelerators customary for such reactions. Palladium, nickel, copper or iron salts or complexes are preferably usable. Examples include copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (I) cyanide, iron (III) acetate, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and l, r-bis (diphenylphosphino) ferrocene palladium (H) chloride.

Palladium or nickel complexes which are generated in the reaction mixture by adding a palladium or a nickel salt and a substance which functions as a complex ligand to the reaction mixture separately are also preferably usable. Examples of ligand formers are: Triethylphosphane, tri-tert-butylphosphine, tricyclohexylphosphine, 2- (dicyclohexylphosphane) - biphenyl, 2- (di-tert.-butylphosphine) biphenyl, 2- (dicyclohexylphosphine) -2 '- (N, N-dimethylamino) biphenyl , Triphenylphosphine, tris (o-tolyl) -phosphine, sodium 3- (diphenylphosphino) benzene sulfonate, tris-2- (methoxyphenyl) phosphine, 2,2'-bis (diphenylphosphine) -l, r-binaphthyl, 1,4-bis (diphenylphosphine) butane, 1,2-bis (diphenylphosphane) ethane, 1,4-bis (dicyclohexylphosphane) butane, 1,2-bis (dicyclohexylphosphane) ethane, 2- (Dicyclohexylphosphine) -2 '- (N, N-dimethylamino) biphenyl, bis (diphenylphosphino) ferrocene and tris (2,4-tert-butylphenyl) phosphite.

The reaction temperatures can be varied within a substantial range when carrying out the first stage of process (a) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 0 ° C and 80 ° C.

When carrying out the first stage of process (a) according to the invention, 1 mol to 10 mol, preferably 1 to 3 mol, of a metal compound of the formula (HI) are generally employed per mol of dihalotriazolo-pyrimidine of the formula (D). The processing takes place according to usual methods.

When carrying out the second stage of the process according to the invention (a, variant α), all customary inert organic solvents are suitable as diluents. Halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane, can preferably be used; Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofirane, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane.

When carrying out the second stage of the process according to the invention (a, variant α), the reaction temperatures can be varied within a substantial range. In general, temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C.

When carrying out the second stage of process (a, variant α), triazolopyrimidine of the formula (Ia) is reacted with an equivalent amount or with an excess of a compound of the formula (IV). The processing takes place according to usual methods. When carrying out the second step of the process according to the invention (a, variant β), all solvents customary for Grignard reactions are suitable as diluents. Ethers such as diethyl ether can preferably be used.

The reaction temperatures can be varied within a certain range when carrying out the second stage of the process according to the invention (a, variant β). In general, temperatures between -20 ° C and 80 ° C, preferably between 0 ° C and 60 ° C.

When carrying out the second stage of the process according to the invention (a, variant β), triazolopyrimidine of the formula (Ia) is reacted with an equivalent amount or else with an excess of the Grignard compound of the formula (V). The processing is again carried out using customary methods.

Suitable diluents for carrying out process (b) according to the invention are all solvents customary for such halogenations. Halogenated aliphatic or aromatic hydrocarbons, such as chlorobenzene, can preferably be used. However, the halogenating agent itself, e.g. Phosphorus oxychloride or a mixture of halogenating agents act.

The temperatures can also be varied within a substantial range when carrying out process (b). In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

When carrying out process (b), dihydroxy-triazolopyrimidine of the formula (VI) is generally reacted with an excess of halogenating agent. The processing takes place according to usual methods.

Suitable diluents for carrying out process (c) are all inert organic solvents which are customary for such reactions. Alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol and tert-butanol can preferably be used.

Suitable acid binders for carrying out process (c) are all inorganic and organic bases customary for such reactions. Tertiary amines such as tributylamine or pyridine can preferably be used. Amine used in excess can also act as a diluent.

The temperatures can be varied within a substantial range when carrying out process (c). In general, temperatures between 20 ° C and 200 ° C, preferably between 50 ° C and 180 ° C. When carrying out process (c), heterocyclylmalonic esters of the formula (VD) and aminotriazole of the formula (VHI) are generally reacted in equivalent amounts. However, it is also possible to use one or the other component in an excess. The processing takes place according to usual methods.

Suitable diluents for carrying out processes (d) and (e) according to the invention are all customary, inert organic solvents. Halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane, can preferably be used; Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with Water or pure water.

Suitable copper salts in carrying out processes (d) and (e) according to the invention are conventional copper salts. Copper (I) chloride or copper (I) bromide can preferably be used.

Suitable acid acceptors for carrying out processes (d) and (e) according to the invention are in each case all of the customary inorganic or organic bases. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, lithium diisopropylamide, sodium methylate, sodium ethylate, potassium tert-butoxide, are preferably usable , Sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate and also ammonium compounds such as ammonium hydroxide, ammonium acetate and ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylanilethyl, N, -benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can also be varied within a substantial range when carrying out processes (d) and (e) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 0 ° C and 80 ° C. When carrying out process (d) according to the invention, 1 to 15 mol, preferably 1.3 to 8 mol, of malonic ester of the formula (X) are generally employed per mol of halopyridine of the formula (TX). The processing takes place according to usual methods.

When carrying out process (e) according to the invention, 1 to 15 mol, preferably 1.3 to 8 mol, of malonic ester of the formula (X) are generally employed per mol of halopyrimidine of the formula (XI). The processing is again carried out using customary methods.

The processes according to the invention are generally carried out under atmospheric pressure. However, it is also possible to work under increased pressure.

The substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.

Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or

Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bre ia lactucae; Peronospora species, such as, for example, Peronospora pisi or P. brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea

(Conidial form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: Drechslera, Syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides. The active compounds according to the invention also have a very good strengthening effect in plants. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms.

Plant-strengthening (resistance-inducing) substances are to be understood in the present context as substances which are able to stimulate the defense system of plants in such a way that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesired microorganisms.

Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses. The substances according to the invention can thus be used to protect plants against attack by the pests mentioned within a certain period of time after the treatment. The period of time within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days, after the plants have been treated with the active compounds.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

The active compounds according to the invention can be used with particularly good success for combating cereal diseases, for example against Erysiphe species, for diseases in wine, fruit and vegetable cultivation, for example against Botrytis, Venturia, Sphaerotheca and Podosphaera species ,

The active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.

If appropriate, the active compounds according to the invention can also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including plant varieties that can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment according to the invention of the plants and parts of plants with the active compounds takes place directly or by acting on their surroundings, living space or storage space according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by coating in one or more layers.

In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.

In the present context, technical materials are understood to mean non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be attacked or decomposed by microorganisms , In the context of the materials to be protected, parts of production systems, for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms. Within the scope of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

Microorganisms of the following genera may be mentioned, for example:

Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger,

Chaetomium, like Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, like Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

Depending on their respective physical and / or chemical properties, the active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV -Cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example 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, and water. With liquefied gaseous extenders or carriers such liquids are keiten meant, which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. As solid carriers there are suitable: for example ground natural minerals, such as kaolins, ^■ clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and syn- synthetic minerals, such as highly disperse silica, alumina and silicates. Solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, pumice, marble, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Suitable emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersants are: eg lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other 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 of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the Emzel components.

The following connections can be considered as mixed partners: fungicides:

2-phenylphenol; 8-hydroxyquinoline sulfate;

Acibenzolar-S-methyl; aldimorph; amidoflumet; Ampropylfos; Ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin;

benalaxyl; Benodanil; benomyl; Benthiavalicarb-isopropyl; Benzamacril; Benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; Blasticidin-S; bromuconazole; Bupirimate; Buthiobate; butylamine;

Calcium polysulfides; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvones; chinomethionat; Chlobenthiazone; Chlorfenazole; chloroneb; chlorothalonil; chlozolinate; Clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram;

Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; Diclomezine; dicloran; diethofencarb; Difenoconazole; diflumetorim; dimethirimol; Dimethomo h; dimoxystrobin; diniconazole; Diniconazole-M; dinocap; diphenylamines; Dipyrithione; Ditalimfos; dithianon; dodine; Drazoxolon;

edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;

famoxadone; fenamidone; Fenapanil; fenarimol; Fenbuconazole; fenfuram; fenhexamid; Fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; Flubenzimine; fludioxonil; flumetover; flumorph; fluoromides; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; Fosetyl-Al; Fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; Furcarbanil; Furmecyclox;

guazatine;

Hexachlorobenzene; hexaconazole; hymexazol;

hnazalil; Imibenconazole; Iminoctadine triacetate; Iminoctadine tris (albesil; Iodocarb; Ipconazole; Iprobefos; Iprodione; Iprovalicarb; Irumamycin; Isoprothiolane; Isovaledione;

kasugamycin; Kresoxim-methyl;

mancozeb; maneb; Meferimzone; mepanipyrim; mepronil; metalaxyl; Metalaxyl-M; Metconazole; methasulfocarb; Methfuroxam; metiram; metominostrobin; Metsulfovax; mildiomycin; myclobutanil; myclozoline; natamycin; nicobifen; Nitro Thal-isopropyl; Noviflumuron; nuarimol;

ofurace; orysastrobin; oxadixyl; Oxolinic acid; Oxpoconazole; oxycarboxin; Oxyfenthiin;

paclobutrazol; Pefurazoate; penconazole; pencycuron; phosdiphen; phthalides; picoxystrobin; piperalin; Polyoxins; Polyoxorim; Probenazole; prochloraz; procymidone; propamocarb; Propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; Pyrazohos; pyrifenox; pyrimethanil; pyroquilon; Pyroxyfur; Pyrrolnitrine;

Quinconazole; quinoxyfen; quintozene;

Simeconazole; spiroxamine; Sulfür;

tebuconazole; tecloftalam; Tecnazene; Tetcyclacis; tetraconazole; thiabendazole; Thicyofen; Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; Triazbutil; triazoxide; Tricyclamide; Tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole;

Uniconazole;

Validamycin A; vinclozolin;

Zineb; ziram; zoxamide;

(2S) -N- [2- [4 - [[3- (4-chlorophenyl) -2-propynyl] oxy] -3-methoxyphenyl] ethyl] -3-methyl-2 - [(methylsulfonyl) amino] butanamide; '

l- (l-naphthalenyl) -lH-pyrrole-2,5-dione;

2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine;

2-amino-4-methyl-N-phenyl-5-thiazole carboxamide;

2-chloro-N- (2,3-dihydro-l, 1,3-trimethyl-lH-inden-4-yl) -3-pyridinecarboxamide;

3,4,5-trichloro-2,6-pyridinedicarbonitrile;

Actinovate;

cis-l- (4-chlorophenyl) -2- (lH-l, 2,4-triazol-l-yl) cycloheptanol;

Methyl 1 - (2,3-dihydro-2,2-dimethyl-1H-inden-1-yϊ) - 1H-imidazole-5-carboxylate; Monokaliumcarbonat;

N- (6-methoxy-3-pyridinyl) -cyclopropanecarboxamide;

sodium tetrathiocarbonate;

as well as copper salts and preparations, such as Bordeaux mixture; copper; Copper naphthenate; copper oxychloride; Copper sulfate; Cufraneb; copper; mancopper; Oxine-copper.

bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, ABG-9008, Acephate, Acequinocyl, Acetamiprid, Acetoprole, Acrinathrin, AKD-1022, AKD-3059, AKD-3088, Alanycarb, Aldicarb, Aldoxycarb, Allethrm, Allethrin lR-Iso ers, Alpha-Cidermethrin), Alphamidermethrin) , Aminocarb, Amitraz, Avermectin, AZ-60541, Azadirachtin, Azamethiphos, Azinphos-methyl, Azinphos-ethyl, Azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, Baculoviruses, Beauveria bassiana, Beauveria tenella; Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Beta-Cyfluthrin, Beta-Cypeπ-nethrin, Bifenazate, Bifenthrin, Binapacryl, Bio-allethrin, Bioallethrin-S-cyclopentyl-isomer, Bioethanomethrin, Biopermethrin, Bioristriflhromine, Bioristriflhromine ethyl, bromopropylate, bromfenvinfos (-methyl), BTG-504, BTG-505, bufencarb, buprofezin, butathiofos, butocarboxim, butoxycarboxim, butylpyridaben,

Cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA 50439, chinomethionate, chlordane, chlordimeform, Chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, Chlorobenzilate, Chloropicrin, Chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl ), Chlovaporthrin, Chromafenozide, Cis-Cypermethrin, Cis-Resmethrin, Cis-Permethrin, Clocythrin, Cloethocarb, Clofentezine, Clothianidin, Clothiazoben, Codlemone, Coumaphos, Cyanofenphos, Cyanophos, Cycloprene, Cycloprothrinine, Cycloprothrinine, Cycloprothrin , Cypermethrin, cyphenothrin (IR-trans isomer), cyromazine, DDT, Deltamethrin, Demeton-S-methyl, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Diazinone, Dichlofenthion, Dichlorvos, Dicofol, Dicrotophos, Dicyclanil, Diflύbenzuron, Dimethoate, Dimethylvinphoc, Diap, Dinaponotononone, Dinobutonone, Dinobutonone, Dinobutonone, Disino Docusat-sodium, Dofenapyn, DOWCO-439,

Eflusilanate, Emamectin, Emamectin-benzoate, Empenthrin (IR-isomer), Endosulfan, Entomothora spp., EPN, Esfenvalerate, Ethiofencarb, Ethiprole, Ethion, Ethoprophos, Etofenprox, Etox-azole, Etrimfos,

Famphur, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenfluthrin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fensulfothion, Fenthion, Fentrifanil, Fluroniluron, Fluefluoronoxyronidone, Fluroniloxyronid, Fluefluoroncytone, Fifronazyronid, Fluentiloxyronid, Fluentiloxyronid, Fluentilonoxyrin, Fluentiloxyronid, Fluentiloxyronid, Fluentiloxyronid, Fluentiloxyrin, Fluentiloxyrin, Fluentiloxyronate , Flucythrinate, Flufenerim, Flufenoxuron, Flufen- prox, Flumethrin, Flupyrazofos, Flutenzin (Flufenzine), Fluvalinate, Fonofos, Formetanate, Formothion, Fosmethilan, Fosthiazate, Fubfenprox (Fluproxyfen), Furathiocarb

Gamma-HCH, Gossyplure, Grandlure, granulovirus,

Halfenprox, Halofenozide, HCH, HCN-801, Heptenophos, Hexaflumuron, Hexyfhiazox, Hydra-methylnone, Hydroprene,

IKA-2002, hnidacloprid, hniprothrin, indoxacarb, iodofenphos, iprobefos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin,

Japonilure,

Kadethrin, nuclear polyhedron viruses, kinoprene,

Lambda-cyhalothrin, lindane, lufenuron,

Malathion, Mecarbam, Mesulfenfos, Metaldehyde, Metam-sodium, Methacrifos, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoprene, Methoxychlor, Methoxyfenozide, Metolcarb, Metoxadiazone, MilevinephinI, Mevincinin MKB, Mevincinin MK5 MON-45700, Monocrotophos, Moxidectin, MTI-800,

Naled, NC-104, NC-170, NC-184, NC-194, NC-196, Niclosa ide, Nicotine, Nitenpyram, Nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, Novaluron , Noviflumuron,

OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl, oxydemeton-ethyl, Paecilomyces fumosoroseus, Parathion-methyl, Parathion (-ethyl), Permethrin (eis, trans-), Petroleum, PH-6045, Phenothrin (lR-trans isomer), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphocarb, Phoxim, Piperonyl butoxide, Pirimicarb, Pirimiphos-methyl, Pirimiphos-ethyl, Prallethrin, Profenofos, Promecarb, Propaphos, Propargite, Propetamphos, Propoxur, Prothiofos, Prothoate, Protrifenbute, Pymetrozine, Pyraclofos, Pyreshridumyl, Pyreshrididhrin, pyreshridium pyrid , Pyrimidifen, pyriproxyfen,

quinalphos,

Resmethrin, RH-5849, Ribavirin, RU-12457, RU-15525,

S-421, S-1833, Salithion, Sebufos, SI-0009, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfluramid, Sulfotep, Sulprofos, SZI-121,

Tau-Fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimfos, Teflubenzuron, Tefluthrin, Temefos, Temivinphos, Terbam, Terbufos, Tetrachlorvinphos, Tetradifon, Tetramethrin, Teframethrin, IR-isulapritomid, thiramidropyrid, thiramiprid, thyridiphenyl , Thiocyclam hydrogen oxalate, Thiodicarb, Thiofanox, Thiometon, Thiosultap-sodium, Thuringiensin, Tolfenpyrad, Tralocythrin, Tralomethrin, Transfluthrin, Triarathene, Triazamate, Triazophos, Triazuron, Trichlophenidine, Trichlumonuron, Trichlarbonuron

Vamidothion, Vaniliprole, Verbutin, Verticillium lecanii,

WL-108477, WL-40027,

YI-5201, YI-5301, YI-5302,

XMC, xylylcarb,

ZA-3274, Zeta-Cypermethrin, Zolaprofos, ZXI-8901,

the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z),

the compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoroethyl) -8-azabicyclo [3.2.1] octane-3-carbonitrile (CAS Reg. No. 185982-80 -3) and the corresponding 3-endo isomer (CAS Reg.No. 185984-60-5) (see WO-96/37494, WO-98/25923),

and preparations containing insecticidally active plant extracts, nematodes, fungi or viruses. A mixture with other known active compounds, such as herbicides or with fertilizers and growth regulators, safeners or semiochemicals, is also possible.

In addition, the compounds of the formula (I) according to the invention also have very good antifungal effects. They have a very broad antimycotic activity spectrum in particular against dermatophytes and yeasts, molds and diphasic fungi (for example against Candida species such as Candida albicans, Candida glabrata), and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, microsporon species such as microsporon canis and audouinii. The list of these fungi in no way represents a limitation of the detectable mycotic spectrum, but is only of an explanatory nature.

The compounds of the formula (I) according to the invention are furthermore suitable for suppressing the growth of tumor cells in humans and mammals. This is based on an interaction of the compounds according to the invention with tubulin and microtubules and by promoting microtubule polymerization.

For this purpose, an effective amount of one or more compounds of formula (I) or pharmaceutically acceptable salts thereof can be administered.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha. As already mentioned above, according to the invention, all plants and their parts can be treated. In a preferred embodiment, wild plant species or plant species and their parts obtained by conventional biological breeding methods, such as crossing or protoplast fusion, are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms) and their parts are treated. The term “parts” or “parts of plants” or “parts of plants” was explained above.

Plants of the plant cultivars which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with new properties (“traits”) which have been cultivated by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, breeds, bio- and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, nutrition), the treatment according to the invention can also cause superadditive ("synergistic") effects. For example, reduced application rates and / or widening the spectrum of action and / or an increase in the action of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher storability and / or workability of the harvested products possible, which go beyond the effects that are actually to be expected.

The preferred transgenic plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher harvest yields, higher quality and / or higher emulsion value of the harvested products, higher storability and / or workability of the Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or vir s and an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants are the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes , Cotton, tobacco and rapeseed are highlighted. The traits are particularly emphasized as the increased defense of the plants against insects, arachnids, namatodes and snails by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (eg by the genes CryΙA (a) , CryIA (b), CryIA (c), CryllA, CryHIA, CryHIB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter referred to as "Bt plants"). Properties ("traits") are also used the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors as well as resistance genes and correspondingly expressed proteins and toxins are particularly emphasized. The properties (“traits”) which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene). The desired properties (“traits”) in each case. conferring genes can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soy varieties and potato varieties that are marketed under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucoton® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soy varieties that are marketed under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g. rapeseed), IMI® (tolerance to hnidazolinone) and STS® (tolerance to sulfonylureas such as corn). The herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties sold under the name Clearfield® (eg maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").

The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized. The preparation and use of the active compounds according to the invention can be seen from the following examples.

Preparation Examples

example 1

Preparation of Grignard solution:

To prepare a Grignard solution, a solution of 5.0 g (28.235 mmol) of 4-methylcyclohexyl bromide in 25 ml of diethyl ether under an argon atmosphere is added dropwise to a mixture of 0.686 g (28.235 mmol) of magnesium turnings and 15 ml of diethyl ether at room temperature. The exothermic reaction begins after brief heating. The reaction mixture is stirred until the magnesium chips have completely dissolved. In this way, a 0.7 molar Grignard solution of 4-methyl-cyclohexyl-magnesium bromide in diethyl ether is obtained, which is used in a freshly prepared state for further synthesis.

Procedure (a)

To a solution of 0.51 g (1.69 mmol) of 5,7-dichloro-6- (5-chloro-4-pyrimidinyl) [1,2,4] triazolo [1,5-a] pyrimidine in 15 ml Tetrahydrofuran, 1.5 ml of N-methylpyrrolidone and 28 mg of iron (III) acetonyl acetonate are added dropwise at room temperature under an argon atmosphere to 2.9 ml of the 0.7 molar solution of 4-methyl-cyclohexyl-magnesium bromide in diethyl ether (Grignard solution). The mixture is stirred at room temperature for 2 hours, another 1 ml of the Grignard solution is added and the mixture is stirred for a further hour. The reaction mixture is then mixed with 10 ml of ethyl acetate and 1 ml of 1 N aqueous hydrochloric acid and stirred for 5 minutes at room temperature.

The organic phase is separated off and the aqueous phase is extracted with a further 10 ml of ethyl acetate. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is filtered with cyclohexane / ethyl acetate (3: 1) through a short column on silica gel. 77 mg (12% of theory) of 5-chloro-6- (5-chloro-4-pyrimidinyl) -7- (4-methylcyclohexyl) [1, 2.4] triazolo [1, 5 -ajpyrimidine are obtained ,

HPLC: logP = 3.27

Example 2

Procedure (a)

To a solution of 0.50 g (1.66 mmol) 5,7-dichloro-6- (5-chloro-4-pyrimidinyl) [1,2,4] triazolo [1,5-a] pyrimidine and 28 mg of iron (-QI) acetonylacetonate in 1.5 ml of tetrahydrofuran and 1.5 ml of N-methylpyrrolidone are added dropwise at room temperature under an argon atmosphere to 1 ml of a 2-molar solution of cyclopentylmagnesium bromide previously prepared in diethyl ether (Grignard solution) , The mixture is stirred for 2 hours at room temperature and 10 ml of ethyl acetate and 1 ml of 1N aqueous hydrochloric acid are then added to the reaction mixture. The organic phase is separated off, dried over sodium sulfate and concentrated under reduced pressure. The remaining residue is filtered with cyclohexane / ethyl acetate = 3: 1 over a short column on silica gel. 73 mg (11.6% of theory) of 5-chloro-6- (5-chloro-4-pyrimidinyl) -7-cyclopentyl [1, 2,4] triazolo [1, 5-a] pyrimidine are obtained.

HPLC: LogP = 2.50

The compounds of the formula (I) listed in Table 1 below are also obtained by the methods given above.

Table 1

# stands for the connecting point

*) The logP values were determined in accordance with EEC Directive 78/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0.1% aqueous phosphoric acid). Production of intermediate products of the formula (TT.

Example 11

Method (b)

8 g (16 mmol) of 6- (3-trifluoromethyl-pvridm-2-yl) - [1,2,4] triazolo [1,5-a] pyrimidine-5,7-diol are stirred with 12 ml of phosphorus oxychloride. 2.7 g of phosphorus pentachloride are added in portions. The mixture is heated under reflux for 2 hours. After cooling, the reaction mixture is concentrated under reduced pressure, mixed with 100 ml of water and extracted 3 times with 100 ml of dichloromethane each time. The combined organic phases are washed twice with 50 ml of water, dried over sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on silica gel using dichloromethane / methyl t-butyl ether (95: 5). 1.4 g (25.7% of theory) of 5,7-dichloro-6- (3-trifluoromethyl-pyridin-2-yl) - [l, 2,4] - triazolof 1,5-a] are obtained pyrimidine.

HPLC: logP = 1.97

Example 12

Method (b)

8 g (16 mmol) of 6- (5-chloro-4-pyrimidinyl) [1,2,4] triazolo [1,5-a] pyrimidine-5,7-diol are stirred with 25 ml of phosphorus oxychloride. 3.1 g of phosphorus pentachloride are added in portions. The mixture is stirred at 110 ° C. for 3 hours. After cooling to room temperature, 300 ml of water are added to the reaction mixture and the mixture is extracted three times with 100 ml of dichloromethane each time. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is mixed with hexane / ethyl acetate (9: 1 - 5: 1) Chromatographed silica gel. 1.4 g (25.7% of theory) of 5,7-dichloro-6- (5-chloro-4-pyrimidinyl) [1, 2,4] triazolo [1, 5-a] pyrimidine are obtained.

HPLC: logP = 1.43

Example 13

A mixture of 2.0 g (10.74 mmol) of 2-thienylmalonic acid and 1.33 g (10.74 mmol) of 3-amino-5-cyclo-propyl-l, 2,4-triazole is added at room temperature 41.13 g (286 mmol) of phosphorus oxychloride were added within 2 minutes while stirring. The mixture is then heated to 90 ° C. for 18 hours and then cooled to room temperature. The reaction mixture is poured into 250 ml of ice water and the resulting suspension is stirred for 1 hour. It is suctioned off and washed with 50 ml of water. For further purification, the product is suspended in 50 ml cyclohexane ethyl acetate = 1: 1 and briefly boiled, then cooled, suction filtered through a short silica gel column and washed 8 times with 50 ml cyclohexane ethyl acetate = 1: 1. The filtrate is dried over sodium sulfate and then filtered again. The filter residue is washed with a little cyclohexane / ethyl acetate = 1: 1. All of the filtrate is concentrated under reduced pressure. 1.73 g (50.7% of theory) of 5,7-dichloro-2-cyclopropyl-6- (thien-3-yl) - [1,2,4] triazolo [1,5-a] are obtained. pyridimidine in the form of a beige solid.

Example 14

In a solution of 6.0 g (19.28 mmol) of 5,7-dichloro-2-cyclopropyl-6- (thien-3-yl) - [l, 2,4] triazolo- [l, 5-a] pyrimidine in 80 ml of acetic acid, a chlorine gas stream is introduced for 2 hours at room temperature. The reaction mixture is then concentrated under reduced pressure. The remaining residue is chromatographed with cyclohexane / ethyl acetate = 2: 1 on silica gel. graphiert. The residue obtained after concentrating the eluate is stirred with cyclohexane / ethyl acetate = 1: 1, then suction filtered and dried. The previously obtained mother liquor is again chromatographed on silica gel using cyclohexane / ethyl acetate = 1: 1 after concentrating under reduced pressure. In this way, 2.7 g (50.5% of theory) of 5,7-dichloro-2-cycloproρyl-6- (2,5-dichlorothien-3-yl) - [1,2,4 ] triazolo [1,5-a] pyrimidine.

Example 15

A solution of 17.0 g (54.89 mmol) of 2-cyclopropyl-6- (4-chlorothiazol-5-yl) - [1,2,4] triazolo [1,5-a] pyrimidin-5, 7-diol in 51.2 ml of phosphorus oxychloride is mixed in portions with stirring at room temperature with 5.72 g (27.44 mmol) of phosphorus pentachloride. After the addition has ended, the reaction mixture is stirred at 110 ° C. for 3 hours, then cooled to room temperature and poured onto ice water. The mixture is extracted several times with dichloromethane, the organic phase is dried over sodium sulfate and concentrated under reduced pressure. The remaining residue is chromatographed on silica gel using cyclohexane / ethyl acetate = 3: 1. In this way, 0.35 g (1.66% of theory) of 5,7-dichloro-2-cyclopropyl-6- (4-chlorothiazol-5-yl) - [1,2,4] triazolo is obtained [l, 5-a] pyrimidine.

HPLC: logP = 2.46

Production of intermediates of formula (VI)

Example 16

Procedure (c) 5.5 g (19.84 mmol) of 2- (3-trifluoromethyl-ρyridin-2-yl) -malonic acid dimethyl ester and 1.67 g (19.84 mmol) of 3-amino-l, 2,4-triazole are in 5 , 2 ml of tributylamine stirred at 180 ° C for 2 hours. The methanol formed during the reaction is continuously distilled off. After cooling, the desired product separates from the tributylamine. The tributylamine is decanted off and the 6- (3-trifluoromethyl-pyridin-2-yl) - [1,2,4] triazolo [1,5-a] pyrimidine-5,7-diol obtained (yield: about 8 g, 60% purity) is used in the next reaction step without further purification.

HPLC: logP = -0.23

Example 17

Procedure (c)

10 g (40.9 mmol) of 2- (5-chloro-pyrimidin-4-yl) -malonic acid dimethyl ester and 3.44 g (40.9 mmol) of 3-amino-l, 2,4-triazole are dissolved in 10.7 ml of tributylamine stirred at 185 ° C for 2 hours. The methanol formed during the reaction is continuously distilled off. After cooling, the desired product separates from the tributylamine. The tributylamine is decanted off and the 6- (5-chloro-4-pyrimidmyl) [1,2,4] triazolo [1,5-a] pyrimidine-5,7-diol obtained (yield: about 15 g,

11% purity, about 15% of theory) is used in the next reaction step without further purification.

HPLC: logP = -0.23

Example 18

A mixture of 8.5 g (34.05 mmol) of dimethyl 2- (4-chlorothiazol-5-yl) malonate, 4.23 g (34.05 mmol) of 3-amino-5-cyclopropyl-1,2 , 4-triazole and 8.92 ml of tri-n-butylamine are stirred at 185 ° C. for 2 hours. The methanol formed during the reaction is continuously distilled off. After cooling, the deposited tri-n-butylamine is decanted off. In this way, 18 g of a product are obtained, since according to HPLC 64% of 2-cyclopropyl-6- (4-chlorothiazol-5-yl) [1,2,4] triazolo [1,5-a] pyrimidine -5,7-diol.

HPLC: logP = 0.10

Production of intermediate products of the formula CVTL-Ά)

Example 19

Method (d)

9 g (207 mmol) of 60% sodium hydride suspension are suspended in 300 ml of dioxane. For this, 27.29 g (206.6 mmol) of dimethyl malonate are added dropwise at 55-60 ° C. and the mixture is stirred for a further 30 minutes at the same temperature. After adding 8.18 g (82.63 mmol) of copper (I) chloride, the mixture is warmed to 80 ° C. and 15 g (82.63 mmol) of 2-chloro-3-trifluoromethylpyridine are then added dropwise. The reaction mixture is then stirred at 100 ° C. for a further 14 hours. After the subsequent cooling to 15-20 ° C., concentrated hydrochloric acid is slowly added dropwise until the mixture is acidic. Now 600 ml of water and 300 ml of dichloromethane are added and insoluble constituents are filtered off. The organic phase is separated off from the filtrate, dried over sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on silica gel using hexane / ethyl acetate (4: 1). 10.1 g (40% of theory) of 2- [3-trifluoromethyl] pyrimidin-2-yl) malonic acid dimethyl ester are obtained.

HPLC: logP = 2.05 Production of precursors of the formula (Nll-b)

Example 20

Method (s)

2.6 g (65.4 mmol) of 60% sodium hydride suspension are suspended in 100 ml of tefrahydrofuran. 6.9 g (52.4 mmol) of dimethyl malonate are added at 0 ° C. and the mixture is stirred at the same temperature for 0.5 hours. A solution of 6.5 g (43.63 mmol) of 4,5-dichloropyrimidine in 50 ml of tefrahydrofuran is then added dropwise and the mixture is stirred for a further 3 hours at room temperature. Then 150 ml of 1N hydrochloric acid are slowly added dropwise and the mixture is then extracted with 100 ml of dichloromethane. The organic phase is separated off, dried over sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on silica gel using methyl t-butyl ether / petroleum ether (1: 9). 7 g (65.6% of theory) of 2- (5-chloro-4-pyrimidin-2-yl) -malonic acid dimethyl ester are obtained.

HPLC: logP = 1.33

Preparation of 4,5-dichloropyrimidine

Example 21

To a solution of 112.5 g (673.7 mmol) of 5-chloro-6-oxo-l, 6-dihydropyrimidin-l-ium chloride in 630 ml of phosphorus oxychloride are added 1.6 ml of dimethylamine and heated under reflux for 3 hours. The excess phosphorus oxychloride is then distilled off under reduced pressure. After cooling, the residue is poured onto 1.5 l of ice water, extracted with 500 ml of dichloromethane, the organic phase is dried over sodium sulfate and concentrated under reduced pressure. 72.3 g (66.3% of theory) of 4,5-dichlo yrimidine are obtained.

HPLC: logP = 1.35

Preparation of 5-chloro-6-oxo-l, 6-dihydropyrimidine-l-ium chloride

Example 22

6.5 g (40 mmol) of iron-m-chloride are added to a solution of 77 g (0.8 mol) of 4 (3H) -pyrimidinone in 770 ml of glacial acetic acid and the mixture is passed at 40-45 ° C. within 2 hours , 6 g (1.6 mol) of chlorine. The reaction mixture is cooled to 15 ° C., the solid product formed is suction filtered and washed with ether. 112.5 g (84% of theory) of 5-chloro-6-oxo-l, 6-dihydropyrimidin-1-ium chloride are obtained. Preparation of 4 (3H) -pyrimidinone

Example 23

A mixture of 103 g (0.804 mol) of 6-mercapto-4 (1H) pyrimidinone (JP 50053381, Chem. Abstr. CAN 84: 17404) and 141.5 g (1.2 mol) of Raney nickel in 1.2 l Ethanol is heated under reflux for 8 hours. The solution is filtered hot, the residue washed with ethanol and the filtrate concentrated under reduced pressure. 67.2 g (87% of theory) of 4 (3H) pyrimidinone are obtained.

use Examples

Example A

Podosphaera test (apple) / protective

Solvent: 24.5 parts by weight of acetone, 24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound 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 activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of the pod mildew pathogen Podosphaera leucotricha. The plants are then placed in the greenhouse at about 23 ° C. and a relative humidity of about 70%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples 1, 2, 3 and 4 show an efficiency of over 85% at an application rate of 100 g / ha.

Example B

Venturia test (apple) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound 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 activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the Venturia inaequalis apple scab pathogen and then remain in an incubation cabin at about 20 ° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in the greenhouse at approximately 21.degree. C. and a relative atmospheric humidity of approximately 90%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples 1, 2, 3 and 4 show an efficiency of 90% and more at an application rate of 100 g / ha.

Example C

Altemaria test (tomato) / protective

Solvent: 49 parts by weight of N, N-dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound 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 activity, young tomato plants are sprayed with the preparation of active compound in the stated application rate. 1 day after the treatment, the plants are inoculated with a spore suspension of Alternaria solani and then stand at 100% rel. Humidity and 20 ° C. Then the plants are at 96% rel. Humidity and a temperature of 20 ° C.

Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples 1, 2 and 3 show an efficiency of 100% at an application rate of 750 g / ha.

Claims

claims

1. Triazolopyrimidines of the formula

in which

R ^{1 represents} optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl or for optionally substituted carbon-linked heterocyclyl,

R ^ represents hydrogen, halogen, optionally substituted alkyl or optionally substituted cycloalkyl,

R ^ represents optionally substituted heterocyclyl and

X represents halogen, cyano, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulfinyl or optionally substituted alkylsulfonyl.

2. triazolopyrimidines of the formula (I) according to claim 1, in which

R ^{1 stands} for alkyl with 1 to 6 carbon atoms, which can be monosubstituted to fivefold, identical or differently substituted by halogen, cyano, alkoxy with 1 to 4 carbon atoms, tri (-C4-alkyl) silyl and / or cycloalkyl with 3 to 6 carbon atoms, which can be monosubstituted to trisubstituted, identical or different, by halogen, haloalkyl having 1 or 2 carbon atoms and 1 to 5

Halogen atoms and / or alkyl with 1 to 4 carbon atoms, or

R ^{1 represents} alkenyl having 2 to 6 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by halogen, cyano, hydroxy, alkoxy having 1 to 4 carbon atoms, tτi (-CC-alkyl) silyl and / or cycloalkyl 3 to 6 carbon atoms, which can be substituted once to three times, in the same way or differently, by halogen, haloalkyl having 1 or 2 carbon atoms. atoms and 1 to 5 halogen atoms and or alkyl having 1 to 4 carbon atoms, or

R represents alkynyl having 3 to 6 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by halogen, cyano, alkoxy having 1 to 4 carbon atoms, tri (C 1 -C 4 -alkyl) silyl and / or cycloalkyl having 3 to 6

Carbon atoms which can be monosubstituted to trisubstituted, identical or different, by halogen, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or alkyl having 1 to 4 carbon atoms, or

R ^{1 stands} for cycloalkyl with 3 to 6 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by halogen, haloalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or alkyl with 1 to 4 carbon atoms, or

R ^{1 stands} for cycloalkenyl with 3 to 6 carbon atoms, which can be monosubstituted to trisubstituted, identical or different, by halogen and / or alkyl having 1 to 4 carbon atoms, or

R represents saturated or unsaturated, carbon-linked heterocyclyl having 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, it being possible for the heterocyclyl to be mono- or disubstituted by halogen, alkyl having 1 to 4 Carbon atoms, cyano, nitro, alkoxy with 1 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms,

Haloalkyl with 1 to 4 carbon atoms and 1 to 9 halogen atoms and / or haloalkoxy with 1 to 4 carbon atoms and 1 to 9 halogen atoms,

R2 represents hydrogen, fluorine, chlorine, bromine, iodine, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms or cycloalkyl having 3 to 6 carbon atoms,

R ^ stands for saturated or unsaturated heterocyclyl with 5 or 6 ring members and 1 to 4 heteroatoms, such as nitrogen, oxygen and / or sulfur, where the heterocyclyl can be substituted one to four times, in the same or different manner, by fluorine, chlorine, bromine, cyano , Nifro

Alkyl, alkoxy, hydroximinoalkyl or alkoximinoalkyl each with 1 to 3

Carbon atoms per al yl part, Haloalkyl or haloalkoxy each having 1 to 3 carbon atoms and 1 to 7 halogen atoms,

and

X represents fluorine, chlorine, bromine, cyano, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, alkylsulfinyl having 1 to 4 carbon atoms or alkylsulfonyl having 1 to 4 carbon atoms.

3. triazolopyrimidines of the formula (I) according to claim 1 or 2, in which

R for a residue of the formula

stands,

or R for a residue of the formula

stands,

or

R ¹ for a radical of the formula

where # marks the point of attachment, R ^ represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, l-trifluoromethyl-2,2,2-trifluoroethyl or heptafluoroisopropyl,

R ^ stands for pyridyl, which is linked in the 2- or 4-position and can be mono- to tetrasubstituted, identical or different, by fluorine, chlorine, bromine,

Cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl, or

R ^ stands for pyrimidyl, which is linked in the 2- or 4-position and can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine,

Bromine, cyano, nifro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl, or

R ^ stands for thienyl, which is linked in the 2- or 3-position and can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine,

Cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl, or

R ^ represents thiazolyl, which in 2-,

4- or 5-position is linked and can be mono- or disubstituted, identical or differently substituted by fluorine, chlorine,

Bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoxyiminomethyl, methoximinoethyl and / or trifluoromethyl and

X represents fluorine, chlorine, bromine, cyano, methyl, methoxy or methylthio.

Process for the preparation of triazolopyrimidines of the formula (I) according to one or more of claims 1 to 3, characterized in that

(a) Dihalotriazolopyrimides of the formula

in which

R R3 and R ^ have the meanings given in Claims 1 to 3,

X ^{1 represents} halogen and

Y ^{1 represents} halogen,

with metal compounds of the formula (IQ),

Ri -Me (in)

in which

R has the meaning given in claims 1 to 3 and

Me for lithium, dihydroxyboranyl or a radical of the formula

or MgHal

stands in what

Shark represents chlorine or bromine,

if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, and if appropriate the triazolopyrimidines of the formula (Ia) thus obtained

in which

R ¹ , R ^, R3 and X ^{1 have} the meanings given in Claims 1 to 3,

either ) with compounds of the formula

R ^ Me ¹ (IV)

in which

R4 represents optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl or cyano and

Me stands for sodium or potassium,

if appropriate in the presence of a diluent,

or

β) with Grignard compounds of the formula

R ⁵ - Mg Shark ¹ (V)

in which

R ^ represents optionally substituted alkyl and

Shark ^{1 represents} chlorine or bromine,

in the presence of a diluent.

5. Agent for combating undesirable microorganisms, characterized by a content of at least one triazolopyrimidine of the formula (I) according to one or more of claims 1 to 3 in addition to extenders and / or surface-active substances.

6. Use of triazolopyrimidines of the formula (I) according to one or more of claims 1 to 3 for combating undesired microorganisms.

7. A method for controlling unwanted microorganisms, characterized in that triazolopyrimidines of the formula (I) according to one or more of claims 1 to 3 are applied to the undesired microorganisms and / or their habitat.

8. A process for the preparation of agents for controlling unwanted microorganisms, characterized in that triazolopyrimidines of the formula (I) according to one or more of claims 1 to 3 mixed with extenders and / or surface-active substances.

9. Dihalogenotriazolopyrimidines of the formula

in which

R ^ represents hydrogen, halogen, optionally substituted alkyl or optionally substituted cycloalkyl,

R3 represents optionally substituted heterocyclyl,

X ^{1 represents} halogen and

Y ^{1 represents} halogen.

10. A process for the preparation of dihalo-friazolopyrimidines of the formula (II) according to claim 9, characterized in that

(b) Dihydroxy-triazolo-pyrimidines of the formula

in which

R-2 and R ^ have the meanings given in claim 9,

with Halogeniemngsmittel, optionally in the presence of a diluent.

11. Dihydroxy-triazolo-pyrimidines of the formula

in which

R ^ represents hydrogen, halogen, optionally substituted alkyl or optionally substituted cycloalkyl and

R ^ represents optionally substituted cycloalkyl.

12. A process for the preparation of dihydroxy-triazolo-pyrimidines of the formula (VI) according to spoke 11, characterized in that

(c) Heterocyclylmalonic esters of the formula

in which

R has the meaning given in spoke 11 and

R "represents alkyl having 1 to 4 carbon atoms,

with aminofriazoles of the formula

in which

R2 has the meaning given in address 11,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

13. Pyridylmalonic ester of the formula

in which

R "represents the alkyl having 1 to 4 carbon atoms and

R ^ represents halogen or haloalkyl.

14. A process for the preparation of pyridylmalone esters of the formula (VH-a) according to claim 13, characterized in that

(d) Halopyridines of the formula

in which

R 'has the meaning given in claim 13 and

Y ^ represents halogen,

with malon esters of the formula

in which

R ° has the meaning given in address 13,

if appropriate in the presence of a diluent, if appropriate in the presence of a copper salt and if appropriate in the presence of an acid acceptor.

15. Pyrimidylmalonic ester of the formula

in which

RÖ stands for alkyl with 1 to 4 carbon atoms,

R ⁰ * represents halogen or haloalkyl, and

R ^ and R ¹ ^ are independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy.

16. A process for the preparation of pyrimidylmalone esters of the formula (VIII-b) according to spoke 15, characterized in that

(e) Halogenpyrirnidines of the formula

in which

R, R9 and R ¹ ^ have the meanings given in spoke 15 and

Y ^ represents halogen,

with malon esters of the formula

in which R "has the meaning given in claim 15,

if appropriate in the presence of a diluent, if appropriate in the presence of a copper salt and if appropriate in the presence of an acid acceptor.