WO2007113136A1 - Use of substituted triazolopyrimidines for controlling phytopathogenic harmful fungi - Google Patents

Abstract

Use of substituted triazolopyrimidines of the formula (I), in which the substituents are as defined in the description, for controlling harmful fungi, novel triazolopyrimidines, processes and intermediates for their preparation, and compositions comprising them.

Description

USE OF SUBSTITUTED TRIAZOLOPYRIMIDINES FOR COMBATING

PHYTO PATHOGEN'S DAMAGED MUSHROOMS

description

The present invention relates to the use of substituted triazolopyrimidine of the formula I,

in which the substituents have the following meanings:

R ¹ Ci-Ci2-alkyl, _Ci-Ci2 haloalkyl, C ₂ -C ₂ -alkenyl, C ₂ -C ₂ haloalkenyl, C ₂ -C ₂ - alkynyl, C ₂ -C ₂ haloalkynyl, C ₃ - C ₈ -Cycloalkyl, C ₃ -C ₈ -halocycloalkyl, C ₃ -C ₆ -

Cycloalkenyl, C ₃ -C 6 halocycloalkenyl, C ₈ alkoxy, Ci-C ₈ haloalkoxy, C ₂ -C ₈ alkenyloxy, C ₂ -C ₈ alkynyloxy, C ₃ -C ₈ cycloalkoxy, NH _2, C 1 -C ₈ -alkylamino, C 1 -C ₈ -alkylamino, phenyl, naphthyl, a five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S. , or

# -CR ³ R ⁴ - (CR ⁵ R ⁶ ) _q - (CR ⁷ R ⁸ ) pYZ where # is the point of attachment to the nitrogen atom and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ independently of one another hydrogen, C 1 -C ₈ -alkyl, C 1 -C ₈ -

Haloalkyl, C ₂ -C ₈ -alkenyl -alkyl, C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ kinyl -alkyl, C ₂ -C ₈ - haloalkynyl, C ₃ -C 6 cycloalkyl, C ₃ -C 6 halocycloalkyl, C ₃ -C ₆ -CyCIo- alkenyl, C ₃ -C 6 halocycloalkenyl, phenyl, naphthyl or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one, two, three or four heteroatoms from the group O, N and S, R ⁵ can also form, with R ³ or R ⁷ together with the atoms to which these radicals are bonded, a five-, six-, seven-, eight-, nine- or ten-membered saturated or partially unsaturated ring which, in addition to carbon atoms one, two or three heteroatoms from the group O, N and S may contain as ring member and / or may carry one or more substituents R ^a ; R ³ with R ^4, R ⁵ with R ^6, R ⁷ with R ⁸ may together also mean the formation of carbonyl oxygen to form in the formation of the spiro groups, a C ₂ -C 5 alkylene or alkenylene, alkynylene, which, through a two or three heteroatoms from the group O, N and S may be interrupted; or one of the groups mentioned in R ¹ ; R ¹ and R ^{3 taken} together with the nitrogen atom to which they are attached may form a five-, six-, seven-, eight-, nine- or ten-membered saturated or partially unsaturated heterocycle containing, in addition to carbon atoms, one, two or three further carbon atoms May contain heteroatoms from the group O, N and S as a ring member; R ¹ and R ³ to R ⁸ may each independently be partially or completely halogenated and / or carry one, two, three or four identical or different groups R ^a :

R ^{a is} halogen, cyano, nitro, hydroxy, carboxyl, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl,

C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkenyl, C ₆ alkoxy, _Ci-C6 haloalkoxy, C2-C6-alkenyloxy, C3-C6-haloalkenyloxy, C3-C6-alkynyloxy, C ₃ -Ce-haloalkynyloxy, C 3 -C 6 -cycloalkoxy, C 3 -C 6 -cycloalkenyloxy, C (O) R ^π , C (O) OR ^π , C (S) OR ^π , C (O) SR ^π , C (S SR ^π , OC (O) OR ^π , C ₁ -C ₆ -alkylthio, C ₁ -C 4 -alkylamino, C ₁ -C ₆ -alkylamino, C (O) NHR ^π , C (O) NR ^π ₂ , C ₆ alkylene,

Oxy-Ci-C4-alkylene, oxy-Ci-C3-alkyleneoxy, wherein divalent groups may be bonded to the same atom or to adjacent atoms, phenyl, naphthyl, five, six, seven, eight, nine or 10-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S;

R ^π d-Cβ-alkyl, C ₃ -C ₈ -alkenyl, C ₃ -C ₈ -alkynyl, C ₃ -C ₆ -cycloalkyl or C ₃ -

Cδ cycloalkenyl; in which the aliphatic, alicyclic or aromatic groups in the abovementioned groups R ^a and R ^{π are in} turn partially halogenated or completely halogenated and / or may carry one, two or three groups R ^b :

R ^{b is} halogen, cyano, nitro, hydroxyl, mercapto, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, Alkoxycarbonyloxy, aminocarbonyl, aminothiocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, the alkyl groups in these radicals containing from 1 to 6 carbon atoms and said alkenyl or alkynyl groups in these radicals containing from 2 to 8 carbon atoms; Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, wherein the cyclic systems are 3 to 10

Ring members included; Aryl, aryloxy, arylthio, aryl-C 1 -C 6 -alkoxy, aryl-C 1 -C 6 -alkyl, hetaryl, hetaryloxy, hetarylthio, where the aryl radicals preferably contain 6 to 10 ring members, the hetaryl radicals contain 5 or 6 ring members, the cyclic systems being partially or completely halogenated and / or may be substituted by alkyl or haloalkyl groups; Y oxygen or sulfur;

Z is hydrogen, carboxyl, formyl, Ci -C ₈ -alkyl, C ₈ haloalkyl, C ₂ -

C ₈ alkenyl, _C2-C8 haloalkenyl, C ₂ -C ₈ kinyl -alkyl, _{C2-C8-halo-alkynyl,} C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkenyl, C (O) R ^π , C (O) OR ^π ,

C (S) OR ^π , C (O) SR ^π , C (S) SR ^π , C (NR ^A ) SR ^π , C (S) R ^π , C (NR ^π ) NR ^A R ^B , C (NR ^π ) R ^A , C (NR ^π ) OR ^A , C (O) NR ^A R ^B , C (S) NR ^A R ^B , C 1 -C 6 -alkylsulfinyl, d-Cβ-alkylthio, C 1 -C 6 -alkylsulfonyl, C (O) -dd-alkylene-NR ^A C (NR ^π ) NR ^A R ^B ,

C (S) -Ci-C ₄ -alkylene-NR ^A C (NR ^π ) NR ^A R ^B ,

C (NR ^π ) -Ci-C ₄ alkylene-NR ^A C (NR ^π ) NR ^A R ^B , phenyl, naphthyl, five, six, seven, eight, nine or ten membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S which is bonded directly or via a carbonyl, thiocarbonyl, C 1 -C ₄ -alkylcarbonyl or C 1 -C ₄ -alkylthiocarbonyl group; wherein in group Z the carbon chains may be substituted by one or more groups R ^b ;

R ^A , R ^B independently of one another are hydrogen, ^C 2 -alkenyl, C 2 -alkynyl or one of the groups mentioned for R ^π ;

R ^A and R ^B can also be taken together with the nitrogen atom to which they are attached, or R ^A and R ^π together with the carbon and hetero atoms through which they are attached, a five- or six-membered saturated, partially unsaturated or aromatic ring form, in addition to carbon atoms, one, two or three further heteroatoms from the group O, N and S contain as a ring member and / or can carry one or more substituents R ^a ; or

Z can also form with R ⁶ or R ⁸ a five- or six-membered saturated or partially unsaturated ring which, in addition to carbon atoms and Y, may contain one or two further heteroatoms from the group O, N and S as ring member and / or one or more can carry ^a plurality of substituents R ^a ; the group Z may be partially or completely halogenated and / or carry one, two or three groups R ^b ; Hydrogen or one of the groups mentioned for R ¹ ; R ¹ and R ² , together with the nitrogen atom to which they are attached, may also form a five-, six-, seven-, eight-, nine- or ten-membered saturated, partially unsaturated or aromatic heterocycle containing, in addition to carbon atoms, one, two or three carbon atoms three further heteroatoms from the group O, N and S may contain as ring member and which contains at least one substituent selected from UO #, US # and UY- (CR ⁵ R ⁶ ) _q -CR ³ R ⁴ -#, and the

Linkage site with the heterocycle and the heterocycle can also carry one, two or three groups R ^a ; U is hydrogen, carboxyl, formyl, C ₅ -C ₈ -alkyl, C ₁ -C ₆ -haloalkyl, C ₂ -C ₈ -

Alkenyl, C ₂ -C ₈ -haloalkenyl, C ₂ -C ₈ -alkynyl, C ₂ -C ₈ -haloalkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₈ -cycloalkenyl, C (O) R ^π , C (O) OR ^π , C (S) OR ^π , C (O) SR ^π ,

C (S) SR ^π , C (NR ^A ) SR ^π , C (S) R ^π , C (NR ^π ) NR ^A R ^B , C (NR ^π ) R ^A , C (NR ^π ) OR ^A , C ( O) NR ^A R ^B, C (S) NR ^A R ^B, _{Ci-C8-alkylsulfinyl,} Ci -C ₈ alkylthio -alkyl, d-Cβ-alkyl sulfonyl, C (O) -Ci-C ₄ alkylene-NR ^A C (NR ^π ) NR ^A R ^B , C (S) -Ci-C ₄ alkylene-NR ^A C (NR ^π ) NR ^A R ^B ,

C (NR ^π ) -Ci-C ₄ alkylene-NR ^A C (NR ^π ) NR ^A R ^B , phenyl, naphthyl, five, six, seven, eight, nine or ten membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S which is bonded directly or via a carbonyl, thiocarbonyl, C 1 -C ₄ -alkylcarbonyl or C 1 -C ₄ -alkylthiocarbonyl group; where in the group Z the carbon chains can carry one, two or three groups R ^b ; p is zero, 1, 2, 3, 4 or 5; q is zero or 1;

W d-Cio-alkyl, Ci-Cio-haloalkyl, C ₂ -Cio-alkenyl, C ₂ -Cio-alkynyl, C ₃ -C ₈ -cycloalkyl, Ca-Cs-cycloalkenyl, phenyl-Ci-Cio-alkyl, wherein W may be unsubstituted or partially or completely halogenated and / or may carry one to three radicals from the group R ^a ;

X is C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -haloalkenyl, C ₂ -C ₆ -alkynyl or C ₂ -C ₆ -halo-genalkinyl; and agriculturally acceptable salts thereof, for controlling phytopathogenic fungi. Moreover, the invention relates to novel triazolopyrimidines, processes and intermediates for the preparation of these compounds, and agents containing them.

Individual 5-methyl-triazolopyrimidines having pharmaceutical activity are described in J. of Med. Chem., Vol. 23, pp. 927-37 (1980, J. Het. Chem. Vol. 5, pp. 691-3 (1968); Kh. Obs. Kh., Vol. 33, pp. 2678-82 (1963), DD 256 327, DD 256 328, JP 2003/71639, JP 03/189895, JP 09/169763, US 5,387,747, and US Pat. WO 05/073398. From EP-A

No. 141,317, WO 03/009687 and WO04 / 041825, 6-alkyl- or 6-cycloalkyl-7-amino-triazolopyrimidines are generally known. WO 2005/087770, WO 2005/087771, WO 2005/095404, WO 2005/095405, WO 2005/120233, WO 2005/123739, WO 2005/113555, WO 2006/000436, WO 2006/027170 and WO 2006/005492 5-alkyl-7-amino-triazolopyrimidines are known. The compounds known from these publications are suitable for controlling harmful fungi.

The compounds according to the invention differ from those described in the abovementioned publications essentially by the configuration of the group X or W. The effect of the known compounds is in many cases unsatisfactory. On this basis, the object of the present invention is to provide compounds with improved activity and / or broadened spectrum of activity.

Accordingly, the compounds defined above were found. Furthermore, processes and intermediates for their preparation, agents containing them and methods for controlling harmful fungi using the compounds I have been found. The compounds of the general formula I according to the invention can be prepared in various ways in analogy to prior art processes according to the syntheses shown in the following Schemes: Conventional syntheses start from 5-aminotriazole of the formula IIa and reaction with corresponding malonates IIb in which R represents alkyl, preferably C 1 -C 6 -alkyl, in particular methyl or ethyl.

This reaction is usually carried out at temperatures of 8O ⁰ C to 25O ⁰ C, preferably 12O ⁰ C to 18O ⁰ C, without solvent or in an inert organic solvent in the presence of a base [cf. EP-A 770 615] or in the presence of acetic acid under the conditions described in Adv. Het. Chem. Vol. 57, p. 81ff. (1993) known conditions. Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, ethers, nitriles, ketones, alcohols, and N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide and dimethylacetamide. The reaction is particularly preferably carried out without a solvent or in chlorobenzene, xylene, dimethyl sulfoxide, N-methylpyrrolidone. It is also possible to use mixtures of the solvents mentioned. Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates and alkali metal bicarbonates, organometallic compounds, especially alkali metal alkyls, alkylmagnesium halides and alkali metal and alkaline earth metal alkoxides and dimethoxymagnesium. also organic bases, for example tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethyl-aminopyridine and bicyclic amines into consideration. Particularly preferred are tertiary amines such as diisopropylethylamine, tributylamine, N-methylmorpholine or N-methylpiperidine.

The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the base and the malonate IIb in an excess based on the triazole.

Substituted malonates of the formula IIb are advantageously prepared from the reaction of corresponding alkyl, alkenyl or alkynyl halides, in particular the bromides, with dialkyl malonates under Cu (I) catalysis [cf. Chemistry Letters, pp. 367-370, 1981; EP-A 10 02 788], or under basic conditions [cf. Organikum, VEB German publishing house of the sciences, Berlin 1988, S. 517] received.

The Dihalogentriazolopyrimidine of the formula II thus obtained are reacted with amines of the formula III,

in which R ¹ and R ^{2 are} as defined in formula I, converted to compounds of formula IV.

This reaction is advantageously carried out at ^{0 0} C to 7O ⁰ C, preferably 1O ⁰ C to 35 ⁰ C, preferably in the presence of an inert solvent such as ethers, eg. As dioxane, diethyl ether or especially tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [cp. WO 98/46608; WO 03/009687].

The use of a base, such as tertiary amines, for example triethylamine or inorganic bases, such as potassium carbonate is preferred; Excess amine of the formula IM can also serve as a base.

Compounds of formula II and III are for. T. known or can be hailed according to the literature cited above.

Compounds of the formula I in which X is C 1 -C ₄ -alkyl, alkenyl or alkynyl, may alternatively also be prepared from compounds IV in which X is in particular chlorine and malonates of the formula V are prepared. In formula VII, X "is hydrogen or C 1 -C 3 -alkyl, alkenyl or alkynyl and R is C 1 -C ₄ -alkyl. They are converted into compounds of the formula VII and decarboxylated to give compounds I [see US 5,994,360].

Malonates V are known in the literature [J. At the. Chem. Soc., Vol. 64, 2714 (1942); J. Org. Chem., Vol. 39, 2172 (1974); Helv. Chim. Acta, Vol. 61, 1565 (1978)] or can be prepared according to the cited literature.

The subsequent saponification of the ester VI is carried out under generally customary conditions, depending on the various structural elements, the alkaline or the acidic saponification of the compounds VI may be advantageous. Under the conditions of the ester saponification, the decarboxylation to I can already take place completely or partially. The decarboxylation is usually carried out at temperatures from 2O ⁰ C to 18O ⁰ C, preferably 5O ⁰ C to 12O ⁰ C, in an inert solvent, optionally in the presence of an acid. Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid. Suitable solvents are water, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert. Butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, the reaction is particularly preferably carried out in hydrochloric acid or acetic acid. It is also possible to use mixtures of the solvents mentioned.

Compounds of the formula I can advantageously also be obtained by the following synthesis route:

Starting from the ketoesters IMa, the 7-hydroxy compounds are obtained. In formulas IMa and IVa, X is preferably C 1 -C ₄ -alkyl. The preparation of the compounds IMa takes place advantageously under known conditions [cf. Chemistry Letters, pp. 367-370, 1981; EP-A 10 02 788; Organikum, VEB German publishing house of the sciences, Berlin 1988, S. 517]. The 5-alkyl-7-hydroxy-6-alkyltriazolopyrimidines IVa thus obtained are reacted with halogenating agents [HAL] under the conditions described above to give the 7-halotriazolopyrimidines of the formula Va in which Hal is a halogen atom. Preference is given to using chlorinating or brominating agents such as phosphorus oxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride. The reaction may be carried out neat or in the presence of a solvent. Typical reaction temperatures are from 0 to 15O ⁰ C or preferably from 80 to 125 ⁰ C.

The reaction of Va with amines Ml takes place under the conditions described above.

Compounds of the formula I in which X is C 1 -C ₄ -alkyl, alkenyl or alkynyl can also be obtained by coupling 5-halotriazolopyrimidines of the formula IV with organometallic reagents of the formula VII. In one embodiment of this process, the reaction is carried out under transition metal catalysis, such as Ni or Pd catalysis.

In formula VII, M is a metal ion of valence Y, such as Mg-HaI to form Grignard compounds, Li, B, Zn or Sn and X "is C 1 -C 3 -alkyl This reaction can be carried out, for example, by the following methods J. Chem. Soc., Perkin Trans. 1, 1187 (1994), ibid. 1, 2345 (1996); WO-A 99/41255; Aust. J. Chem., 43, 733 (1990); Chem., Vol. 43, 358 (1978); J. Chem. Soc. Chem. Commun., 866 (1979); Tetrahedron Lett, Vol. 34, 8267 (1993); ibid., Vol. 33, 413 (1992 ).

The compounds of the formula I in which Z in R ^{1 is} not hydrogen may also be prepared from hydroxy- or mercaptotriazolopyrimidines of the formula Ia.

For this purpose, the 7-hydroxy, or mercaptoaminotriazolopyrimidine of the formula Ia is reacted with an alkylating or acylating agent Z-L, where L is a nucleophilic cleavable group. Usually halides, especially chlorides and bromides, carboxylic anhydrides, such as. As acetic anhydride, or carboxylic acid chlorides, carboxylic acids used in conjunction with coupling reagents, such as di-cyclohexylcarbodiimide or acids, such as HCl. The reaction conditions suitable for the prevention or esterification are generally known to the person skilled in the art [cf .: Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin (1981)]. The compounds of formula Ia are z. T. known from the documents cited above.

The reaction mixtures are worked up in the usual way, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products. The intermediate and end products are z.T. in the form of colorless or slightly brownish, viscous oils which are freed from volatile constituents under reduced pressure and at moderately elevated temperature. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.

If individual compounds I are not accessible in the above-described ways, they can be prepared by derivatization of other compounds I.

However, if isomer mixtures are obtained in the synthesis, separation is generally not necessary since the individual isomers may partially interconvert during preparation for use or during use (eg, under the action of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled. In the definitions of the symbols given in the above formulas, collective terms were used which are generally representative of the following substituents:

Halogen: fluorine, chlorine, bromine and iodine; Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, e.g. C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

Haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), in which groups the hydrogen atoms may be partially or completely replaced by halogen atoms as mentioned above: in particular C 1 -C 2 -haloalkyl, such as chloromethyl, Bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2- yl; Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6 or 8 carbon atoms and one or two double bonds in any position, e.g. C2-C6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1 Methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3 Methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl 3-Butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl , 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1 pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3 Methyl 3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1 Dimethyl 2-butenyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1 -butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-centenyl, 1, 3-dimethyl 3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3.3 Dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl , 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1 -propenyl and 1-ethyl-2-methyl-2-propenyl;

Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 8 carbon atoms and having one or two double bonds in any position tion (as mentioned above), wherein in these groups, the hydrogen atoms may be partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;

Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for example C ₂ -C ₆ alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl , 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2 Methyl 3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5 Hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl , 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl 3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1 Ethyl-1-methyl-2-propynyl; Cycloalkyl: mono- or bicyclic, saturated hydrocarbon groups having 3 to 6 or 8 carbon ring members, for example C 1 -C 8 -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; 5- to 10-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S: 5- or 6-membered heterocyclyl containing one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl , 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolindinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl , 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2-yl, 2-pyrrol-in-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-piperidinyl, 3-piperidinyl , 4-piperidinyl, 1, 3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyri dazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl;

5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-membered heteroaryl groups, which besides carbon atoms can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members. eg 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1, 3,4-triazol-2-yl;

6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6- ring heteroaryl groups, which in addition to carbon atoms may contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl,

4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl; Alkylene: divalent linear chains of 3 to 5 Chb groups, eg, CH _2, CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH _2, and CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ;

Oxyalkylene: divalent unbranched chains of 2 to 4 Chb groups, wherein a valence is bonded to the skeleton via an oxygen atom, for example OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ and OCH ₂ CH ₂ CH ₂ CH ₂ ;

Oxyalkylenoxy: divalent unbranched chains of 1 to 3 Chb groups, both valences being bonded to the skeleton via an oxygen atom, for example OCH ₂ O, OCH ₂ CH ₂ O and OCH ₂ CH ₂ CH ₂ O;

Included within the scope of the present invention are the (R) and (S) isomers and the racemates of compounds of formula I having chiral centers.

The particularly preferred embodiments of the intermediates with respect to the variables correspond to those of the formula I.

With regard to their intended use of the triazolopyrimidines of the formula I, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:

One embodiment relates to compounds I in which R ^{1 is} C ¹ -C ₄ -alkyl, such as methyl or ethyl, in particular methyl. One embodiment relates to compounds I in which R ^{1 is} C 1 -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₃ -C ₆ -cycloalkyl which is 1, 2, 3 or 4 times by halogen or C 1 -C ₄ -AlkVl can be substituted, or d-Cs-haloalkyl. Among these, a particularly preferred embodiment relates to compounds of

Formula I, where R ^{1 is} a group B:

wherein

Z ^{1 is} hydrogen, fluorine or C ¹ -C ₄ -fluoroalkyl, Z ^{2 is} hydrogen or fluorine, or Z ¹ and Z ² together form a double bond; j is 0 or 1; and

R ^{16 is} hydrogen or methyl.

If R ¹ and / or R ² contain haloalkyl or haloalkenyl groups with chiral centers, the (S) - isomers are preferred for these groups. In the case of halogen-free alkyl or alkenyl groups with chiral centers in R ¹ or R ² , the (R) -configured isomers are preferred.

A further embodiment relates to compounds I in which R ¹ is C ₃ -C 6 -cycloalkyl which may be substituted by C 1 -C ₄ -alkyl.

A further embodiment relates to compounds I in which R ¹ and R ² together with the nitrogen atom to which they are bonded are saturated or simply unsaturated. saturated, in particular 5 or 6-membered heterocyclyl as defined above. Preferred among these are those compounds in which R ¹ and R ² together with the nitrogen atom to which they are attached form an optionally substituted piperidinyl, morpholinyl or thiomorpholinyl ring, especially a piperidinyl ring. In particular, heterocyclyl is unsubstituted or substituted by 1, 2 or 3 substituents R ^a , with preferred substituents R ^a of heterocyclyl being selected from halogen, C 1 -C ₄ -alkyl and C 1 -C ₄ -haloalkyl. Of these, particular preference is given to compounds I in which R ¹ and R ² together with the nitrogen atom to which they are attached are a 4-methylpiperidine ring, a 4-trifluoromethylpiperidine ring, a morpholine ring or a 3,4-dimethylpiperidine ring and especially a 4-methyl - form piperidine ring or a 3,4-dimethylpiperidine ring.

Another object of the invention are compounds I in which R ¹ and R ^2, together with the nitrogen atom to which they are attached, are 5- or 6-membered heteroaryl as defined above, which may be unsubstituted or substituted, preferably by 1 , 2 or 3 groups R ^a . In particular, then forms the group

NR ¹ R ^{2 is} a pyrazole ring, which is optionally substituted in the manner described above, and especially by 1 or 2 of the following radicals: halogen, -C ₄ -alkyl or -C ₄ -haloalkyl, in particular by 2 methyl groups or 2 Trifluormethylgrup- pen 3, 5 position. Another object of the invention are compounds I, wherein R ^{1 is} selected from: CH (CHa) -CH ₂ CH ₃ , CH (CH ₃ ) -CH (CH ₃ ) 2, CH (CH ₃ ) -C (CH ₃ ) ₃ , CH (CH ₃ ) -CF ₃ , CH ₂ C (CHs) = CH ₂ , CH ₂ CH = CH ₂ , cyclopentyl or cyclohexyl; and R ^{2 is} hydrogen or methyl; and compounds I wherein R ¹ and R ² together are - (CH ₂ ) ₂ CH (CH ₃ ) (CH ₂ ) ₂ -, - (CH ₂ ) ₂ CH (CF ₃ ) (CH ₂ ) ₂ - or - (CH ₂ ) ₂ O (CH ₂ ) ₂ - mean. A further embodiment relates to compounds I in which the group NR ¹ R ^{2 is} ethylglycinol, leucinol, tert-leucinol, valinol, norvalinol, methioninol, phenylalaninol, lysinol, argininol, histidinol, asparaginol, glutaminol, serinol, isoleucinol, cysteinol, hydroxymethylpiperidine, cis-2-hydroxymethyl-4-methyl-piperidine, trans-2-hydroxymethyl-4-methyl-piperidine, cyclohexylgylcinol, cyclopentylglycinol, butylglycinol, pentylglycinol, cis-2-aminocyclohexanol, trans-2-aminocyclohexanol, cis 2-aminocyclopentanol, trans-2-aminocyclopentanol, cis-1-amino-2-hydroxyindane or trans-1-amino-2-hydroxyindane.

Another object of the invention are compounds I, in which R ¹ # -CR ³ R ⁴ - (CR ⁵ R ⁶ ) _q - (CR ⁷ R ⁸ ) pYZ, where # is the point of attachment to the nitrogen atom.

One embodiment relates to compounds I in which R ^{2 is} hydrogen or C 1 -C 6 -alkyl, such as hydrogen or methyl or ethyl.

Another embodiment relates to compounds I in which R ^{2 is} hydrogen. A further embodiment relates to compounds I in which R ^{3 is} straight-chain or branched C ₁ -C 8 -alkyl, C ₃ -C -alkenyl or C ₃ -C 6 -cycloalkyl, in particular Ci-Cβ-alkyl or C3-C6-cycloalkyl, preferably iso-propyl, iso-butyl, tert. Butyl, sec. Pen- tyl, cyclopropyl or cyclopentyl, in particular tert. Butyl.

Another embodiment relates to compounds I in which R ^{3 is} not hydrogen or methyl. In a further embodiment, the group R ^{3 has} a branching on the α-carbon atom.

In one embodiment, the group R ³ is substituted by heteroatom-bonded groups, such as halogen, alkoxy, alkylthio, amino, alkylamino, dialkylamino or formyl, carboxyl, alkoxycarbonyl, alkoxythiocarbonyl or alkenyl, alkynyl groups or C 2 -C 5 -alkylene, both valences the same carbon atom are bonded.

In a further embodiment, the group R ³ is substituted by C 3 -C 6 -cycloalkyl or C 3 -C 8 -cycloalkenyl.

In another embodiment, the group R ³ is C (O) R ^A , C (O) OR ^A , C (S) OR ^A , C (O) NR ^A R ^B , C (S) NR ^A R ^B , C (NR ^A ) R ^B , C (O) SR ^π or C (S) SR ^π substituted.

R ^π is preferably d-Cs-alkyl or C3-C6-cycloalkyl, which groups may be partially or completely halogenated.

In a further embodiment, the group R ^{3 is represented} by a five, six, seven, eight, nine or ten membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S, substituted.

A further embodiment relates to compounds I in which R ^{4 is} hydrogen, straight-chain or branched C 1 -C 5 -alkyl or C 3 -C 6 -cycloalkyl, in particular hydrogen, C 1 -C 6 -alkyl or C 3 -C 6 -cycloalkyl, preferably hydrogen, iso -Propyl, tert. Butyl. If R ^{4 is} an alkyl group, R ⁴ preferably has the same meaning as R ³ .

In a further embodiment of the compounds of the formula I, R ³ and R ⁴ together form a C 3 -C 6 -alkylene, in particular a C 3 -C 4 -alkylene group, where the carbon chains may be substituted by heteroatom-bonded groups, such as halogen, alkoxy, alkylthio , Amino, alkylamino, dialkylamino or alkoxycarbonyl.

In a further embodiment of the compounds of the formula I, R ³ and R ⁴ together form a C 3 -C 6 -alkylene, in particular a C 3 -C 4 -alkylene group, the carbon chains being interrupted by one or two heteroatoms from the group O, N and S. and may be substituted by heteroatom-bonded groups, such as halogen, alkoxy, alkylthio, amino, alkylamino, dialkylamino or alkoxycarbonyl.

In a further embodiment of the compounds of the formula I, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} each hydrogen or C 1 -C ₄ -alkyl, preferably hydrogen, methyl or ethyl, in particular hydrogen. The substitution of the groups R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ can be carried out according to the group R ³ . In a further embodiment of the compounds of the formula I, R ³ and R ⁵ together form a C 3 -C 6 -alkylene, C 3 -C 6 -oxyalkylene or C 2 -C 5 -oxyalkyenoxy, in particular a C 3 -C 4 -alkylene group.

In a further embodiment of the compounds of formula I R ⁵ and R ⁶ form and / or R ⁷ and R ⁸ respectively together denote a C3-C6-Alkyen-, C3-C6-Oxyalkyen- or C2- Cs-Oxyalkyenoxy-, in particular a C3 C4-Alkyengruppe.

In a further embodiment of the compounds of the formula I, the index q has the value zero.

Another embodiment relates to compounds I in which the index q is 1. Another embodiment relates to compounds I in which the index p is zero or 1, in particular zero.

In a further embodiment of the compounds of the formula I, R ⁵ and R ^{6 are} preferably hydrogen, provided that the index p has the value zero.

In a further embodiment of the compounds of the formula I, R ^{7 is} not hydrogen and R ⁸ is hydrogen, provided that the index p is not equal to zero.

In a further embodiment of the compounds of the formula I, the index p has the value zero or 1 and the index q the value 1.

In a further embodiment of the compounds of the formula I, R ⁷ and R ^{8 are} preferably hydrogen. In a further embodiment of the compounds of the formula I, R ^{7 is} not hydrogen and R ⁸ is hydrogen.

In a further preferred embodiment of the compounds of the formula I, Y is oxygen.

In a further embodiment of the compounds of the formula I, Z represents a monovalent group.

A further embodiment relates to compounds I in which Z is C 1 -C 4 -alkylcarbonyl, in particular acetyl, n-propan-1-one, 2-methylpropan-1-one or butan-1-one.

Another embodiment relates to compounds I in which Z is hydrogen.

Another embodiment relates to compounds I in which Z is carboxyl. Another embodiment relates to compounds I in which Z is formyl.

Another embodiment relates to compounds I in which Z is C 1 -C 8 -alkyl.

Another embodiment relates to compounds I in which Z is C 1 -C 8 haloalkyl.

A further embodiment relates to compounds I in which Z is C 2 -C 8 -alkenyl.

Another embodiment relates to compounds I in which Z is C2-C8-haloalkenyl.

A further embodiment relates to compounds I in which Z is C2-Cs-alkynyl. Another embodiment relates to compounds I in which Z is C2-C8-haloalkynyl. Another embodiment relates to compounds I in which Z is C3-C6-cycloalkyl.

Another embodiment relates to compounds I in which Z is Ca-Cβ-cycloalkenyl. A further embodiment relates to compounds I in which Z is C (O) R ^{1 "1} .

A further embodiment relates to compounds I in which Z is C (O) OR ^{1 "1} .

A further embodiment relates to compounds I in which Z is C (S) OR ^{1 "1} .

A further embodiment relates to compounds I in which Z is C (O) SR ^{1 "1} .

A further embodiment relates to compounds I in which ZC (S) SR is ^π . A further embodiment relates to compounds I in which Z is C (NR ^A ) SR ^π .

A further embodiment relates to compounds I in which Z is C (S) R ^π .

A further embodiment relates to compounds I in which Z is C (NR ^π ) NR ^A R ^B.

A further embodiment relates to compounds I in which Z is C (NR ^π ) R ^A. A further embodiment relates to compounds I in which Z is C (NR ^π) OR ^A means.

Another embodiment relates to compounds I in which Z is C (O) NR ^A R ^B.

Another embodiment relates to compounds I in which Z is C (S) NR ^A R ^B.

Another embodiment relates to compounds I in which Z is C 1 -C 5 -alkylsulfinyl. Another embodiment relates to compounds I in which Z is C 1 -C 6 -alkylthio.

A further embodiment relates to compounds I in which Z is C 1 -C 5 -alkylsulfonyl.

A further embodiment relates to compounds I in which Z is C (O) -Ci-C ₄ -alkylene-NR ^A C (NR ^π ) NR ^A R ^B.

A further embodiment relates to compounds I in which Z is C (S) -Ci-C ₄ -alkylene-NR ^A C (NR ^π ) NR ^A R ^B.

A further embodiment relates to compounds I in which Z is C (NR ^π ) -Ci-C ₄ -alkylene-NR ^A C (NR ^π ) NR ^A R ^B. Another embodiment relates to compounds I in which Z is phenyl.

Another embodiment relates to compounds I in which Z is naphthyl.

A further embodiment relates to compounds I in which Z is a five-, six-, seven-, eight-, nine- or ten-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S which is bonded directly or via a carbonyl, thiocarbonyl, C 1 -C ₄ -alkylcarbonyl or C 1 -C ₄ -alkylthiocarbonyl group.

The abovementioned groups Z can be substituted by one or more groups R ^b .

In a further embodiment, the group Z is substituted by one, two, three or four groups R ^b , such as halogen, or basic or acidic groups, such as NR ^A R ^B , guanidyl, amidyl, hydroxy, carboxyl or sulfonic acids.

One embodiment relates to compounds I in which X is not methyl. Another embodiment relates to compounds I in which X is alkyl, such as ethyl or n-propyl, in particular ethyl.

Another embodiment relates to compounds I in which X is C ₂ -C ₄ -alkenyl or C ₂ -C ₄ -haloalkenyl, such as CH = CH ₂ or CH ₂ CH = CH ₂ . A further embodiment relates to compounds I in which X is C ₃ -C ₄ -alkynyl or C ₃ -C ₄ -haloalkynyl, such as CH ₂ C≡CH or CH ₂ CH ₂ C≡CH.

One embodiment of groups R ^A and R ^B is hydrogen is Ci-C ₄ alkyl or CrC ₄ - haloalkyl, preferably hydrogen and methyl.

An embodiment for groups R ^π is C 1 -C ₄ -alkyl or C 1 -C ₄ -haloalkyl, preferably methyl.

One embodiment of the group W relates to straight-chain or branched CrCl ₂ -alkyl.

In one embodiment of the group W, the alkyl, alkenyl or alkynyl group is represented by a saturated, in particular five- or six-membered, partially unsaturated or aromatic heterocycle having a five, six, seven, eight, nine or ten membered, containing one, two, three or four heteroatoms from the group O, N and S, substituted.

Embodiments for alkenyl groups in the position W are the groups W.a and W.b:

where # denotes the bindu to the triazolopyrimidine skeleton and

W ^1, W ² is hydrogen, halogen, Ci _-C4 -alkyl, Ci-C ₄ haloalkyl, _{Ci-C4-cyanoalkyl,} Ci-C ₄ hydroxyalkyl;

W ³ , W ⁴ Cö-Cβ-alkyl or one of the groups mentioned in W ¹ . W ¹ and W ² independently represent, for example, hydrogen; Halogen, such as fluorine, chlorine, bromine; C 1 -C ₄ -alkyl, such as CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ ; C ₁ -C ₄ -haloalkyl, such as CH ₂ Cl, CH ₂ F, CH ₂ Br, CHCH ₂ , CHF ₂ , CCI ₃ , CF ₃ , CH ₂ CH ₂ Cl, CH ₂ CH ₂ F, CH ₂ CH ₂ Br, CH ₂ CHCl ₂ , CH ₂ CHF ₂ , CH ₂ CHBr ₂ , CH ₂ CCI ₃ , CH ₂ CF ₃ , CCI ₂ CCI ₃ , CF ₂ CF ₃ , CH ₂ CH ₂ CH ₂ Cl, CH ₂ CH ₂ CH ₂ F, CH ₂ CH ₂ CH ₂ Br, CH ₂ CH ₂ CHF ₂ , CH ₂ CH ₂ CHCl ₂ , CF ₂ CF ₂ CF ₃ , CH ₂ CH ₂ CHBr ₂ , CH ₂ CH ₂ CCI ₃ , CH ₂ CH ₂ CF ₃ , CCI ₂ CCI ₂ CCI ₃ , CF ₂ CF ₂ CF ₃ , CH (CH ₃ ) CH ₂ Cl, CH (CH ₃ ) CH ₂ F, CH (CH ₃ ) CH ₂ Br, CH (CH ₃ ) CHCl ₂ , CH ( CH ₃ ) CHF ₂ ,

CH (CH ₃₎ CHBr _2, CH (CH ₃₎ CCI _3, CH (CH ₃₎ CF _3, CCI (CCb) _2, CF (CF _{3) 2;} C 1 -C ₄ -alkoxy, such as OCH ₃ ; hydroxy; cyano; substituted C 1 -C ₄ -alkyl, such as CH ₂ OH, CH ₂ CN, CH ₂ OCH ₃ , CH (CN) ₂ , CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CN, CH ₂ CH (CN) ₂ , CH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ CN, CH ₂ CH ₂ CH (CN) ₂ , CH (CH ₃ ) CH ₂ OH, CH ( CH ₃ ) CH ₂ OCH ₃ , CH (CH ₃ ) CH ₂ CN, CH (CH ₃ ) CH (CN) ₂ , CH (CH ₂ OH) ₂ , CH (CH ₂ OCHa) ₂ , CH (CH ₂ CN) ₂ ;

W ³ and W ⁴ independently of one another are, for example, C ₄ -C 6 -alkyl, such as CH ₂ CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) CH ₂ CH ₃ , CH ₂ CH (CHa) ₂ , C (CH ₃ ) ₃ , CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) CH ₂ CH ₂ CH ₃ , CH ₂ CH (CH ₃ ) CH ₂ CH ₃ , CH ₂ CH ₂ CH (CHa) ₂ , CH (CH ₃ ) CH (CHa) ₂ , CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₃ , CH ₂ CH (CH ₃ ) CH ₂ CH ₂ CH ₃ , CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₃ , CH (CH ₃ ) CH (CH ₃ ) CH ₂ CH ₃ , CH ₂ CH (CH ₂ CHa) ₂ or one of the groups mentioned above for W ¹ .

A preferred embodiment for alkynyl groups in the position W is the group W.c:

wherein # denotes the bond to the triazolopyrimidine skeleton and W ₁ W ² and W ^{3 have} the meanings given above.

W ¹ and W ² in the group Wc independently of one another are, for example, hydrogen; Halogen, such as fluorine, chlorine, bromine; C 1 -C ₄ -alkyl, such as CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ ; Halomethyl such as CH ₂ Cl, CH ₂ F, CH ₂ Br, CHCH ₂ , CHF ₂ , CCI ₃ , CF ₃ ; C 1 -C ₄ -alkoxy, such as OCH ₃ ; hydroxy; cyano; substituted C ₁ -C ₂ -alkyl such as CH ₂ OH, CH ₂ CN, CH ₂ OCH ₃ , CH (CN) ₂ , CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CN, CH ₂ CH (CN) ₂ , CH ₂ CH ₂ OH.

W ³ in the group Wc is, for example, branched C ₄ -C 6 -alkyl, such as CH (CH ₃ ) CH ₂ CH ₃ , CH ₂ CH (CH ₂ ) ₂ , C (CH ₃ ) ₃ , CH (CH ₃ ) CH ₂ CH ₂ CHs, CH ₂ CH (CH ₃ ) CH ₂ CH ₃ , CH ₂ CH ₂ CH (CHs) ₂ , CH (CH ₃ ) CH (CHs) ₂ , CH (CH ₃ ) CH ₂ CH ₂ CH ₂ CHS,

CH ₂ CH (CH ₃ ) CH ₂ CH ₂ CHS, CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CHS, CH (CH ₃ ) CH (CHS) CH ₂ CH ₃ , CH ₂ CH (CH ₂ CHs) ₂ or one of the above in W ¹ groups.

A preferred embodiment for alkyl groups in position W is the group W.d:

wherein # denotes the bond to the triazolopyrimidine skeleton and W ¹ , W ² and W ^{3 have} the meaning given above.

W ¹ means, for example, hydrogen in the group Wd; Halogen, such as fluorine, chlorine, bromine; C 1 -C ₄ -alkyl such as CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CHs) ₂ ; C ₁ -C ₄ -haloalkyl, such as CH ₂ Cl, CH ₂ F, CH ₂ Br, CHCH ₂ , CHF ₂ , CCI ₃ , CF ₃ , CH ₂ CH ₂ Cl, CH ₂ CH ₂ F,

CH ₂ CH ₂ Br, CH ₂ CHCl ₂ , CH ₂ CHF ₂ , CH ₂ CCI ₃ , CH ₂ CF ₃ , CCI ₂ CCI ₃ , CF ₂ CF ₃ , CH ₂ CH ₂ CH ₂ Cl, CH ₂ CH ₂ CH ₂ F, CH ₂ CH ₂ CH ₂ Br, CH ₂ CH ₂ CHF ₂ , CH ₂ CH ₂ CHCl ₂ , CF ₂ CF ₂ CF ₃ , CH ₂ CH ₂ CHBr ₂ , CH ₂ CH ₂ CCI ₃ , CH ₂ CH ₂ CF ₃ , CCI ₂ CCI ₂ CCIS, CF ₂ CF ₂ CF ₃ , CH (CH ₃ ) CH ₂ Cl, CH (CH ₃ ) CH ₂ F, CH (CH ₃ ) CH ₂ Br; C 1 -C ₄ -alkoxy, such as OCH ₃ ; hydroxy; cyano; substituted C 1 -C ₄ -alkyl, such as CH ₂ OH, CH ₂ CN, CH ₂ OCH ₃ , CH (CN) ₂ , CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CN, CH ₂ CH (CN) ₂ , CH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ OCHs, CH ₂ CH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ CN, CH ₂ CH ₂ CH (CN) ₂ .

W ² means in the group Wd, for example, hydrogen or methyl, in particular hydrogen. W ³ in the group Wd is, for example, C ₃ -C ₆ -alkyl, such as CH (CH ₃ ) ₂ ,

CH ₂ CH ₂ CH ₂ CH _3, CH (CH ₃₎ CH ₂ CH _3, CH ₂ CH (CHs) _2, C (CHs) _3, CH ₂ CH ₂ CH ₂ CH ₂ CH _3, CH (CH) CH ₂ CH ₂ CH ₃ , CH ₂ CH (CHs) CH ₂ CH ₃ , CH ₂ CH ₂ CH (CHS) ₂ , CH (CH ₃ ) CH (CHS) ₂ , CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CHS, CH (CH ₃ ) CH ₂ CH ₂ CH ₂ CHS, CH ₂ CH (CH ₃ ) CH ₂ CH ₂ CHS, CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CHS, CH (CH ₃ ) CH (CHS) CH ₂ CH ₃ , CH ₂ CH (CH ₂ CHS) ₂ ; C ₃ -C ₄ halo genalkyl, such as CH (CH ₃ ) CHCl ₂ , CH (CH ₃ ) CHF ₂ , CH (CH ₃ ) CHBr ₂ , CH (CH ₃ ) CCI ₃ , CH (CH ₃ ) CF ₃ , CCI (CCb) ₂ , CF (CF ₃ ) ₂ ; substituted C ₃ -C ₄ -alkyl, such as CH (CH ₃ ) CH ₂ OH, CH (CH ₃ ) CH ₂ OCH ₃ , CH (CH ₃ ) CH ₂ CN, CH (CH ₃ ) CH (CN) ₂ , CH (CH ₂ OH) ₂ , CH (CH ₂ OCHa) ₂ , CH (CH ₂ CN) ₂ or one of the groups mentioned above for W ¹ .

One embodiment of the group W relates to cycloalkyl groups in which the hydrogen atoms are partially or completely replaced by groups R ^a .

A further embodiment of the group W are cycloalkyl groups, where at least one group R ^{a is} ortho to the point of attachment to the triazolopyrimidine scaffold.

Preferred embodiments of cycloalkyl groups in the position W are the groups W.e to W.h:

wherein # denotes the bond to the triazolopyrimidine skeleton and W ¹ , W ² and W ^{3 have} the meanings given above.

W ¹ in the group We means, for example, hydrogen or methyl;

W ² and W ³ in the group We independently of one another represent, for example, hydrogen; cyano; Halogen, such as chlorine or bromine; C ₁ -C ₃ -alkyl, such as CH ₃ , CH ₂ CH ₃ ; C 1 -C 6 alkoxy, such as OCH ₃ ; Halomethyl such as CH ₂ Cl, CH ₂ F, CH ₂ Br, CHCH ₂ , CHF ₂ , CCI ₃ , CF ₃ .

In an embodiment of group We, W ² and W ^{3 are the} same.

W ¹ and W ² in the groups Wf, Wg and Wh are preferably hydrogen.

Preferred embodiments of compounds of the formula I correspond to the formulas La to l.h, where the variables have the meanings given above.

A further embodiment of the invention relates to compounds of the formula 1.1:

in which the variables are as defined above.

A further embodiment of the invention relates to compounds of the formula I.2,

in which the variables are as defined above.

In particular, with regard to their use according to the invention, the compounds I compiled in the following tables are preferred.

One embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} H. Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} CH ₃ .

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} CF ₃ .

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} CN.

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} OH.

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} OCH ₃ . Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} F.

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} Cl.

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} Br.

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} CH ₂ CH ₃ .

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} CH ₂ CH ₂ OH. Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} CH ₂ CCI ₃ .

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} CH ₂ CH ₂ CH ₃ .

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} C (CH ₃ ) ₃ . Another embodiment relates to compounds of Tables 1 to 2340 in which X is CH ₃ and W ^{2 is} CH ₂ CH ₂ CH ₂ CN.

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} CH (CH ₃ ) ₂ .

Another embodiment relates to compounds of Tables 1 to 2340 in which X is CH ₃ and W ^{2 is} CH (CH ₃ ) CH ₂ OCH ₃ .

Another embodiment relates to compounds of Tables 1 to 2340, in which X is CH ₃ and W ^{2 is} CH ₂ CH ₂ CH ₂ CH ₃ .

Another embodiment relates to compounds of Tables 1 to 2340 in which X is CH ₃ and W ^{2 is} CH (CH ₃ ) CH ₂ CH ₃ .

Another embodiment relates to compounds of Tables 1 to 2340 in which X is CH ₃ and W ^{2 is} CH ₂ CH (CHs) ₂ .

The combination of R ¹ and R ² for a compound corresponds in each case to one row of Table A. The groups mentioned in the tables for a substituent, taken alone, independently of the combination in which they are mentioned, also represent a particularly preferred embodiment of the group relevant substituents.

Table A

- - - - - - -

Table j Z - Heterocyclic groups

is bound

The compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, Basidiomycetes and Peronospomycetes (Syn. Oomycetes). They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.

They are particularly important for the control of a variety of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers. Beans, tomatoes, potatoes and pumpkins, as well as the seeds of these plants. They may also be used in cultures tolerant by breeding, including genetic engineering, herbicidal or insect or fungal attack. In addition, they are suitable for the control of Botryosphaeria species, Cylindrocarpon species, Eutypa lata, Neonectria liriodendri and Stereum hirsutum, which attack, among other things, the wood or the roots of grapevines.

In particular, they are suitable for controlling the following plant diseases:

Alternaria species on vegetables, oilseed rape, sugarbeet, fruit, rice, soybeans, as well as on potatoes (for example A. solani or A. alternata) and tomatoes (for example A. solani or A. alternata) and Alternaria ssp. (Spikelet) on wheat,

Aphanomyces species of sugar beets and vegetables,

Ascochyta species on cereals and vegetables e.g. Ascochyta tritici (leaf drought) on wheat, bipolar and Drechslera species on maize (e.g., D. maydis), cereals, rice and turf,

Blumeria graminis (powdery mildew) on cereals (such as wheat or barley),

Botrytis cinerea (gray mold) on strawberries, vegetables, flowers, vines and wheat (spike mold),

Bremia lactucae on lettuce, Cercospora species on corn, rice, sugar beet and e.g. Cercospora sojina (leaf spot) or Cercospora kikuchii (leaf spot) on soybeans,

Cladosporium herbarum (earwars) on wheat, Cochliobolus species on corn, cereals (eg Cochliobolus sativus) and rice (eg Cochliobolus miyabeanus),

Colletotricum species on cotton and e.g. Colletotrichum truncatum (antracnose) on soya beans Corynespora cassiicola (leaf spot) on soybeans,

Dematophora necatrix (root / stem rot) on soybeans,

Diaporthe phaseolorum (stalk disease) on soybeans,

Drechslera species, Pyrenophora species on maize, cereals, rice and turf, barley (eg D. teres) and wheat (eg D. tritici-repentis), Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum, and Formitipora punctata (syn. Phellinus punctatus),

Elsinoe ampelina on grapevine,

Epicoccum spp. (Spikelet) on wheat,

Exserohilum species on maize, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Fusarium and Verticillium species on different plants: e.g. F. graminearum or F. culmorum (root rot) on cereals (e.g., wheat or barley) or e.g. F. oxysporum on tomatoes and Fusarium solani (stalk disease) on soybeans

Gaeumanomyces graminis (root black) on cereals (for example wheat or cereals),

Gibberella species on cereals and rice (e.g., Gibberella fujikuroi),

Glomerella cingulata on grapevine and other plants,

Grainstaining complex on rice,

Guignardia budwelli on grapevine, Helminthosporium species on maize and rice, Isariopsis clavispora on grapevine,

Macrophomina phaseolina (root / stem rot) on soybeans,

Michrodochium nivale (snow mold) on cereals (for example wheat or barley),

Microsphaera diffusa (powdery mildew) on soybeans, Mycosphaerella species on cereals, bananas and peanuts, e.g. M. graminicola on wheat or M. fijiensis on bananas,

Peronospora species on cabbage (e.g., P. brassicae), bulbous plants (e.g., P. destructor) and e.g. Peronospora manshurica (downy mildew) on soybeans

Phakopsara pachyrhizi (soybean rust) and Phakopsara meibomiae (soybean rust) on soybeans,

Phialophora gregata (stalk disease) on soybeans

Phomopsis species on sunflowers, grapevine (e.g., P. viticola) and soybeans (e.g., Phomopsis phaseoli),

Phytophthora species on various plants e.g. P. capsici on peppers, Phytophthora megasperma (BladtwSgel rot) on soybeans, Phytophthora infestans on potatoes and tomatoes,

Plasmopara viticola on vines, Podosphaera leucotricha on apple,

Pseudocercosporella herpotrichoides (culm shift) on cereals (wheat or cereals),

Pseudoperonospora on various plants e.g. P. cubensis on cucumber or P. humili on hops,

Pseudo-pedicel tracheiphilai on grapevine,

Puccinia species on various plants e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals (for example wheat or barley) or asparagus (for example P. asparagi), Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum,

Pyrenophora tritici-repentis (leaf drought) on wheat or Pyrenophora teres (net spots) on barley, Entyloma oryzae on rice,

Pyricularia grisea on lawn and cereals, Pythium spp. on turf, rice, corn, wheat, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants (for example P. ultiumum or P. aphanidermatum),

Ramularia collo-cygni (Ramularia / sunburn complex / Physiological leaf spots) on barley,

Rhizoctonia species on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e.g. Rhizoctonia solani (root / stem rot) on soybeans or Rhizoctonia cerealis (pointed eye spot) on wheat or barley,

Rhynchosporium secalis on barley, rye and triticale,

Sclerotinia species on oilseed rape, sunflowers and e.g. Sclerotinia sclerotiorum (stenotic disease) or Sclerotinia rolfsii (stalk disease) on soybeans,

Septoria glycines (leaf spots) on soybeans,

Septoria tritici (leaf septoria) and Stagonospora nodorum on wheat,

Erysiphe (Syn. Uncinula) necator on grapevine,

Setospaeria species on maize and turf, Sphacelotheca reilinia on maize,

Stagonospora nodorum (ear septoria) on wheat,

Thievaliopsis species on soybeans and cotton,

Tilletia species of cereals,

Typhula incarnata (snow) on wheat or barley, Ustilago species on cereals, maize (e.g. U. maydis) and sugar cane,

Venturia species (scab) on apples (e.g., V. inaequalis) and pears.

In particular, they are suitable for controlling harmful fungi from the class of Peronosporomycetes (syn.Oomyceten), such as Peronospora species, Phytophthora species, Plasmopara viticola, Pseudoperonospora species and Pythium species. The compounds I are also suitable for controlling harmful fungi in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In wood preservation, the following harmful fungi in particular Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.

The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.

The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.

In the seed treatment, in general, amounts of active ingredient of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of seed are needed.

When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.

The compounds of the formula I can be present in various crystal modifications, which may differ in their biological activity. They are also the subject of the present invention. The compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention. The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

- water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), Acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used

- Carriers such as ground natural minerals (eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene) Fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin liquors and methylcellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

Examples of formulations are: 1. Products for dilution in water A Water-soluble concentrates (SL, LS)

10 parts by weight of the active ingredients are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content. B Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight C Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content. D emulsions (EW, EO, ES)

25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E suspensions (SC, OD, FS)

20 parts by weight of the active ingredients are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active compounds are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H Gel Formulations (GF) In a ball mill, 20 parts by weight of the active ingredients, 10 parts by weight of dispersant, 1 part by weight of swelling agent ("gelling agent") and 70 parts by weight of water or of an organic solvent become one When diluted with water, a stable suspension with 20% by weight active substance content results.

2. Products for direct application I dusts (DP, DS)

5 parts by weight of the active ingredients are finely ground and finely divided with 95 parts by weight Kaolin intimately mixed. This gives a dust with 5 wt .-% active ingredient content.

J Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

K ULV solutions (UL) 10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with 10 wt .-% active ingredient content.

For seed treatment, water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are usually used. These formulations can be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing. The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, litter, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare from active substance wetting, adhesion, dispersing or emulsifying agents and any solvents or oil concentrates which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%. The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, possibly also just immediately before use (tank mix), are added. These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1. As adjuvants in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ^® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluronic RPE 2035 ^® and Genapol B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e.g. B. Leophen RA ^®.

The agents according to the invention, in the form of application as fungicides, may also be present together with other active substances, e.g. with herbicides, insecticides, growth regulators, fungicides or with fertilizers. When mixing the compounds (I) or the agents containing them with one or more further active compounds, in particular fungicides, for example, in many cases, the activity spectrum can be broadened or development of resistance can be prevented. In many cases, synergistic effects are obtained.

The following list of fungicides with which the compounds according to the invention can be used together is intended to illustrate, but not limit, the possible combinations.

strobilurins

Azoxystrobin, Dimoxystrobin, Enestroburin, Fluoxastrobin, Kresoxim-methyl, Methominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Pyribencarb, Trifloxystrobin, 2- (2- (6- (3-chloro-2-methylphenoxy) -5-fluoropyrimidine 4-yloxy) -phenyl) -2-methoxyimino-N-methyl-acetamide, 2- (ortho - ((2,5-dimethylphenyl-oxymethylene) -phenyl) -3-methoxy-acrylic acid methyl ester, 3-methoxy-2- (2 - (N- (4-methoxy-phenyl) -cyclopropanecarbox-imidoylsulfanylmethyl) -phenyl) -acrylic acid methyl ester;

Carboxylic Acid Amides - Carboxylic Anilides: Benalaxyl, Benalaxyl-M, Benodanil, Bixafen, Boscalid, Carboxine, Fenfuram, Fenhexamide, Flutolanil, Furametpyr, Isotianil, Kiralaxyl, Mepronil, Metalaxyl, Ofurace, Oxadixyl, Oxycarboxine, Penthiopyrad, Tecloftalam, Thifluzamide, Tiadinil, 2- Amino-4-methylthiazole-5-carboxylic anilide, 2-chloro-N- (1,1,3-trimethyl-indan-4-yl) -nicotinamide, N- (3 ', 4'-dichloro-5-fluoro -biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid [2- (1, 3 -dimethyl-butyl) -phenyl] -amide, N- (4'-chloro-3 ', 5-difluoro-biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (4'-chloro-3 ', 5-difluoro-biphenyl-2-yl) -3-trifluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (3', 4'-dichloro) 5-fluoro-biphenyl-2-yl) -3-trifluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (3 ', 5-difluoro-4'-methyl-biphenyl-2-yl ) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (3 ', 5-difluoro-4'-methyl-biph enyl-2-yl) -3-trifluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (2-bicyclopropyl-2-yl-phenyl) -3-difluoro-methyl-1-methyl-1H pyrazole-4-carboxylic acid amide, N- (cis-2-bicyclopropyl-2-yl-phenyl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (trans-2-bicyclo propyl-2-yl-phenyl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide,

- Carboxylic acid morpholides: Dimethomorph, Flumorph; Benzoic acid amides: flumetover, fluopicolide, fluopyram, zoxamide, N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3-formylamino-2-hydroxybenzamide;

Other carboxamides: carpropamide, diclocymet, mandipropamide, oxytetracycline, silthiofam, N- (6-methoxypyridin-3-yl) cyclopropanecarboxamide; azoles

- Triazoles: azaconazole, bitertanol, bromuconazoles, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothiocona - zole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1- (4-chloro-phenyl) -2 - ([1, 2,4] triazol-1-yl) -cycloheptanol;

- imidazoles: cyazofamide, imazalil, imazalil sulfate, pefurazoate, prochloraz, triflumizole;

Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; Other: Ethaboxam, Etridiazole, Hymexazole, 1- (4-Chloro-phenyl) -1- (propyn-2-yl-oxy) -3- (4- (3,4-dimethoxyphenyl) -isoxazole-5- yl) -propan-2-one; Nitrogen-containing heterocyclyl compounds

- Pyridines: fluazinam, pyrifenox, 3- [5- (4-chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine, 2,3,5,6-tetrachloro-4-methanesulphonyl-pyidin 3,4,5-trichloropyridine-2,6-dicarbonitrile, N- (1- (5-bromo-3-chloro-pyridin-2-yl) -ethyl) -2,4-dichloro-nicotinamide , N - ((5-

Bromo-S-chloro-pyridin ^ -ylJ-methyl ^^ - dichloro-nicotinamide;

- pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil;

- Pyrroles: fludioxonil, fenpiclonil; - morpholines: aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph;

Dicarboximides: fluoroimide, iprodione, procymidone, vinclozolin;

- Other: acibenzolar-S-methyl, amisulbrom, anilazine, blasticidin-S, captafol, captan, quinomethionate, dazomet, debacarb, diclomethine, difenzoquat, difenzoquat-methylsulphate, famoxadone, fenamidone, fenoxanil, fenpropidin,

Folpet, octhilinone, oxolinic acid, piperaline, samplesazoles, proquinazide, pyroquilon, quinoxyfen, triazoxide, tricyclazoles, triforines, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluoro -phenyl) - [1,2,4] triazolo [1,5-a] pyimidine, 2-butoxy-6-iodo-3-propylgamate A-ismi dithiocarbamate - thio- and dithiocarbamate: Ferbam, Mancozeb, Maneb, Metam , Methasulphocarb, Metiram, Propineb, Thiram, Zineb, Ziram;

- Carbamates: Diethofencarb, Benthiavalicarb, Iprovalicarb, Propamocarb, Propamocarb hydrochloride, Valiphenal, N- (1- (1- (4-cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid (4-fluorophenyl) ester; Other fungicides

Guanidines: dodine, dodine free base, guazatine, guazatine acetate, iminoctadine, iminoctadine triacetate, iminoctadine tris (albesilat); - antibiotics: kasugamycin, kasugamycin hydrochloride hydrate, polyoxins, streptomycin, validamycin A;

Nitrophenyl derivatives:

Binapacryl, dicloran, dinobutone, dinocap, nitrothal-isopropyl, tecnazene; Organometallic compounds: Fentin salts such as, for example, fentin acetate, fentin chloride, fentin hydroxide;

Sulfur-containing heterocyclyl compounds: isoprothiolanes, dithianone;

Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl; Organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophen, flusulfamides, hexachlorobenzene, pencycuron, pentachlorophenol and its salts, phtha-Nd, quintozene, thiophanate-methyl, tolylfluanid, N- (4-chloro-2-nitrophenyl) -N- ethyl-4-methyl-benzenesulfonamide;

- Inorganic active substances: Phosphorous acid and its salts, sulfur, Bordeaux broth, copper salts such as copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate;

- Other: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamine, metrafenone, mildiomycin, oxine-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N- (cyclopropylmethoxyimino- (6-difluoromethoxy-2,3-difluorophenyl) - methyl) -2-phenylacetamide, N '- (4- (4-chloro-3-trifluoromethyl-phenoxy) -2,5-dimethylphenyl) -N-ethyl-N-methylformamidine, N' - 4-fluoro-3-trifluoromethyl-phenoxy) -2,5-dimethyl-phenyl) -N-ethyl-N-methylformamidine, N '- (2-methyl-5-trifluoromethyl-4- (3-trimethylsilanyl-propoxy) ) -phenyl) -N-ethyl-N-methylformamidine, N '- (5-difluoromethyl-2-methyl-4- (3-trimethylsilanyl-propoxy) -phenyl) -N-ethyl-N-methylformamidine.

synthesis Examples

The instructions given in the Synthesis Examples below were used with appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the following table with physical data.

Example 1: Preparation of (6-cyclopentyl-5-methyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-yl) - (S-2,2,2-trifluoro-1-methyl -ethyl) -amine [I-48]

Step A: 2-Cyclopentyl-3-oxo-butyric acid ethyl ester A solution of 5.75 g (0.25 mol) of sodium in 75 ml of ethanol was added dropwise within 15 min with 32.5 g (0.25 mol) of ethyl acetonate, Stirred 15 minutes further at 20 to 25 ° C, then added dropwise at 75 ° C 37.25 g (0.25 mol) of cyclopentyl bromide. After a further 15 hours of stirring at 75 ° C, the suspension was added to ice-water, extracted with methyl tert-butyl ether (MTBE), the combined MTBE phases with water and sat. NaCl solution. washed, dried and freed from the solvent. From the residue, 36 g of the title compound was fractionally distilled.

Step B: 6-Cyclopentyl-5-methyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ol 1 g (5 mmol) of the product from Step A was refluxed with 0.42 g (5 mmol) of amitrole and 10 ml of propionic acid for 15 hrs. The mixture was freed of solvent and poured into water. After neutralization with NaOH, the crystallized title compound was filtered off. 0.7 g of light brown crystals were obtained. Step C: / -chloro-θ-cyclopentyl-S-methyl-fi ^ triazoloπ.S-alpyrimidine

2 g (9 mmol) of the product from stage B were refluxed in 20 ml of POCb for 15 hours, then the POCb was distilled off and the residue was taken up in ethyl acetate / water, after phase separation the organ. Phase with 5% NaHCO 3 solution. and sat. NaCl solution. washed, dried and freed from the solvent. After chromatography on silica gel (mobile phase cyclohexane / MTBE 0 to 40%), 1.15 g of the title compound were obtained as pale yellow crystals.

Step D: (6-Cyclopentyl-5-methyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-yl) - (S-2,2,2-trifluoro-1-methyl-ethyl ) amine

100 mg (0.46 mmol) of the product from Step C were stirred with 520 mg (0.46 mmol) of (S) -trifluoroisopropylamine and 1 drop of dimethylformamide (DMF) at 60 ° C for 10 days. Then the solution was taken up in CH 2 Cl 2 and washed with 10% HCl and water, dried and freed of solvent. Reverse phase chromatography (CH 3 CN / H 2 O 65/35) gave 80 mg of the title compound.

Example 2: Preparation of 6-cyclopentyl-5-methyl-7- (4-methylpiperidin-1-yl) -

[1, 2,4] triazolo [1,5-a] pyrimidine [I-49]

100 mg (0.46 mmol) of the product from Step C were treated with 90 mg (0.92 mmol) of methylpiperidine and 69 mg (0.609 mmol) of triethylamine in 2 ml of CH ₂ Cl ₂ at 20 to 25 ° C three

Days stirred. The solution was taken up in CH ₂ Cl ₂ and washed with 10% HCl and water, dried and freed from the solvent. There remained 110 mg of the

Title compound as white crystals back.

The HPLC retention times (RT) in the following table were determined using the RP-18 column Chromolith Speed ROD (Merck KGaA, Germany) with the eluent acetonitrile + 0.1% trifluoroacetic acid (TFA) / water + 0, 1% TFA in one

Gradients from 5:95 to 95: 5 in 5 min at 40 ° C determined. Mass spectrometry was performed under Quadropol electrospray ionization, 80V (positive mode).

Examples of the effect against harmful fungi

The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments: The active compounds were prepared as a stock solution with 25 mg of active compound which was treated with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and Dispersing effect based on ethoxylated alkylphenols) in the volume ratio solvent-emulsifier of 99 to 1 ad 10 ml was made up. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.

Use Example 1 - Action against the gray mold on pepper leaves caused by Botrytis cinerea at 1 day of protective use. After 2-3 leaves had developed well, an aqueous suspension in the concentration of active compound stated below was used to drip point sprayed. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 × 10 ⁶ spores / ml in a 2% aqueous biomalt solution. The test plants were then placed in a climatic chamber at 22 to 24 ° C, darkness and high humidity. After 5 days, the extent of fungal attack on the leaves could be determined visually in%.

In this test, the plants treated with 250 ppm of the active compounds 1-1, I-23, I-46 to I-48, and I-49 did not show more than 20% infestation, while the untreated plants were 90% infected ,

Use Example 2 - Efficacy against vine peronospora caused by

Plasmopara viticola

Leaves of pot fry were sprayed to drip point with aqueous suspension in the concentration of active compound given below. The following day, the undersurfaces of the leaves were inoculated with an aqueous sporangia suspension of Plasmopara viticola. Thereafter, the vines were first set up for 24 hours in a water vapor-saturated chamber at 24 ⁰ C and then for 5 days in a greenhouse at temperatures between 20 and 30 ⁰ C. After this time, the plants were again placed in a humid chamber for 16 hours to accelerate the sporangiopathic outbreak. Then the extent of infestation on the undersides of the leaves was visually determined.

In this test, those containing 250 ppm of the active compounds 1-1, I-5, I-6, I-7, 1-15, I-23, I-25, I-29, I-32, I-33, I-36, I-38 and I-39, respectively, did not treat more than 20% of the infected plants, while the untreated plants were 90% infected. Use Example 3 - Protective efficacy against septoria leaf spot disease of wheat caused by Septoria tritici

Leaves of potted wheat seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. Twenty-four hours after the spray coating had dried on, they were inoculated with an aqueous spore suspension of Septoria tritici. The test plants were then placed in the greenhouse for 3 days at temperatures between 16 and 22 ° C and a relative humidity near 100%, then at a relative humidity of about 70%. After 4 weeks, the extent of disease development was determined visually in% infestation of the total leaf area.

In this test, those containing 250 ppm of the active compounds 1-1, I-4, I-6, I-9, 1-12, I-23, I-25, I-27, I-39, and I- 40 and those treated with 63 ppm of the active ingredients I-2, and I-22 plants did not exceed 20% infestation, while the untreated plants were 90% infected.

microtests

The active ingredients were formulated separately as stock solution with a concentration of

10,000 ppm in DMSO.

Use Example 4 - Activity against the causative agent of gray mold Botrytis cinerea

The stock solution is pipetted into a microtiter plate (MTP) and diluted with an aqueous malt-based mushroom nutrient medium to the stated active substance concentration. This was followed by the addition of an aqueous spore suspension of Botrytis cinerea. The plates were placed in a water vapor saturated chamber at temperatures of 18 ° C. With an absorbance photometer, the MTPs were measured at 405 nm on the 7th day after inoculation.

The measured parameters were compared with the growth of the active ingredient-free control variant and the fungus-free and active substance-free blank value in order to determine the relative growth in% of the pathogens in the individual active substances.

In this test, those with 125 ppm of compounds I-23, 1-25, 1-32, 1-36, 1-40, 1-42 to I-45, 1-48, 1-49, 1-59, or 1-61 treated samples a maximum of 19% relative growth of the pathogens.

Use Example 5 - Activity against the causative agent of the late blight Phytophthora infestans

The stock solution is pipetted into a microtiter plate (MTP) and diluted to the indicated drug concentration with an aqueous, pea-based, mushroom nutrient medium. This was followed by the addition of an aqueous zoospore suspension of Phytophthora infestans. The plates were placed in a steam-saturated chamber at temperatures of 18 ° C. With an absorbance photometer, the MTPs were measured at 405 nm on the 7th day after inoculation. The evaluation was carried out analogously to application example 4.

In this assay, samples treated with 125 ppm compound I-33 showed complete growth inhibition of the pathogens.

Use Example 6 - Activity against the causative agent of rice blast Pyricularia oryzae

The stock solution is pipetted into a microtiter plate (MTP) and diluted with an aqueous malt-based fungal nutrient medium to the stated active substance concentration. This was followed by the addition of an aqueous spore suspension of Pyricularia oryzae. The plates were placed in a water vapor saturated chamber at temperatures of 18 ° C. With an absorbance photometer, the MTPs were measured at 405 nm on the 7th day after inoculation. The evaluation was carried out analogously to application example 4. In this test, those with 125 ppm of the compounds I-2, 1-26, 1-27, 1-29, 1-30, 1-31, I-33, 1-38, 1 -41, 1-56, 1-57, 1-58, and I-60 treated samples maximally 15% relative growth of the pathogens.

Use Example 7 - Activity against the causative agent of Septoria leaf drought Septoria tritici The stock solution is pipetted into a microtiter plate (MTP) and diluted to the stated active compound concentration with a malt-based aqueous mushroom nutrient medium. This was followed by the addition of an aqueous spore suspension of Septoria tritici. The plates were placed in a water vapor saturated chamber at temperatures of 18 ° C. With an absorbance photometer, the MTPs were measured at 405 nm on the 7th day after inoculation.

The evaluation was carried out analogously to application example 4.

In this test, those containing 125 ppm of compounds I-2, 1-24 to I-27, 1-31, 1-32, I-36, 1-38, 1-40 to I-45, I-50, or 1-61 treated samples a maximum of 6% relative growth of the pathogens.

Comparative tests

The beneficial fungicidal properties of the compounds of the invention have been demonstrated over structurally similar prior art compounds in the following comparative experiments. The following compounds known from WO 03/009687 were used as comparisons:

Microtests The active compounds were formulated as described before Application Example 4.

Comparative Experiment 1 - Activity against the causative agent of the late blight Phytophthora infestans

In a further experiment according to Application Example 5, the samples treated with 31 ppm of the compounds I-37, I-63, and I-64 showed 0 to 2% growth of the pathogens, while those containing 31 ppm of the comparative compounds A, C, or D treated samples showed 52 to 100% growth.

Comparative experiment 2 - activity against the causative agent of the gray mold Botrytis cinerea

In another experimental setup according to Use Example 4, the samples treated with 31 ppm of Compound I-62 showed 25% growth of the pathogens, while the samples treated with 31 ppm of Compound Compound G showed 67% growth.

Greenhouse experiments

The active compounds were formulated as described before Application Example 1.

Comparative Experiment 3 - Efficacy against barley spot disease caused by Pyrenophora teres at 1 day of protective use

Leaves of potted barley seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. 24 hours after the spray coating had dried, the test plants were treated with a aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch inoculation. Subsequently, the test plants were placed in the greenhouse at temperatures between 20 and 24 ⁰ C and 95 to 100% relative humidity. After 6 days, the extent of disease development was determined visually as% of total leaf area.

In this test, plants treated with 63 ppm of Compound I-67 showed 30% infestation while plants treated with 63 ppm of Compound Compound F were 100% infested.

Comparative Experiment 4 - Protective activity against rice blast caused by Pyricularia oryzae

Leaves of potted rice seedlings of the cultivar "Tai-Nong 67" were sprayed to drip point with aqueous suspension in the concentration of active compound stated below. The following day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. Subsequently, the test plants were placed in climatic chambers at 22 - 24 ⁰ C and 95 - 99% relative humidity for 6 days. Then the extent of infestation on the leaves was visually determined. In this test, the plants treated with 63 ppm of Compound I-49 showed 5% infestation, while the plants treated with 63 ppm of Compound Compound H were 90% infested.

Comparative Experiment 5 - Activity against tomato blight caused by tomato

Phytophthora infestans in protective treatment

Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. The following day, the leaves were infected with an aqueous sporangium suspension of Phytophthora infestans. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 18 and 20 ° C. After 6 days, the late blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.

In this test, plants treated with 63 ppm of Compound I-68 showed 7% infestation while plants treated with 63 ppm of Compound Compound B were 100% infested.

Comparative Experiment 5 - Activity against vine peronospora caused by Plas- mopara viticola

In a further experiment according to Application Example 2, the plants treated with 63 ppm of the compounds I-66 or I-67 showed 20 or 40% infestation, while the plants treated with 63 ppm of the comparative compounds E and F were 100% infected , Comparative Experiment 6 - Protective efficacy against Septoria leaf spot disease of wheat caused by Septoria tritici

In a further experiment according to application example 3, the plants treated with 63 ppm of compound 1-66 did not show any infestation, while those treated with 63 ppm of comparative compound E had 60% and the untreated plants 90%.

Claims

claims

1. Use of substituted triazolopyrimidines of the formula I,

in which the substituents have the following meanings:

R ¹ Ci-Ci2-alkyl, _Ci-Ci2 haloalkyl, C ₂ -C ₂ -alkenyl, C ₂ -C ₂ haloalkenyl, C ₂ -C ₂ alkynyl, C ₂ -C ₂ haloalkynyl, C3-C ₈ cycloalkyl, C3-C cycloalkyl _8-halo, C3-C6-cycloalkenyl, C3-C6 halocycloalkenyl, C ₈ alkoxy, Ci-Cs-haloalkoxy, C ₂ -C 8 alkenyloxy, C ₂ -C8- Alkynyloxy, C 3 -C ₈ -cycloalkoxy, NH ₂ , C 1 -C ₈ -alkylamino, C 1 -C ₈ -alkylamino, phenyl, naphthyl, a five- or six-membered saturated, partially unsaturated or aromatic heterocycle, comprising two, three or four heteroatoms from the group O, N and S, or # -CR ³ R ⁴ - (CR ⁵ R ⁶ ) _q - (CR ⁷ R ⁸ ) _P -YZ, where # is the point of attachment to the nitrogen atom and :

R ^3, R ^4, R ^5, R ^6, R ^7, R ⁸ are independently hydrogen, Ci-C ₈ alkyl, Ci-Cs-haloalkyl, C ₂ -C ₈ -alkenyl -alkyl, C ₂ -C ₈ haloalkenyl , C ₂ -C ₈ -alkynyl, C ₂ -C ₈ -haloalkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -halocycloalkyl, C ₃ -C ₆ -cycloalkenyl, C ₃ -C ₆ -halocycloalkenyl, phenyl, naphthyl or a five-membered or a six-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S, R ⁵ can also be reacted with R ³ or R ⁷ together with the atoms to which these radicals are bonded, form a five-, six-, seven-, eight-, nine- or ten-membered saturated or partially unsaturated ring which, in addition to carbon atoms, can contain one, two or three heteroatoms from the group O, N and S as ring member and / or one or may carry ^a plurality of substituents R ^a ; R ³ with R ^4, R ⁵ with R ^6, R ⁷ with R ⁸ may together also mean the formation of carbonyl groups and oxygen to form Spirogrup- pen a C ₂ -Cs-alkylene or alkenylene, alkynylene form obtained by one, two or three heteroatoms from the group O, N and S may be interrupted; or one of the groups mentioned in R ¹ ; R ¹ and R ^{3 taken} together with the nitrogen atom to which they are attached may form a five-, six-, seven-, eight-, nine- or ten-membered saturated or partially unsaturated heterocycle containing, in addition to carbon atoms, one, two or three carbon atoms may contain three further heteroatoms from the group O, N and S as a ring member; R ¹ and R ³ to R ⁸ may each independently be partially or completely halogenated and / or carry one, two, three or four identical or different groups R ^a :

R ^{a is} halogen, cyano, nitro, hydroxy, carboxyl, Ci-C ₆ alkyl, Ci-C ₆ -HaIo- genalkyl, C ₂ -C ₈ alkenyl, C 2 -C ₈ haloalkenyl, C ₂ -C ₆ -Al kynyl, C ₂ -C ₆ -

Haloalkynyl, C3-C ₆ cycloalkyl, C ₃ -C ₈ cycloalkenyl, C ₆ alkoxy, Ci-C ₆ haloalkoxy, C ₂ -C ₆ alkenyloxy, _C3-C6 haloalkenyloxy, _C3-C6 alkynyloxy, _C3-C6 haloalkynyloxy, C3-C, C ₃ -C ₆ cycloalkoxy ₆ - cycloalkenyloxy, C (O) R ^π, C (O) OR ^π, C (S) OR ^π, C (O) SR ^π , C (S) SR ^π , OC (O) OR ^π , C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino,

C (O) NHR ^π , C (O) NR ^π ₂ , C ₁ -C ₆ -alkylene, oxy-C ₁ -C ₄ -alkylene, oxy-C ₁ -C ₃ -alkylenoxy, where divalent groups are attached to the same atom or to adjacent ones Atoms, phenyl, naphthyl, five, six, seven, eight, nine or ten membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S. ; R ^π Ci-Cs-alkyl, C ₃ -C ₈ -alkenyl, C ₃ -C ₈ -alkynyl, C ₃ -C ₆ -cycloalkyl or

C ₃ -C ₆ -cyclo or kenyl; where the aliphatic, alicyclic or aromatic groups in the abovementioned groups R ^a and R ^{π are in} their turn partially or completely halogenated and / or may carry one, two or three groups R ^b :

R ^{b is} halogen, cyano, nitro, hydroxyl, mercapto, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, Alkylcarbonyloxy, alkoxycarbonyloxy, aminocarbonyl, aminothiocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, where the alkyl groups in these radicals contain 1 to 6 carbon atoms and said alkenyl or alkynyl groups in these radicals contain 2 to 8 carbon atoms; Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, wherein the cyclic systems contain 3 to 10 ring members; Aryloxy, arylthio, aryl-C ₁ -C ₆ -alkoxy, aryl-C ₁ -C ₆ -alkyl, hetaryl, hetaryloxy, hetarylthio, where the aryl radicals preferably contain 6 to 10 ring members, the hetaryl radicals contain 5 or 6 ring members, the cyclic systems being partially or may be completely halogenated and / or substituted by alkyl or haloalkyl groups; Y oxygen or sulfur;

Z is hydrogen, carboxyl, formyl, Ci-C ₈ alkyl, _Ci-C8 haloalkyl, CΣrCβ alkenyl, C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ -alkyl kinyl, C ₂ -C ₈ - Haloalkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₈ -cycloalkenyl, C (O) R ^π , C (O) OR ^π , C (S) OR ^π , C (O) SR ^π , C (S) SR ^π , C (NR ^A ) SR ^π , C (S) R ^π , C (NR ^π ) NR ^A R ^B , C (NR ^π ) R ^A , C (NR ^π ) OR ^A , C (O) NR ^A R ^B , C (S) NR ^A R ^B , C 1 -C 6 -alkylsulfinyl, C 1 -C ₈ -alkylthio, C 1 -C ₆ -alkylsulfonyl, C (O) -Cl-C ₄ -alkylene-NR ^A C ( NR ^π ) NR ^A R ^B ,

C (S) -Ci-C ₄ -alkylene-NR ^A C (NR ^π ) NR ^A R ^B , C (NR ^π ) -Ci-C ₄ -alkylene-NR ^A C (NR ^π ) NR ^A R ^B , Phenyl , Naphthyl, five-, six-, seven-, eight-, nine- or ten-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group

O, N and S which is bonded directly or via a carbonyl, thiocarbonyl, C 1 -C ₄ -alkylcarbonyl or C 1 -C ₄ -alkylthiocarbonyl group; wherein in group Z the carbon chains may be substituted by one or more groups R ^b ; R ^A , R ^B independently of one another hydrogen, ^C 2 alkenyl, C 2

Alkynyl or one of the groups mentioned for R ^π ;

R ^A and R ^B can also be taken together with the nitrogen atom to which they are attached, or R ^A and R ^π together with the carbon and hetero atoms through which they are attached, a five- or six-membered saturated, partially unsaturated or aromatic ring form, in addition to carbon atoms one, two or three further heteroatoms from the group O, N and S as a ring member and / or one or more substituents R ^a can carry; or

Z can also form with R ⁶ or R ⁸ a five- or six-membered saturated or partially unsaturated ring which, in addition to carbon atoms and Y, may contain one or two further heteroatoms from the group O, N and S as ring member and / or one or more substituents R ^a can carry; the group Z may be partially or completely halogenated and / or carry one, two or three groups R ^b ; R ^{2 is} hydrogen or one of the groups mentioned at R ¹ , R ¹ and R ² can also, together with the nitrogen atom to which they are attached, have a saturated, saturated, saturated, saturated, form partially unsaturated or aromatic heterocycle which, in addition to carbon atoms, may contain one, two or three further heteroatoms from the group O, N and S as ring member and which contains at least one substituent selected from UO #, US # and UY- (CR ⁵ R ⁶ ) _q -CR ³ R ⁴ - #, and # is the point of attachment to the heterocycle and the heterocycle can also carry one, two or three groups R ^a ; U is hydrogen, carboxyl, formyl, C ₅ -C ₈ alkyl, Ci-C ₈ haloalkyl, C ₂ - Cs alkenyl, _C2-C8 haloalkenyl, C ₂ -C ₈ kinyl -alkyl, C ₂ -C ₈ -Haloalkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₈ -cycloalkenyl, C (O) R ^π , C (O) OR ^π , C (S) OR ^π , C (O) SR ^π , C (S) SR ^π , C (NR ^A ) SR ^π , C (S) R ^π , C (NR ^π ) NR ^A R ^B , C (NR ^π ) R ^A , C (NR ^π ) OR ^A , C (O ) NR ^A R ^B , C (S) NR ^A R ^B , C 1 -C ₈ -alkylsulfinyl,

_{Ci-C8-alkylthio,} Ci-C ₈ alkylsulfonyl, C (O) -C-C ₄ -alkylene-NR ^A C (NR ^π) NR ^A R ^B, C (S) -C-C ₄ alkylene- NR ^A C (NR ^π ) NR ^A R ^B ,

C (NR ^π ) -Ci-C ₄ alkylene-NR ^A C (NR ^π ) NR ^A R ^B , phenyl, naphthyl, five, six, seven, eight, nine or ten membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S, which is bonded directly or via a carbonyl, thiocarbonyl, Ci-C ₄ alkylcarbonyl or Ci-CrAlkylthiocarbonylgruppe; where in the group Z the carbon chains can carry one, two or three groups R ^b ; p is zero, 1, 2, 3, 4 or 5; q is zero or 1; W is C ₁ -C 10 -alkyl, C ₁ -C 10 -haloalkyl, C ₂ -C 10 -alkenyl, C ₂ -C 10 -alkynyl, C ₃ -C ₈ -cycloalkyl, C ₃ -C ₈ -cycloalkenyl or phenyl-C ₁ -C 10 -ione alkyl, where W may be unsubstituted or partially or completely halogenated and / or may carry one to three radicals from the group R ^a , X is C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ -

haloalkynyl; and agriculturally acceptable salts thereof, for controlling phytopathogenic fungi.

2. Use according to claim 1, wherein X is Ci-Cβ alkyl, C3-C6-alkenyl, C3-C6 haloalkenyl, _C2-C6 alkynyl or C3-C6 haloalkynyl stands.

3. Use according to claim 1, wherein X is methyl.

4. Compounds of formula I according to claim 1, wherein not both groups X and W are methyl at the same time and W is unsubstituted or unsubstituted. Biphenylmethyl stands.

5. Compounds of formula I according to any one of claims 1 to 4, wherein X is ethyl or n-propyl and W is unsubstituted or unsubstituted. Biphenylmethyl stands.

6. Compounds of formula I according to any one of claims 1 to 4, wherein X is C ₂ -Cδ alkenyl, C ₂ -C 6 haloalkenyl, C ₂ -C 6 alkynyl or C ₂ -C 6 haloalkynyl.

7. Compounds of formula I according to any one of claims 1 to 4, wherein X is C3-C6 alkenyl, C3-C6 haloalkenyl, C ₂ -C6 alkynyl or C3-C6 haloalkynyl.

8. Compounds of formula I according to any one of claims 1 to 7, wherein W is unsubstituted or substituted Ci-Ci2-alkyl.

9. Compounds of formula I according to any one of claims 1 to 7, wherein W is unsubstituted or substituted alkenyl.

10. Compounds of formula I according to any one of claims 1 to 7, wherein W is unsubstituted or substituted alkynyl.

1 1. A compound of formula I according to any one of claims 1 to 7, wherein W is unsubstituted or substituted cycloalkyl.

12. A process for the preparation of compounds of the formula I according to any one of the proviso Proverbs 4 to 11, characterized in that 2-aminotriazole of the formula

IIa

with malonates of formula IIb,

In which R is alkyl, 7-hydroxoimidaziridines of the formula Nc

which converts to compounds of formula II,

in which Hal is chlorine or bromine, halogenated, and II with amines of the formula III

in which R ¹ and R ^{2 are} defined according to claim 1, to compounds of formula IV

reacted with malonates of the formula V,

in which X "is hydrogen or alkynyl and R is C 1 -C ₄ -alkyl, into the esters of the formula VI

which are decarboxylated to compounds of the formula I.

13. A process for the preparation of compounds of the formula I according to any one of the proviso Proverbs 4 to 11, characterized in that 2-aminotriazole of the formula

IIa according to claim 12 with keto esters of the formula IIIa,

in which R is Ci-C ₄ -AlkVl and X is defined according to claim 3, to

7-Hydroxytriazolopyrimidinen of the formula IVa

which are reacted with amines of the formula IM according to claim 12.

14. Compounds of the formula VI according to claim 12.

15. A composition comprising a solid or liquid carrier and a compound of the formula I according to one of claims 1 to 11.

16. A composition according to claim 15, containing a further active ingredient.

17. Seed containing a compound of formula I according to any one of claims 1 to 1 1 in an amount of 1 to 1000 g per 100 kg.

18. A method for controlling phytopathogenic harmful fungi, characterized in that treating the fungi, or to be protected against fungal attack materials, plants, the soil or seeds with an effective amount of a compound of formula I according to any one of claims 1 to 1 1.