EP1689750A1 - 6-(2,4,6-trifluorophenyl)-triazolopyrimidines, method for the production thereof, use thereof for controlling harmful fungi, and substances containing the same - Google Patents

Abstract

Disclosed are 6-(2,4,6-trifluorophenyl)-triazolopyrimidines of formula (I), wherein the substituents have the following meaning: R<1> represents alkyl, alkyl halide, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, cycloalkenyl, alkinyl, haloalkinyl, or cycloalkinyl, phenyl, naphthyl, or a five-membered or six-membered saturated, partially unsaturated, or aromatic heterocycle containing one to four heteroatoms from the group comprising O, N, and S; R<2> represents hydrogen or one of the groups mentioned for R<1>, R<1> and R<2> also optionally forming a five-membered or six-membered ring along with the nitrogen atom to which the same are bonded, said ring being interrupted by an atom from the group comprising O, N, and S, and/or R<1> and/or R<2> being optionally substituted according to the description; X represents cyano, C1-C4 alkoxy, C3-C4 alkenyloxy, C1-C2 haloalkoxy, or C3-C4 haloalkenyloxy. Also disclosed are a method for producing said compounds, substances containing the same, and the use thereof for controlling plant-pathogenic fungi.

Description

6- (2,4,6-trifluorophenyl) triazolopyrimidines, processes for their preparation and their use in combating harmful fungi and compositions containing them

description

The present invention relates to 6- (2,4,6-trifluorophenyl) triazolopyrimidines of the formula I.

in which the substituents have the following meaning:

R ¹ -C ₈ alkyl, C _r C ₈ haloalkyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ halocycloalkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ haloalkenyl, C ₃ -C _β cycloalkenyl, C ₃ -C ₆ halocycloalkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic hetero- cycle containing one to four heteroatoms from the group O, N or S,

R ^{2 is} 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 can also form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contain a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, -C-C _β- alkyl, d-Cβ-haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C Ce alkoxy, dC _β -haloalkoxy , C ₃ -Cβ-alkenyloxy, C ₃ -C ₆ -haloalkenyloxy, CrC ₆ -alkylene and oxy-dC ₃ -alkyleneoxy can carry;

R ¹ and / or R ² can carry one to four identical or different groups R ^a : R ^a halogen, cyano, nitro, hydroxyl, dC ₆ -alkyl, Ci-Cβ-haloalkyl, dC ₆ - alkylcarbonyl, C ₃ -C _β -Cycloalkyl, dC ₆ -alkoxy, Ci-Cβ-haloalkoxy, dC _β - alkoxycarbonyl, dC ₆ -alkylthio, C Cβ-alkylamino, di-Ci-Cβ-alkylamino, C ₂ -C ₆ alkenyl, C ₂ -C ₆ -Alkenyloxy, C ₃ -C _β -alkynyloxy, oxy-CrC ₃ -alkyleneoxy, C ₃ -Cβ-cycloalkyl, phenyl, naphthyl, five- or six-membered saturated, partially unsaturated or aromatic heterocycle, containing one to four heteroatoms from the group O. , N or S, these aliphatic, alicyclic or aromatic groups can in turn be partially or completely halogenated

X cyano, Crd-alkoxy, C ₃ -C ₄ alkenyloxy, -C-C ₂ haloalkoxy or C ₃ -C haloalkenyloxy.

In addition, the invention relates to a process for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.

5-Halogen-6- (2,4,6-trifluorophenyl) triazolopyrimidines are generally known from WO 98/46607. 5-cyano- and 5-alkoxy-triazolopyrimidines are disclosed in WO 02/083677. Triazolopyrimidines with optically active amino substituents in the 7-position are generally proposed in WO 02/38565.

The compounds described in the abovementioned documents are suitable for combating harmful fungi.

However, their effects are not always completely satisfactory in every respect. Proceeding from this, the present invention is based on the object of providing compounds with improved activity and / or broadened activity spectrum.

Accordingly, the compounds defined at the outset were found. Furthermore, a process for their preparation, compositions comprising them and processes for combating harmful fungi using the compounds I have been found.

The compounds according to the invention differ from those described in the abovementioned document by the substitution in the 5-position of the triazolopyrimidine skeleton.

The compounds of the formula I have an increased activity or a broader spectrum of activity against harmful fungi than the known compounds.

The compounds according to the invention can be obtained in various ways. They are advantageously obtained starting from the 5-halo-6- (2,4,6-trifluorophenyl) triazolopyrimidines of the formula II known from WO 98/98/46607 by reaction with compounds MX (formula III). Depending on the meaning of the group X to be introduced, compounds III represent an inorganic cyanide or an alkoxylate. The reaction is advantageously carried out in the presence of an inert solvent. The cation M in formula III is of little importance; for practical reasons, Ammonium, tetraalkylammonium or alkali or alkaline earth metal salts are preferred.

The reaction temperature is usually from 0 to 120 ° C., preferably from 10 to 40 ° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].

If R ^{2 is} hydrogen, a removable protective group is advantageously introduced before reaction with III [cf. Greene, Protective Groups in Organic Chemistry, J. Willey & Sons, (1981)].

Suitable solvents include ethers such as dioxane, diethyl ether and, preferably tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene or acetonitrile.

The reaction mixtures are worked up in a conventional manner, e.g. by mixing with water, separation of the phases and, if necessary, chromatographic purification of the crude products. The intermediate and end products fall in part. in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or cleaned under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting.

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

If isomer mixtures are obtained in the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (e.g. 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 formulas above, 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 with 1 to 4, 6 or 8 carbon atoms, e.g. d-Co-alkyl such as methyl, ethyl, propyl, 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 with 1 to 2, 4, 6 or 8 carbon atoms (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be 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 with 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in any position, for example C ₂ -C ₆ 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, 2nd -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-3pentenyl, 3-Me thyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1- Dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3- Dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2- propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl; Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 8 carbon atoms and one or two double bonds in any position (as mentioned above), the hydrogen atoms in these groups being partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine could be;

Alkynyl: straight-chain or branched hydrocarbon groups with 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for example C ₂ -C _β -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 -butinyl, 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 with 3 to 6 or 8 carbon ring members, for example C ₃ -C ₈ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;

five- or six-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, e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isoliazolidiazolidinyl Pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2- yl, 2-pyrrolin-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-tetrahydro thienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 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-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms Substance atoms and a sulfur or oxygen atom as ring members can contain, for example 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, can 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: saturated, straight-chain or branched hydrocarbon radicals with 1 to 4 or 6 carbon atoms, which are bonded to the skeleton via a double bond, e.g. B. = CH ₂ , = CH-CH ₃ , = CH-CH ₂ -CH ₃ ;

Oxyalkyleneoxy: divalent unbranched chains of 1 to 3 CH ₂ groups, both valences being bound 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;

The scope of the present invention includes the (R) and (S) isomers and the racemates of compounds of the formula I which have chiral centers.

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

Compounds I are preferred in which R ^{1 is} dC ₄ alkyl, C ₂ -C ₆ alkenyl or dC ₈ haloalkyl.

Compounds I are preferred in which R ^{1 represents} a group A: wherein

Z ^{1 is} hydrogen, fluorine or dC ₆ fluoroalkyl, Z ^{2 is} hydrogen or fluorine, or Z ¹ and Z ² together form a double bond; q is 0 or 1; and R ^{3 is} hydrogen or methyl. In addition, compounds I are preferred in which R ^{1 is} C ₃ -C ₆ cycloalkyl, which can be substituted by CC alkyl.

In particular, compounds I are preferred in which R ^{2 is} hydrogen.

Equally preferred are compounds I in which R ^{2 is} methyl or ethyl.

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

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

in the

GC ₂ -C ₆ alkyl, in particular ethyl, n- and i-propyl, n-, sec-, tert-butyl, and dC - alkoxymethyl, in particular ethoxymethyl, or C ₃ -C _β- cycloalkyl, in particular cyclopentyl or cyclohexyl; R ^{2 is} hydrogen or methyl; and X is cyano, methoxy or ethoxy.

Another preferred embodiment of the invention relates to compounds of the formula I.2.

in which Y is hydrogen or -CC ₄ alkyl, in particular methyl and ethyl, and X is cyano, methoxy or ethoxy.

A further preferred embodiment of the invention relates to compounds in which R ¹ and R ² together with the nitrogen atom to which they are attached form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and a further hetero atom from the group O , N and S included as a ring member and / or one or more substituents from the group halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, -C-C ₆ alkoxy, dC ₆ - Halogenoalkoxy, C ₃ -C ₈ alkenyloxy, C ₃ -C ₆ haloalkenyloxy, dC ₆ alkylene and oxy-dC ₃ - alkyleneoxy can wear. These compounds correspond in particular to formula I.3,

in the

D together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, dC Can carry _4- alkyl, dC -alkoxy and dC ₂ -haloalkyl; and

X is cyano, methoxy or ethoxy.

Furthermore, compounds I are preferred in which R ¹ and R ² together with the nitrogen atom to which they are attached form a piperidinyl, morpholinyl or thimorpholinyl ring, in particular a piperidinyl ring which may be halogenated by one to three groups, dC -alkyl or dC -haloalkyl is substituted. The compounds in which R ¹ and R ² together with the nitrogen atom to which they are attached form a 4-methylpiperidine ring are particularly preferred.

Another preferred object of the invention are compounds I in which R ¹ and R ² together with the nitrogen atom to which they are attached form a pyrazole ring which may be halogen, dC -alkyl or dC ₄ by one or two groups - Haloalkyl, in particular substituted by 3,5-dimethyl or 3,5-di (trifluoromethyl).

In addition, compounds of the formula I are particularly preferred in which R ^{1 is} CH (CH ₃ ) -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 (CH ₃ ) = CH ₂ , CH ₂ CH = CH ₂ , cyclopentyl or cyclohexyl; R ^{2 is} hydrogen or methyl; or R ¹ and R ² together - (CH ₂ ) 2CH (CH ₃ ) (CH ₂ ) 2-, - (CH ₂ ) ₂ CH (CF ₃ ) (CH ₂ ) ₂ - or - (CH ₂ ) ₂ O ( CH ₂ ) ₂ - mean.

Furthermore, compounds I are particularly preferred in which X is cyano, methoxy or ethoxy, in particular cyano or methoxy. In particular, in view of their use, the compounds I compiled in the tables below are preferred. The groups mentioned for a substituent in the tables also represent a particularly preferred embodiment of the substituent in question, regardless of the combination in which they are mentioned.

Table 1

Compounds of the formula I in which X is cyano and the combination of R ¹ and R ² for each compound corresponds to one row of Table A.

Table 2

Compounds of the formula I in which X is methoxy and the combination of R ¹ and R ² for each compound corresponds to one row of Table A.

Table 3

Compounds of the formula I in which X is ethoxy and the combination of R ¹ and R ² for each compound corresponds to one row of Table A.

Table A

The compounds I are suitable as fungicides. They are characterized by a her. excellent activity against a wide spectrum of phytopathogenic fungi, especially from the class of Ascomycetes, Deuteromycetes, Oomycetes and ßasidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as Cucumbers, beans, tomatoes, potatoes and squash, as well as on the seeds of these plants. They are particularly suitable for combating the following plant diseases: Altemaria species on vegetables and fruits, Bipolaris and Drechslera species on cereals, rice and lawn, Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Fusarium and Verticillium species on various plants, Mycosphaerella species on cereals, bananas and peanuts, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Podosphaera leidespotella on wheat and barley, Pseudoperonospora species on hops and cucumbers, Puccinia plants on cereals, Pyricularia oryzae on rice, Rhizoctonia species on cotton, rice and turf, Septoria tritici and Stagonospora nodorum on wheat, Uncinula necator on vines, Ustilago plants on cereals and sugar cane, and Veπ / w / a species (scab) on apples and pears.

The compounds I are also suitable for combating harmful fungi such as Pacilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.

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 active amount of the active compounds. The application can take place 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% by weight of active ingredient.

Depending on the type of effect desired, the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per ha.

In the case of seed treatment, amounts of active compound of 1 to 1000 g / 100 kg, preferably 5 to 100 g, are generally required per 100 kg of seed. When used in material or stock protection, the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of treated material.

The compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the connection 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. The following are essentially considered as solvents / auxiliaries:

- Water, aromatic solvents (e.g. Solvesso products, xylene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butryolactone), 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 natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.

Alkali, alkaline earth, and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated naphthalene naphthalene and sulfonated dehydrogenated naphthalene derivatives of sulfonated formaldehyde derivatives and sulfonated dehydrogenated naphthalenedaphthalene from sulfonates, as well as condensation products with sulfated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene ether and condensation products , Condensation products of naphthalene or of naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tri-butylphenyl polyglycol ether, trihylphenyl polyglycol ether, alkyl alcoholoxy ethoxylated alcohol, alkyl alcoholoxy ethoxylated alcohol , Laurylalkoholpolyglykoletheracetal, sorbitol ester, lignin sulfite waste liquors and methyl cellulose into consideration.

Mineral oil fractions of medium to high boiling point, such as kerosene, are used to produce directly sprayable solutions, emulsions, pastes or oil dispersions. sin or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone , strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, 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% by weight, preferably between 0.1 and 90% by weight, of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of formulations are: 1. Products for dilution in water

A Water-soluble concentrates (SL)

10 parts by weight of a compound according to the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other aids are added. The active ingredient dissolves when diluted in water.

B Dispersible concentrates (DC)

20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with the addition of a dispersant e.g. Dissolved polyvinyl pyrrolidone. When diluted in water, a dispersion results.

C Emulsifiable concentrates (EC)

15 parts by weight of a compound according to the invention are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each). Dilution in water results in an emulsion. D emulsions (EW, EO)

40 parts by weight of a compound according to the invention are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each). This mixture is introduced into water using an emulsifying machine (Ultraturax) and brought to a homogeneous emulsion. Dilution in water results in an emulsion.

E suspensions (SC, OD)

20 parts by weight of a compound according to the invention are added in one with the addition of dispersing and wetting agents and water or an organic solvent

Agitator ball mill crushed into a fine active ingredient suspension. Dilution in water results in a stable suspension of the active ingredient.

F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersants and wetting agents and are prepared as water-dispersible or water-soluble granules by means of technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution in water results in a stable dispersion or solution of the active ingredient.

G Water-dispersible and water-soluble powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.

2. Products for direct application

H dusts (DP) 5 parts by weight of a compound according to the invention are finely ground and intimately mixed with 95% finely divided kaolin. This gives a dusting agent.

I granules (GR, FG, GG, MG)

0.5 part by weight of a compound according to the invention is ground finely and combined with 95.5% carriers. Common processes are extrusion

Spray drying or the fluidized bed. This gives granules for direct application.

J ULV solutions (UL) 10 parts by weight of a compound according to the invention are in an organic Solvent eg xylene dissolved. This gives you a product for direct application.

The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes; 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. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. 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 process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.

Various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.

In the use form as fungicides, the compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases. The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:

Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl,

• Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph

Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl,

Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,

Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazol, triazolazol, trichazonazol, trichlorazolol, prochlorazolol, prochlorazolol, trichlorazolol, prochlorazolol, trichlorazol, trichlorazol, trichlorazol, trichlorazol, trichazolazol, trichazolazol, trichazolazol, trichlorazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichlorazol Dicarboximides such as iprodione, myclozolin, procymidone, vinclozolin,

Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb,

Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronazidolomolol, probolil, probolil, nuarol, probolil, probolil Quinoxyfen, silthiofam, thiabenzazole, thifluzamide, thiophanate methyl, tiadinil, tricyclazole, triforins,

• copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate, • nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthaloisopropyl

Phenylpyrroles such as fenpiclonil or fludioxonil,

• sulfur

• Other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, Dazomet, diclomezin, diclocymet, Diethofen-carb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fennosetanyl, ferim Fosetyl aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide

• strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, • sulfenoic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid

• Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph. synthesis Examples

The instructions given in the synthesis examples below were used with the appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the table below with physical information.

Example 1 - Preparation of 5-methoxy-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidinyl) - 1, 2,4-triazolo [1,5a] pyrimidine

A solution of 0.6 g (1.5 mmol) of 5-chloro-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidinyl) -1,2,4-triazolo [1,5a ] pyrimidine (cf. WO 98/46607) in 10 ml of methanol were mixed with 0.32 g (1.8 mmol) of 30% sodium methoxide solution. added and stirred at 20-25 ° C overnight. After dilution of the reaction mixture with dil. Hydrochloric acid, extraction of the aqueous phase with methyl t-butyl ether (MTBE) and phase separation, the combined organic phases were concentrated. The residue was purified by means of MPLC over silica gel RP-18 with acetonitrile / water mixtures. 0.3 g of the title compound was obtained as a pale crystal mass (mp 172-174 ° C.).

¹ H NMR (CDCI ₃ , δ in ppm): 8.25 (s, 1H); 6.8 (t. 2H); 4.0 (s, 3H); 3.6 (d. 2H); 2.8 (m, 2H); 1.65 (m, 2H); 1.55 (m, 1H); 1.35 (m, 2H); 1.0 (d, 3H)

Example 2 - Preparation of 5-cyano-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidinyl) - 1, 2,4-triazolo [1,5a] pyrimidine

A solution of 1 g (2.5 mmol) of 5-chloro-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidinyl) - 1,2,4-triazolo [1,5a] pyrimidine (WO 98/46607) in 20 ml of acetonitrile, 1.9 g (6.5 mmol) of tetrabutylammonium cyanide were added and the mixture was stirred at 20-25 ° C. overnight. After dilution of the reaction mixture with dil. Hydrochloric acid, extraction of the aqueous phase with methyl t-butyl ether (MTBE) and phase separation, the combined organic phases were concentrated. The residue was purified by means of MPLC over silica gel RP-18 with acetonitrile / water mixtures. 0.3 g of the title compound was obtained as a pale crystal mass (mp. 205-206 ° C.).

¹ H NMR (CDCI ₃ , δ in ppm): 8.5 (s, 1 H); 7.9 (t, 2H); 3.8 (d. 2H); 2.9 (m. 2H); 1.7 (m, 2H); 1.6 (m, 1H); 1.35 (m, 2H); 1.0 (d, 3H) Table I - Compounds of Formula I.

Examples of the action against harmful fungi

The fungicidal activity of the compounds of the formula I was demonstrated by the following tests:

The active ingredients were prepared separately or together as a stock solution with 0.25% by weight of active ingredient in acetone or DMSO. 1% by weight of Uniperol® EL emulsifier (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and diluted with water to the desired concentration. Example of use 1 - Efficacy against mildew on cucumber leaves caused by Sphaerotheca fuliginea in protective use

Leaves of cucumber seedlings of the "Chinese snake" variety, grown in pots, were sprayed in the cotyledon stage with an aqueous suspension in the active substance concentration given below to runoff. 20 hours after the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of cucumber mildew (Sphaerotheca fuliginea). The plants were then cultivated in a greenhouse at temperatures between 20 and 24 ° C. and 60 to 80% relative atmospheric humidity for 7 days. The extent of mildew development was then determined visually in% of the cotyledon area.

In this test, the plants treated with 63 ppm of the compounds 1-1, 1-2, 1-3 or I-5 showed no infection, while the untreated plants were 100% infected. Example of use 2 - Efficacy against the barley net spot disease caused by Pyrenophora teres with 1 day of protective application

Leaves of barley seedlings grown in pots were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. 24 hours after the spray coating had dried on, the test plants were treated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net spot disease. The test plants were then placed in the greenhouse at temperatures between 20 and 24 ° C. and 95 to 100% relative atmospheric humidity. After 6 days, the extent of the development of the disease was determined visually in% of the total leaf area.

In this test, the plants treated with 63 ppm of the compounds 1-1, 1-2, 1-3 and I-5 showed no infection, while the untreated plants were 90% infected.

Claims

claims

1. 6- (2,4,6-trifluorophenyl) triazolopyrimidines of the formula I.

in which the substituents have the following meaning:

R ¹ d-Cβ-alkyl, dC ₈ haloalkyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ halocycloalkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ haloalkenyl, C ₃ - C ₆ -Cycloalkenyl, C ₃ -C ₆ - halocycloalkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S,

R ^{2 is} 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 can also form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contain a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, Ci-Ce-alkyl, dC ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, dC ₆ -alkoxy, C ₆ haloalkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C _β -haloalkenyloxy, dC ₆ alkylene and oxy-C C ₃ - alkyleneoxy can carry; R ¹ and / or R ² can carry one to four identical or different groups R ^a :

R ^a halogen, cyano, nitro, hydroxy, dC ₆ -alkyl, dC _e -haloalkyl, dC ₈ -alkylcarbonyl, C ₃ -C _β -cycloalkyl, dC _β -alkoxy, dC ₆ -haloalkoxy, dC ₆ -alkoxycarbonyl, d-Cβ-alkylthio, -C-C _β -alkylamino, di- dC ₆ -alkylamino, C ₂ -C ₆ -alkenyl, C ₂ -C _e -alkenoxy, C ₃ -C ₆ -alkynyloxy, oxy-dC ₃ -alkyleneoxy , C ₃ -C ₆ cycloalkyl, phenyl, naphthyl, five- or six-membered saturated, partially unsaturated or aromatic heterocycle, containing one to four heteroatoms from the group O, N or S, these aliphatic, alicyclic or aromatic groups can in turn be partially or completely halogenated;

X cyano, dC ₄ alkoxy, C ₃ -C alkenyloxy, C ₁ -C ₂ haloalkoxy or C ₃ -C ₄ haloalkenyloxy.

2. Compounds of formula I according to claim 1, in which X is cyano.

3. Compounds of formula I according to claim 1, in which X is methoxy.

4. Compounds of formula I according to one of claims 1 to 3, in which R ¹ and R ^{2 have the} following meaning:

R ¹ CH (CH ₃ ) -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 (CH ₃ ) = CH ₂ , CH ₂ CH = CH ₂ , cyclopentyl, cyclohexyl;

R ^{2 is} hydrogen or methyl; or

R ¹ and R ² together form - (CH ₂ ) ₂ CH (CH ₃ ) (CH ₂ ) ₂ -, - (CH ₂ ) ₂ CH (CF ₃ ) (CH ₂ ) ₂ -

5. Compounds of the formula 1.1:

in the GC ₂ -C ₆ alkyl, -CC ₄ alkoxymethyl or C ₃ -C ₆ cycloalkyl; R ^{2 is} hydrogen or methyl; and X is cyano, methoxy or ethoxy.

Compounds of the formula I.2.

in which Y is hydrogen or dC -alkyl and X is cyano, methoxy or ethoxy. Compounds of the formula 1.3

in the

D together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, dC ₄ - Can carry alkyl, dC ₄ alkoxy and CC ₂ haloalkyl; and

X is cyano, methoxy or ethoxy.

8. A process for the preparation of the compounds of the formula I according to claim 1, by reacting 5-halo-6- (2,4,6-trifluorohenyl) triazolopyrimidines of the formula II

in the shark represents a halogen atom, with compounds of the formula III MX IM in which M represents an ammonium, tetraalkylammonium or alkali metal or alkaline earth metal cation and X has the meaning according to claim 1.

9. Agent containing a solid or liquid carrier and a compound of formula I according to claim 1.

10. Seed containing a compound of formula I according to claim 1 in an amount of 1 to 1000 g / 100 kg

11. A method for controlling phytopathogenic harmful fungi, characterized in that the fungi or the materials, plants, soil or seeds to be protected against fungal attack are treated with an effective amount of a compound of the formula I according to claim 1.