EP1761538A1 - 6-(2-fluorophenyl)-triazolopyrimidines, method for the production thereof, use thereof for controlling harmful fungi, and agents containing the same - Google Patents

Abstract

Disclosed are substituted triazolopyrimidines of formula (I), wherein the substituents have the following meaning: R1 represents alkyl, halocycloalkyl, alkenyl, cycloalkyl, cycloalkenyl, halocycloalkenyl, alkinyl, haloalkinyl, 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, or S; R2 represents hydrogen, alkyl, or one of the groups mentioned for R1, R1 and/or R2 being able to carry one to four identical or different groups Ra, Ra representing chloride, bromine, iodine, cyano, nitro, hydroxy, alkyl, alkylcarbonyl, cycloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, alkylamino, di-alkylamino, alkenyl, cycloalkenyl, alkenyloxy, haloalkenyloxy, alkinyl, haloalkinyl, alkinyloxy, haloalkinyloxy, cycloalkoxy, cycloalkenyloxy, oxyalkyleneoxy, naphthyl, a five-membered to ten-membered saturated, partially unsaturated, or aromatic heterocycle containing one to four heteroatoms from the group comprising O, N, or S, said aliphatic, alicyclic, or aromatic groups being optionally substituted according to the description; and X represents halogen. Also disclosed are a method for producing said compounds, agents containing the same, and the use thereof for controlling plant-pathogenic fungi.

Description

6- (2-fluorophenyl) triazolopyrimidines, processes for their preparation and their use for controlling harmful fungi, and agents containing them

description

The present invention relates to substituted triazolopyrimidines of the formula I.

in which the substituents have the following meaning:

R ¹ C ₄ -C ₈ alkyl, C ₃ -C ₈ halocycloalkyl, C ₂ -C ₈ alkenyl, C ₃ -C ₆ cycloalkenyl, C ₃ -C ₆ halocycloalkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ haloalkynyl or 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 / or R ² can carry one to four identical or different R ^a groups: R ^a chlorine, bromine, iodine, cyano, nitro, hydroxy, C 1 -C ₆ -alkyl, d-Ce-alkylcarbonyl, C ₃ -C ₆ -Cycloalkyl, CC ₆ -alkoxy, CrCe-haloalkoxy, CrCe-alkoxycarbonyl, d-Ce-alkylthio, CC ₆ -alkylamino, di-d-Ce-alkylamino, C ₂ -C ₈ - alkenyl, C ₃ -C ₈ -Cycloalkenyl, C ₂ -C ₆ -alkenyloxy, C ₃ -C ₆ -haloalkenyloxy, C ₂ -C ₆ -alkynyl, C ₂ -C ₆ -haloalkynyl, C ₃ -C ₆ -alkynyloxy, C ₃ -C ₆ -halogen - alkynyloxy, C ₃ -C ₆ -cycloalkoxy, C ₃ -C ₆ -cycloalkenyloxy, oxy-CrC-ralkylene-oxy, naphthyl, five- to ten-membered saturated, partially unsaturated or aromatic heterocycle, containing one to four heteroatoms from the group O , N or S, where these aliphatic, alicyclic or aromatic groups can in turn carry one to three groups R ^b :

R ^b chlorine, bromine, iodine, cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, formyl, Alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, 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; and / or one to three of the following residues:

Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, the cyclic systems containing 3 to 10 ring members; Aryl, aryloxy, arylthio, aryl-dC ₆ -alkoxy, aryl-dC ₆ -alkyl, hetaryl, hetaryloxy, het-arylthio, the aryl radicals preferably containing 6 to 10 ring members, the hetaryl radicals containing 5 or 6 ring members, the cyclic systems being partial or may be fully halogenated or substituted by alkyl or haloalkyl groups;

X halogen.

The invention also relates to processes for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.

Certain 5-halo-6- (2-fluorophenyl) -7-aminotriazolopyrimidines are known from EP-A 550 113, EP-A 989 130 and GB 23 55 261. These compounds are known for combating harmful fungi.

The compounds according to the invention differ from those described in the abovementioned documents by the configuration of the substituents of the 7-amino group.

In many cases, however, the action of the known compounds is unsatisfactory. 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, processes and intermediates for their preparation, compositions comprising them and processes for combating harmful fungi using compounds I have been found.

The compounds according to the invention can be obtained in various ways. They are advantageous by reacting 5-aminotriazole of the formula II with correspondingly substituted phenylmalonates of the formula III in which R represents alkyl, preferably dC ₆ -alkyl, in particular methyl or ethyl.

This reaction is usually carried out at temperatures from 80 ° C. to 250 ° C., preferably 120 ° C. to 180 ° 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 among those from Adv. Het. Chem. Vol. 57, pp. 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 also 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. Mixtures of the solvents mentioned can also be used.

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, alkali metal amides, alkali metal and alkaline earth metal and Al come kalimetallhydrogencarbonate, organometallic compounds, particularly alkali tallalkyle, alkyl magnesium halides and alkali metal and alkaline earth metal and dimethoxymagnesium, also organic bases, e.g. Tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines are also considered. Tertiary amines such as tri-isopropylethylamine, tributylamine, N-methylmorpholine or N-methylpiperidine are particularly preferred.

The bases are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, 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 III in an excess based on the triazole. Phenylmalonates of the formula III are advantageously obtained from the reaction of appropriately substituted bromobenzenes with dialkylmalonates under Cu (I) catalysis [cf. Chemistry Letters, pp. 367-370, 1981; EP-A 10 02 788].

The dihydroxytriazolopyrimidines of the formula IV are converted under the conditions known from WO-A 94/20501 into the dihalopyrimidines of the formula V in which shark means a halogen atom, preferably a bromine or a chlorine atom, in particular a chlorine atom. A halogenating agent [HAL] is advantageously a chlorinating agent or a brominating agent, such as phosphorus oxybromide or phosphorus oxychloride, optionally in the presence of a solvent.

This reaction is usually carried out at 0 ° C. to 150 ° C., preferably at 80 ° C. to 125 ° C. [cf. EP-A 770 615].

Dihalotriazolopyrimidines of the formula V are further reacted with compounds of the formula I using amines of the formula VI, R ¹ V + ^ NH - 1 (X = halogen) VI in which R ¹ and R ² are defined as in formula I.

This reaction is advantageously carried out at 0 ° C to 70 ° C, preferably 10 ° C to 35 ° C, preferably in the presence of an inert solvent such as ether, e.g. B. dioxane, diethyl ether or in particular tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [cf. WO-A 98/46608].

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

The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products by chromatography. The intermediate and end products are partly in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or purified under reduced pressure and at a moderately elevated temperature. If the Intermediate and end products are obtained as solids, the cleaning can also be carried out 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 occur during 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, especially chlorine;

Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for example dC 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;

Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 4, 6 or 8 carbon atoms and one or two double bonds in any position, e.g. 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, 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-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-pent- enyl, 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-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;

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 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, 2nd -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 -Hexyl, 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-dimethyM-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- to ten-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-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-tetrahydrothienyl, 3- Hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyI 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 and one sulfur or oxygen atom as ring members can, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5th -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;

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.

The particularly preferred embodiments of the intermediates in terms of the variables correspond to those of the radicals L and R ^{3 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 individually or in combination, are particularly preferred:

Compounds I are particularly preferred in which R ^{1 is} C ₄ -C ₈ alkyl or C ₃ -C ₈ alkenyl.

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.

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 ₂ C (CH ₃ ) = CH ₂ or CH ₂ CH = CH ₂ and R ^{2 are} hydrogen or methyl. A preferred embodiment of the invention relates to compounds of the formula 1.1:

in the

GC ₂ -C ₆ alkyl, especially ethyl, n- and i-propyl, n-, sec-, partially butyl, and dC -alkoxymethyl, especially ethoxymethyl, or C ₃ -C ₆ -cycloalkyl, especially cyclopentyl or cyclohexyl; and

R ^{2 is} hydrogen or methyl.

Compounds of the formula 1.1 in which GC ₂ -C ₆ alkyl, in particular ethyl, n- and isopropyl, n-, sec-, tert-butyl and R ^{2 are} hydrogen, are particularly preferred.

In particular, in view of their use, the compounds I compiled in the tables below are preferred. The groups mentioned in the tables for a substituent 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 chlorine and the combination of R ¹ and R ² for a compound corresponds in each case to one line of Table A.

The compounds I are suitable as fungicides. They are characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as foliar, stain and soil fungicides.

They are of particular importance 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 vegetable plants 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: Alternaria species on vegetables and fruits, • Bipolaris and Drechslera plants 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 pumpkin plants, Fusarium and Verticillium men on various plants, • Mycosphaerella-Aύen on cereals, bananas and peanuts, Phakopsora pachyrhizi and P. meibomiae on soybeans, Plasmytophara viticola on vines, Podosphaera leucotricha on apples, • Pseudocercosporella herpotrichoides on wheat and barley, Pseudoperonospora Aen on hops and cucumber, Pucc / n / a species on cereals, Pyricularia oryzae on rice, Rhizoctonia species on cotton, rice and lawn, • Septoria tritici and Stagonospora nodorum on wheat, Uncinula necator on vines, Ustilago seeds on cereals and sugar cane, and so on he Venturia-Aήen (scab) on apples and pears.

The compounds I are also suitable for combating harmful fungi such as Pacilomyces variotii in the protection of materials (for example 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 of seed, preferably 1 to 200 g / 100 kg, in particular 5 to 100 g / 100 kg, are generally used.

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 rock powder (e.g. kaolins, clays, talc, chalk) and synthetic rock powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose. Alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and supplemented fatty alcohol naphthalene and sulfonated dehydrogenated naphthalene and sulfonated formaldehyde derivatives of sulfonated formaldehyde derivatives as well as condensation products with sulfonated formaldehyde derivatives and sulfated condensation products, as well as condensation products with sulfonated formaldehyde derivatives and sulfated dehydrogenated naphthalenedaphthalene and sulfated condensation products with sulfonated dehydrogenated naphthalene 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.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils as well as 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, strongly polar solvents, e.g. Dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

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 comminuted in a stirred ball mill to form a fine active ingredient suspension with the addition of dispersing and wetting agents and water or an organic solvent. 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. at 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 fluidized bed. This gives granules for direct application.

J ULV solutions (UL)

10 parts by weight of a compound according to the invention are dissolved in an organic solvent e.g. 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, wetting agents, adhesives, dispersants or emulsifiers, and possibly solvents or oil, can also be prepared from active substance and 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 which, e.g. with herbicides, insecticides, growth regulators, fungicides or also 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, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, metconazole, myclobutanil, pencon , Triticonazole,

Dicarboximides such as iprodione, myclozolin, procymidon, vinclozolin, dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram, zineb,

• Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronil, probarilol, probarilid, pyrinolifen, pyrinolipenol, probinil, prozolid, proinil, pyrid Pyroquilon, Quinoxyfen, Silthio- fam, SYP-Z048, thiabendazole, 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, cyflufenamide, cymoxanil, diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, namimzone, fluazi, fluazi, fluazi Fosetyl aluminum, iprovalicarb, hexachlorobenzene, mandipropamide, metrafenone, pencycuron, propamocarb, phosphorous acid, phthalide, toloclofos-methyl, quintozene, zoxamide

Strobilurins such as azoxystrobin, dimoxystrobin, enestroburin (SYP-Z071), 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-chloro-6- (2-fluorophenyl) -7- (3-methylbut-2-yl) -1, 2,4-triazolo [1,5a] pyrimidine

0.15 g (0.53 mmol) 1.5,7-dichloro-6- (2-fluoro-phenyl) -1, 2,4-triazolo [1,5a] pyrimidine (cf. WO 03/80615), 0.054 (0.54 mmol) triethylamine and 0.047 g (0.54 mmol) 3-methyl-2-butylamine in 1.5 ml dichloromethane were stirred at 20-25 ° C. overnight. The reaction mixture was then washed with dilute hydrochloric acid and water, then dried and freed from the solvent. 0.11 g of the title compound remained as a light solid, mp 116-118 ° C.

¹ H NMR (CDCI _3> δ in ppm): 8.35 (s, 1 H); 7.5 (m, 1H); 7.2-7.4 (m, 3H); 6.2 (s, broad, 1H); 3.1 (s, broad, 1H); 1.6 (m, broad, 1H); 1, 0; 1.1 (2 d, 3H); 0.8 (2 d, 6H).

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 as a stock solution with 0.25% by weight of active ingredient in acetone or DMSO. 1% by weight of the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and diluted with water to the desired concentration. Compound A known from EP-A 550 113 as Example No. 41 of Table 1 was used as the comparative active ingredient:

Comparative Experiment 1 - Efficacy against gray mold caused by Botrytis cinerea when used protectively

Paprika plants of the "California Wonder" variety grown in pots were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. The suspension or emulsion was prepared by dilution with water from a stock solution with 5% active ingredient, 94% cyclohexanone and 1% emulsifier (Tween 20). 2 - 5 hours after the spray coating had dried on, spores of the gray mold (Botrytis cinerea) were dusted. The test plants were then incubated in a humidity chamber at temperatures between 20 and 22 ° C and 100% relative humidity. After approx. 3 days, the extent of pathogen development was determined visually in% of the entire leaf area.

In this test, the plants treated with 200 ppm of the compounds I-5, 1-14 and 1-18, respectively, showed 3 to 20% infection, while the plants treated with 200 ppm of the comparison compound A showed 90% and the untreated plants were 100% infected.

Example of use 2 - effectiveness against Altemaria solani on tomatoes (protective)

Leaves of tomato plants of the "Pixie II" variety, which had been cultivated in pots up to the 4-leaf stage, were treated with aqueous active compound preparation which was prepared with a stock solution of 5% active compound, 94% acetone and 1% emulsifier (Tween 20). sprayed to dripping wet. After the spray coating had dried on (3-5 h), the leaves were inoculated with an aqueous spore suspension of Altemaria solani (density 15 × 10 ³ spores per ml). The test plants were then placed in climatic chambers at 22-24 ° C. and 96-99% relative atmospheric humidity for 36 hours and then cultivated in the greenhouse at 21-23 ° C. and approximately 95% relative atmospheric humidity for a further 2 to 3 days. The extent of the development of the infestation on the leaves was then determined visually. In this test, those with 200 ppm of the active ingredients I-3, 1-4, 1-5 and 1-11 showed no or up to 3% infection, while the untreated plants were 90% infected.

Example of use 3 - Efficacy against the drought stain disease of the tomato caused by Altemaria solani

Leaves of potted plants of the "Golden Princess" variety were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. The following day, the leaves were infected with an aqueous spore suspension of Altemaria solani in 2% biomalt solution with a density of 0.17 x 10 ⁶ spores / ml. The plants were then placed in a water vapor-saturated chamber at temperatures between 20 and 22 ° C. After 5 days the disease had developed so strongly on the untreated but infected control plants that the infestation could be determined visually in%.

In this test, the plants treated with 250 ppm of the active ingredients 1-14 to 1-19 showed no infection, while the untreated plants were 100% infected.

Claims

claims

1. Triazolopyrimidines of the formula I.

in which the substituents have the following meaning:

R ¹ C ₄ -C ₈ alkyl, C ₃ -C ₈ halocycloalkyl, C ₂ -C ₈ alkenyl, C ₃ -C ₆ cycloalkenyl, C ₃ -C ₆ halocycloalkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ haloalkynyl or 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, CC ₃ alkyl or one of the groups mentioned for R ¹ ; R ¹ and / or R ² can carry one to four identical or different groups R ^a :

R ^a chlorine, bromine, iodine, cyano, nitro, hydroxy, dC ₆ -alkyl, CC ₆ -Alkylcarbonyl, C ₃ -C ₆ -cycloalkyl, dC ₆ -alkoxy, dC ₆ -haloalkoxy, Ci-Ce-alkoxycarbonyl, dC ₆ alkylthio, dC ₆ alkylamino, di-dC ₆ alkylamino, C ₂ -C ₈ alkenyl, C ₃ -C ₈ cycloalkenyl, C ₂ -C ₆ alkenyloxy, C ₃ - C ₆ haloalkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ alkynyloxy, C ₃ -C ₆ haloalkynyloxy, C ₃ -C ₆ cycloalkoxy, C ₃ -C ₆ cycloalkenyloxy , Oxy-C C ₃ -alkyleneoxy, naphthyl, five- to ten-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 in turn one to three groups R ^{b can} wear:

R ^b chlorine, bromine, iodine, cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, Alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkyl laminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, the alkyl groups in these Residues contain 1 to 6 carbon atoms and said alkenyl or alkynyl groups in these residues contain 2 to 8 carbon atoms; and / or one to three of the following residues:

Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, the cyclic systems containing 3 to 10 ring members; Aryl, aryloxy, arylthio, aryl -CC ₆ -alkoxy, aryl-dC ₆ -alkyl, hetaryl, hetaryloxy, hetarylthio, the aryl radicals preferably containing 6 to 10 ring members, the hetaryl radicals containing 5 or 6 ring members, where the cyclic systems can be partially or completely halogenated or substituted by alkyl or haloalkyl groups; and

X halogen.

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

3. Compounds according to claim 1 or 2, which correspond to formula 1.1 G.

in the

GC ₂ -C _β alkyl, dC ₄ alkoxymethyl or C ₃ -C ₆ cycloalkyl; R ^{2 is} hydrogen or methyl; and X is halogen.

4. A process for the preparation of the compounds of formula I according to any one of claims 1 to 3 by reacting 5-aminotriazole of formula II with phenymalonates of the formula

in which R represents alkyl, to dihydroxytriazolopyrimidines of the formula IV,

Halogenation to the dihalo compounds of formula V,

and reaction of V with amines of the formula VI 2 ^ NH VI to give compounds of the formula I.

5. Fungicidal composition comprising a solid or liquid carrier and a compound of the formula I according to claim 1.

6. Fungicidal composition according to claim 5, containing a further fungicidal active ingredient.

7. A method for controlling phytopathogenic harmful fungi, characterized in that the fungi, or the materials, plants, the 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.

8. The method according to claim 7, characterized in that 0.01 and 2.0 kg of active ingredient are applied per ha.

9. The method according to claim 7, characterized in that 1 to 1000 g / 100 kg of seeds are applied.

10. Seed containing 1 to 1000 g of a compound of formula I according to claim 1 per 100 kg.