EP1761543A1 - Use of 6-(2-tolyl)-triazolopyrimidines as fungicides, novel 6-(2-tolyl)-triazolopyrimidines, method for the production thereof, use thereof for controlling harmful fungi, and agents containing the same - Google Patents

Abstract

Disclosed is the use of substituted triazolopyrimidines of formula (I), wherein R1 represents alkyl, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, 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 or a group R1, R1 and/or R2 being optionally substituted as indicated in the description; and X represents halogen, as fungicides. Also disclosed are novel 6-(2-tolyl)-triazolopyrimidines, a method for producing said compounds, agents containing the same, and the use thereof for controlling plant-pathogenic fungi.

Description

Use of 6- (2-tolyl) -triazolopyπmιdιnen as fungicides, new 6- (2-tolyl) -triazolopyrimidines, processes for their preparation and their use for controlling harmful fungi and agents containing them

description

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

in which the substituents have the following meaning:

R ¹ d-Cβ-alkyl, 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 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 groups R ^a :

R ^a chlorine, bromine, iodine, cyano, nitro, hydroxy, dC _β -alkyl, d-Ce-haloalkyl, d-Ce-alkylcarbonyl, C ₃ -C ₆ -cycloalkyl, CrC ₆ -alkoxy, dC ₆ -haloalkoxy, dC ₆ -alkoxycarbonyl, dC ₆ -alkylthio, d-Ce-alkylamino, di-Cι-C ₆ -alkylamino, C ₂ -C ₈ -alkenyl, C ₂ -C ₈ -halogenalkenyl, C ₃ -C ₈ -cycloalkenyl, C ₂ -C ₆ alkenyloxy, C ₃ -C ₆ haloalkenyloxy, C ₂ -C ₆ alkynyl, C _∑ -Ce haloalkynyl, C ₃ -C ₆ alkynyloxy, C ₃ -C ₆ haloalkynyloxy, C ₃ - C ₆ cycloalkoxy, C ₃ -C ₆ - cycloalkenyloxy, oxy-dC ₃ -alkyleneoxy, naphthyl, a five- to ten-membered saturated, partially unsaturated or aromatic heterocycle which tend contained one to four heteroatoms from the group O, N or S, where these aliphatic, alicyclic or aromatic groups in turn can carry one to three groups R ^b : R ^b chlorine, bromine, iodine, cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyl loxy, alkynyloxy, alkoxy, haloalkoxy , Alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycar- bonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, the alkyl groups in these radicals containing 1 to 6 carbon atoms and the alkenyl or alkynyl groups mentioned in these radicals containing 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-CrC _e -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 can be partially or fully halogenated or substituted by alkyl or haloalkyl groups; and

X halogen;

as fungicides.

The invention also relates to new 6- (2-tolyl) -triazolopyrimidines, processes for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.

5-Chloro-6- (2-tolyl) -7-aminotriazolopyrimidines are generally known from EP-A 71 792 and EP-A 550 113. WO 98/46608 discloses 6- (2-tolyl) -7-aminotriazolopyrimidines with special 7-amino groups. WO 03/008417 proposes 6- (2-tolyl) -7-aminotriazolopyrimidines whose phenyl group bears an additional substituent. These compounds are known for combating harmful fungi.

Individual 6- (2-tolyl) -7-aminotriazolopyrimidines with pharmaceutical activity are described in WO 02/02563. A fungicidal activity of these compounds is not known.

The compounds according to the invention differ from the compounds mentioned in the abovementioned publications by the configuration of the substituents of the 7-amino group or by the less complex substitution of the 6-phenyl ring.

In many cases, however, the fungicidal activity of the known compounds is unsatisfactory. Based on this, the present invention has the object based on providing compounds with improved activity and / or broadened spectrum of activity.

Accordingly, the initially defined use of compounds of the formula I was found. Furthermore, new triazolopyrimidines according to Claim 3, processes for their preparation, compositions comprising them and processes for combating harmful fungi using the compounds I have been found.

The new compounds according to the invention can be obtained in various ways.

They are advantageously prepared by reacting 5-aminotriazole of the formula II with appropriately substituted phenylmalonates of the formula III in which R is alkyl, preferably C ₁ -C ₆ -alkyl, in particular methyl or ethyl.

This reaction usually takes place 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 kalimetallhydrogencarbonate, organometallic compounds, particularly alkali tallalkyle, alkyl magnesium halides and alkali metal and alkaline earth metal and Dimethoxymagnesium, also organic bases, for example tertiary amines such as trimethylamine, methylamine, tri-isopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethyl aminopyridine and bicyclic amines. 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 IM are advantageously obtained from the reaction of appropriately substituted bromobenzenes with dialkylmalonates with 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].

Dihalopyrimidines of formula V are reacted with amines of the formula VI, R V + _{R 2} -H * - I VI are defined in the R ¹ and R ² as in formula I, to give compounds of the formula I, in which X is halogen, reacted further ,

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 hydrocarbon fe, 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 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 purified 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 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-pent enyl, 4-methyl-3-pent-enyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pent-enyl, 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-pentinyl, 4-methyl-1-pentinyl, 4-methyl-2-pentinyl,

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- 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-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 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, 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;

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 of the formula I are preferred in which R ^{1 is} not hydrogen.

Compounds I are particularly preferred in which R ^{1 is} C ₄ -C ₈ alkyl or C ₄ -C ₈ alkenyl. In addition, compounds I are preferred in which R represents C ₃ -C ₆ cycloalkyl, which may be substituted by dC ₄ 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.

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 , CH ₂ CH = CH ₂ , cyclopentyl or cyclohexyl; R ^{2 is} hydrogen or methyl.

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

in the

GC ₂ -C ₆ alkyl, especially ethyl, n- and i-propyl, n-, sec-, tert-butyl, and -CC alkoxymethyl, especially ethoxymethyl, or C ₃ -C ₆ cycloalkyl, especially cyclopentyl or Cyclohexyl mean.

Compounds of formula I, except compounds of formula LA

in which Y is hydrogen or tert-butyl are new.

Compounds of the formula I in which R ^{1 is} C ₃ -C ₈ -cycloalkyl, C ₃ -C ₈ -halogenocycloalkyl, C ₂ -C ₈ -alkenyl, C ₂ -C ₈ -halogenalkenyl, C ₃ -C _{6 are} preferred -Cycloalkenyl, C ₃ -C ₆ halo-cycloalkenyl, 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, which can be substituted as defined in the introduction.

Compounds of the formula I.1G are particularly preferred

in which X and R ^{2 are} defined according to claim 1 and G represents ethyl, n- and iso-propyl, n- and sec-butyl.

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 A

Compounds of formula I in which X is chlorine.

The compounds I are suitable as fungicides in crop protection. 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 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: Alterna a-Aen on vegetables and fruit, 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 cucurbitaceae, Fusarium and Verticillium species on various plants, Mycosphaerella-A en on cereals, bananas and peanuts, Phakopsora pachyrhizi and P. meibomiae on soybeans, Phytophelnora infest viticola on vines, Podosphaera leucotricha on apples, Pseudocercosporella herpotrichoides on wheat and barley, Pseudoperonospora species on hops and cucumbers, Puccinia species on cereals, Pyricula a oryzae on rice, Rhizoctonia species on cotton, rice and lawn, Septoria tritici and Stagonospora nodorum on Uncinula necatoran vines, Ustilago species on cereals and sugar cane, and Ventuha-A en (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 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 customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; it should be in everyone Case ensure a fine and uniform distribution of the compound of 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 waste 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.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions from medium to high boiling points, 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, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as 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 dispersing and wetting agents and produced as technical equipment (e.g. 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.

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 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, for example 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 can be applied. 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, 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, isoprothiolan, mandipropamide, probinolone, probinilone Pyrifenox, pyroquilon, quinoxyfen, silthiofam, SYP-Z048, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforine, • copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate,

• Nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl

Phenylpyrroles such as fenpiclonil or fludioxonil,

• sulfur • other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanaz, namimzone Fosetyl, fosetyl aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phosphorous acid, phthalide, toloclofos-methyl, quintocene, zoxamide

Strobilurins such as azoxystrobin, dimoxystrobin, enestroburin (SYP-Z071), fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,

• Sulfenic 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-methylphenyl) -7- (3-methylbut-2-yl) -1, 2,4-triazolo [1,5a] pyrimidine

0.2 g (0.72 mmol) 5,7-dichloro-6- (2-methylphenyl) -1, 2,4-triazolo [1,5a] pyrimidine (cf. WO 03/80615), 0.073 g (0.74 mmol) triethylamine and 0.063 g (0.74 mmol) 3-methyl-2-butylamine in 2 ml dichloromethane were stirred at 20-25 ° C overnight. The reaction mixture was then washed with dil. HCl solution and water, then dried and freed from the volatile constituents. 0.12 g of the title compound remained as a light solid, mp 110-112 ° C.

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 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.

Example of use 1 - 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 each of the compounds 1-16 to 1-21 showed at most 15% infection, while the untreated plants were 100% infected.

Use Example 2 - Activity against Venturia inaequalis (protective) Leaves of potted apple seedlings of the "Common" variety were treated with aqueous active ingredient preparation which was prepared using a stock solution of 5% active ingredient, 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 Venturia inequalis. The test plants were then placed in climatic chambers at 22-24 ° C. and 95-99% relative atmospheric humidity for 2 days and then in the greenhouse at 21-23 ° C. and approximately 95%. relative humidity cultivated for another 2 weeks. The extent of the development of the infestation on the leaves was then determined visually.

In this test, the plants treated with 200 ppm each of the compounds 1-4, 1-5, 1-6, 1-8, 1-9 and 1-10 showed at most 15% infection, while the untreated plants were 90% were infected.

Claims

claims

1. Use of triazolopyrimidines of the formula I.

in which the substituents have the following meaning:

R ¹ -C ₈ alkyl, 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 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 groups R ^a :

R ^a chlorine, bromine, iodine, cyano, nitro, hydroxy, dC ₆ alkyl, dC ₆ alkyl carbonyl, C ₃ -C ₆ cycloalkyl, dC ₆ alkoxy, dC ₆ haloalkoxy, d-Ce alkoxycarbonyl, CC ₆ alkylthio, d-Ce alkylamino, di-dC ₆ alkylamino, C ₂ -C ₈ alkenyl, C ₂ -C ₈ haloalkenyl, 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-dC 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 in turn being aliphatic, alicyclic or aromatic groups can 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, 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; as fungicides.

2. Use according to claim 1, wherein the compounds correspond to the formula 1.1: G

in which X and R ^{2 are} defined according to claim 1 and GC ₂ -C ₆ alkyl, in particular ethyl, n- and i-propyl, n-, sec-, tert-butyl, and dC ₄ -alkoxymethyl, in particular ethoxymethyl, or C ₃ -C ₆ cycloalkyl, in particular cyclopentyl or cyclohexyl.

3. Compounds of formula I according to claim 1, wherein compounds of formula LA

in which Y means hydrogen or tert-butyl, remain excluded.

4. Compounds of formula I according to claim 3, in which R ¹ is 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 -Halogencycloalkenyl, C ₂ -C ₈ -alkynyl, C ₂ -C ₈ -Halogenalkinyl 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 means and can be substituted according to claim 1.

5. Compounds of formula I according to claim 3 or 4, in which X is chlorine.

6. Compounds of formula 1.1, G

in which X and R ^{2 are} defined according to claim 1 and G represents ethyl, n- and isopropyl, n- and sec-butyl.

7. A process for the preparation of the compounds of formula I according to claim 3, by reaction of 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 -H VI to compounds of the formula I.

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

9. Fungicidal composition according to claim 8, containing a further fungicidal active ingredient.

10. 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.

11. The method according to claim 10, characterized in that 0.01 and 2.0 kg of active ingredient are applied per ha.

12. The method according to claim 10, characterized in that 1 to 1000 g / 100 kg of seeds are applied.

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