MXPA06007752A - 6-(2-chloro-5-halophenyl)-triazolopyrimidine, method for production and use thereof for controlling fungal pests and agents comprising the same - Google Patents

Abstract

The invention relates to substituted triazolopyrimidines of formula (I), with the substituents as follows:R1, R2=H, alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, cycloalkenyl, halocycloalkenyl, alkinyl, haloalkinyl, phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle, comprising one to four heteroatoms of the group O, N or S, R1 and R2 can, together with the nitrogen atom to which it is attached, form a five- or six-membered heterocycle or heteroaryl, bonded via N and containing one to three further heteroatoms from the group O, N and S as ring members, substituted as per the description, L1=fluorine, chlorine or bromine, L2=H, alkyl or alkoxy and X=halogen, cyano, alkyl, haloalkyl, alkoxy or haloalkoxy. The invention further relates to methods and intermediates for production of said compounds, agents comprising the same and use thereof for controlling fungal pests harmful to plants.

Description

6- (2-Chloro-5-halogenophenyl) -triazolopyrimidines, processes for their preparation and the use thereof to combat harmful fungi, as well as products containing them Description The present invention relates to substituted triazolopyrimidines of the formula I wherein the substituents have the following meanings: R 1, R 2 independently represent hydrogen, C 1 -C 8 alkyl, 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 6 cycloalkenyl, C 3 -C 6 halocycloalkenyl, C2-C8 alkynyl, C2-C8 haloalkynyl or phenyl, naphthyl, or a saturated, partially unsaturated or aromatic heterocycle with five or six members, containing one to four heteroatoms of the group: O, N or S, R1 and R2 can also form together with the nitrogen atom, to which they are attached, a heterocyclyl or heteroaryl having five or six members, which is linked by means of N and can contain one to three additional heteroatoms of the group: O, N and S as ring members and / or contain one or more substituents of the group: halogen, CrCe alkyl, haloalkyl C ^ Ce, C2-C6 alkenyl, C2-C6 haloalkenyl, CrC6 alkoxy, CrC6 haloalkoxy, C3-C6 alkenyloxy, C3-C6 haloalkenyloxy , C6-C-alkylene and oxy-alkylenoxy CrC3; R1 and / or R2 can carry one to four equal or different Ra groups: R a is halogen, cyano, nitro, hydroxy, C 6 alkyl, C 6 halogenalkyl, CrC 6 alkylcarbonyl, C 3 -C 6 cycloalkyl, C 6 alkoxy, Cr C 6 haloalkoxy, CrC 6 alkoxycarbonyl, CrC 6 alkylthio, C 6 alkylamino, C 6 alkylamino, C 2 alkylamino -C8, C2-C8 haloalkenyl, C3-C8 cycloalkenyl, C2-C2 alkenyloxy, C3-C6 haloalkenyloxy, C2-C8 alkynyl, C2-C8 haloalkynyl, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C3-C6 cycloalkoxy, C3- C6-cycloalkeneoxy, CrC3-oxyalkyleneoxy, phenyl, naphthyl, saturated, partially unsaturated or aromatic heterocycle of five or ten members, containing one to four heteroatoms of the group: O, N or S, these aliphatic, alicyclic or aromatic groups may in turn be partially or completely halogenated or carry one to three Rb groups, R is halogen, cyano, nitro, hydroxy, mercapto, amino, carboxy, 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 containing in these radicals 1 to 6 carbon atoms and the alkenyl or alkynyl groups mentioned in these radicals 2 to 8 carbon atoms; and / or one to three of the following radicals: cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, the cyclic systems being able to contain 3 to 10 ring members; aryl, aryloxy, arylthio, aryl-alkoxy CrC6, aryl-alkyl CrC6, hetaryl, hetaryloxy, het-arylthio, the aryl radicals preferably containing 6 to 10 ring members, the hetaryl radicals 5 or 6 ring members, the systems cyclics are partially or completely halogenated or substituted by alkyl or haloalkyl groups; L1 is fluorine, chlorine or bromine; L is hydrogen, C4 alkyl or CrC4 alkoxy; Y X is halogen, cyano, CrC 4 alkyl, haloalkyl CrC 4, C 4 alkoxy or halo C 2 alkoxy.

Furthermore, the invention relates to a process for obtaining these compounds, to products that contain them, as well as to their use for combating fungal pathogenic fungi.

From EP-A 71 792, EP-A 550 113, 5-cioro-6-phenyl-7-amino-triazolopyrimidines are generally known. In EP-A 550 113, FR-A 27 84 991 -, US 5 994 360, WO 98/46608, JP-A 2002/308 879, WO 02/38565, WO 02/083677, WO 02/088125, WO 02/088126 and WO 02/088127 are proposed in general terms, 6- (2-CI-phenyl) -7-amino-triazolo-pyrimidines, whose 6-phenyl group has another additional d -halogen substitution. Triazolopyrimidines, where the 6-phenyl group carries 4-alkyl or 4-alkoxy substituents are known from WO 98/48893, WO 03/008417 and WO 03/093271. These compounds are known to fight harmful fungi.

The compounds according to the invention are distinguished from the compounds described in the aforementioned publications in the 2,5-disubstitution of the 6-phenyl ring.

The effect of the known compounds is not satisfactory in many cases. Starting from this, the present invention aims to provide compounds with improved effect and / or broader spectrum of action.

Therefore, the compounds defined at the beginning were found. In addition, procedures were found for their production, products that contain them, as well as procedures to control harmful fungi using these compounds I.

The compounds according to the invention can be prepared, using different methods. Advantageously, starting from 5-aminotriazole of the formula II with correspondingly substituted phenyl malonates of the formula III, wherein R means alkyl, preferably C 1 -C 6 alkyl, especially methyl or ethyl.

This reaction is usually carried out at a temperature of 80 ° C to 250 ° C, preferably 120 ° C to 180 ° C, without solvent or in an organic solvent, in the presence of a base [see EP-A 770 615] or in presence of acetic acid under the known conditions of Adv. Het. Chem. Vol. 57, p. 81 and next (1993).

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, such as toluene, or, m- and p-xylene, halogenated hydrocarbons, ethers, nitriles, ketones, alcohols, as well as N-methylpyrrolidone, dimethyl sulfoxide dimethylformamide and dimethylacetamide. Most preferably, the reaction is carried out without solvent or in chlorobenzene, xylene, dimethyl sulfoxide, n-methylpyrrolidone. Mixtures of the mentioned solvents 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 hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates, as well as hydrogen carbonate carbonates. alkali metal, organic metal compounds, especially alkali metal alkyls, alkylmagnesium halides, as well as alkali metal and alkaline earth metal alcoholates and dimethoxymagnesium, furthermore, organic bases, eg tertiary amines, such as trimethylamine, triethylamine, tri -isopropylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethyl-aminopyridine, as well as bicyclic amines. Especially preferred are tertiary amines, such as tri-isopropylamine, tributylamine, N-methylmorpholine or N-methylpiperidine.

The bases are usually used in catalytic quantities, but it is also possible to use them in an equimolar quantity, in excess, or, if necessary, as a solvent.

The educts are usually reacted together in equimolar quantities. But for the yield it may be advantageous to use the base and the malonate III in excess with respect to the triazole.

Phenyl malonates of the formula III are advantageously prepared by reacting appropriately substituted bromobenzenes with dialkyl malonates under Cu (I) catalysis [see Chemistry Letters, p. 367-370, 1981; EP-A 10 02 788].

The dihydroxytriazolopyrimidines of the formula IV are transformed under the conditions known from WO-A 94/20501 into the dihalopyrimidines of the formula V, in which Y denotes a halogen atom, preferably a bromine or chlorine atom, especially a chlorine atom. As the halogenating agent [HAL], a chlorinating or brominating agent is preferably used, for example, phosphorus oxybromide or phosphorus oxychloride, optionally in the presence of a solvent.

This reaction is used, generally, at 0 ° C to 150 ° C, preferably at 80 ° C to 125 ° C [see EP-A 770 615].

The dihalopyrimidines of the formula V are further transformed with amines of the formula VI, V + halogen) VI wherein R and R2 have the definitions indicated in the formula I, in compounds of the formula I, wherein X means halogen.

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

It is preferable to use a base, e.g., a tertiary amine, such as triethylamine or an inorganic base, such as, for example, potassium carbonate; or also excessive amine of formula VI can serve as a basis.

Compounds of the formula I, wherein X is cyano, CrC6 alkoxy or halogenoalkoxy dC2, can be advantageously prepared by reacting compounds I, wherein X means halogen, preferably chlorine, with compounds M-X '(formula VII). The compounds VII represent, depending on the meaning of the group X 'to be incorporated, an inorganic cyanide, an alkoxylate or a haloalkoxylate. The reaction is advantageously carried out in the presence of an inert solvent. The cation M in the formula VII is of little importance, but for practical reasons ammonium, tertralkylammonium or alkali metal or alkaline earth metal salts are preferred.

I (X = halogen) + M-X 'I (X = X') Vil The reaction temperature is generally from 0 to 120 ° C, preferably from 10 to 40 ° C [see J. Heterocycl. Chem., Vol.12, p. 861-863 (1975)].

Suitable solvents are: ethers, such as dioxane, diethyl ether and, preferably tetrahydrofuran, alcohols, such as methanol or ethanol, halogenated hydrocarbons, such as, for example, dichloromethane and aromatic hydrocarbons, such as, for example, toluene or acetonitrile.

Compounds of the formula I, in which X stands for C-C4-alkyl or C-C4-haloalkyl, can advantageously be prepared using the following synthesis method: Starting from keto Illa esters, the 5-alkyl-7-hydroxy-6-phenyltriazolo-pyrimidines IVa are obtained. In the formulas Illa and IVa X 1 represents C 1 alkyl or halogeno Cr-C 4. The 5-methyl-7-hydroxy-6-phenyltriazolopyrimidines, which are a preferred object of the present invention, are obtained by using the esters of 2-phenylacetic acid (Illa with X = CH 3) which are a preferred object of the present invention [see Chem. Pharm. . Bull., 9, 801, (1961)]. The starting compounds Illa are advantageously prepared under the conditions described in EP-A 10 02 788.

The 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines thus obtained are transformed with halogenation agents [HAL] under the conditions described above in the 7-haiogenotriazolopyrimidines of the formula Va, where Y means a halogen atom. Preferably a chlorinating or brominating agent is used, for example, phosphorus oxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride. The reaction can be carried out in the absence or presence of a solvent. Typical reaction temperatures are 0 to 150 ° C or preferably 80 to 125 ° C.

VI (X = alkyl) The reaction of Va. with amines VI is carried out under the conditions described above.

The compounds of the formula I, wherein X means CrC 4 alkyl, can be prepared, alternatively, from compounds I, wherein X means halogen, especially chlorine, and malonates of the formula VIII. In formula VIII, X "means hydrogen or alkyl CrC3 and R is alkyl d-C4, they are transformed into compounds of formula X and decarboxylated into compounds I [see US 5 994 360].

? / H + IX (X = C4 alkyl) Malonates IX are known from the literature [J. Am. Chem. Soc, Vol. 64, 2714 (1942); J. Org. Chem., Vol. 39, 2172 (1974); Helv. Chim. Acta, Vol. 61, 1565 (1978)] or can be prepared according to the cited literature.

The subsequent saponification of ester IX is carried out under generally known conditions; Depending on the different structural elements, an alkaline or acid saponification of the compounds IX may be advantageous. Under the conditions of ester saponification, decarboxylation can already be carried out partially or completely in I.

The decarboxylation is generally carried out at temperatures of 20 ° C to 180 ° C, preferably 50 ° C to 120 ° C, in an inert solvent, if appropriate in the presence of an acid.

Suitable acids are: hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid. Suitable solvents are: water, aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petrol ether, aromatic hydrocarbons, such as toluene, or, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as as diethyl ether, diisopropyl ether, tert.-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.-butyl methyl ketone, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, very preferably, the reaction is carried out in hydrochloric acid or acetic acid. You can also use mixtures of solvents mentioned.

The compounds of the formula I, wherein X means CrC alkyl, can also be prepared by coupling 5-halogentriazolopyrimidines of the formula I, wherein X means halogen, with organic metal reagents of the formula X. In one embodiment This reaction is carried out under catalysis of a transient metal, for example, Ni or Pd catalysis. l (X = Hal) + Mv (-X ") and I (X = C4 alkyl) X In the formula X, M represents a metal ion of the valence Y, for example, B, Zn or Sn and X "means alkyl d-C3 This reaction can be carried out, for example, in analogy to the following methods: Chem. Soc. Perkin Trans., 1, 1187 (1994), loc cit., 1, 2345 (1996), WO-A 99/41255, Aust. J. Chem., Vol. 43, 733 (1990); Org. Chem., Vol. 43, 358 (1978); J. Chem. Soc. Chem. Commun. 866 (1979); Tetrahedron Lett., Vol. 34, 8267 (1993); loc.cit, Vol. 33, 413 (1992).

The reaction mixtures are usually further processed in a known manner, for example by mixing them with water, separating the phases and optionally purifying the crude products by chromatography. The intermediate and final products are obtained, in part, in the form of colorless or slightly brownish viscous oils, which are released from the volatile components under reduced pressure and at slightly elevated or purified temperatures. If the intermediate or final products are obtained in the form of solids, then they can also be purified by recrystallization or digestion.

If some of the compounds I can not be prepared by the methods described above, then they can be obtained by derivatization of other compounds & If isomeric mixtures are obtained in the synthesis, it is generally not necessary to separate them, since the different isomers can be converted, in part, during the preparation for the application or in the application (eg under the action of light or acids or bases) in each other. Corresponding conversions may also take place in the application, for example, in the plant itself or in the noxious fungus to be fought when they are treated.

In the definitions of the symbols of the formulas represented above collective terms representative of the following substituents were used: halogen: fluoro, chloro, bromo and iodo; alkyl: branched or linear hydrocarbon radicals saturated with 1 to 4, 6 or 8 carbon atoms, eg C6 alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2- methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 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: linear or branched alkyl groups with 1 to 2, 4 or 6 carbon atoms (as mentioned above), in which groups the hydrogen atoms may be partially or completely substituted by halogen atoms, such as those mentioned above: C2-C2 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: branched or linear hydrocarbon radicals unsaturated with 2 to 4, 6 or 8 carbon atoms and one or two double bonds in an arbitrary position, eg C2-C6 alkenyl) such as ethenyl, 1 -propenyl, 2- propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2- methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentynyl, 3-methyl-1-pentynyl, 4-methyl-1-pentynyl, 1-methyl-2-pentenyl, 2-methyl-2- pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3pent enyl, 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- etii-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: linear or branched unsaturated hydrocarbon radicals with 2 to 8 carbon atoms and one or two double bonds in an arbitrary position (as mentioned above), the hydrogen atoms in these groups being partially or completely substituted by halogen atoms , as those mentioned above, especially, fluorine, chlorine and bromine; alkynyl: branched or linear hydrocarbon radicals unsaturated with 2 to 4, 6, or 8 carbon atoms and one or two triple bonds in an arbitrary position, eg C2-C6 alkynyl, such as: ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentnyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1- methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3- Hexylin, 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 -pentinyl, 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 hydrocarbon group with 3 to 6 or 8 carbon ring members, for example C3-C8-cycloalkyl, eg cyclopropyl, cyclobutyl, cyclopentyl, ciciohexilo, cicioheptilo and cyclooctyl; saturated, partially unsaturated or aromatic heterocycle of five to ten members, containing from one to four heteroatoms of the group O, N or S: - or 6-membered, containing one to three nitrogen atoms and / or an oxygen atom or sulfur or one or two oxygen atoms and / or sulfur atoms, eg 2-tetrahydrofuranyl, 3-tetrahydrofuranyl , 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-¡soxazolidinilo, 5-isoxazolidinyl, 3-¡sotiazolidinilo, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl 5-pirazolidlnilo, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolidin-2-yl, 2-pyrroline-3 -yl, pyrrolidin-3-yl-2, 3-pyrroline-3-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1, 3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2 -tetrahidrotienilo, 3-hexahidropiridacinilo, 4-hexahidropiridacinilo, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl; five-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur atom or oxygen: pentacyclic heteroaryl groups which, besides carbon atoms can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur atom or oxygen as ring members, eg 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3- isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-tiazoliIo, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl and 1,4-triazol-2-yl; six-membered heteroaryl, containing one to three or one to four nitrogen atoms: heterocyclic hexacyclic groups, which in addition to carbon atoms may contain one to three or one to four nitrogen atoms as ring members, eg 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl alkylene: unbranched divalent chains from 3 to H CH2 groups, for example: CH2, CH2CH2, CH2CH2CH2, CH2CH2CH2CH2 and CH2CH2CH2CH2CH2; oxyalkylene: unbranched divalent chains from 1 to 4 CH2 groups, where a valence is linked by means of an oxygen atom to the backbone, eg OCH2CH2, OCH2CH2CH2 and OCH2CH2CH2CH2; oxyalkyleneoxy: divalent unbranched chains from 1 to 4 CH2 groups, where both valences may be linked through an oxygen atom to the skeleton, eg OCH2CH2, OCH2CH2CH2 and OCH2CH2CH2CH2.

Within the scope of the present invention are included the (R) and (S) isomers and the racemates of the compounds of the formula I, which have chiral centers.

The especially preferred embodiments of the intermediates with respect to the variables correspond to those of the radicals L of the formula I.

As for the use to which the triazolopyrimidines of the formula I are intended, the following meanings of the substituents are especially preferred, both by themselves and also in combinations: Preferred are compounds of formula I, wherein R 1 does not mean hydrogen.

Preferred are compounds I, wherein R 1 means C 1 -C 6 alkyl, C 2 -C 6 alkenyl or C 1 -C 8 haloalkyl.

Preferred are compounds I, wherein R 1 is a group A: where Z1 means hydrogen, fluoro or fluoroalkyl-CrC6, Z2 signifies hydrogen or fluoro, or Z1 and Z2 together form a double bond; q is 0 or 1; and R3 means hydrogen or methyl.

In addition, compounds I are preferred, wherein R 1 is C 3 -C 6 cycloalkyl, which may be substituted by C 1 -C 4 alkyl. Compounds I, in which R2 means hydrogen, are especially preferred.

Also preferred are compounds I, wherein R2 means methyl or ethyl.

Q IO If R1 and / or R2 comprise haloalkyl or haloalkenyl groups with centers of chirality, then the (S) isomers are preferred. In the case of halogen-free alkyl or alkenyl groups with centers of chirality in R 1 or R 2, isomers with the (R) configuration are preferred.

In addition, compounds I are preferred, in which R1 and R2 together with the nitrogen atom, to which they are bound, form a piperidinyl, morpholinyl or thiomorpholinyl ring, especially a piperidinyl ring, which is optionally substituted by one to three halogen groups, CrC4 alkyl or C4 haloalkyl. Especially preferred are compounds I, in which R1 and R2 together with the Nitrogen atom, to which they are bound, a 4-methylpiperidine ring.

Another preferred object of the present invention are compounds I, in which R1 and R2 together with the nitrogen atom, to which they are bound, form a pyrazole ring, which is optionally substituted by one or two halogen, dC alkyl or haloalkyl 25 CrC, especially, by 3,5-dimethyl or 3,5-di- (trifluoromethyl).

Additionally, compounds of the formula I, wherein R 1 means CH (CH 3) -CH 2 CH 3, CH (CH 3) -CH (CH 3) 2, CH (CH 3) -C (CH 3), CH (CH 3) - are especially preferred. CF3, CH2C (CH3) = CH2, CH2CH = CH2, cyclopentyl or cyclohexyl; R2 is hydrogen or methyl; or R1 and R2 together form - (CH2) 2CH (CH3) (CH2) 2, - (CH2) 2CH (CF3) (CH2) 2-or - (CH2) 2O (CH2) 2-.

Preference is given to compounds I, in which X is halogen, CrC, cyano or CrC 4 alkoxy, for example chlorine, methyl, cyano, methoxy or ethoxy, especially chlorine or methyl, especially chlorine.

A preferred object of the present invention are compounds I, wherein L 1 means chlorine.

Another preferred object of the present invention are compounds I, wherein L 1 means fluorine.

In another embodiment of the present invention, L 1 means bromine.

An especially preferred object of the present invention are compounds I, wherein L2 means hydrogen.

In another embodiment of the present invention, L2 means methyl or methoxy.

A preferred embodiment of the invention relates to compounds of formula 1.1: wherein G means C2-C6 alkyl, especially ethyl, n- and i-propyl, n, sec, tert-butyl, and alkoxymethyl CrC4, especially, ethoxymethyl, or C3-C6 cycloalkyl, especially, cyclopentyl or cyclohexyl, R2 is hydrogen or methyl; Y X means, chlorine, methyl, cyano, methoxy or ethoxy, and L1 and L2 have the meanings indicated for formula I.

Another embodiment of the invention relates to compounds, in which R1 and R2 form, together with the nitrogen atom, to which they are bound, a six-membered heterocyclyl or heteroaryl, which is linked by means of N and which may contain Another heteroatom of the group: O, N and S as ring members and / or one or more substituents of the group: halogen, CrCe alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, CrC6 alkoxy, CrC6 haloalkoxy, C3- alkenyloxy C6, haloalkenyloxy C3-Ce, alkylene C Ce and oxy-alkyleneoxy CrC3. These compounds correspond, especially to formula 1.2, 1. 2 where D forms together with the nitrogen atom a heterocyclyl or heteroaryl having five or six members, which is linked by means of N and which may contain another heteroatom of the group: O, N and S as ring members and / or one or more substituents of the group: halogen, CrC 4 alkyl, CrC 4 alkoxy and CrC 2 haloalkyl; and X means chloro, methyl, cyano, methoxy or ethoxy, and L1 and L2 have the meanings indicated for formula I.

Another preferred embodiment of. the invention are compounds of formula 1.3. wherein Y means hydrogen or C4 alkyl, especially methyl and ethyl, and X means chloro, methyl, cyano, methoxy or ethoxy and L1 and L2 have the meanings according to formula I.

Another preferred embodiment of the invention relates to compounds, wherein L 1 means fluorine and L 2 means alkyl or alkoxy, especially methyl or methoxy.

Another preferred embodiment of the invention relates to compounds, wherein L 1 means chlorine and L 2 means alkyl or alkoxy, especially methyl or methoxy.

Especially, with respect to their use, the compounds I listed in the following Tables are preferred. The groups mentioned in the Tables for a substituent are, considered by themselves, independently of the combination in which they are mentioned, an especially preferred variant of the corresponding substituent.

Table 1 Compounds of the formula I, wherein X means chlorine, L1 means chlorine, L2 means hydrogen and the combination of R1 and R2 equals one compound respectively of Table A Table 2 Compounds of the formula I, in which X signifies cyano, L1 signifies chlorine, L2 signifies hydrogen and the combination of R1 and R2 signifies a compound respectively of Table A Table 3 Compounds of the formula I, wherein X means methyl, L1 means chlorine, L2 means hydrogen and the combination of R1 and R2 equals one compound respectively of Table A Table 4 Compounds of the formula I, in which X signifies methoxy, L1 signifies chlorine, L2 signifies hydrogen and the combination of R1 and R2 is equivalent to a compound respectively of Table A Table 5 Compounds of the formula I, in which X means chlorine, L1 means fluorine, L2 means hydrogen and the combination of R1 and R2 equals one compound respectively of Table A Table 6 Compounds of the formula I, wherein X means cyano, L represents fluorine, L2 means hydrogen and the combination of R1 and R2 equals one compound respectively of Table A Table 7 Compounds of the formula I, in which X means methyl, L1 means fluorine, L2 means hydrogen and the combination of R1 and R2 equals one compound respectively of Table A Table 8 Compounds of the formula I, wherein X means methoxy, L1 means fluorine, L2 means hydrogen and the combination of R1 and R2 equals one compound respectively of Table A Table 9 Compounds of the formula I, wherein X means chlorine, L1 means bromine, L2 means hydrogen and the combination of R1 and R2 is equivalent to a compound respectively of Table A Table 10 Compounds of the formula I, wherein X means cyano, L1 means bromine, L2 means hydrogen and the combination of R1 and R2 equals one compound respectively of Table A Table 11 Compounds of the formula I, wherein X means methyl, L1 means bromine, L2 means hydrogen and the combination of R and R2 equals one compound respectively of Table A Table 12 Compounds of the formula I, wherein X means methoxy, L1 means bromine, L2 means hydrogen and the combination of R1 and R2 equals one compound respectively of Table A Table 13 Compounds of the formula I, wherein X means chlorine, L1 means chlorine, L2 means methyl and the combination of R1 and R2 equals one compound respectively of Table A Table 14 Compounds of formula I, in which X signifies cyano, L1 signifies chlorine, L2 signifies methyl and the combination of R1 and R2 is equivalent to a compound respectively of Table A Table 15 Compounds of formula I, in which X means methyl, L1 means chlorine, L2 means methyl and the combination of R1 and R2 equals one compound respectively of Table A Table 16 Compounds of the formula I, in which X signifies methoxy, L 1 signifies chlorine, L 2 signifies methyl and the combination of R 1 and R 2 signifies a compound respectively of Table A Table 17 Compounds of the formula I, wherein X means chlorine, L1 means fluorine, L2 means methyl and the combination of R1 and R2 is equivalent to a compound respectively of Table A Table 18 Compounds of the formula I, wherein X signifies cyano, L1 signifies fluorine, L2 signifies methyl and the combination of R1 and R2 is equivalent to a compound respectively of Table A Table 19 Compounds of the formula I, in which X means methyl, L1 means fluorine, L2 means methyl and the combination of R1 and R2 is equivalent to a compound respectively of Table A Table 20 Compounds of the formula I, in which X means methoxy, L1 means fluorine, L2 means methyl and the combination of R and R2 equals one compound respectively of Table A Table 21: Compounds of the formula I, wherein X means chlorine, L1 means bromine, L2 means methyl and the combination of R1 and R2 equals one compound respectively of Table A Table 22: Compounds of the formula I, wherein X means cyano, L1 means bromine, L2 means methyl and the combination of R1 and R2 equals one compound respectively of Table A Table 23 Compounds of the formula I, wherein X means methyl, L1 means bromine, L2 means methyl and the combination of R1 and R2 equals one compound respectively of Table A Table 24 Compounds of the formula I, in which X means methoxy, L1 means bromine, L2 means methyl and the combination of R1 and R2 is equivalent to a compound respectively of Table A Table 25 Compounds of the formula I, in which X means chlorine, L1 means chlorine, L2 means methoxy and the combination of R1 and R2 is equivalent to a compound respectively of Table A Table 26 Compounds of formula I, wherein X means cyano, L1 means chloro, L2 means methoxy and the combination of R1 and R2 is equivalent to a compound respectively of Table A 0 Table 27 Compounds of the formula I, in which X means methyl, L1 means chlorine, L2 means methoxy and the combination of R1 and R2 equals one compound respectively from Table A-5 Table 28 Compounds of formula I, wherein X signifies methoxy, L 1 signifies chlorine, L 2 signifies methoxy and the combination of R 1 and R 2 equals one compound respectively of Table A 0 Table 29 Compounds d e formula I, wherein X means chlorine, L1 means fluorine, L2 means methoxy and the combination of R1 and R2 is equivalent to a compound respectively of Table A 5 Table 30 Compounds of formula I, in which X stands for cyano , L1 means fluorine, L2 means methoxy and the combination of R1 and R2 equals one compound respectively of Table A Table 31 Compounds of the formula I, wherein X means methyl, L1 means fluorine, L2 means methoxy and the combination of R1 and R2 equals one compound respectively of Table A Table 32 Compounds of the formula I, wherein X means methoxy, L1 means fluorine, L2 means methoxy and the combination of R1 and R2 equals one compound respectively of Table A Table 33 Compounds of formula I, wherein X means chlorine, L1 means bromine, L2 means methoxy and the combination of R1 and R2 equals one compound respectively of Table A Table 34 Compounds of the formula I, in which X means cyano, L1 means bromine, L2 means methoxy and the combination of R1 and R2 is equivalent to a compound respectively of Table A Table 35 Compounds of the formula I, in which X means methyl, L1 means bromine, L2 means methoxy and the combination of R1 and R2 equals one compound respectively of Table A Table 36 Compounds of the formula I, wherein X means methoxy, L1 means bromine, L2 means methoxy and the combination of R1 and R2 equals one compound respectively of Table A Table A The compounds I are suitable as fungicides. They stand out for being excellently effective against a broad spectrum of phytopathogenic fungi, especially from the class of Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. In part they are systemically active and can be used in the protection of plants such as foliar and soil fungicides.

They are especially important for combating multiple fungi in different crop plants, such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans, coffee, sugar cane, grapes, fruits and ornamental plants and legumes. , such as beans, tomatoes and cucurbits, as well as in the seeds of these plants.

They are especially suitable for combating the following plant diseases: Alternaria species in. legumes and fruits, Bipolaris and Drechslera species in cereals, rice and grass, Blumeria graminis (powdery mildew) in cereals, Botrytis cinerea (gray mold) in strawberries, legumes, ornamental plants and vine, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Fusarium and Verticillium species in different plants, Mycosphaerella species in cereals, bananas and peanuts, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticulture in grapevine, Podosphaera leucotricha in apples, Pseudocercosporella herpotrichoides in wheat and barley, Pseudoperonospora species in hops and cucumbers, Puccinia species in cereals, Pyricularia oryzae in rice, Rhizoctonia species in cotton, rice and turf, Septoria tritici and Stagonospora nodorum in wheat, • Uncinula necator in vine, • Ustilago species in cereals and sugar cane, as well as • Venturia species (scab) in apples and pears.

The compounds I are also suitable for combating noxious fungi, such as Paecilomyces variotii, in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.

The compounds I are applied, treating fungi or plants, seeds, materials or the soil to be protected against a fungal infection with an active fungicidal amount of the active ingredients. The application can be made before or after the infection of the materials, plants or seeds by fungi Generally, the fungicidal products contain between 0.1 and 95, preferably, 0.5 and 90% by weight of active ingredient.

When used in the protection of plants, the application amounts vary from 0.01 to 2.0 kg of active ingredient per ha, depending on the type of effect desired.

In the treatment of the seeds, the amounts of active ingredient of 1 to 1000 g / 100 kilograms of seeds, preferably from 1 to 200 g / 100 kg, especially 5 to 100/100 kg, are generally required.

In the protection of stored materials or products, the amount of active ingredient application depends on the nature of the application and the desired effect.

The application amounts generally used for the protection of materials vary, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active ingredient per cubic meter of the treated material.

The compounds I can be transformed into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. The form of application depends on the respective purpose, but in any case a fine and uniform dispersion of the compound according to the invention must be ensured.

The formulations are prepared in known manner, for example, by diluting the active principle with solvents and / or supports, if desired, using emulsifiers and dispersants. As solvents / auxiliary substances, substantially, for this purpose: - water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone) , gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acids. Basically, solvent mixtures can also be used, - support substances, such as powders of natural stones (eg kaolins, clays, talc, chalk) and synthetic stone powders (eg highly disperse silicic acid, silicates); emulsifiers, such as non-ionogenic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants, such as sulphite residual liquors and methylcellulose.

Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of lignin sulphonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutyl naphthalene sulfonic acid, alkylaryl sulphonates, alkyl sulfates, alkyl sulfonate, fatty alcohol sulfates, fatty acids and fatty alcohol glycol ethers sulphonates, in addition, sulfonated naphthalene condensates and naphthalene derivatives with formaldehyde, naphthalene or naphthalene sulfonic acid condensates with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl- polyglycol ether, polyether alkylaryl alcohols, alcohol and fatty alcohol condensates / ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, polyglycol ether acetal lauryl alcohol, sorbitol esters, lignin residual liquors o-sulphites and methylcellouose.

Suitable substances for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are: fractions of mineral oil from medium boiling point to high, such as eg kerosene or diesel oil, in addition, coal tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives , methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example, dimethyl sulfoxide, N-methylpyrrolidone and water.

Powders, spraying and spraying agents can be prepared by mixing or grinding together the active substances with a solid support.

Granules (eg coated, impregnated or homogeneous granules) can be prepared by joining the active ingredient with a solid support, hexyl solid charges are: mineral earth, such as silica gel, silicic acid, silica gel, silicates, talc, kaolin , limestone, lime, bol, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics, as well as fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, bark, wood and nut skins, cellulose powders or other solid supports.

Generally, the formulations contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of the active principle. The active ingredients are used in a purity of 90% to 100%, preferably, 95% to 100% (according to NMR spectrum). Examples of formulations are: 1. Products for dilution with water A) Water soluble concentrates (SL) parts by weight of the active ingredients are dissolved in water or in a water-soluble solvent. Alternatively, humectants or other auxiliaries may be added. The active ingredient dissolves when it is diluted with water.

B) Dispersible concentrates (DC) parts by weight of the active ingredients are dissolved in cyclohexanone by adding a dispersant, for example, polyvinylpyrrolidone. Diluting with water, a dispersion is obtained.

C) Emulsifiable concentrates (EC) parts by weight of the active ingredients are dissolved in xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% respectively). Diluting with water, an emulsion is obtained.

D) Emulsions (EW, EO) 40 parts by weight of the active ingredients are dissolved in xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% respectively). This mixture is introduced into water by means of an emulsifier (Ultraturrax) and transformed into a homogeneous emulsion. Diluting with water, an emulsion is obtained.

E) Suspensions (SC, OD) In a ball mill, 20 parts by weight of the active ingredients are comminuted by adding a dispersant, humectant and water or an organic solvent, obtaining a fine suspension of active ingredient. By diluting with water, a stable suspension of the active ingredient is obtained.

F) Granules dispersible in water and granules soluble in water (WG, SG) 50 parts by weight of the active ingredients are ground finely, adding dispersants and humectants, and transformed into water-dispersible or water-soluble granulates by technical des (eg, extruder, spray tower, fluidized bed). By diluting with water, a dispersion or stable solution of the active principle is obtained.

G) Dispersible powders in water and water soluble powders (WP, SP) 75 parts by weight of the active ingredients are ground in a rotor-stator mill adding dispersant, humectants and silica gel. Diluting with water, a stable dispersion or solution is obtained with the active principle. 2. Products for direct application H) Sprayable powders (DP) parts by weight of the active ingredients are finely ground and intimately mixed with 95% of a finely divided kaolin. A sprayable powder is obtained.

I) Granules (GR, FG, GG, MG) 0.5 parts by weight of the active ingredients are ground finely and associated with 95.5% support. Current methods are: extrusion, spray drying and fluidized bed. Granules are obtained that can be applied without dilution.

J) Ultra low volume solutions (UL) parts by weight of the active ingredients are dissolved in an organic solvent, for example xylene. You get a product that can be applied without dilution The active ingredients can be used as such, in the form of their formulations or the forms of application prepared therefrom, for example, as solutions, powders, suspensions or dispersions, emulsions, directly sprayable oil dispersions, pastes, sprayable powders. , spraying agent or watering agent. The forms of application depend entirely on the purpose of application, but in any case it is necessary to ensure a distribution as fine as possible of the active ingredients according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, substances can be homogenized as such or dissolved in an oil or solvent in water with the aid of a humectant, adhesion promoter, dispersant or emulsifier. Alternatively, concentrates composed of the active substance, wetting agent, tackifier, dispersant or emulsifier, if appropriate, solvent or oil, can be prepared and such concentrates are suitable to be diluted with water.

The active substance concentrations in ready-to-use preparations can vary widely. In general, they vary from 0.0001 to 10%, preferably from 0.01 to 1%.

The active ingredients can also be used successfully in the ultra low volume (ULV) process, formulations with more than 95% by weight of active ingredient, or even the active ingredient without additives, can be applied.

Several types of oil, humectants, adjuvants, herbicides, fungicides or other pesticides or bactericides can be added to the active ingredients, if necessary, just before application (tank mixture). These agents can be mixed with the agents according to the invention in a weight ratio of 1:10 to 10: 1.

When used as fungicides, the fungicides of the invention may also be present together with other active ingredients, for example, with herbicides, insecticides, growth regulators, fungicides or other fertilizers. When the compounds I or the compositions according to the invention are mixed as fungicides with other fungicides, then the spectrum of action is often extended.

The following list of fungicides with which the compounds according to the invention can be mixed serves to illustrate the possible combinations, but is not to be construed as limiting: • acylalanines, such as benalaxyl, matalaxyl, ofurace, oxadixyl, • amine derivatives, such as aldimorf, dodine, dodemorf, phenpropimorf, fenpropidin, guazatin, iminoctadine, esprixamine, tridemorph, • anilinopyrimidines, such as pyrimethanil, mepanipyrim or cyprodinil, • antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, • azoles, such as bitertanol, bromoconazole, ciproconazole, diphenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, metconazole, myclobutanil , penconazole, propiconazole, prochloraz, protioconazole, tebuconazole, triadimefonone, triadimenol, triflumizole, triticonazole, • dicarboximides, such as iprodione, myclozoline, procymidone, vinclozoline, • dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram, zineb, • heterocyclic compounds, such as anilazine, benomyl, boscalide, carbendazim, carboxime, oxycarboxine, cysophamide, dazomet, dithianone , famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpir, isoprothiolane, mepronil, nuarimol, probenazole, proquinazide, pirifenox, pyroquilone, quinoxifene, silthiopham, thiabendazole, trifluzamide, thiophanate-methyl, thiadinyl, tricyclazole, triforin, • copper fungicides, such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate, • nitrophenyl derivatives, such as binapacriio, dinocap, dinobutone, nitroftal- isopropyl, • phenylpyrroles, such as fenpiclonil or fludioxonil, • sulfur • other fungicides, such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonyl, cyflufenamide, cymoxanil, dazomet ,. diclomezine, diclocimet, dietofencarb, edifenfos, etaboxam, fenhexamida, fentina-acetate, fenoxanilo, ferimzona, fluazinam, fosetilo, fosetilo-aluminum, provalicarb, hexachlorobenzene, metrafenona, pencicurona, propamocarb, ftalida, toloclofos-methyl, quintozeno, zoxamida, • strobilurins, such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, methominostrobin, orisastrobin, picostrobin, pyraclostrobin or trifloxystrobin, • sulfenic acid derivatives, such as captafol, captan, diclofluanide, folpet, tolylfluanide, • cinnamic acid amides and the like, such as dimetomorf, flumetover or flumorf.

Synthesis examples The prescriptions indicated in the following synthesis examples can be used, the starting compounds varying correspondingly, for the generation of other compounds 1. The compounds thus obtained are indicated in the following Tables with their physical data.

Example 1: Preparation of diethyl 2-chloro-5-fluorophenylmalonate A suspension of sodium hydride (0.51 mol) in 140 ml of 1,4-dioxane was mixed at about 60 ° C for two hours with diethyl malonate. After stirring for another 10 minutes, 0.05 mol of CuBr was added. After 15 min 0.25 mol of 2-chloro-5-fluorobromobenzene in 10 ml of dioxane was added. The reaction mixture was maintained approx. 14 hours at 100 ° C, then mixed at approx. 15 ° C slowly with 35 ml of 12N hydrochloric acid. The precipitate was filtered and the filtrate was extracted with diethyl ether. After separation of the phases, the organic phase was dried and then freed from the solvent. 42 g of the compound indicated in the title remained.

Example 2: Preparation of 5,7-dihydroxy-6- (2-chloro-5-fluorophenylphenyl) - [1, 2,4] -triazolo [1,5-a] -pyrimidine A mixture of 12 g 3-amino-1,2,4-triazole, 0.17 mol of the ester of Example 1 and 50 ml of tributylamine (50 ml) was stirred for approximately six hours at 180 ° C. At approx. 70 ° C a mixture of 21 g of NaOH in 200 ml of water was added and the mixture was stirred for another 30 min. The organic phase was separated and the aqueous phase was extracted with diethyl ether. The product was precipitated from the aqueous phase after acidification with concentrated hydrochloric acid. By fitration they obtained 33 g of the compound indicated in the title.

Example 3: Preparation of 5,7-dichloro-6- (2-chloro-5-fluorophenyl) - [1, 2,4] -triazolo [1,5-a] -pyrimidine A mixture of 30 g of the triazolopyrimidine of Example 2 and 50 ml of POCI3 was heated for eight hours under reflux, with a little bit of POCI3 ab distilled off. The residue was poured into a mixture of CH2Cl2-water, the organic phase was separated, washed and dried and then the solvent was removed. 27 g of the compound indicated in the title of p.p. of 137 ° C.

Example 4: Preparation of 5-chloro-6- (2-chloro-5-fluorophenyl) -7-but-2-ylamino- [1, 2,4] -triazolo [1, 5-a] pyrimidine [I-3 ] A solution of 1.5 mmol of the product of Example 3 in 10 ml of dichloromethane was mixed under stirring with a solution of 1.5 mmol of 2-butylamine, 1.5 mmol of triethylamine in 10 ml of dichloromethane. The reaction mixture was stirred for approx. 16 hours at 20 to 25 ° C and then washed with dilute hydrochloric acid. The organic phase was separated, dried and freed from the solvent. After chromatography on silica gel, 35 mg of the compound indicated in the title of m.p. from 171 ° C.

HPLC / MS: HPLC column: RP-18 (Chromolith Speed ROD, Fa.Merck KgaA, Germany); eluent: acetonitrile + 0.1% trifluoroacetic acid (TFA) / water + 0.1% TFA in gradients of 5:95 - 95: 5 (5 min) / 40 ° C. MS: Quadrupol Elektrospray lonization, 80 V (positive mode) The fungicidal effect of the compounds of the formula I can be demonstrated by the following tests: The active ingredients were prepared as a stock solution with 25 mg of active ingredient, which was completed with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (humectant with emulsifying and dispersing effect based on ethoxylated alkylphenols) in the volume ratio of solvent: emulsionate of 99: ad 10 ml. Next, it was completed with water ad 100 ml. This stock solution was diluted with the solvent-emulsifier-water mixture at the concentration of active principle indicated below.

Application example 1: Efficiency against early tomato wilt caused by Alternaria solani The leaves of plants grown in pots of the variety "Goldene Prinzessin" were sprayed until they dripped with an aqueous suspension of the active substance concentration indicated below. The next day the leaves were infected with an aqueous spore suspension of Alternaria solani in 2% biomalt solution with a density of 0.17 x 106 spores / ml. Next, the plants were placed in a chamber saturated with water vapor at temperatures between 20 and 22 ° C. After 5 days, the disease had developed so strongly in untreated but infected control plants that the infestation could be visually determined in percent.

In this test plants treated with 63 ppm compounds 1-3, 1-13, 1-15, I-23 to 1-35, 1-38, or I-39 an infection of, at most, 20 %, while untreated plants were infected by up to 80%.

Application example 2: Healing effect against wheat rust caused by recondite Puccinia The leaves of wheat seedlings grown in pots of the "Kanzler" variety were inoculated with a suspension of spores of rust (Puccinia recondita). Next, the pots were placed for 24 hours in a chamber with high humidity (90 to 95%) and 20 to 22 ° C. During this time the spores germinated and the germ tubes penetrated the tissue of the leaves. The next day, the infected plants were sprayed with an aqueous suspension of the concentration in active principle below indi - vidual. The suspension or emulsion was prepared in the manner described above. Once the sprayed layer was dry, the test plants were grown for 7 days in the greenhouse at temperatures between 20 and 22 ° C and 65 to 70% relative humidity of the air. Then the development of the fungus on the leaves was determined.

In this test they presented the plants treated with 63 ppm of compounds 1-3, 1-13, 1-15, 1-16, 1-18 to 1-21, 1-23 to I-27, I-29, 1 -34 to I-39, or I-40 an infection of, at most, 20%, while untreated plants were infected by up to 85 to 90%.

Claims (16)

Claims

1. Triazolopyrimidines of the formula wherein the substituents have the following meanings: R \ R2 signify, independently, hydrogen, CrC8 alkyl, CrC8 haloalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C2-C8 alkenyl, C2-C8 haloalkenyl, C3-C6 cycloalkenyl, C3-C6 haloalkylcycloalkenyl, C2-C8 alkynyl, C2-C8 haloalkynyl or phenyl, naphthyl, or a saturated, partially unsaturated or aromatic heterocycle with five or six members, containing one to four heteroatoms of the group: O, N or S, R1 and R2 can also form together with the nitrogen atom, to which they are attached, a heterocyclyl or heteroaryl having five or six members, which is linked by means of N and can contain one to three additional heteroatoms of the group: O, N and S as ring members and / or contain one or more substituents of the group: halogen, CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, CrC6 alkoxy, CrC6 haloalkoxy, C3-C6 alkenyloxy, C3-C6 haloalkenyloxy, alkylene C C6 and oxy-alkylenoxy CrC3; R1 and / or R2 can carry one to four equal or different Ra groups: Ra is halogen, cyano, nitro, hydroxy, CrC6 alkyl, C6 halogenalkyl, CrC6 alkylcarbonyl, C3-Ce cycloalkyl, C1-C6 alkoxy, CrC6 halo-alkoxy, CrC6 alkoxycarbonyl, CrC6 alkylthio, CrC6 alkylamino, CrC6 di-alkylamino , C2-C8 alkenyl, C2-C8 haloalkenyl, C3-C8 cycloalkenyl, C2-C6 alkenyloxy, C3-C6 haloalkenyloxy, C2-C8 alkynyl, C2-C8 haloalkynyl, C3-C6 alkynyloxy > C3-C6 haloalkyloxy, C3-C6 cycloalkoxy, C3-C6 cycloalkeneoxy, CrC3 oxyalkyleneoxy, phenyl, naphthyl, saturated, partially unsaturated or aromatic heterocyclic of five or ten members, containing one to four heteroatoms of the group: O, N or S, these aliphatic, alicyclic or aromatic groups may in turn be partially or completely halogenated or carry one to three Rb groups, Rb is halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkyllio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, the alkyl groups containing in these radicals 1 to 6 carbon atoms and the alkenyl or alkynyl groups mentioned in these radicals 2 to 8 carbon atoms; and / or one to three of the following radicals: cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, the cyclic systems being able to contain 3 to 10 ring members; aryl, aryloxy, arylthio, aryl-alkoxy CrC6, aryl-alkyl CrC6, hetaryl, hetaryloxy, hetarylthio, the aryl radicals preferably containing 6 to 10 ring members, hetaryl radicals 5 or 6 ring members, cyclic systems being able to be partially or completely halogenated or substituted by alkyl or haloalkyl groups; L1 is fluorine, chlorine or bromine; L2 is hydrogen, C4 alkyl or C4 alkoxy; Y X is halogen, cyano, CrC alkyl, haloalkyl CrC4, alkoxy CrC4 or halogenalkoxy C C2.

2. Compounds of the formula I according to claim 1, wherein L2 means hydrogen.

3. Compounds of the formula I according to claim 1, wherein L2 means alkyl or alkoxy.

4. Compounds of the formula I according to one of claims 1 to 3, wherein L 1 means fluorine.

5. Compounds of the formula I according to one of claims 1 to 3, wherein L 1 means chlorine.

6. . Compounds of the formula 1 according to one of claims 1 to 5, wherein R 1 does not mean hydrogen.

7. Compounds of the formula I according to one of claims 1 to 6, wherein X means chlorine.

8. Compounds of the formula 1.1: wherein G means C2-C6 alkyl, CrC alkoxymethyl or C3-C6 cycloalkyl; R2 is hydrogen or methyl and X is chloro, methyl, cyano, methoxy or ethoxy and L1 and L2 have the definitions according to one of claims 1 to 5.

Compounds of formula 1.2: where D forms together with the nitrogen atom a heterocyclyl or heteroaryl of five or six members, which is linked by means of N and which contains another additional heteroatom of the group: O, N and S as ring members, and / or carries one or various substituents of the group: halogen, C, C4 alkyl, CrC4 alkoxy and C, C2 haloalkyl; X is chloro, methyl, cyano, methoxy or ethoxy and L1 and L2 according to the definitions according to one of claims 1 to 5.

10. Compounds of the formula I.3: where Y is hydrogen or C C4 alkyl; X means chlorine, methyl, cyano, methoxy or ethoxy and L1 and L2 have the definitions according to one of claims 1 to 5.

11. Process for the preparation of the compounds of formula I according to one of claims 1 or 3, wherein X means halogen, cyano, CrC 4 alkyl, CrC 4 alkoxy or C 2 haloalkoxy, by reaction of 5-aminotriazole of the formula with phenyl malonates of the formula where R means alkyl, in dihydroxytriazolopyrimidines of formula IV, halogenation in the dihalogen compounds of the formula V, and transformation of V with amines of the formula VI in compounds of the formula I, wherein X means halogen, if desired for the preparation of compounds I, in which X means cyano, alkoxy, C C4 or halogenoalakoxy CrC2, transformation of compounds I, in which X means halogen, with compounds of the formula Vil, MX 'Vil which, depending on the group X 'to be incorporated, is an inorganic cyanide, an alkoxylate or a haloalkoxylate and where M represents an ammonium, tetraalkylammonium, alkali metal or alkaline earth metal cation and, if desired for the preparation of compounds of the formula I according to formula 1, wherein X means alkyl, by reaction of the compounds I, in which X represents halogen, with malonates of the formula HIV, where X "means hydrogen or CrC3 alkyl and R means CrC alkyl, giving compounds of formula IX and decarboxylation in compounds I, wherein X means alkyl.

12. Process for the preparation of the compounds of formula I according to one of claims 1 to 3, wherein X means C 4 alkyl or haloalkyl Cr C, by reaction of 5-aminotriazole of formula II according to claim 11 with keto esters of the formula Illa, wherein X 1 means C 4 alkyl or C 1 -C 4 haloalkyl and R means C-C alkyl, in 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines of the formula IVa halogenation of IV a in 7-halogenotriazoiopyrimidines of the formula and transformation of Va with amines of the formula VI according to claim 11 in the compounds I.

13. Compounds of formulas IV, IVa, V and Va according to claims 11 and 12.

14. Fungicidal product, which contains a solid or liquid support and a compound of the formula I according to one of claims 1 to 7.

15. Seeds, containing 1 to 1000 g of a compound of formula I according to one of claims 1 to 3 per 100 kg.

16. Process for combating phytopathogenic fungi, characterized in that fungi or materials, plants, soils or seeds to be protected against fungal infection are treated with an active amount of a compound of formula I according to claims 1 to 7. Summary Substituted triazolopyrimidines of the formula wherein the substituents have the following meanings: R1, R2 is alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, cycloalkenyl, halogenocycloalkenyl, alkynyl, haloalkynyl or phenyl, naphthyl, or a saturated, partially unsaturated or aromatic heterocycle with five or six members, containing one to four heteroatoms of the group: O, N or S, R1 and R2 can also form together with the nitrogen atom, to which they are attached, a heterocyclyl or heteroaryl having five or six members, which is linked by means of N and which may contain one to three additional heteroatoms of the group: O, N and S as ring members and may be substituted according to the description; L means fluorine, chlorine or bromine; L2 means hydrogen, alkyl or alkoxy; Y X means halogen, cyano, alkyl, haloalkyl, alkoxy or haloalkoxy; procedure and intermediate products for the preparation of these compounds, products that contain them, as well as their use to combat phytopathogenic noxious fungi Summary Substituted triazolopyrimidines of the formula I wherein the substituents have the following meanings: R1, R2 is alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, cycloalkenyl, halogenocycloalkenyl, alkynyl, haloalkynyl or phenyl, naphthyl, or a saturated, partially unsaturated or aromatic heterocycle with five or six members, containing one to four heteroatoms of the group: O, N or S, R1 and R2 can also form together with the nitrogen atom, to which they are attached, a heterocyclyl or heteroaryl having five or six members, which is linked by means of N and which may contain one to three additional heteroatoms of the group: O, N and S as ring members and may be substituted according to the description; L1 means fluorine, chlorine or bromine; L2 means hydrogen, alkyl or alkoxy; Y X means halogen, cyano, alkyl, haloalkyl, alkoxy or haloalkoxy; procedure and intermediate products for the preparation of these compounds, products that contain them, as well as their use to combat phytopathogenic noxious fungi