+

WO2007006723A1 - Composes de 7-amino-6-tetrazolyl-1,2,4-triazolo[1,5-a]pyrimidine et utilisation de ceux-ci pour lutter contre des champignons nuisibles - Google Patents

Composes de 7-amino-6-tetrazolyl-1,2,4-triazolo[1,5-a]pyrimidine et utilisation de ceux-ci pour lutter contre des champignons nuisibles Download PDF

Info

Publication number
WO2007006723A1
WO2007006723A1 PCT/EP2006/063969 EP2006063969W WO2007006723A1 WO 2007006723 A1 WO2007006723 A1 WO 2007006723A1 EP 2006063969 W EP2006063969 W EP 2006063969W WO 2007006723 A1 WO2007006723 A1 WO 2007006723A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
formula
compounds
methyl
halogen
Prior art date
Application number
PCT/EP2006/063969
Other languages
German (de)
English (en)
Inventor
Oliver Wagner
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2007006723A1 publication Critical patent/WO2007006723A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

Definitions

  • the present invention relates to 7-amino-6-tetrazolyl-1, 2,4-triazolo [1, 5-a] pyrimidines of the formula (I)
  • Het is tetrazolyl which is unsubstituted or substituted by one or two identical or different substituents L:
  • n 0, 1 or 2;
  • a 1 is hydrogen, hydroxy, (Ci-C 8) -alkyl, (Ci-C 8) haloalkyl,
  • a 2 is one of the groups mentioned under A 1 or (C 2 -C 8 ) -alkenyl, (C 2 -
  • R 5, R 6 are independently hydrogen, (Ci-C 8) -alkyl, (Ci-C 8) - haloalkyl, (C 2 -Cs) -alkyl keny I, (C 2 -C 8) -haloalkenyl, (C 2 -C 8 ) - Alkynyl, (C2-C8) -haloalkynyl, (C 3 -C 8) -cycloalkyl, (C 3 -C 8) - halocycloalkyl, (C3-C8) cycloalkenyl, or (C 3 -C 8) halo- cycloalkenyl,
  • R L is halogen, cyano, (C 1 -C 8 ) -alkoxy, (C 2 -C 8 ) -alkenyloxy, (C 2 -C 8 ) -alkinyloxy, (C 3 -C 8 ) -cycloalkyl, (C 3 -C 8) cycloalkenyl, (C 3 -C 8) - cycloalkoxy, (C 3 -C 8) -cycloalkenyloxy, (Ci-C 8) -Alkoximino- (Ci-C 8) -Alkoximino- (Ci-C 8)
  • R 1, R 2 are independently hydrogen, (Ci-C 8) -alkyl, (Ci-C8) alkyl-halo, (C 2 -Cs) -alkyl keny I, (C 2 -C 8) -haloalkenyl, (C 2 -Cs) -alkyl kiny I, (C 2 -C 8) - haloalkynyl, (C4-Cio) alkadienyl, (C4-Cio) -Halogenalkadienyl, (Ci-C8) - alkoxy, (Ci-C 8 ) -haloalkoxy, (C 2 -C 8 ) -alkenyloxy, (C 2 -C 8 ) -haloalkenyloxy, (C 2 -Cs) -alkyloxy, (C 2 -C 8 ) -haloalkynyloxy, (C 3 -C 8 ) -cycloal
  • R 1 and R 2 may also together with the nitrogen atom to which they are attached form a five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one, two or three further heteroatoms from the group O, N and S as ring members , in which
  • R 1 and / or R 2 or a heterocycle formed from R 1 and R 2 may carry one, two, three or four identical or different groups R a and / or two substituents bound to adjacent ring atoms for (Ci-C 6 ) alkylene , Oxy- (C 2 -C 4 ) -alkylene or oxy- (C 1 -C 3 ) -alkyleneoxy; where R a means:
  • R a is halogen, cyano, nitro, hydroxy, carboxyl, amino (C 1 -C 8 ) -alkyl, (d-
  • C 8 ) -haloalkyl (C 2 -Cs) -alkene I, (C 2 -C 8 ) -haloalkenyl, (C 2 -C 8 ) -alkynyl, (C 2 -C 8 ) -haloalkynyl, (C 4 -C) alkadienyl, (C 1 -C 8 ) -alkoxy,
  • R a may in turn carry one, two or three identical or different groups R b :
  • R b is halogen, cyano, nitro, hydroxy, carboxyl, mercapto, amino, formyl, aminocarbonyl, aminothiocarbonyl, (C 1 -C 8 ) -alkyl, (C 1 -C 8 ) -haloalkyl, (C 2 -Cs) -alkylene I , (C 2 -C 8 ) -haloalkenyl, (C 4 -C 10) -alkadienyl, (C 2 -Cs) -alkynyl, (C 2 -Cs) -haloalkynyl, (C 1 -C 8 ) -
  • the present invention relates to compositions containing at least one of the compounds according to the invention, processes for the preparation of these compounds, intermediates for the preparation of the compounds and the agriculturally acceptable salts thereof, the preparation of the intermediates and the use of the compounds according to the invention for controlling phytopathogenic fungi ,
  • the compounds of the formula (I) can have one or more centers of chirality and are then present as enantiomer or diastereomer mixtures.
  • the invention relates to both the pure enantiomers or diastereomers or rotamers and mixtures thereof.
  • Suitable compounds of formula (I) also include all possible stereoisomers (cis / trans isomers) and mixtures thereof.
  • the compounds according to the invention can be present in various crystal modifications which may differ in their biological activity. They are also the subject of the present invention.
  • EP-A 613 900 is directed to 7-amino-1,2,4-triazolo [1,5-a] pyrimidine compounds and their use as fungicides. These compounds may have in the 6-position an optionally substituted cycloalkyl ring or a heterocyclic group.
  • a heterocyclic group means a 3- to 6-, preferably 5- to 6-membered ring system.
  • a thien-3-yl residue is disclosed as the heterocyclyl residue at position 6.
  • WO 01/96341 discloses intermediates of the formula (II) which are used to prepare fungicidally active triazolopyrimidine-7-ylideneamines.
  • the intermediates have in position 6 a phenyl, cycloalkyl or a five- or six-membered heteroaryl group.
  • WO 01/96314 discloses intermediates of the formula (II) which are used to prepare fungicidally active 2- (cyanoamino) pyrimidines.
  • a phenyl, cycloalkyl or a 5- or 6-membered heteroaryl group may be present.
  • WO 04/011467 is directed to 1, 2,4-triazolo [1, 5-a] pyrinnidines which have in the 6-position a 5- or 6-membered heterocyclyl group which optionally substituted pyrrolyl, thienyl, pyrazolyl, imidazolyl, Oxazolyl, isoxazolyl, thiazolyl, isothiazolyl or pyrimidinyl.
  • WO 04/108727 discloses 1, 2,4-triazolo [1, 5a] pyrimidines and their use for controlling undesirable microorganisms. Position 6 of the pyrimidine ring is substituted by either a pyridyl or a pyrimidyl group.
  • WO 04/113342 relates to 1, 2,4-triazolo [1, 5a] pyrimidines.
  • position 6 there is a 5- or 6-membered heterocyclyl group having 1 to 4 heteroatoms such as nitrogen, oxygen and / or sulfur, pyridyl, pyrimidyl, thienyl and thiazolyl being preferred as Heterocyclylrest.
  • 1,2,4-triazolo [1,5-a] pyrimidines known from the prior art are in some cases unsatisfactory with regard to their fungicidal activity or have undesirable properties, such as low crop tolerance.
  • the present invention is therefore based on the object to provide new compounds with better fungicidal activity and / or better crop compatibility.
  • suitable agriculturally acceptable salts are, in particular, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the fungicidal action of the compounds according to the invention.
  • the ions of the alkali metals preferably sodium or potassium, the alkaline earth metals, preferably calcium, magnesium or barium, the transition metals, preferably manganese, copper, zinc or iron, or the ammonium ion, the desired one to four (Ci-C4 ) Alkyl substituents and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably Tn- (C 1 -C 4) -alkylsulfonium and sulfoxonium ions, preferably tri (Ci -C4) -alkylsulfoxonium, into consideration.
  • the alkali metals preferably sodium or potassium
  • the alkaline earth metals preferably calcium, magnesium or barium
  • the transition metals preferably manganese,
  • Anions of advantageously usable acid addition salts are, for example, chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of (C 1 -C 4) -alkanoic acids, preferably formate , Acetate, propionate and butyrate. You can by reaction of the invention
  • the method at temperatures ranging from 0 ° C to 7O 0 C, preferably 1O 0 C to 35 0 C.
  • the reaction is preferably carried out in an inert solvent, for example an ether, e.g. Dioxane, diethyl ether, diisopropyl ether, tert-butyl methyl ether or especially tetrahydrofuran, a halogenated hydrocarbon such as dichloromethane or dichloroethane or an aromatic hydrocarbon such as toluene or o-, m-, p-xylene or in a mixture of the aforementioned solvents.
  • an ether e.g. Dioxane, diethyl ether, diisopropyl ether, tert-butyl methyl ether or especially tetrahydrofuran
  • a halogenated hydrocarbon such as dichloromethane or dichloroethane or an aromatic hydrocarbon such as toluene or o-, m-, p-xylene or in a mixture of the aforementioned solvents.
  • a base such as, for example, tertiary amines, in particular triethylamine, biscyclohexylmethylamine, pyridine, picoline or inorganic bases, such as potassium carbonate.
  • a base such as, for example, tertiary amines, in particular triethylamine, biscyclohexylmethylamine, pyridine, picoline or inorganic bases, such as potassium carbonate.
  • Excess amine H2NR 1 can also serve as a base.
  • the amines HNR 1 R 2 used in this process are generally commercially available or can be prepared by methods well known to those skilled in the art.
  • Another object of the present invention are compounds of the formula (II)
  • Hal is halogen and Het and Y have the meanings given for compounds of the formula (I).
  • Hal is preferably chlorine or bromine.
  • Particularly preferred compounds of the formula (I) according to the invention can be obtained starting from compounds of the formula (II) in which Het and Y have the meanings given in Tables 1 to 24.
  • 5,7-Dihalogentriazolopyrimidines of the formula (II) can be obtained, for example, by reacting the corresponding 5,7-dihydroxytriazolopyrimidine of the formula (III)
  • Phosphorus (V) halide such as phosphorus pentachloride, phosphorus oxybromide or phosphorus oxychlorid or a mixture of phosphorus oxychloride and phosphorus pentachloride used.
  • reaction of the compounds of the formula (III) with the halogenating agent is usually carried out at 0 ° C. to 150 ° C., preferably at 80 ° C. to 125 ° C. [cf. also EP-A 770 615].
  • the reaction may be carried out in bulk or in an inert solvent, e.g. a halogenated hydrocarbon, such as dichloromethane, dichloroethane or an aromatic hydrocarbon, such as toluene or o-, m-, p-xylene or in a mixture of said solvents.
  • a halogenated hydrocarbon such as dichloromethane, dichloroethane or an aromatic hydrocarbon, such as toluene or o-, m-, p-xylene or in a mixture of said solvents.
  • Another object of the present invention are compounds of formula (IM) wherein Het and Y have the meanings given for compounds of the formula (I).
  • Particularly preferred compounds of the formula (I) according to the invention can be obtained starting from compounds of the formula (III) (via the corresponding compounds of the formula (M)) in which Het and Y have the meanings given in Tables 1 to 24.
  • 5,7-Dihydroxytriazolopyrimidines of the formula (III) can be prepared in various ways, for example in analogy to those described in Adv. Het. Chem. Vol. 57, p. 81ff. (1993).
  • 5,7-dihydroxytriazolopyrimidines of the formula (III) can be prepared by reacting the corresponding hepatoeroaroarylmalonate of the formula (IV)
  • Het is as defined for formula (I) and R is alkyl, preferably (C 1 -C 4) -alkyl, in particular methyl or ethyl.
  • the reaction of 3-amino-1, 2,4-triazole (V) with a Heteroarylmalonat (IV) is usually carried out at temperatures of 80 0 C to 250 0 C, preferably from 120 0 C to 180 0 C.
  • the reaction is carried out without solvent, or an inert organic solvent is used.
  • a base may be preferred [cf. EP-A 770 615].
  • it may also be preferred to carry out the reaction in the presence of acetic acid under conditions well known to those skilled in the art.
  • Suitable solvents are, for example, aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, ethers, nitriles, ketones, alcohols, and N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide and dimethylacetamide.
  • the reaction is particularly preferably carried out without a solvent or in chlorobenzene, xylene, dimethyl sulfoxide or N-methylpyrrolidone. It is also possible to use mixtures of the solvents mentioned.
  • catalytic amounts of acids such as p-toluenesulfonic acid, acetic acid or propionic acid, may also be added.
  • Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates and alkali metal bicarbonates, such as potassium carbonate, organometallic compounds, in particular alkali metal alkyls, alkylmagnesium halides and alkali metal and alkaline earth metal alkoxides and dimethoxymagnesium , also organic bases, eg tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particular preference is given to using tertiary amines, such
  • the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the base and the heteroarylmalonate (IV) in excess, based on the 3-amino-1, 2,4-triazole (V).
  • Another object of the present invention are compounds of the formula
  • Particularly preferred compounds of the formula (I) according to the invention can be obtained starting from compounds of the formula (IV) (via the corresponding compounds of the formula (III) or (M)) in which Het 5-methyltetrazol-1-yl, 5-methyltetrazole 2-yl, 5-chlorotetrazol-1-yl, 5-chlorotetrazol-2-yl, 5-bromotetrazol-1-yl, 5-bromotetrazol-2-yl, 1-methyltetrazol-5-yl or 2-methyltetrazole-5 -yl means.
  • Heteroarylmalonates of the formula (IV) can be prepared starting from heteroaryl compounds of the formula (VI) Het Rz / CH 2 (VI) by reaction with one or two equivalents of a Kohlenquipreesters or
  • R z being hydrogen or a (C 1 -C 4 ) -alkoxycarbonyl group, Het having the meanings given for formula (I), Q being halogen or (C 1 -C 4 ) -alkoxy, in particular methoxy or ethoxy, and R is (Ci-C 4 ) alkyl.
  • the reaction described above is usually carried out in the presence of strong bases.
  • R z is hydrogen
  • alkali metal amides such as sodium amide or lithium diisopropylamide, or lithium organic compounds such as phenyl lithium or butyl lithium as base. In this case, one will use the base at least equimolar, based on the compound (VI) in order to achieve complete conversion.
  • R z is hydrogen
  • the reaction of the compound (VI) with compounds of the formula (VII) can be carried out in one stage or in two separate stages, in which latter case the intermediate (VI) is obtained in which R z is an alkoxycarbonyl group.
  • the reaction of compound (VI) with (VII) can be carried out analogously to the method described in J. Med. Chem. 25, 1982, p. 745.
  • R z is an alkoxycarbonyl group
  • an alkali metal alcoholate for example sodium or potassium ethanolate, sodium or potassium butoxide, sodium or potassium methoxide as the base.
  • malonates of the formula (IV) is also advantageously achieved by reaction of corresponding bromine heteroaryl compounds Br-Het with dialkyl malonates under Cu (I) catalysis [cf. Chemistry Letters, pp. 367-370, 1981; EP-A 10 02 788].
  • Z in the compounds ZY is a cation
  • Y is hydroxide, cyanide, (Ci-CeJ-alkoxylate, (Ci-C ⁇ J-haloalkoxylate or (Ci-C ⁇ J-alkylthiolate, in the compounds ZY so it depends on the group to be introduced a hydroxide, inorganic cyanide (such as KCN, NH 4 CN), a (halo) alkoxylate or a thiolate
  • the cation Z is of minor importance and may be of various types, for practical reasons usually ammonium, tetraalkyl - Ammonium salts such as tetramethylammonium or tetraethylammonium salts or alkali or alkaline earth metal salts are preferred.
  • the reaction with Z-Y is preferably carried out in an inert solvent.
  • suitable solvents include ethers such as dioxane, diethyl ether, methyl tert-butyl ether and, preferably tetrahydrofuran, halogenated hydrocarbons such as dichloromethane or dichloroethane, aromatic hydrocarbons such as toluene, and mixtures thereof.
  • the reaction temperature is usually 0 to 120 ° C., preferably 10 to 40 ° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].
  • reaction mixtures resulting from the preparation of the compounds of formula (I) or intermediates thereof can be worked up in conventional manner, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products.
  • the intermediate and end products are z.T. in the form of colorless or pale brownish, viscous oils, which can be freed from volatile constituents under reduced pressure and at moderately elevated temperature or purified. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
  • Halogen fluorine, chlorine, bromine or iodine
  • Alkyl and the alkyl moieties in assembled groups saturated, straight-chain or branched hydrocarbon radicals.
  • the alkyl radicals are preferably (C 1 -C 8 ) -alkyl, in particular (C 1 -C 6) -alkyl radicals.
  • it may be preferable to use short-chain alkyl groups such as (C 1 -C 4) -alkyl, but it may also be advantageous to use longer-chain alkyl groups such as (Cs-Cs) -AlkVl.
  • alkyl groups which are preferred according to the invention are 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
  • Haloalkyl alkyl as defined above, wherein in these groups at least one of the hydrogen atoms or all the hydrogen atoms are replaced by halogen atoms as defined above.
  • the alkyl groups are substituted at least once or completely by a particular halogen atom, preferably fluoro, chloro or bromo. In a further embodiment, the alkyl groups are partially or completely halogenated by various halogen atoms; for mixed halogen substitutions, the combination of chlorine and fluorine is preferred.
  • Examples of preferred mixed-substituted haloalkyl radicals are chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl.
  • Alkenyl and the alkenyl moieties in assembled groups monounsaturated, straight-chain or branched hydrocarbon radicals with one double bond in any position.
  • Preferred are (C 2 -C 8 ) -alkenyl radicals, more preferably (C 4 -C 6 ) -alkenyl radicals.
  • alkenyl groups are ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3
  • Pentenyl 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl 2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl , 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4 Methyl
  • Haloalkenyl alkenyl as defined above, wherein in these groups at least one of the hydrogen atoms or all the hydrogen atoms are replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Alkadienyl diunsaturated, straight-chain or branched hydrocarbon radicals having two double bonds in any positions, but not adjacent. Preference is given to (C 4 -C 10) -alkadienyl radicals, more preferably (C 6 -C 8 ) -alkadienyl radicals.
  • alkadienyl radicals are 1, 3-butadienyl, 1-methyl-1, 3-butadienyl, 2-methyl-1,3-butadienyl, penta-1,3-dien-1-yl, hexa-1,4-diene 1-yl, hexa-1, 4-dien-3-yl, hexa-1, 4-dien-6-yl, hexa-1, 5-dien-1-yl, hexa-1, 5-diene-3 -yl, hexa-1, 5-dien-4-yl, hepta-1, 4-dien-i-yl, hepta-1, 4-dien-3-yl, hepta-1, 4-dien-6-yl , Hepta-1, 4-dien-7-yl, hepta-1, 5-dien-1-yl, hepta-1, 5-dien-3-yl, hepta-1, 5-dien-4-yl, hepta -1, 5-dien-7
  • Haloalkadienyl alkadienyl as defined above, wherein in these groups at least one of the hydrogen atoms or all the hydrogen atoms is replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Alkynyl and the alkynyl moieties in assembled groups straight-chain or branched hydrocarbon radicals of one or two triple bonds in any, but not adjacent position.
  • Preferred are (C 2 -C 8) -alkynyl radicals, more preferably (C 4 -C 6) -alkynyl radicals.
  • Preferred alkynyl radicals are: ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3 pentynyl, 2-methyl-4-pentyny
  • Haloalkynyl alkynyl, as defined above, wherein in these groups at least one of the hydrogen atoms or all are replaced by halogen atoms, as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Cycloalkyl and the cycloalkyl parts in composite groups monocyclic, saturated hydrocarbon groups.
  • Preferred are (C 3 -C 8 ) -cycloalkyl radicals, more preferred are (C 4 -C 6 ) -cycloalkyl radicals.
  • Examples of preferred cycloalkyl radicals are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
  • Halogencycloalkyl cycloalkyl as defined above, wherein in these groups at least one of the hydrogen atoms or all hydrogen atoms are replaced by halogen atoms, as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Cycloalkenyl and the cycloalkenyl moieties in assembled groups monocyclic monounsaturated hydrocarbon radicals with one double bond in any position. Preference is given to (C 3 -C 8 ) -cycloalkenyl, furthermore preferred are (C 5 -C 6 ) -cycloalkenyl.
  • Examples of preferred cycloalkenyl radicals are cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl;
  • Halocycloalkenyl cycloalkenyl as defined above, wherein in these groups at least one of the hydrogen atoms or all the hydrogen atoms are replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Bicycloalkyl bicyclic hydrocarbon radical, with (C5-Cio) -bicycloalkyl being preferred. Also preferred are (C7-C9) -Bicycloalkylreste.
  • bicycloalkyl radicals examples include bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] -hept-2-yl, bicyclo [2.2.1] hept-7-yl, bicyclo [2.2.2] octyl 1-yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.3.0] octyl, bicyclo [4.4.0] decyl;
  • Halogenbicycloalkyl bicycloalkyl, as defined above, wherein in these groups at least one of the hydrogen atoms or all the hydrogen atoms are replaced by halogen atoms, as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Alkoxy for an alkyl group bonded via an oxygen atom as defined above. Preference is given to (C 1 -C 6 -alkoxy radicals, furthermore preferred being (C 2 -C 6) -alkoxy radicals.
  • alkoxy radicals are: methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethyl propoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy;
  • Haloalkoxy Alkoxy, as defined above, wherein in these groups at least one of the hydrogen atoms or all hydrogen atoms are replaced by halogen atoms, as described above under haloalkyl, in particular fluorine, chlorine or bromine.
  • haloalkoxy groups such as (Ci- C4) -haloalkoxy to use
  • relatively long haloalkoxy groups such as (C 5 -C 8) -haloalkoxy use.
  • Examples of preferred short-chain halogenoalkoxy radicals are OCH 2 F, OCHF 2 , OCF 3 , OCH 2 Cl, OCHCl 2 , OCCl 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2- Difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC 2 F 5, 2- Fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromo
  • haloalkoxy radicals are 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;
  • Alkenyloxy Alkenyl as defined above, which is bonded via an oxygen atom. Preferred are (C 2 -Cs) -alkhenyloxy, more preferably (C 3 -C 6) -alkenyloxy. In the present invention, it may be preferable to use short-chain alkenyloxy groups such as (C 2 -C 4) alkenyloxy, but on the other hand, it may also be preferable to use longer-chain alkenyloxy groups such as (C 5 -C 8) alkenyloxy.
  • alkenyloxy radicals are 1-propenyloxy, 2-propenyloxy, 1-methyl-ethenyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-1-propenyloxy, 2-methyl-1-propenyloxy, 1-methyl 2-propenyloxy, 2-methyl-2-propenyloxy, 1-pentenyl-oxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-1-butenyloxy, 2-methyl-1-butenyloxy, 3-methyl 1-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, 1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3 -butenyloxy, 1-ethyl, 1, 1-dimethyl-2-propenyloxy, 1, 2-dimethyl-1-propenyloxy, 1, 2-dimethyl-2 propenyloxy
  • Haloalkenyloxy alkenyloxy as defined above, wherein in these groups at least one of the hydrogen atoms or all the hydrogen atoms is replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Alkynyloxy Alkynyl as mentioned above, which is bonded via an oxygen atom. Preference is given to (C 2 -C 8) -alkynyloxy radicals, furthermore preferably (C 3 -C 6) -alkynyloxy radicals. In the present invention, it may be preferable to use short chain alkynyloxy groups such as (C 2 -C 4 ) alkynyloxy, but on the other hand, it may also be preferable to use longer chain alkynyloxy groups such as (C 5 -C 8 ) alkynyloxy.
  • alkynyloxy radicals are 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-2-butynyl-oxy, 1-methyl 3-butynyloxy, 2-methyl-3-butynyloxy, 1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl-3 pentynyloxy;
  • Haloalkynyloxy alkynyloxy as defined above, wherein in these groups at least one of the hydrogen atoms or all the hydrogen atoms is replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Alkylene divalent linear chains of CH 2 groups. Preference is given to (C 1 -C 6 ) -alkylene, more preferably (C 2 -C 4 ) -alkylene, and furthermore it may be preferable to use (C 1 -C 3 ) -alkylene groups.
  • Examples of preferred alkylene radicals are CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 (CH 2 J 2 CH 2 , CH 2 (CH 2 ) 3 CH 2 and CH 2 (CH 2 ) 4 CH 2 ;
  • Oxyalkylene Alkylene, as defined above, wherein a valence is bonded to the skeleton via an oxygen atom. Examples of preferred oxyalkylene radicals are OCH 2 , OCH 2 CH 2 , OCH 2 CH 2 CH 2 and OCH 2 (CH 2 ) 2 CH 2 ;
  • Oxyalkyleneoxy alkylene as defined above wherein both valencies are above
  • Oxygen atom are bonded to the skeleton.
  • Examples of preferred oxyalkyleneoxy radicals are OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O.
  • Alkylthio Alkyl as defined above attached via an S atom.
  • Alkylsulfinyl alkyl as defined above bonded through an SO group.
  • Alkylsulfonyl Alkyl as defined above attached via an S (O) 2 group.
  • Aryl aromatic hydrocarbon radical, preference being given to (C 6 -C 4 ) -aryl radicals and (C 6 -C 10) -aryl radicals being particularly preferred.
  • Examples of preferred aryl radicals are phenyl, naphthyl and anthryl.
  • aryl radicals may be substituted by at least one halogen atom or completely by halogen atoms as defined above. According to the invention it may be advantageous to use haloaryl groups, wherein aryl is as defined above. Particularly preferred may be halophenyl and halonaphthyl.
  • Aryloxy Aryl as defined above, wherein the aryl radical is bonded to the skeleton via an oxygen atom.
  • Arylthio aryl, as defined above, wherein the aryl radical is linked to the skeleton via a sulfur atom.
  • the heterocycle is preferably a five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and S, as defined below.
  • the respective heterocycle may be attached via a carbon atom or via a nitrogen atom, if present. It may be preferred according to the invention that the respective heterocycle is bonded via carbon, on the other hand it may also be preferred that the heterocycle is bonded via nitrogen. Examples of five- to ten-membered heterocycles are:
  • heterocycles containing one, two, three or four heteroatoms from the group oxygen, nitrogen and sulfur as ring members: for example, mono- and bicyclic heterocycles with 7
  • Ring members containing in addition to carbon ring members one to three nitrogen atoms and / or an oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, for example tetra- and Hexahydroazepinyl such as 2,3,4 I 5-tetrahydro [1 H] azepine-1 - I -2-, -3-, -A-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro [2H] azepine-2-, -3-, -A-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro [1 H] azepine-1,
  • heterocyclyl Five- or six-membered saturated or partially unsaturated heterocycle (hereinafter also heterocyclyl) containing one, two, three or four heteroatoms from the group oxygen, nitrogen and sulfur as ring members: for example, monocyclic saturated or partially unsaturated heterocycles containing in addition to carbon ring members up 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, A-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidiny
  • aromatic heterocycle is attached via nitrogen. Examples are:
  • Nitrogen atoms and / or a sulfur or oxygen atom 5-membered heteroaryl groups, which besides carbon atoms may contain one to four nitrogen atoms or one to three nitrogen atoms and / or one sulfur or oxygen atom as ring members, e.g.
  • carbon-bonded 5-membered heteroaryl groups may be preferred, containing one to three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members.
  • Examples of these are: 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxa zolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thia- zolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2, 4-thiadiazol-5-yl, 1, 2,4-triazol-3-yl, 1, 3,4-
  • carbon-bonded five-membered heteroaryl groups containing an oxygen atom or a sulfur atom such as 2-furyl, 3-furyl, 2-thienyl, 3-thienyl;
  • nitrogen-bonded 5-membered heteroaryl groups containing one to three nitrogen atoms as ring members, for example pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl, 1,2,3-triazole 1-yl, 1,2,4-triazol-1-yl and 1-tetrazolyl;
  • 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-membered ring heteroaryl groups, which in addition to carbon atoms may contain one to three or one to four nitrogen atoms as ring members, e.g. Pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,2,3-triazinyl, 1, 2,4-triazinyl, 1, 3,5-triazinyl, especially 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4 Pyridazinyl, 2-
  • Heteroaryloxy Heteroaryl, as defined above, wherein the heteroaryl radical is bonded to the skeleton via an oxygen atom.
  • Heteroarylthio heteroaryl as defined above, wherein the heteroaryl radical is linked to the skeleton via a sulfur atom.
  • the (R) and (S) isomers or rotomers and racemates are comprised of compounds of formula (I) having chiral centers.
  • the compounds according to the invention can be present in various crystal modifications which may differ in their biological activity. They are also the subject of the present invention.
  • the following meanings of the substituents in each case alone or in combination, are particularly preferred.
  • the preferred substituents or preferred combinations of substituents apply correspondingly to the precursors of the compounds of the formula (I):
  • the compounds of the present invention are characterized by having at the 6-position an optionally substituted tetrazolyl radical which may be linked to the triazolopyrimidine skeleton via a ring carbon or via a ring nitrogen.
  • Preferred het are tetrazol-1-yl, tetrazol-2-yl and tetrazol-5-yl.
  • the tetrazolyl group may preferably contain one or two identical or different substituents L, preferably identical substituents L, wherein L is as defined above. Het most preferably contains a substituent L.
  • L is particularly preferably each selected from halogen, cyano, nitro, (C 1 -C 4 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 4 ) -cycloalkoxy, -COO (C 1 -C 4 ), -CONH 2 or -CSNH 2 ;
  • L is particularly preferably methyl, ethyl, isopropyl, cyclopropyl, fluorine, chlorine, bromine, iodine, COOCH.sub.3 or CN.
  • het has one, two or three identical or different substituents L selected from halogen, cyano, nitro, amino, (C 1 -C 6) -alkylamino, di (C 1 -C 6) -alkylamino , (Ci-C 6) -alkyl, (Ci-C 6) -haloalkyl, (Ci-C 6) alkoxy, (Ci-C 6) -haloalkoxy, NH (CO) - (Ci-C 6) alkyl , C (S) A 2 and C (O) A 2 , wherein A 2 has the abovementioned meanings and preferably (C 1 -C 4 ) -alkoxy, NH 2 , (C 1 -C 4 ) -alkylamino or di (Ci C 4 ) alkylamino.
  • substituents L selected from halogen, cyano, nitro, amino, (C 1 -C 6) -alkyla
  • L are selected from fluorine, chlorine, bromine, cyano, nitro, (d- C4) alkyl, (Ci-C 4) -haloalkyl, (Ci-C 4) alkoxy and (Ci-C 4) - Alkylcarbonyl, particularly preferably fluorine, chlorine, (C 1 -C 2 ) -alkyl, such as methyl or ethyl, (C 1 -C 2 ) -fluoroalkyl, such as trifluoroalkyl, (C 1 -C 2 ) -alkoxy, such as methoxy, or (C 1 -C 2 ) Alkoxycarbonyl such as methoxycarbonyl.
  • Het has a substituent which is ortho to the point of attachment to the framework to which Het is bound.
  • the ortho-position L is fluorine, chlorine, (C 1 -C 2 ) -alkyl, such as methyl or ethyl, (C 1 -C 2 ) -fluoroalkyl, such as trifluoroalkyl or (C 1 -C 2 ) -alkoxy, such as methoxy.
  • L when L is bonded to a ring nitrogen of Het, it is particularly preferred that L each independently is
  • L is (Ci-C ⁇ J alkyl or (Ci-C6) haloalkyl, more preferably (Ci C 4) alkyl or (Ci-C 4) -haloalkyl, in particular methyl or ethyl, particularly preferably Methyl.
  • L is independently:
  • a 1 is amino, (Ci-C 6) -alkyl, (Ci-C 6) -haloalkyl, (Ci-C 6) alkylamino or
  • n 0, 1 or 2;
  • R 5 , R 6 are independently hydrogen or (Ci-C ⁇ J-alkyl, (Ci-C ⁇ ) - haloalkyl, (C 2 -C 8 ) -haloalkenyl, (C 2 -C 8 ) -alkynyl, (C 2 -C 8 ) - haloalkynyl, (C 3 -C 8 -) - cycloalkyl, (C 3 -C 8 -) - halocycloalkyl, (C 3 - C 8 ) -cycloalkenyl or (C 3 -C 8 ) -halocycloalkenyl.
  • L when it is bonded to a ring nitrogen of Het, in each case particularly preferably (C 1 -C 4 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, -COO (C 1 -C 4 ), -CONH 2 or -CSNH 2 , in particular methyl, ethyl, isopropyl, cyclopropyl or -COOCH 3.
  • R 2 is hydrogen.
  • R 2 is hydrogen and R 1 is other than hydrogen.
  • at least one of R 1 and R 2 is other than hydrogen.
  • Equally preferred are compounds of formula (I) in which R 1 and R 2 are different from hydrogen. Preferred among these are compounds of the formula (I) in which R 2 is (C 1 -C 4 ) -alkyl, especially methyl or ethyl.
  • R 1 and R 2 are both hydrogen
  • R 1 is straight-chain or branched, unsubstituted or substituted (C 1 -C 5) -alkyl, (C 1 -C 5) -haloalkyl, (C 2 -C 5) -alkylene I, (C 2 - Cs) -Al kiny I, (C3-Cs) -cycloalkyl, unsubstituted or substituted phenyl or naphthyl or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N and p.
  • R 1 is, in particular (Ci-C 6) -alkyl, (C2 -Ce) -Al keny I, (C 2 -Ce) -Al kiny I, (C 3 -C 6) - cycloalkyl, where these radicals 1 , 2, 3, 4 or 5 times by halogen, (Ci-C 6 ) -alkyl or (Ci-C 6 ) -haloalkyl may be substituted.
  • a particularly preferred embodiment relates to compounds of
  • Z 1 is hydrogen, fluorine or (C 1 -C 4 ) -fluoroalkyl
  • Z 2 is hydrogen or fluorine, or Z 1 and Z 2 together form a double bond; q is 0 or 1; and R 7 is hydrogen or methyl.
  • compounds of the formula (I) in which R 1 is (C 3 -C 6) -cycloalkyl which may be substituted by (C 1 -C 4 ) -alkyl are furthermore particularly preferred.
  • R 1 and R 2 together with the nitrogen atom to which they are bonded represent saturated or monounsaturated, in particular 5 or 6-membered heterocyclyl, as defined above.
  • R 1 and R 2 together with the nitrogen atom to which they are attached are optionally substituted
  • heterocyclyl is unsubstituted or substituted by 1, 2 or 3 substituents R a , with preferred substituents R a of heterocyclyl being selected from halogen, (C 1 -C 4) -alkyl and (C 1 -C 4) -haloalkyl.
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a 4-methylpiperidine ring, a 4-trifluoromethylpiperidine ring, a morpholine ring or a 3,4-dimethylpiperidine ring and especially a 4-methylpiperidine ring Methyl piperidine ring or a 3,4-dimethylpiperidine ring.
  • R 1 and R 2 together with the nitrogen atom to which they are attached, are 5- or 6-membered heteroaryl as defined above, which may be unsubstituted or substituted , preferably by 1, 2 or 3 groups R a .
  • the group NR 1 R 2 forms a pyrazole ring which is optionally substituted in the manner described above and especially by 1 or 2 of the following radicals: halogen, (Ci-C 4 ) alkyl or (Ci-C 4 ) -haloalkyl , in particular by 2 methyl groups or two trifluoromethyl groups in the 3,5-position.
  • X has the meanings given above.
  • X is hydrogen, halogen, (Ci-C 4) alkoxy, (Ci-C 4) -haloalkoxy, cyano, (Ci-C 4) alkylthio, (Ci-C 4) alkylsulfinyl or (Ci-C 4 is ) alkylsulfoxyl.
  • X is particularly preferably halogen, (C 1 -C 4 ) -alkoxy, in particular methoxy, halomethoxy or ethoxy, or cyano.
  • X is halogen, in particular fluorine, chlorine or bromine, preferably chlorine.
  • X is (C 1 -C 5) -alkoxy or (C 1 -C 6 -halogenoalkoxy, preferably (C 1 -C 4 -alkoxy or (C 1 -C 4 ) -halogenoalkoxy, in particular methoxy or ethoxy.
  • X is cyano
  • Y is preferably hydrogen, halogen, preferably fluorine, chlorine or bromine, (Ci-C 4) alkyl, (Ci-C4) - haloalkyl, (C 3 - C 6 ) -cycloalkyl or (C 3 -C 6 ) -halocycloalkyl.
  • Y is halogen, preferably fluorine, chlorine or bromine.
  • Y is (Ci-C 4) -alkyl or (Ci-C 4) haloalkyl, preferably (Ci-C 2) alkyl or (Ci-C 2) - haloalkyl, in particular methyl or Ethyl, which may be substituted by one, two or three halogen atoms.
  • Y is (C 3 -C 6 ) -cycloalkyl or (C 3 -C 6 ) -halocycloalkyl, particularly preferably cyclopropyl or halocyclopropyl, which may carry one to three halogen atoms.
  • Y is hydrogen
  • R 5 and R 6 independently of one another are preferably hydrogen or (C 1 -C 4 ) -alkyl.
  • a 1 is preferably hydrogen, (C 1 -C 6 -alkyl or amino.
  • the index n is preferably 0, 1 or 2.
  • a 2 is preferably (C 1 -C 4 ) -alkoxy, NH 2 , (C 1 -C 4 ) -alkylamine or di- (C 1 -C 4 ) -alkylamino.
  • Examples of preferred compounds of the formula (I) are the compounds (Ia), (Ib), (Ic), (Id), (Ie) and (If) which are compiled in the following Tables 1 to 24.
  • the groups mentioned in Tables 1 to 24 for a substituent Het are also individually considered, independently of the combination in which they are mentioned, a particularly preferred embodiment of the relevant substituent.
  • Table 4 corresponds to compounds of the formula (Ia), (Ib), (Ic), (Id), (Ie) and (If) in which X is chlorine and Het is 5-chlorotetrazol-1-yl and the combination of R 1 and R 2 for a compound in each case one row of Table B, Table 4 corresponds to compounds of the formula (Ia), (Ib), (Ic), (Id), (Ie) and (If) in which X is chlorine and Het
  • Het 5-methyltetrazol-1-yl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table B.
  • Chlortetrazol-1-yl and the combination of R 1 and R 2 for each compound corresponds to one row of Table B corresponds to Table 12
  • Table 12 Compounds of the formula (Ia), (Ib), (Ic), (Id), (Ie) and (If) where X CN and Het 5
  • Chlortetrazol-2-yl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table B corresponds to Table 13
  • Bromtetrazol-2-yl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table B.
  • the compounds I and / or their agriculturally acceptable salts are useful as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, Basidiomycetes and Peronosporomycetes (syn. Oomycetes). They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.
  • Cochliobolus species on corn, cereals, rice e.g. Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice
  • Drechslera species Pyrenophora species on maize, cereals, rice and turf, e.g. D.teres to barley or D. tritici-repentis to wheat
  • Fusarium and Verticillium species on various plants e.g. F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of plants, e.g. tomatoes
  • Peronospora species on cabbage and bulbous plants such as P. brassicae on cabbage or P. destructor on onion • Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans
  • Phytophthora species on various plants e.g. P.capsici on paprika
  • Pseudoperonospora on various plants e.g. P. cubensis on cucumber or P. humili on hops
  • Puccinia species on various plants e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals, or P. asparagi on asparagus
  • Venturia species scab
  • apples and pears like. e.g. V. inaequalis to apple.
  • the compounds of formula (I) may also be used in cultures tolerant of insect or fungal growth by breeding, including genetic engineering methods.
  • Another object of the present invention is therefore the use of the inventive 7-amino-6-heteroaryl-1, 2-4-triazolo [1, 5-a] pyrimidines of the formula (I) and / or their agriculturally acceptable salts for controlling phytopathogenic fungi.
  • the compounds I and / or their agriculturally acceptable salts are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. in the
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .
  • Basidiomycetes such as Coniophora
  • Tyromyces spp. Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.
  • the compounds I and / or their agriculturally acceptable salts are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of Treated drugs.
  • the application can take place both before and after the infection of the materials, plants or sannen by the mushrooms.
  • Another object of the present invention is therefore a method for combating phytopathogenic fungi, which is characterized in that the fungi or the fungal infection to be protected materials, plants, the soil or seeds with an effective amount of at least one compound of the invention Formula (I) and / or an agriculturally acceptable salt thereof.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.
  • the application rates in the application in crop protection depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.
  • Seed treatment generally requires amounts of active substance of 1 to 1000 g / 100 kg, preferably 1 to 200 g / 100 kg, in particular 5 to 100 g / 100 kg of seed.
  • Another object of the present invention is therefore seed, comprising a compound of formula (I) in an amount of 1 to 1000 g per 100 kg.
  • the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.
  • a further subject of the present invention is an agent for controlling phytopathogenic fungi comprising at least one compound of the formula (I) according to the invention and / or an agriculturally acceptable salt thereof and at least one solid or liquid carrier.
  • the compounds of the formula I and / or their agriculturally acceptable salts can be present in various crystal modifications, which may differ in their biological activity. They are also the subject of the present invention.
  • the compounds I and / or their agriculturally acceptable salts can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, e.g. by stretching the active compound with solvents and / or excipients, if desired under
  • Suitable solvents / auxiliaries are essentially:
  • Aromade e.g., Solvesso products, xylene
  • paraffins e.g., petroleum fractions
  • alcohols e.g., methanol, butanol, pentanol, benzyl alcohol
  • ketones e.g., cyclohexanone, gamma-butyrolactone
  • NMP pyrrolidones
  • glycol diacetate glycol diacetate
  • dimethyl fatty acid amides dimethyl fatty acid amides
  • fatty acids fatty acid esters.
  • solvent mixtures can also be used
  • Carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates);
  • ground natural minerals e.g., kaolins, clays, talc, chalk
  • ground synthetic minerals e.g., fumed 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 liquors and methyl cellulose.
  • nonionic and anionic emulsifiers e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates
  • dispersants such as lignin liquors and methyl cellulose.
  • the surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
  • Granules for example coated, impregnated and homogeneous granules, can be prepared by binding the active compounds 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, bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • 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
  • the formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • formulations are: 1. Products for dilution in water
  • a Water-soluble concentrates (SL, LS)
  • DC Dispersible Concentrates
  • the active ingredients 20 parts by weight of the active ingredients are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.
  • the active ingredient content in the formulation is 20% by weight.
  • Water-dispersible and water-soluble granules 50 parts by weight of the active compounds are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the formulation has an active ingredient content of 50% by weight.
  • Water-dispersible and water-soluble powders 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the active ingredient content of the formulation is 75% by weight.
  • LS water-soluble concentrates
  • FS suspensions
  • DS dusts
  • WS water-dispersible and water-soluble powders
  • ES emulsions
  • EC emulsifiable concentrates
  • gel formulations GF
  • the active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, litter, granules by spraying, misting, dusting, scattering or pouring.
  • the forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume
  • wetting agents eg. Break Thru S 240 ®
  • Alcohol alkoxylates eg. As Atplus 245 ®, Atplus MBA 1303 ®, Plurafac LF 300 ® and Lutensol ON 30 ®
  • EO-PO block polymers eg. B.
  • Pluronic RPE 2035 ® and Genapol B ® Alcohol ethoxylates, eg. As Lutensol XP 80 ®; and sodium dioctylsulfosuccinate, e.g. B. Leophen RA ®.
  • the compounds of the invention may also be present in the application form as fungicides together with other active substances, e.g. with herbicides, insecticides, growth regulators, fungicides or with fertilizers.
  • active substances e.g. with herbicides, insecticides, growth regulators, fungicides or with fertilizers.
  • fungicides for example, in many cases, the activity spectrum can be broadened or development of resistance can be prevented. In many cases, synergistic effects are obtained.
  • Another object of the present invention is a combination of at least one compound of the invention of the formula (I) and / or an agriculturally acceptable salt thereof and at least one further fungicidal, insecticidal, herbicidal and / or growth-regulating active ingredient.
  • fungicides with which the compounds according to the invention can be used together is intended to illustrate but not limit the possible combinations: strobilurins azoxystrobin, dimoxystrobin, enestroburine, fluoxastrobin, kresoxim-methyl,
  • Metominostrobin picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-chloro-5- [1- (6-methyl -pyridin-2-ylmethoxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, 2- (ortho- (2,5-dimethylphenyl-oxymethylene) -phenyl) -3-methoxy-acrylic acid methyl ester; carboxamides
  • Benzoic acid amides flumetover, fluopicolide (picobenzamide), zoxamide; - Other carboxamides: carpropamide, diclocymet, mandipropamide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonyl-amino- 3-methyl-butyramide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl) -ethyl) -2-ethanesulfonyl-amino-3-methyl- butyrannid; azoles
  • Triazoles Bitertanol, Bromuconazole, Cyproconazole, Difenoconazole, Diniconazole, Enilconazole, Epoxiconazole, Fenbuconazole, Flusilazole, Fluquinconazole, Flutriafol, Hexaconazole, Imibenconazole, Ipconazole, Metconazole, Myclobutanil, Penconazole, Propiconazole, Prothioconazole, Simeconazole, Tebuconazole, Tetraconazole, Triadimenol, Triadimefon , Triticonazole;
  • - imidazoles cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole;
  • Benzimidazoles benomyl, carbendazim, fuberidazole, thiabendazole;
  • Pyrimidines bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil;
  • - piperazines triforins
  • - Pyrroles fludioxonil, fenpiclonil
  • Dicarboximides iprodione, procymidone, vinclozolin;
  • guanidines dodine, iminoctadine, guazatine
  • Organometallic compounds fentin salts
  • Sulfur-containing heterocyclyl compounds isoprothiolanes, dithianone
  • Organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and their salts;
  • Organochlorine compounds thiophanates methyl, chlorothalonil, dichlofluanid, tolylfluanid, flusulfamides, phthalides, hexachlorobenzene, pencycuron, quintozene;
  • Nitrophenyl derivatives binapacryl, dinocap, dinobuton;
  • the present invention relates to the pharmaceutical use of the compounds of the formula (I) according to the invention and / or the pharmaceutically acceptable salts thereof, in particular their use for the treatment of tumors in mammals, such as in humans.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

La présente invention concerne des composés de 7-amino-6-tétrazolyl-1,2,4-triazolo[1,5-a]pyrimidine de formule (I) dans laquelle Het, R1, R2, X et Y ont les significations définies dans la description.
PCT/EP2006/063969 2005-07-13 2006-07-06 Composes de 7-amino-6-tetrazolyl-1,2,4-triazolo[1,5-a]pyrimidine et utilisation de ceux-ci pour lutter contre des champignons nuisibles WO2007006723A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005033159.9 2005-07-13
DE102005033159 2005-07-13

Publications (1)

Publication Number Publication Date
WO2007006723A1 true WO2007006723A1 (fr) 2007-01-18

Family

ID=37012052

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/063969 WO2007006723A1 (fr) 2005-07-13 2006-07-06 Composes de 7-amino-6-tetrazolyl-1,2,4-triazolo[1,5-a]pyrimidine et utilisation de ceux-ci pour lutter contre des champignons nuisibles

Country Status (1)

Country Link
WO (1) WO2007006723A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002050077A2 (fr) * 2000-12-18 2002-06-27 Bayer Cropscience Ag Triazolopyrimidines
WO2004011467A1 (fr) * 2002-07-29 2004-02-05 Hokko Chemical Industry Co., Ltd. Derives de triazolopyrimidine et fongicides utilises dans l'agriculture et l'horticulture
WO2004108727A1 (fr) * 2003-06-04 2004-12-16 Bayer Cropscience Aktiengesellschaft Triazolopyrimidines
WO2004113342A1 (fr) * 2003-06-25 2004-12-29 Bayer Cropscience Aktiengesellschaft Triazolopyrimidines
WO2006066799A1 (fr) * 2004-12-17 2006-06-29 Basf Aktiengesellschaft 7-amino-6-heteroaryl-1,2,4-triazolo[1,5-a]pyrimidines et leur utilisation pour lutter contre les champignons pathogenes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002050077A2 (fr) * 2000-12-18 2002-06-27 Bayer Cropscience Ag Triazolopyrimidines
WO2004011467A1 (fr) * 2002-07-29 2004-02-05 Hokko Chemical Industry Co., Ltd. Derives de triazolopyrimidine et fongicides utilises dans l'agriculture et l'horticulture
WO2004108727A1 (fr) * 2003-06-04 2004-12-16 Bayer Cropscience Aktiengesellschaft Triazolopyrimidines
WO2004113342A1 (fr) * 2003-06-25 2004-12-29 Bayer Cropscience Aktiengesellschaft Triazolopyrimidines
WO2006066799A1 (fr) * 2004-12-17 2006-06-29 Basf Aktiengesellschaft 7-amino-6-heteroaryl-1,2,4-triazolo[1,5-a]pyrimidines et leur utilisation pour lutter contre les champignons pathogenes

Similar Documents

Publication Publication Date Title
WO2008015250A1 (fr) Composés de pyrimidine pour la lutte contre les champignons nuisibles et le cancer
EP1648890A2 (fr) Composes de 3-arylpyridine arylcondenses et leur utilisation pour lutter contre des champignons pathogenes
WO2007012642A1 (fr) Composes de 7-amino-6-thiadiazolyl- et -oxadiazolyl- 1, 2, 4-triazolo [1, 5 -a] pyrimidine et leur utilisation pour lutter contre les champignons nuisibles
WO2007036477A1 (fr) Hydroxylaminopyrimidines 2-substituees, procede permettant de les produire et leur utilisation comme pesticide
WO2007023018A1 (fr) Composes 7-amino-6-triazolyl-1,2,4-triazolo[1,5-a]pyrimidine et utilisation dans la lutte contre des champignons parasites
WO2007023020A1 (fr) Composes 7-amino-6-heteroaryl-1,2,4-triazolo[1,5-a]pyrimidine et utilisation dans la lutte contre des champignons parasites
WO2007093527A1 (fr) Pyrimidines substituées en position 2 et leur utilisation comme pesticides
EP1828191A2 (fr) 7-amino-6-hetaryl-1,2,4-triazolo[1,5-a]pyrimidines et leur utilisation pour lutter contre des champignons nuisibles
EP1620436A1 (fr) Composes heterocycliques utilises en tant que fongicides
WO2007006724A1 (fr) Composes de 5-alkyl-7-amino-6-heteroaryl-1,2,4-triazolo[1,5-a]pyrimidine et utilisation de ceux-ci pour lutter contre des champignons nuisibles
EP1828190A1 (fr) 7-amino-6-heteroaryl-1,2,4-triazoloý1,5-a¨pyrimidines et leur utilisation pour lutter contre les champignons pathogenes
WO2007006723A1 (fr) Composes de 7-amino-6-tetrazolyl-1,2,4-triazolo[1,5-a]pyrimidine et utilisation de ceux-ci pour lutter contre des champignons nuisibles
WO2007118844A1 (fr) Pyrazolopyrimidines substituées, leur procédé de préparation, leur utilisation pour lutter contre les champignons nuisibles, et agents les contenant
EP1891015A1 (fr) 5-hydroxypyrazolines fongicides, procede de production de ces composes et agents contenant lesdits composes
WO2008107398A2 (fr) Composés de pyrazine
WO2007006722A1 (fr) Composes de 7-amino-6-heteroaryl-1,2,4-triazolo[1,5-a]pyrimidine 2-substitues et utilisation de ceux-ci pour lutter contre des champignons nuisibles
EP1761544A1 (fr) Composes tirazolopyrimidine et leur utilisation pour lutter contre des champignons nuisibles
EP1797097A1 (fr) Composes 7-aminomethyl-1,2,4-triazolo[1,5-a]pyrimidine et leur utilisation pour lutter contre des champignons nuisibles
EP1895845A1 (fr) Utilisation de 5-hydroxypyrazolines fongicides, procede de fabrication et agents contenant ces composes
WO2006122740A2 (fr) 7-amino-6-hetarylimidazolo[1,2-a]pyrimidines et leur utilisation pour lutter contre des champignons nuisibles
EP1751162A1 (fr) Composes triazolopyrimidine et leur utilisation pour reguler des champignons pathogenes
DE102007012627A1 (de) Substituierte Imidazolopyrimidine, Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung von Schadpilzen sowie sie enthaltende Mittel
EP2117312A1 (fr) Utilisation d'azolopyrimidines pour la lutte contre des champignons parasites phytopathogenes
EP1758906A2 (fr) 1, 2, 4-triazolo[1,5a]pyrimidines et leur utilisation pour lutter contre des champignons pathogenes des plantes
WO2007054472A1 (fr) Derive de pyridine et de pyrimidine, leur procede de fabrication et leur utilisation en tant que pesticides

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06777615

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载