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

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

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Publication number
EP1689750A1
EP1689750A1 EP04797968A EP04797968A EP1689750A1 EP 1689750 A1 EP1689750 A1 EP 1689750A1 EP 04797968 A EP04797968 A EP 04797968A EP 04797968 A EP04797968 A EP 04797968A EP 1689750 A1 EP1689750 A1 EP 1689750A1
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EP
European Patent Office
Prior art keywords
formula
compounds
alkyl
methyl
cyano
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP04797968A
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German (de)
French (fr)
Inventor
Jordi Tormo I Blasco
Carsten Blettner
Bernd Müller
Markus Gewehr
Wassilios Grammenos
Thomas Grote
Joachim Rheinheimer
Peter Schäfer
Frank Schieweck
Anja Schwögler
Oliver Wagner
Maria Scherer
Siegfried Strathmann
Ulrich Schöfl
Reinhard Stierl
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BASF SE
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BASF SE
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Application filed by BASF SE filed Critical BASF SE
Publication of EP1689750A1 publication Critical patent/EP1689750A1/en
Withdrawn legal-status Critical Current

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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 6- (2,4,6-trifluorophenyl) triazolopyrimidines of the formula I.
  • R 2 is hydrogen or one of the groups mentioned for R 1 ,
  • R 1 and R 2 together with the nitrogen atom to which they are attached can also form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contain a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, -C-C ⁇ - alkyl, d-C ⁇ -haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C Ce alkoxy, dC ⁇ -haloalkoxy , C 3 -C ⁇ -alkenyloxy, C 3 -C 6 -haloalkenyloxy, CrC 6 -alkylene and oxy-dC 3 -alkyleneoxy can carry;
  • R 1 and / or R 2 can carry one to four identical or different groups R a : R a halogen, cyano, nitro, hydroxyl, dC 6 -alkyl, Ci-C ⁇ -haloalkyl, dC 6 - alkylcarbonyl, C 3 -C ⁇ -Cycloalkyl, dC 6 -alkoxy, Ci-C ⁇ -haloalkoxy, dC ⁇ - alkoxycarbonyl, dC 6 -alkylthio, C C ⁇ -alkylamino, di-Ci-C ⁇ -alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 -Alkenyloxy, C 3 -C ⁇ -alkynyloxy, oxy-CrC 3 -alkyleneoxy, C 3 -C ⁇ -cycloalkyl, phenyl, naphthyl, five- or six-membered saturated, partially unsatur
  • the invention relates to a process for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.
  • 5-Halogen-6- (2,4,6-trifluorophenyl) triazolopyrimidines are generally known from WO 98/46607.
  • 5-cyano- and 5-alkoxy-triazolopyrimidines are disclosed in WO 02/083677.
  • Triazolopyrimidines with optically active amino substituents in the 7-position are generally proposed in WO 02/38565.
  • the present invention is based on the object of providing compounds with improved activity and / or broadened activity spectrum.
  • the compounds according to the invention differ from those described in the abovementioned document by the substitution in the 5-position of the triazolopyrimidine skeleton.
  • the compounds of the formula I have an increased activity or a broader spectrum of activity against harmful fungi than the known compounds.
  • the compounds according to the invention can be obtained in various ways. They are advantageously obtained starting from the 5-halo-6- (2,4,6-trifluorophenyl) triazolopyrimidines of the formula II known from WO 98/98/46607 by reaction with compounds MX (formula III). Depending on the meaning of the group X to be introduced, compounds III represent an inorganic cyanide or an alkoxylate. The reaction is advantageously carried out in the presence of an inert solvent.
  • the cation M in formula III is of little importance; for practical reasons, Ammonium, tetraalkylammonium or alkali or alkaline earth metal salts are preferred.
  • the reaction temperature is usually from 0 to 120 ° C., preferably from 10 to 40 ° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].
  • R 2 is hydrogen
  • a removable protective group is advantageously introduced before reaction with III [cf. Greene, Protective Groups in Organic Chemistry, J. Willey & Sons, (1981)].
  • Suitable solvents include ethers such as dioxane, diethyl ether and, preferably tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene or acetonitrile.
  • reaction mixtures are worked up in a conventional manner, e.g. by mixing with water, separation of the phases and, if necessary, chromatographic purification of the crude products.
  • the intermediate and end products fall in part. in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or cleaned under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting.
  • isomer mixtures are obtained in the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (e.g. under the action of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.
  • Halogen fluorine, chlorine, bromine and iodine
  • Alkyl saturated, straight-chain or branched hydrocarbon radicals with 1 to 4, 6 or 8 carbon atoms, e.g. d-Co-alkyl such as methyl, ethyl, propyl, methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2 , 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2 -Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl
  • Haloalkyl straight-chain or branched alkyl groups with 1 to 2, 4, 6 or 8 carbon atoms (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above: in particular C 1 -C 2 -haloalkyl such as chloromethyl , Bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 -Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,
  • Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl , 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2nd -Pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2 - butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2
  • Alkynyl straight-chain or branched hydrocarbon groups with 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for example C 2 -C ⁇ -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl , 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3 -butinyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -Methyl
  • Cycloalkyl mono- or bicyclic, saturated hydrocarbon groups with 3 to 6 or 8 carbon ring members, for example C 3 -C 8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
  • 5- or 6-membered heterocyclyl containing one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isoliazolidiazolidinyl Pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2-
  • 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms
  • Substance atoms and a sulfur or oxygen atom as ring members can contain, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl , 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1,3,4-triazol-2-yl;
  • 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;
  • Oxyalkyleneoxy divalent unbranched chains of 1 to 3 CH 2 groups, both valences being bound to the skeleton via an oxygen atom, for example OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O;
  • the scope of the present invention includes the (R) and (S) isomers and the racemates of compounds of the formula I which have chiral centers.
  • R 1 is dC 4 alkyl, C 2 -C 6 alkenyl or dC 8 haloalkyl.
  • Z 1 is hydrogen, fluorine or dC 6 fluoroalkyl
  • Z 2 is hydrogen or fluorine, or Z 1 and Z 2 together form a double bond
  • q is 0 or 1
  • R 3 is hydrogen or methyl.
  • R 1 is C 3 -C 6 cycloalkyl, which can be substituted by CC alkyl.
  • R 1 and / or R 2 contain haloalkyl or haloalkenyl groups with a chiral center, the (S) isomers are preferred for these groups.
  • the (R) -configured isomers are preferred.
  • a preferred embodiment of the invention relates to compounds of the formula 1.1:
  • GC 2 -C 6 alkyl in particular ethyl, n- and i-propyl, n-, sec-, tert-butyl, and dC - alkoxymethyl, in particular ethoxymethyl, or C 3 -C ⁇ - cycloalkyl, in particular cyclopentyl or cyclohexyl;
  • R 2 is hydrogen or methyl;
  • X is cyano, methoxy or ethoxy.
  • Another preferred embodiment of the invention relates to compounds of the formula I.2.
  • Y is hydrogen or -CC 4 alkyl, in particular methyl and ethyl, and X is cyano, methoxy or ethoxy.
  • a further preferred embodiment of the invention relates to compounds in which R 1 and R 2 together with the nitrogen atom to which they are attached form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and a further hetero atom from the group O , N and S included as a ring member and / or one or more substituents from the group halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, -C-C 6 alkoxy, dC 6 - Halogenoalkoxy, C 3 -C 8 alkenyloxy, C 3 -C 6 haloalkenyloxy, dC 6 alkylene and oxy-dC 3 - alkyleneoxy can wear.
  • These compounds correspond in particular to formula I.3,
  • D together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, dC Can carry 4- alkyl, dC -alkoxy and dC 2 -haloalkyl; and
  • X is cyano, methoxy or ethoxy.
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidinyl, morpholinyl or thimorpholinyl ring, in particular a piperidinyl ring which may be halogenated by one to three groups, dC -alkyl or dC -haloalkyl is substituted.
  • the compounds in which R 1 and R 2 together with the nitrogen atom to which they are attached form a 4-methylpiperidine ring are particularly preferred.
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a pyrazole ring which may be halogen, dC -alkyl or dC 4 by one or two groups - Haloalkyl, in particular substituted by 3,5-dimethyl or 3,5-di (trifluoromethyl).
  • R 2 is hydrogen or methyl; or R 1 and R 2 together - (CH 2 ) 2CH (CH 3 ) (CH 2 ) 2-, - (CH 2 ) 2 CH (CF 3 ) (CH 2 ) 2 - or - (CH 2 ) 2 O ( CH 2 ) 2 - mean.
  • compounds I are particularly preferred in which X is cyano, methoxy or ethoxy, in particular cyano or methoxy.
  • X is cyano, methoxy or ethoxy, in particular cyano or methoxy.
  • the compounds I compiled in the tables below are preferred.
  • the groups mentioned for a substituent in the tables also represent a particularly preferred embodiment of the substituent in question, regardless of the combination in which they are mentioned.
  • the compounds I are suitable as fungicides. They are characterized by a her. excellent activity against a wide spectrum of phytopathogenic fungi, especially from the class of Ascomycetes, Deuteromycetes, Oomycetes and ßasidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.
  • the compounds I are also suitable for combating harmful fungi such as Pacilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • harmful fungi such as Pacilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds.
  • the application can take place both before and after the infection of the materials, plants or seeds by the fungi.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
  • the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per ha.
  • amounts of active compound of 1 to 1000 g / 100 kg, preferably 5 to 100 g, are generally required per 100 kg of seed.
  • the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of treated material.
  • the compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the connection according to the invention.
  • the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants.
  • solvents and auxiliaries The following are essentially considered as solvents / auxiliaries:
  • aromatic solvents e.g. Solvesso products, xylene
  • paraffins e.g. petroleum fractions
  • alcohols e.g. methanol, butanol, pentanol, benzyl alcohol
  • ketones e.g. cyclohexanone, gamma-butryolactone
  • pyrrolidones NMP, NOP
  • Acetates glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters.
  • solvent mixtures can also be used
  • Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • natural stone powder e.g. kaolins, clays, talc, chalk
  • synthetic stone powder e.g. highly disperse silica, silicates
  • Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • Mineral oil fractions of medium to high boiling point are used to produce directly sprayable solutions, emulsions, pastes or oil dispersions.
  • sin or diesel oil also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone , strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral earths such as silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics,
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • formulations are: 1. Products for dilution in water
  • a compound according to the invention 10 parts by weight of a compound according to the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other aids are added. The active ingredient dissolves when diluted in water.
  • a compound according to the invention 20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with the addition of a dispersant e.g. Dissolved polyvinyl pyrrolidone. When diluted in water, a dispersion results.
  • a dispersant e.g. Dissolved polyvinyl pyrrolidone.
  • a compound according to the invention 40 parts by weight of a compound according to the invention are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each).
  • This mixture is introduced into water using an emulsifying machine (Ultraturax) and brought to a homogeneous emulsion. Dilution in water results in an emulsion.
  • Water-dispersible and water-soluble granules 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersants and wetting agents and are prepared as water-dispersible or water-soluble granules by means of technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution in water results in a stable dispersion or solution of the active ingredient.
  • Water-dispersible and water-soluble powders 75 parts by weight of a compound according to the invention are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • H dusts (DP) 5 parts by weight of a compound according to the invention are finely ground and intimately mixed with 95% finely divided kaolin. This gives a dusting agent.
  • J ULV solutions (UL) 10 parts by weight of a compound according to the invention are in an organic Solvent eg xylene dissolved. This gives you a product for direct application.
  • the active ingredients as such in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring.
  • the application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.
  • the active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume process
  • compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases.
  • the following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:
  • Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl,
  • Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph
  • Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl,
  • Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,
  • Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazol, triazolazol, trichazonazol, trichlorazolol, prochlorazolol, prochlorazolol, trichlorazolol, prochlorazolol, trichlorazol, trichlorazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, tricha
  • Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb,
  • Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronazidolomolol, probolil, probolil, nuarol, probolil, probolil Quinoxyfen, silthiofam, thiabenzazole, thifluzamide, thiophanate methyl, tiadinil, tricyclazole, triforins,
  • copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate, • nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthaloisopropyl
  • Phenylpyrroles such as fenpiclonil or fludioxonil
  • fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, Dazomet, diclomezin, diclocymet, Diethofen-carb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fennosetanyl, ferim Fosetyl aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide
  • strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, • sulfenoic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid
  • Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.
  • the active ingredients were prepared separately or together as a stock solution with 0.25% by weight of active ingredient in acetone or DMSO. 1% by weight of Uniperol® EL emulsifier (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and diluted with water to the desired concentration.
  • Uniperol® EL emulsifier wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols

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  • Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract

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

Description

6-(2,4,6-Trifluorphenyl)-triazolopyrimidine, Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung von Schadpilzen sowie sie enthaltende Mittel6- (2,4,6-trifluorophenyl) triazolopyrimidines, processes for their preparation and their use in combating harmful fungi and compositions containing them
Beschreibungdescription
Die vorliegende Erfindung betrifft 6-(2,4,6-Trifluorphenyl)-triazolopyrimidine der Formel IThe present invention relates to 6- (2,4,6-trifluorophenyl) triazolopyrimidines of the formula I.
in der die Substituenten folgende Bedeutung haben: in which the substituents have the following meaning:
R1 Cι-C8-Alkyl, CrC8-Halogenalkyl, C3-C8-Cycloalkyl, C3-C8-Halogencycloalkyl, C2-C8-Alkenyl, C2-C8-Halogenalkenyl, C3-Cβ-Cycloalkenyl, C3-C6-Halogencyclo- alkenyl, C2-C8-Alkinyl, C2-C8-Halogenalkinyl oder Phenyl, Naphthyl, oder ein fünf- oder sechsgliedriger gesättigter, partiell ungesättigter oder aromatischer Hetero- cyclus, enthaltend ein bis vier Heteroatome aus der Gruppe O, N oder S,R 1 -C 8 alkyl, C r C 8 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 haloalkenyl, C 3 -C β cycloalkenyl, C 3 -C 6 halocycloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic hetero- cycle containing one to four heteroatoms from the group O, N or S,
R2 Wasserstoff oder eine der bei R1 genannten Gruppen,R 2 is hydrogen or one of the groups mentioned for R 1 ,
R1 und R2 können auch zusammen mit dem Stickstoffatom, an das sie gebunden sind, ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bilden, welches über N gebunden ist und ein weiteres Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, Cι-Cβ-Alkyl, d-Cβ-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Halogen- alkenyl, C Ce-Alkoxy, d-Cβ-Halogenalkoxy, C3-Cβ-Alkenyloxy, C3-C6-Halogen- alkenyloxy, CrC6-Alkylen und Oxy-d-C3-alkylenoxy tragen kann;R 1 and R 2 together with the nitrogen atom to which they are attached can also form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contain a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, -C-C β- alkyl, d-Cβ-haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C Ce alkoxy, dC β -haloalkoxy , C 3 -Cβ-alkenyloxy, C 3 -C 6 -haloalkenyloxy, CrC 6 -alkylene and oxy-dC 3 -alkyleneoxy can carry;
R1 und/oder R2 können eine bis vier gleiche oder verschiedene Gruppen Ra tragen: Ra Halogen, Cyano, Nitro, Hydroxy, d-C6-Alkyl, Ci-Cβ-Halogenalkyl, d-C6- Alkylcarbonyl, C3-Cβ-Cycloalkyl, d-C6-Alkoxy, Ci-Cβ-Halogenalkoxy, d-Cβ- Alkoxycarbonyl, d-C6-Alkylthio, C Cβ-Alkylamino, Di-Ci-Cβ-alkylamino, C2-C6-Alkenyl, C2-C6-Alkenyloxy, C3-Cβ-Alkinyloxy, Oxy-CrC3-alkylenoxy, C3-Cβ-Cycloalkyl, Phenyl, Naphthyl, fünf- oder sechsgliedriger gesättigter, partiell ungesättigter oder aromatischer Heterocyclus, enthaltend ein bis vier Heteroatome aus der Gruppe O, N oder S, wobei diese aliphatischen, alicyclischen oder aromatischen Gruppen ihrerseits partiell oder vollständig halogeniert sein könnenR 1 and / or R 2 can carry one to four identical or different groups R a : R a halogen, cyano, nitro, hydroxyl, dC 6 -alkyl, Ci-Cβ-haloalkyl, dC 6 - alkylcarbonyl, C 3 -C β -Cycloalkyl, dC 6 -alkoxy, Ci-Cβ-haloalkoxy, dC β - alkoxycarbonyl, dC 6 -alkylthio, C Cβ-alkylamino, di-Ci-Cβ-alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 -Alkenyloxy, C 3 -C β -alkynyloxy, oxy-CrC 3 -alkyleneoxy, C 3 -Cβ-cycloalkyl, phenyl, naphthyl, five- or six-membered saturated, partially unsaturated or aromatic heterocycle, containing one to four heteroatoms from the group O. , N or S, these aliphatic, alicyclic or aromatic groups can in turn be partially or completely halogenated
X Cyano, Crd-Alkoxy, C3-C4-Alkenyloxy, Cι-C2-Halogenalkoxy oder C3-C -Halo- genalkenyloxy.X cyano, Crd-alkoxy, C 3 -C 4 alkenyloxy, -C-C 2 haloalkoxy or C 3 -C haloalkenyloxy.
Außerdem betrifft die Erfindung ein Verfahren zur Herstellung dieser Verbindungen, sie enthaltende Mittel sowie ihre Verwendung zur Bekämpfung von pflanzenpathogenen Schadpilzen.In addition, the invention relates to a process for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.
5-Halogen-6-(2,4,6-trifluorphenyl)-triazolopyrimidine sind aus WO 98/46607 allgemein bekannt. 5-Cyano- und 5-Alkoxy-triazolopyrimidine sind in WO 02/083677 offenbart. Triazolopyrimidine mit optisch aktiven Aminosubstituenten in 7-Position werden in WO 02/38565 allgemein vorgeschlagen.5-Halogen-6- (2,4,6-trifluorophenyl) triazolopyrimidines are generally known from WO 98/46607. 5-cyano- and 5-alkoxy-triazolopyrimidines are disclosed in WO 02/083677. Triazolopyrimidines with optically active amino substituents in the 7-position are generally proposed in WO 02/38565.
Die in den vorgenannten Schriften beschriebenen Verbindungen sind zur Bekämpfung von Schadpilzen geeignet.The compounds described in the abovementioned documents are suitable for combating harmful fungi.
Ihre Wirkung ist jedoch nicht immer in jeder Hinsicht völlig zufriedenstellend. Davon ausgehend liegt der vorliegenden Erfindung die Aufgabe zugrunde, Verbindungen mit verbesserter Wirkung und/oder verbreitertem Wirkungsspektrum bereitzustellen.However, their effects are not always completely satisfactory in every respect. Proceeding from this, the present invention is based on the object of providing compounds with improved activity and / or broadened activity spectrum.
Demgemäss wurden die eingangs definierten Verbindungen gefunden. Desweiteren wurde ein Verfahren zu ihrer Herstellung, sie enthaltende Mittel sowie Verfahren zur Bekämpfung von Schadpilzen unter Verwendung der Verbindungen I gefunden.Accordingly, the compounds defined at the outset were found. Furthermore, a process for their preparation, compositions comprising them and processes for combating harmful fungi using the compounds I have been found.
Die erfindungsgemäßen Verbindungen unterscheiden sich von den in der vorgenannten Schrift beschriebenen durch die Substitution in der 5-Position des Triazolopyrimi- din-Gerüstes.The compounds according to the invention differ from those described in the abovementioned document by the substitution in the 5-position of the triazolopyrimidine skeleton.
Die Verbindungen der Formel I weisen eine gegenüber den bekannten Verbindungen erhöhte Wirksamkeit, bzw. ein verbreitertes Wirkungsspektrum gegen Schadpilze auf.The compounds of the formula I have an increased activity or a broader spectrum of activity against harmful fungi than the known compounds.
Die erfindungsgemäßen Verbindungen können auf verschiedenen Wegen erhalten werden. Vorteilhaft werden sie ausgehend von den aus WO 98/98/46607 bekannten 5-Halogen-6-(2,4,6-trifluorphenyl)-triazolopyrimidinen der Formel II durch Umsetzung mit Verbindungen M-X (Formel III) erhalten. Verbindungen III stellen je nach der Bedeutung der einzuführenden Gruppe X ein anorganisches Cyanid oder ein Alkoxylat dar. Die Umsetzung erfolgt vorteilhaft in Anwesenheit eines inerten Lösungsmittels. Das Kation M in Formel III hat geringe Bedeutung; aus praktischen Gründen sind übli- cherweise Ammonium-, Tetraalkylammonium- oder Alkali- oder Erdalkalimetallsalze bevorzugt.The compounds according to the invention can be obtained in various ways. They are advantageously obtained starting from the 5-halo-6- (2,4,6-trifluorophenyl) triazolopyrimidines of the formula II known from WO 98/98/46607 by reaction with compounds MX (formula III). Depending on the meaning of the group X to be introduced, compounds III represent an inorganic cyanide or an alkoxylate. The reaction is advantageously carried out in the presence of an inert solvent. The cation M in formula III is of little importance; for practical reasons, Ammonium, tetraalkylammonium or alkali or alkaline earth metal salts are preferred.
Üblicherweise liegt die Reaktionstemperatur bei 0 bis 120°C, bevorzugt bei 10 bis 40°C [vgl. J. Heterocycl. Chem., Bd.12, S. 861-863 (1975)].The reaction temperature is usually from 0 to 120 ° C., preferably from 10 to 40 ° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].
Sofern R2 Wasserstoff bedeutet, wird vorteilhaft vor Umsetzung mit III eine abspaltbare Schutzgruppe eingeführt [vgl. Greene, Protective Groups in Organic Chemistry, J. Wi- ley & Sons, (1981)].If R 2 is hydrogen, a removable protective group is advantageously introduced before reaction with III [cf. Greene, Protective Groups in Organic Chemistry, J. Willey & Sons, (1981)].
Geeignete Lösungsmittel umfassen Ether, wie Dioxan, Diethylether und, bevorzugt Tetrahydrofuran, halogenierte Kohlenwasserstoffe wie Dichloromethan und aromatische Kohlenwasserstoffe, wie Toluol oder Acetonitril.Suitable solvents include ethers such as dioxane, diethyl ether and, preferably tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene or acetonitrile.
Die Reaktionsgemische werden in üblicher Weise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenenfalls chromatographische Reinigung der Rohprodukte. Die Zwischen- und Endprodukte fallen z.T. in Form farbloser oder schwach bräunlicher, zäher Öle an, die unter vermindertem Druck und bei mäßig erhöhter Temperatur von flüchtigen Anteilen befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren erfolgen.The reaction mixtures are worked up in a conventional manner, e.g. by mixing with water, separation of the phases and, if necessary, chromatographic purification of the crude products. The intermediate and end products fall in part. in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or cleaned under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting.
Sofern einzelne Verbindungen I nicht auf den voranstehend beschriebenen Wegen zugänglich sind, können sie durch Derivatisierung anderer Verbindungen I hergestellt werden.If individual compounds I are not accessible in the ways described above, they can be prepared by derivatizing other compounds I.
Sofern bei der Synthese Isomerengemische anfallen, ist im allgemeinen jedoch eine Trennung nicht unbedingt erforderlich, da sich die einzelnen Isomere teilweise während der Aufbereitung für die Anwendung oder bei der Anwendung (z.B. unter Licht-, Säure- oder Baseneinwirkung) ineinander umwandeln können. Entsprechende Umwandlungen können auch nach der Anwendung, beispielsweise bei der Behandlung von Pflanzen in der behandelten Pflanze oder im zu bekämpfenden Schadpilz erfolgen.If isomer mixtures are obtained in the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (e.g. under the action of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.
Bei den in den vorstehenden Formeln angegebenen Definitionen der Symbole wurden Sammelbegriffe verwendet, die allgemein repräsentativ für die folgenden Substituenten stehen: Halogen: Fluor, Chlor, Brom und Jod;In the definitions of the symbols given in the formulas above, collective terms were used which are generally representative of the following substituents: Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: gesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 4, 6 oder 8 Kohlenstoffatomen, z.B. d-Co-Alkyl wie Methyl, Ethyl, Propyl, -Methylethyl, Butyl, 1-Methyl-propyl, 2-Methylpropyl, 1,1-Dimethylethyl, Pentyl, 1-Methylbutyl, 2-Me- thylbutyl, 3-Methylbutyl, 2,2-Di-methylpropyl, 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-Dime- thylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Tri- methylpropyl, 1-Ethyl-1-methylpropyl und 1-Ethyl-2-methylpropyl;Alkyl: saturated, straight-chain or branched hydrocarbon radicals with 1 to 4, 6 or 8 carbon atoms, e.g. d-Co-alkyl such as methyl, ethyl, propyl, methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2 , 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2 -Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2 -Trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
Halogenalkyl: geradkettige oder verzweigte Alkylgruppen mit 1 bis 2, 4, 6 oder 8 Kohlenstoffatomen (wie vorstehend genannt), wobei in diesen Gruppen teilweise oder vollständig die Wasserstoffatome durch Halogenatome wie vorstehend genannt ersetzt sein können: insbesondere Cι-C2-Halogenalkyl wie Chlormethyl, Brommethyl, Dichlor- methyl, Trichlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, 1-Chlorethyl, 1-Bromethyl, 1-Fluorethyl, 2-Fluor- ethyl, 2,2-Difluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluorethyl, 2,2-Dichlor-2-fluorethyl, 2,2,2-Trichlorethyl, Pentafluorethyl oder 1,1,1 -Trifluorprop-2-yl;Haloalkyl: straight-chain or branched alkyl groups with 1 to 2, 4, 6 or 8 carbon atoms (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above: in particular C 1 -C 2 -haloalkyl such as chloromethyl , Bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 -Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1 -trifluoroprop-2 yl;
Alkenyl: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 4, 6, 8 oder 10 Kohlenstoffatomen und einer oder zwei Doppelbindungen in beliebiger Position, z.B. C2-C6-Alkenyl wie 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-Me- thyl-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-bu- tenyl, 1,1-Dimethyl-2-propenyl, 1 ,2-Dimethyl-1 -propenyl, 1 ,2-Dimethyl-2-propenyl, 1- Ethyl-1 propenyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5- Hexenyl, 1-Methyl-1-pentenyl, 2-Methyl-1-pentenyl, 3-Methyl-1-pentenyl, 4-Methyl-1- pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2- pentenyl, 1-Methyl-3-pentenyl, 2-Methyl-3pentenyl, 3-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-bu- tenyl, 1,3-Dimethyl-3-butenyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Di- methyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3-Dimethyl-1-butenyl, 3,3-Dimethyl-2-bu- tenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 2-Ethyl-1-butenyl, 2-Ethyl- 2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Ethyl-1-methyl-2-propenyl, 1-Ethyl-2-methyl-1 -propenyl und 1-Ethyl-2-methyl-2-propenyl; Halogenalkenyl: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 8 Kohlenstoffatomen und einer oder zwei Doppelbindungen in beliebiger Position (wie vorstehend genannt), wobei in diesen Gruppen die Wasserstoffatome teilweise oder vollständig gegen Halogenatome wie vorstehend genannt, insbesondere Fluor, Chlor und Brom, ersetzt sein können;Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl , 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2nd -Pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2 - butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1, 2 -Dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1 propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5- Hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3pentenyl, 3-Me thyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1- Dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3- Dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2- propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl; Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 8 carbon atoms and one or two double bonds in any position (as mentioned above), the hydrogen atoms in these groups being partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine could be;
Alkinyl: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 4, 6 oder 8 Kohlenstoffatomen und einer oder zwei Dreifachbindungen in beliebiger Position, z.B. C2-Cβ-Alkinyl wie Ethinyl, 1-Propinyl, 2-Propinyl, 1-Butinyl, 2-Butinyl, 3-Butinyl, 1-Methyl-2-propinyl, 1-Pentinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, 1-Methyl-2-butinyl, 1-Methyl-3-butinyl, 2-Methyl-3-butinyl, 3-Methyl-1-butinyl, 1,1-Dimethyl-2-propinyl, 1 -Ethyl-2-propinyl, 1-Hexinyl, 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, 1-Methyl-2- pentinyl, 1-Methyl-3-pentinyl, 1-Methyl-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4- pentinyl, 3-Methyl-1-pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-1-pentinyl, 4-Methyl-2- pentinyl, 1 , 1 -Dimethyl-2-butinyl, 1 , 1 -Dimethyl-3-butinyl, 1 ,2-Dimethyl-3-butinyl, 2,2- Dimethyl-3-butinyl, 3,3-Dimethyl-1-butinyl, 1-Ethyl-2-butinyl, 1-Ethyl-3-butinyl, 2-Ethyl- 3-butinyl und 1-Ethyl-1-methyl-2-propinyl;Alkynyl: straight-chain or branched hydrocarbon groups with 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for example C 2 -C β -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl , 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3 -butinyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -Methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl -4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl , 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1 -methyl-2-propynyl;
Cycloalkyl: mono- oder bicyclische, gesättigte Kohlenwasserstoffgruppen mit 3 bis 6 oder 8 Kohlenstoffringgliedern, z.B. C3-C8-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyc- lopentyl, Cyclohexyl, Cycloheptyl und Cyclooctyl;Cycloalkyl: mono- or bicyclic, saturated hydrocarbon groups with 3 to 6 or 8 carbon ring members, for example C 3 -C 8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
fünf- oder sechsgliedriger gesättigter, partiell ungesättigter oder aromatischer Hetero- cyclus, enthaltend ein bis vier Heteroatome aus der Gruppe O, N oder S:five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S:
5- oder 6-gliedriges Heterocyclyl, enthaltend ein bis drei Stickstoffatome und/oder ein Sauerstoff- oder Schwefelatom oder ein oder zwei Sauerstoff- und/oder Schwefelatome, z.B. 2-Tetrahydrofuranyl, 3-Tetrahydrofuranyl, 2-Tetrahydrothienyl, 3-Tetrahydrothienyl, 2-Pyrrolidinyl, 3-Pyrrolidinyl, 3-lsoxazolidinyl, 4-lsoxazolidinyl, 5-lsoxazolidinyl, 3-lsothiazolidinyl, 4-lsothiazolidinyl, 5-lsothiazolidinyl, 3-Pyrazolidinyl, 4-Pyrazolidinyl, 5-Pyrazolidinyl, 2-Oxazolidinyl, 4-Oxazolidinyl, 5-Oxazolidinyl, 2-Thia- zolidinyl, 4-Thiazolidinyl, 5-Thiazolidinyl, 2-lmidazolidinyl, 4-lmidazolidinyl, 2-Pyrrolin-2- yl, 2-Pyrrolin-3-yl, 3-Pyrrolin-2-yl, 3-Pyrrolin-3-yl, 2-Piperidinyl, 3-Piperidinyl, 4-Piperi- dinyl, 1 ,3-Dioxan-5-yl, 2-Tetrahydropyranyl, 4-Tetrahydropyranyl, 2-Tetrahydro- thienyl, 3-Hexahydropyridazinyl, 4-Hexahydropyridazinyl, 2-Hexahydropyrimidinyl, 4-Hexahydropyrimidinyl, 5-Hexahydropyrimidinyl und 2-Piperazinyl;5- or 6-membered heterocyclyl containing one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isoliazolidiazolidinyl Pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2- yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1, 3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydro thienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl;
5-gliedriges Heteroaryl, enthaltend ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom: 5-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis vier Stickstoffatome oder ein bis drei Stick- stoffatome und ein Schwefel- oder Sauerstoffatom als Ringglieder enthalten können, z.B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 2-Pyrrolyl, 3-Pyrrolyl, 3-Pyrazolyl, 4-Pyrazo- lyl, 5-Pyrazolyl, 2-Oxazolyl, 4-Oxazolyl, 5-Oxazolyl, 2-Thiazolyl, 4-Thiazolyl, 5-Thiazo- lyl, 2-lmidazolyl, 4-lmidazolyl, und 1,3,4-Triazol-2-yl;5-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms Substance atoms and a sulfur or oxygen atom as ring members can contain, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl , 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1,3,4-triazol-2-yl;
6-gliedriges Heteroaryl, enthaltend ein bis drei bzw. ein bis vier Stickstoffatome: 6-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis drei bzw. ein bis vier Stickstoffatome als Ringglieder enthalten können, z.B. 2-Pyridinyl, 3-Pyridinyl, 4-Pyridinyl, 3-Pyridazinyl, 4-Pyridazinyl, 2-Pyrimidinyl, 4-Pyrimidinyl, 5-Pyrimidinyl und 2-Pyrazinyl;6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;
Alkylen: gesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 4 oder 6 Kohlenstoffatomen, welche über eine Doppelbindung an das Gerüst gebunden sind, z. B. =CH2, =CH-CH3, =CH-CH2-CH3;Alkylene: saturated, straight-chain or branched hydrocarbon radicals with 1 to 4 or 6 carbon atoms, which are bonded to the skeleton via a double bond, e.g. B. = CH 2 , = CH-CH 3 , = CH-CH 2 -CH 3 ;
Oxyalkylenoxy: divalente unverzweigte Ketten aus 1 bis 3 CH2-Gruppen, wobei beide Valenzen über ein Sauerstoffatom an das Gerüst gebunden ist, z.B. OCH2O, OCH2CH2O und OCH2CH2CH2O;Oxyalkyleneoxy: divalent unbranched chains of 1 to 3 CH 2 groups, both valences being bound to the skeleton via an oxygen atom, for example OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O;
In dem Umfang der vorliegenden Erfindung sind die (R)- und (S)-Isomere und die Ra- zemate von Verbindungen der Formel I eingeschlossen, die chirale Zentren aufweisen.The scope of the present invention includes the (R) and (S) isomers and the racemates of compounds of the formula I which have chiral centers.
Im Hinblick auf ihre bestimmungsgemäße Verwendung der Triazolopyrimidine der Formel I sind die folgenden Bedeutungen der Substituenten, und zwar jeweils für sich allein oder in Kombination, besonders bevorzugt:With regard to their intended use of the triazolopyrimidines of the formula I, the following meanings of the substituents, in each case individually or in combination, are particularly preferred:
Verbindungen I werden bevorzugt, in denen R1 für d-C4-Alkyl, C2-C6-Alkenyl oder d-C8-Halogenalkyl steht.Compounds I are preferred in which R 1 is dC 4 alkyl, C 2 -C 6 alkenyl or dC 8 haloalkyl.
Verbindungen I sind bevorzugt, in denen R1 für eine Gruppe A steht: worinCompounds I are preferred in which R 1 represents a group A: wherein
Z1 Wasserstoff, Fluor oder d-C6-Fluoroalkyl, Z2 Wasserstoff oder Fluor, oder Z1 und Z2 bilden gemeinsam eine Doppelbindung; q 0 oder 1 ist; und R3 Wasserstoff oder Methyl bedeuten. Außerdem werden Verbindungen I bevorzugt, in denen R1 für C3-C6-Cycloalkyl steht, welches durch C C -Alkyl substituiert sein kann.Z 1 is hydrogen, fluorine or dC 6 fluoroalkyl, Z 2 is hydrogen or fluorine, or Z 1 and Z 2 together form a double bond; q is 0 or 1; and R 3 is hydrogen or methyl. In addition, compounds I are preferred in which R 1 is C 3 -C 6 cycloalkyl, which can be substituted by CC alkyl.
Insbesondere werden Verbindungen I bevorzugt, in denen R2 Wasserstoff bedeutet.In particular, compounds I are preferred in which R 2 is hydrogen.
Gleichermaßen bevorzugt sind Verbindungen I, in denen R2 für Methyl oder Ethyl steht.Equally preferred are compounds I in which R 2 is methyl or ethyl.
Sofern R1 und/oder R2 Halogenalkyl oder Halogenalkenylgruppen mit Chiralitätszentrum beinhalten, sind für diese Gruppen die (S)- Isomere bevorzugt. Im Fall halo- genfreier Alkyl oder Alkenylgruppen mit Chiralitätszentrum in R1 oder R2 sind die (R)- konfigurierten Isomere bevorzugt.If R 1 and / or R 2 contain haloalkyl or haloalkenyl groups with a chiral center, the (S) isomers are preferred for these groups. In the case of halogen-free alkyl or alkenyl groups with a chiral center in R 1 or R 2 , the (R) -configured isomers are preferred.
Eine bevorzugte Ausführungsform der Erfindung betrifft Verbindungen der Formel 1.1 :A preferred embodiment of the invention relates to compounds of the formula 1.1:
in der in the
G C2-C6-Alkyl, insbesondere Ethyl, n- und i-Propyl, n-, sek-, tert- Butyl, und d-C - Alkoxymethyl, insbesondere Ethoxymethyl, oder C3-Cβ-Cycloalkyl, insbesondere Cyclopentyl oder Cyclohexyl; R2 Wasserstoff oder Methyl; und X Cyano, Methoxy oder Ethoxy bedeuten.GC 2 -C 6 alkyl, in particular ethyl, n- and i-propyl, n-, sec-, tert-butyl, and dC - alkoxymethyl, in particular ethoxymethyl, or C 3 -C β- cycloalkyl, in particular cyclopentyl or cyclohexyl; R 2 is hydrogen or methyl; and X is cyano, methoxy or ethoxy.
Eine weitere bevorzugte Ausführungsform der Erfindung betrifft Verbindungen der Formel I.2.Another preferred embodiment of the invention relates to compounds of the formula I.2.
in der Y für Wasserstoff oder Cι-C4-Alkyl, insbesondere für Methyl und Ethyl, und X für Cyano, Methoxy oder Ethoxy steht. in which Y is hydrogen or -CC 4 alkyl, in particular methyl and ethyl, and X is cyano, methoxy or ethoxy.
Eine weitere bevorzugte Ausführungsform der Erfindung betrifft Verbindungen, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bilden, welches über N gebunden ist und ein weiteres Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, Ci-Cβ-Alkyl, d-Cβ-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, Cι-C6-Alkoxy, d-C6-Halo- genalkoxy, C3-C8-Alkenyloxy, C3-C6-Halogenalkenyloxy, d-C6-Alkylen und Oxy-d-C3- alkylenoxy tragen kann. Diese Verbindungen entsprechen insbesondere Formel I.3,A further preferred embodiment of the invention relates to compounds in which R 1 and R 2 together with the nitrogen atom to which they are attached form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and a further hetero atom from the group O , N and S included as a ring member and / or one or more substituents from the group halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, -C-C 6 alkoxy, dC 6 - Halogenoalkoxy, C 3 -C 8 alkenyloxy, C 3 -C 6 haloalkenyloxy, dC 6 alkylene and oxy-dC 3 - alkyleneoxy can wear. These compounds correspond in particular to formula I.3,
in der in the
D zusammen mit dem Stickstoffatom ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bildet, welches über N gebunden ist und ein weiteres Hetero- atom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, d-C4-Alkyl, d-C -Alkoxy und d-C2-Halogenalkyl tragen kann; undD together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, dC Can carry 4- alkyl, dC -alkoxy and dC 2 -haloalkyl; and
X Cyano, Methoxy oder Ethoxy bedeuten.X is cyano, methoxy or ethoxy.
Weiterhin werden Verbindungen I bevorzugt, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Piperidinyl-, Morpholinyl- oder Thio- morpholinylring bilden, insbesondere einen Piperidinylring, der ggf. durch eine bis drei Gruppen Halogen, d-C -Alkyl oder d-C -Halogenalkyl substituiert ist. Besonders bevorzugt sind die Verbindungen, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 4-Methylpiperidinring bilden.Furthermore, compounds I are preferred in which R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidinyl, morpholinyl or thimorpholinyl ring, in particular a piperidinyl ring which may be halogenated by one to three groups, dC -alkyl or dC -haloalkyl is substituted. The compounds in which R 1 and R 2 together with the nitrogen atom to which they are attached form a 4-methylpiperidine ring are particularly preferred.
Ein weiterer bevorzugter Gegenstand der Erfindung sind Verbindungen I, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Pyrazol- ring bilden, der ggf. durch eine oder zwei Gruppen Halogen, d-C -Alkyl oder d-C4- Halogenalkyl, insbesondere durch 3,5-Dimethyl oder 3,5-Di-(trifluormethyl) substituiert ist.Another preferred object of the invention are compounds I in which R 1 and R 2 together with the nitrogen atom to which they are attached form a pyrazole ring which may be halogen, dC -alkyl or dC 4 by one or two groups - Haloalkyl, in particular substituted by 3,5-dimethyl or 3,5-di (trifluoromethyl).
Daneben sind auch Verbindungen der Formel I besonders bevorzugt, in denen R1CH(CH3)-CH2CH3 , CH(CH3)-CH(CH3)2 , CH(CH3)-C(CH3)3 , CH(CH3)-CF3 , CH2C(CH3)=CH2 ,CH2CH=CH2 , Cyclopentyl oder Cyclohexyl; R2 Wasserstoff oder Me- thyl; oder R1 und R2 gemeinsam -(CH2)2CH(CH3)(CH2)2-, -(CH2)2CH(CF3)(CH2)2- oder -(CH2)2O(CH2)2- bedeuten.In addition, compounds of the formula I are particularly preferred in which R 1 is CH (CH 3 ) -CH 2 CH 3 , CH (CH 3 ) -CH (CH 3 ) 2 , CH (CH 3 ) -C (CH 3 ) 3 , CH (CH 3 ) -CF 3 , CH 2 C (CH 3 ) = CH 2 , CH 2 CH = CH 2 , cyclopentyl or cyclohexyl; R 2 is hydrogen or methyl; or R 1 and R 2 together - (CH 2 ) 2CH (CH 3 ) (CH 2 ) 2-, - (CH 2 ) 2 CH (CF 3 ) (CH 2 ) 2 - or - (CH 2 ) 2 O ( CH 2 ) 2 - mean.
Weiterhin werden Verbindungen I besonders bevorzugt, in denen X Cyano, Methoxy oder Ethoxy, insbesondere Cyano oder Methoxy bedeutet. Insbesondere sind im Hinblick auf ihre Verwendung die in den folgenden Tabellen zusammengestellten Verbindungen I bevorzugt. Die in den Tabellen für einen Substituenten genannten Gruppen stellen außerdem für sich betrachtet, unabhängig von der Kombination, in der sie genannt sind, eine besonders bevorzugte Ausgestaltung des betreffenden Substituenten dar.Furthermore, compounds I are particularly preferred in which X is cyano, methoxy or ethoxy, in particular cyano or methoxy. In particular, in view of their use, the compounds I compiled in the tables below are preferred. The groups mentioned for a substituent in the tables also represent a particularly preferred embodiment of the substituent in question, regardless of the combination in which they are mentioned.
Tabelle 1Table 1
Verbindungen der Formel I, in denen X Cyano bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 2Table 2
Verbindungen der Formel I, in denen X Methoxy bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 3Table 3
Verbindungen der Formel I, in denen X Ethoxy bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is ethoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle ATable A
Die Verbindungen I eignen sich als Fungizide. Sie zeichnen sich aus durch eine her- . vorragende Wirksamkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten, Deuteromyceten, Oomyceten und ßa- sidiomyceten. Sie sind zum Teil systemisch wirksam und können im Pflanzenschutz als Blatt- und Bodenfungizide eingesetzt werden.The compounds I are suitable as fungicides. They are characterized by a her. excellent activity against a wide spectrum of phytopathogenic fungi, especially from the class of Ascomycetes, Deuteromycetes, Oomycetes and ßasidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.
Besondere Bedeutung haben sie für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen wie Weizen, Roggen, Gerste, Hafer, Reis, Mais, Gras, Ba- nanen, Baumwolle, Soja, Kaffee, Zuckerrohr, Wein, Obst- und Zierpflanzen und Gemüsepflanzen wie Gurken, Bohnen, Tomaten, Kartoffeln und Kürbisgewächsen, sowie an den Samen dieser Pflanzen. Speziell eignen sie sich zur Bekämpfung folgender Pflanzenkrankheiten: Altemaria-Arten an Gemüse und Obst, Bipolaris- und Drechslera-Arten an Getreide, Reis und Rasen, Blumeria graminis (echter Mehltau) an Getreide, Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Zierpflanzen und Reben, Erysiphe cichoracearum und Sphaerotheca fuliginea an Kürbisgewächsen, Fusarium- und Verticillium-Arten an verschiedenen Pflanzen, Mycosphaerella-Arten an Getreide, Bananen und Erdnüssen, Phytophthora infestans an Kartoffeln und Tomaten, Plasmopara viticola an Reben, Podosphaera leucotricha an Äpfeln, Pseudocercosporella herpotrichoides an Weizen und Gerste, Pseudoperonospora-Arten an Hopfen und Gurken, Puccinia-Aύen an Getreide, Pyricularia oryzae an Reis, Rhizoctonia-Arten an Baumwolle, Reis und Rasen, Septoria tritici und Stagonospora nodorum an Weizen, Uncinula necator an Reben, Ustilago-Aήen an Getreide und Zuckerrohr, sowie Veπ/w/a-Arten (Schorf) an Äpfeln und Birnen.They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as Cucumbers, beans, tomatoes, potatoes and squash, as well as on the seeds of these plants. They are particularly suitable for combating the following plant diseases: Altemaria species on vegetables and fruits, Bipolaris and Drechslera species on cereals, rice and lawn, Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Fusarium and Verticillium species on various plants, Mycosphaerella species on cereals, bananas and peanuts, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Podosphaera leidespotella on wheat and barley, Pseudoperonospora species on hops and cucumbers, Puccinia plants on cereals, Pyricularia oryzae on rice, Rhizoctonia species on cotton, rice and turf, Septoria tritici and Stagonospora nodorum on wheat, Uncinula necator on vines, Ustilago plants on cereals and sugar cane, and Veπ / w / a species (scab) on apples and pears.
Die Verbindungen I eignen sich außerdem zur Bekämpfung von Schadpilzen wie Pae- cilomyces variotii im Materialschutz (z.B. Holz, Papier, Dispersionen für den Anstrich, Fasern bzw. Gewebe) und im Vorratsschutz.The compounds I are also suitable for combating harmful fungi such as Pacilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
Die Verbindungen I werden angewendet, indem man die Pilze oder die vor Pilzbefall zu schützenden Pflanzen, Saatgüter, Materialien oder den Erdboden mit einer fungizid wirksamen Menge der Wirkstoffe behandelt. Die Anwendung kann sowohl vor als auch nach der Infektion der Materialien, Pflanzen oder Samen durch die Pilze erfolgen.The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds. The application can take place both before and after the infection of the materials, plants or seeds by the fungi.
Die fungiziden Mittel enthalten im allgemeinen zwischen 0,1 und 95, vorzugsweise zwischen 0,5 und 90 Gew.-% Wirkstoff.The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
Die Aufwandmengen liegen bei der Anwendung im Pflanzenschutz je nach Art des gewünschten Effektes zwischen 0,01 und 2,0 kg Wirkstoff pro ha.Depending on the type of effect desired, the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per ha.
Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 1 bis 1000 g/100 kg, vorzugsweise 5 bis 100 g je 100 Kilogramm Saatgut benötigt. Bei der Anwendung im Material- bzw. Vorratsschutz richtet sich die Aufwandmenge an Wirkstoff nach der Art des Einsatzgebietes und des gewünschten Effekts. Übliche Aufwandmengen sind im Materialschutz beispielsweise 0,001 g bis 2 kg, vorzugsweise 0,005 g bis 1 kg Wirkstoff pro Qubikmeter behandelten Materials.In the case of seed treatment, amounts of active compound of 1 to 1000 g / 100 kg, preferably 5 to 100 g, are generally required per 100 kg of seed. When used in material or stock protection, the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of treated material.
Die Verbindungen I können in die üblichen Formulierungen überführt werden, z.B. Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsform richtet sich nach dem jeweiligen Verwendungszweck; sie soll in jedem Fall eine feine und gleichmäßige Verteilung der erfindungsgemäßen Verbindung ge- währleisten.The compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the connection according to the invention.
Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gewünschtenfalls unter Verwendung von Emulgiermitteln und Dispergiermitteln. Als Lösungsmittel / Hilfsstoffe kom- men dafür im wesentlichen in Betracht:The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. The following are essentially considered as solvents / auxiliaries:
- Wasser, aromatische Lösungsmittel (z.B. Solvesso Produkte, Xylol), Paraffine (z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Butanol, Pentanol, Benzylalkohol), Keto- ne (z.B. Cyclohexanon, gamma-Butryolacton), Pyrrolidone (NMP, NOP), Acetate (Glykoldiacetat), Glykole, Dimethylfettsäureamide, Fettsäuren und Fettsäureester. Grundsätzlich können auch Lösungsmittelgemische verwendet werden,- Water, aromatic solvents (e.g. Solvesso products, xylene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butryolactone), pyrrolidones (NMP, NOP), Acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used
- Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, Silikate); Emulgiermittel wie nichtionogene und anionische Emulgatoren (z.B. Polyoxyethylen- Fettalkohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergiermittel wie Lignin- Sulfitablaugen und Methylcellulose.- Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
Als oberflächenaktive Stoffe kommen Alkali-, Erdalkali-, Ammoniumsalze von Ligninsul- fonsäure, Naphthalinsulfonsäure, Phenolsulfonsäure, Dibutylnaphthalinsulfonsäure, Alkylarylsulfonate, Alkylsulfate, Alkylsulfonate, Fettalkoholsulfate, Fettsäuren und sulfa- tierte Fettalkoholglykolether zum Einsatz, ferner Kondensationsprodukte von sulfonier- tem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphtalinsulfonsäure mit Phenol und Formaldehyd, Polyoxyethy- lenoctylphenolether, ethoxyliertes Isooctylphenol, Octylphenol, Nonylphenol, Alkylphe- nolpolyglykolether, Tributylphenylpolyglykolether, Tristerylphenylpolyglykolether, Alkyl- arylpolyetheralkohole, Alkohol- und Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether, ethoxyliertes Polyoxypropylen, Laurylalkoholpoly- glykoletheracetal, Sorbitester, Ligninsulfitablaugen und Methylcellulose in Betracht.Alkali, alkaline earth, and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated naphthalene naphthalene and sulfonated dehydrogenated naphthalene derivatives of sulfonated formaldehyde derivatives and sulfonated dehydrogenated naphthalenedaphthalene from sulfonates, as well as condensation products with sulfated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene ether and condensation products , Condensation products of naphthalene or of naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tri-butylphenyl polyglycol ether, trihylphenyl polyglycol ether, alkyl alcoholoxy ethoxylated alcohol, alkyl alcoholoxy ethoxylated alcohol , Laurylalkoholpolyglykoletheracetal, sorbitol ester, lignin sulfite waste liquors and methyl cellulose into consideration.
Zur Herstellung von direkt versprühbaren Lösungen, Emulsionen, Pasten oder öldis- persionen kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kero- sin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Toluol, Xy- lol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Cyclohexanon, Isophoron, stark polare Lösungsmittel, z.B. Dimethylsulfoxid, N-Methylpyrrolidon oder Wasser in Betracht.Mineral oil fractions of medium to high boiling point, such as kerosene, are used to produce directly sprayable solutions, emulsions, pastes or oil dispersions. sin or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone , strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate, können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind z.B. Mineralerden, wie Kieselgele, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie z.B. Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte, wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver und andere feste Trägerstoffe.Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
Die Formulierungen enthalten im allgemeinen zwischen 0,01 und 95 Gew.-%, vorzugs- weise zwischen 0,1 und 90 Gew.-% des Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) eingesetzt.The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
Beispiele für Formulierungen sind: 1. Produkte zur Verdünnung in WasserExamples of formulations are: 1. Products for dilution in water
A Wasserlösliche Konzentrate (SL)A Water-soluble concentrates (SL)
10 Gew.-Teile einer erfindungsgemäßen Verbindung werden in Wasser oder einem wasserlöslichen Lösungsmittel gelöst. Alternativ werden Netzmittel oder andere Hilfsmittel zugefügt. Bei der Verdünnung in Wasser löst sich der Wirkstoff.10 parts by weight of a compound according to the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other aids are added. The active ingredient dissolves when diluted in water.
B Dispergierbare Konzentrate (DC)B Dispersible concentrates (DC)
20 Gew.-Teile einer erfindungsgemäßen Verbindung werden in Cyclohexanon unter Zusatz eines Dispergiermittels z.B. Polyvinylpyrrolidon gelöst. Bei Verdünnung in Wasser ergibt sich eine Dispersion.20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with the addition of a dispersant e.g. Dissolved polyvinyl pyrrolidone. When diluted in water, a dispersion results.
C Emulgierbare Konzentrate (EC)C Emulsifiable concentrates (EC)
15 Gew.-Teile einer erfindungsgemäßen Verbindung werden in Xylol unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 %) gelöst. Bei der Verdünnung in Wasser ergibt sich eine Emulsion. D Emulsionen (EW, EO)15 parts by weight of a compound according to the invention are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each). Dilution in water results in an emulsion. D emulsions (EW, EO)
40 Gew.-Teile einer erfindungsgemäßen Verbindung werden in Xylol unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 %) gelöst. Diese Mischung wird mittels einer Emulgiermaschine (Ultraturax) in Wasser eingebracht und zu einer homogenen Emulsion gebracht. Bei der Verdünnung in Wasser ergibt sich eine Emulsion.40 parts by weight of a compound according to the invention are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each). This mixture is introduced into water using an emulsifying machine (Ultraturax) and brought to a homogeneous emulsion. Dilution in water results in an emulsion.
E Suspensionen (SC, OD)E suspensions (SC, OD)
20 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von Disper- gier- und Netzmitteln und Wasser oder einem organischen Lösungsmittel in einer20 parts by weight of a compound according to the invention are added in one with the addition of dispersing and wetting agents and water or an organic solvent
Rührwerkskugelmühle zu einer feinen Wirkstoffsuspension zerkleinert. Bei der Verdünnung in Wasser ergibt sich eine stabile Suspension des Wirkstoffs.Agitator ball mill crushed into a fine active ingredient suspension. Dilution in water results in a stable suspension of the active ingredient.
F Wasserdispergierbare und wasserlösliche Granulate (WG, SG) 50 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von Disper- gier- und Netzmitteln fein gemahlen und mittels technischer Geräte (z.B. Extrusion, Sprühturm, Wirbelschicht) als wasserdispergierbare oder wasserlösliche Granulate hergestellt. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs.F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersants and wetting agents and are prepared as water-dispersible or water-soluble granules by means of technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution in water results in a stable dispersion or solution of the active ingredient.
G Wasserdispergierbare und wasserlösliche Pulver (WP, SP) 75 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von Disper- gier- und Netzmitteln sowie Kieselsäuregel in einer Rotor-Strator Mühle vermählen. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirk- Stoffs.G Water-dispersible and water-soluble powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.
2. Produkte für die Direktapplikation2. Products for direct application
H Stäube (DP) 5 Gew.Teile einer erfindungsgemäßen Verbindung werden fein gemahlen und mit 95 % feinteiligem Kaolin innig vermischt. Man erhält dadurch ein Stäubemittel.H dusts (DP) 5 parts by weight of a compound according to the invention are finely ground and intimately mixed with 95% finely divided kaolin. This gives a dusting agent.
I Granulate (GR, FG, GG, MG)I granules (GR, FG, GG, MG)
0.5 Gew-Teile einer erfindungsgemäßen Verbindung werden fein gemahlen und mit 95.5 % Trägerstoffe verbunden. Gängige Verfahren sind dabei die Extrusion, die0.5 part by weight of a compound according to the invention is ground finely and combined with 95.5% carriers. Common processes are extrusion
Sprühtrocknung oder die Wirbelschicht. Man erhält dadurch ein Granulat für die Direktapplikation.Spray drying or the fluidized bed. This gives granules for direct application.
J ULV- Lösungen (UL) 10 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einem organischen Lösungsmittel z.B. Xylol gelöst. Dadurch erhält man ein Produkt für die Direktapplikation.J ULV solutions (UL) 10 parts by weight of a compound according to the invention are in an organic Solvent eg xylene dissolved. This gives you a product for direct application.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus berei- teten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder Dispersionen, Emulsionen, öldispersionen, Pasten, Stäubemitteln, Streumitteln, Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfin- dungsgemäßen Wirkstoffe gewährleisten.The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Wässrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver, Öldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder öldispersionen können die Sub- stanzen als solche oder in einem öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermitttel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen können in größeren Bereichen variiert werden. Im allgemeinen liegen sie zwischen 0,0001 und 10%, vorzugsweise zwischen 0,01 und 1%.The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
Die Wirkstoffe können auch mit gutem Erfolg im Ultra-Low-Volume-Verfahren (ULV) verwendet werden, wobei es möglich ist, Formulierungen mit mehr als 95 Gew.-% Wirkstoff oder sogar den Wirkstoff ohne Zusätze auszubringen.The active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
Zu den Wirkstoffen können öle verschiedenen Typs, Netzmittel, Adjuvants, Herbizide, Fungizide, andere Schädlingsbekämpfungsmittel, Bakterizide, gegebenenfalls auch erst unmittelbar vor der Anwendung (Tankmix), zugesetzt werden. Diese Mittel können zu den erfindungsgemäßen Mitteln im Gewichtsverhältnis 1:10 bis 10:1 zugemischt werden.Various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.
Die erfindungsgemäßen Mittel können in der Anwendungsform als Fungizide auch zusammen mit anderen Wirkstoffen vorliegen, der z.B. mit Herbiziden, Insektiziden, Wachstumsregulatoren, Fungiziden oder auch mit Düngemitteln. Beim Vermischen der Verbindungen I bzw. der sie enthaltenden Mittel in der Anwendungsform als Fungizide mit anderen Fungiziden erhält man in vielen Fällen eine Vergrößerung des fungiziden Wirkungsspektrums. Die folgende Liste von Fungiziden, mit denen die erfindungsgemäßen Verbindungen gemeinsam angewendet werden können, soll die Kombinationsmöglichkeiten erläutern, nicht aber einschränken:In the use form as fungicides, the compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases. The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:
• Acylalanine wie Benalaxyl, Metalaxyl, Ofurace, Oxadixyl,Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl,
• Aminderivate wie Aldimorph, Dodine, Dodemorph, Fenpropimorph, Fenpropidin, Guazatine, Iminoctadine, Spiroxamin, Tridemorph• Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph
• Anilinopyrimidine wie Pyrimethanil, Mepanipyrim oder Cyrodinyl,Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl,
• Antibiotika wie Cycloheximid, Griseofulvin, Kasugamycin, Natamycin, Polyoxin oder Streptomycin,Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,
• Azole wie Bitertanol, Bromoconazol, Cyproconazol, Difenoconazole, Dinitrocona- zol, Epoxiconazol, Fenbuconazol, Fluquiconazol, Flusilazol, Hexaconazol, Imazalil, Metconazol, Myclobutanil, Penconazol, Propiconazol, Prochloraz, Prothioconazol, Tebuconazol, Triadimefon, Triadimenol, Triflumizol, Triticonazol, • Dicarboximide wie Iprodion, Myclozolin, Procymidon, Vinclozolin,Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazol, triazolazol, trichazonazol, trichlorazolol, prochlorazolol, prochlorazolol, trichlorazolol, prochlorazolol, trichlorazol, trichlorazol, trichlorazol, trichlorazol, trichazolazol, trichazolazol, trichazolazol, trichlorazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichazolazol, trichlorazol Dicarboximides such as iprodione, myclozolin, procymidone, vinclozolin,
• Dithiocarbamate wie Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propi- neb, Polycarbamat, Thiram, Ziram, Zineb,Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb,
• Heterocylische Verbindungen wie Anilazin, Benomyl, Boscalid, Carbendazim, Car- boxin, Oxycarboxin, Cyazofamid, Dazomet, Dithianon, Famoxadon, Fenamidon, Fenarimol, Fuberidazol, Flutolanil, Furametpyr, Isoprothiolan, Mepronil, Nuarimol, Probenazol, Proquinazid, Pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam, Thiaben- dazol, Thifluzamid, Thiophanat-methyl, Tiadinil, Tricyclazol, Triforine,Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronazidolomolol, probolil, probolil, nuarol, probolil, probolil Quinoxyfen, silthiofam, thiabenzazole, thifluzamide, thiophanate methyl, tiadinil, tricyclazole, triforins,
• Kupferfungizide wie Bordeaux Brühe, Kupferacetat, Kupferoxychlorid, basisches Kupfersulfat, • Nitrophenylderivate, wie Binapacryl, Dinocap, Dinobuton, Nitrophthal-isopropyl• copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate, • nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthaloisopropyl
• Phenylpyrrole wie Fenpiclonil oder Fludioxonil,Phenylpyrroles such as fenpiclonil or fludioxonil,
• Schwefel• sulfur
• Sonstige Fungizide wie Acibenzolar-S-methyl, Benthiavalicarb, Carpropamid, Chlo- rothalonil, Cyflufenamid, Cymoxanil, Dazomet, Diclomezin, Diclocymet, Diethofen- carb, Edifenphos, Ethaboxam, Fenhexamid, Fentin-Acetat, Fenoxanil, Ferimzone, Fluazinam, Fosetyl, Fosetyl-Aluminium, Iprovalicarb, Hexachlorbenzol, Metrafenon, Pencycuron, Propamocarb, Phthalid, Toloclofos-methyl, Quintozene, Zoxamid• Other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, Dazomet, diclomezin, diclocymet, Diethofen-carb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fennosetanyl, ferim Fosetyl aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide
• Strobilurine wie Azoxystrobin, Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin oder Trifloxystrobin, • Sulfensäurederivate wie Captafol, Captan, Dichlofluanid, Folpet, Tolylfluanid• strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, • sulfenoic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid
• Zimtsäureamide und Analoge wie Dimethomorph, Flumetover oder Flumorph. Synthesebeispiele• Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph. synthesis Examples
Die in den nachstehenden Synthesebeispielen wiedergegebenen Vorschriften wurden unter entsprechender Abwandlung der Ausgangsverbindungen zur Gewinnung weiterer Verbindungen I benutzt. Die so erhaltenen Verbindungen sind in der anschließenden Tabelle mit physikalischen Angaben aufgeführt.The instructions given in the synthesis examples below were used with the appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the table below with physical information.
Beispiel 1 - Herstellung von 5-Methoxy-6-(2,4,6-trifluorphenyl)-7-(4-methylpiperidinyl)- 1 ,2,4-triazolo[1 ,5a]pyrimidinExample 1 - Preparation of 5-methoxy-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidinyl) - 1, 2,4-triazolo [1,5a] pyrimidine
Eine Lösung von 0,6 g (1,5 mmol) 5-Chlor-6-(2,4,6-trifluorphenyl)-7-(4-methylpiperi- dinyl)-1,2,4-triazolo[1,5a]pyrimidin (vgl. WO 98/46607) in 10 ml Methanol wurden mit 0,32 g (1 ,8 mmol) 30%iger Natriummethanolat-Lsg. versetzt und über Nacht bei 20- 25°C gerührt. Nach Verdünnen der Reaktionsmischung mit verd. Salzsäure, Extraktion der wässrigen Phase mit Methyl-t-butylether (MTBE) und Phasentrennung wurden die vereinigten organischen Phasen eingeengt. Der Rückstand wurde mittels MPLC über Kieselgel RP-18 mit Acetonitril/Wasser-Gemischen gereinigt. Man erhielt 0,3 g der Titelverbindung als blasse Kristallmasse (Fp. 172-174°C).A solution of 0.6 g (1.5 mmol) of 5-chloro-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidinyl) -1,2,4-triazolo [1,5a ] pyrimidine (cf. WO 98/46607) in 10 ml of methanol were mixed with 0.32 g (1.8 mmol) of 30% sodium methoxide solution. added and stirred at 20-25 ° C overnight. After dilution of the reaction mixture with dil. Hydrochloric acid, extraction of the aqueous phase with methyl t-butyl ether (MTBE) and phase separation, the combined organic phases were concentrated. The residue was purified by means of MPLC over silica gel RP-18 with acetonitrile / water mixtures. 0.3 g of the title compound was obtained as a pale crystal mass (mp 172-174 ° C.).
1H-NMR (CDCI3, δ in ppm): 8,25 (s, 1H); 6,8 (t, 2H); 4,0 (s, 3H); 3,6 (d, 2H); 2,8 (m, 2H); 1,65 (m, 2H); 1,55 (m, 1H); 1,35 (m, 2H); 1,0 (d, 3H) 1 H NMR (CDCI 3 , δ in ppm): 8.25 (s, 1H); 6.8 (t. 2H); 4.0 (s, 3H); 3.6 (d. 2H); 2.8 (m, 2H); 1.65 (m, 2H); 1.55 (m, 1H); 1.35 (m, 2H); 1.0 (d, 3H)
Beispiel 2 - Herstellung von 5-Cyano-6-(2,4,6-trifluorphenyl)-7-(4-methylpiperidinyl)- 1 ,2,4-triazolo[1 ,5a]pyrimidinExample 2 - Preparation of 5-cyano-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidinyl) - 1, 2,4-triazolo [1,5a] pyrimidine
Eine Lösung von 1 g (2,5 mmol) 5-Chlor-6-(2,4,6-trifluorphenyl)-7-(4-methylpiperidinyl)- 1,2,4-triazolo[1,5a]pyrimidin (WO 98/46607) in 20 ml Acetonitril wurde mit 1,9 g (6,5 mmol) Tetrabutylammoniumcyanid versetzt und über Nacht bei 20-25°C gerührt. Nach Verdünnen der Reaktionsmischung mit verd. Salzsäure, Extraktion der wässrigen Phase mit Methyl-t-butylether (MTBE) und Phasentrennung wurden die vereinigten organischen Phasen eingeengt. Der Rückstand wurde mittels MPLC über Kieselgel RP-18 mit Acetonitril/Wasser-Gemischen gereinigt. Man erhielt 0,3 g der Titelverbindung als blasse Kristallmasse (Fp. 205-206°C).A solution of 1 g (2.5 mmol) of 5-chloro-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidinyl) - 1,2,4-triazolo [1,5a] pyrimidine (WO 98/46607) in 20 ml of acetonitrile, 1.9 g (6.5 mmol) of tetrabutylammonium cyanide were added and the mixture was stirred at 20-25 ° C. overnight. After dilution of the reaction mixture with dil. Hydrochloric acid, extraction of the aqueous phase with methyl t-butyl ether (MTBE) and phase separation, the combined organic phases were concentrated. The residue was purified by means of MPLC over silica gel RP-18 with acetonitrile / water mixtures. 0.3 g of the title compound was obtained as a pale crystal mass (mp. 205-206 ° C.).
1H-NMR (CDCI3, δ in ppm): 8,5 (s, 1 H); 7,9 (t, 2H); 3,8 (d, 2H); 2,9 (m, 2H); 1 ,7 (m, 2H); 1,6 (m, 1H); 1,35 (m, 2H); 1,0 (d, 3H) Tabelle I - Verbindungen der Formel I 1 H NMR (CDCI 3 , δ in ppm): 8.5 (s, 1 H); 7.9 (t, 2H); 3.8 (d. 2H); 2.9 (m. 2H); 1.7 (m, 2H); 1.6 (m, 1H); 1.35 (m, 2H); 1.0 (d, 3H) Table I - Compounds of Formula I.
Beispiele für die Wirkung gegen Schadpilze Examples of the action against harmful fungi
Die fungizide Wirkung der Verbindungen der Formel I ließ sich durch die folgenden Versuche zeigen:The fungicidal activity of the compounds of the formula I was demonstrated by the following tests:
Die Wirkstoffe wurden getrennt oder gemeinsam als eine Stammlösung aufbereitet mit 0,25 Gew.-% Wirkstoff in Aceton oder DMSO. Dieser Lösung wurde 1 Gew.-% Emulga- tor Uniperol® EL (Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxy- lierter Alkylphenole) zugesetzt und entsprechend der gewünschten Konzentration mit Wasser verdünnt. Anwendungsbeispiel 1 - Wirksamkeit gegen Mehltau an Gurkenblättern verursacht durch Sphaerotheca fuliginea bei protektiver AnwendungThe active ingredients were prepared separately or together as a stock solution with 0.25% by weight of active ingredient in acetone or DMSO. 1% by weight of Uniperol® EL emulsifier (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and diluted with water to the desired concentration. Example of use 1 - Efficacy against mildew on cucumber leaves caused by Sphaerotheca fuliginea in protective use
Blätter von in Töpfen gewachsenen Gurkenkeimlingen der Sorte "Chinesische Schlange" wurden im Keimblattstadium mit wässriger Suspension in der unten angegebenen Wirk- Stoffkonzentration bis zur Tropfnässe besprüht. 20 Stunden nach dem Antrocknen des Spritzbelages wurden die Pflanzen mit einer wässrigen Sporensuspension des Gurkenmehltaus (Sphaerotheca fuliginea) inokuliert. Anschließend wurden die Pflanzen im Gewächshaus bei Temperaturen zwischen 20 und 24°C und 60 bis 80 % relativer Luftfeuchtigkeit für 7 Tage kultiviert. Dann wurde das Ausmaß der Mehltauentwicklung visuell in %- Befall der Keimblattfläche ermittelt.Leaves of cucumber seedlings of the "Chinese snake" variety, grown in pots, were sprayed in the cotyledon stage with an aqueous suspension in the active substance concentration given below to runoff. 20 hours after the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of cucumber mildew (Sphaerotheca fuliginea). The plants were then cultivated in a greenhouse at temperatures between 20 and 24 ° C. and 60 to 80% relative atmospheric humidity for 7 days. The extent of mildew development was then determined visually in% of the cotyledon area.
In diesem Test zeigten die mit 63 ppm der Verbindungen 1-1 , 1-2, 1-3, bzw. I-5 behandelten Pflanzen keinen Befall, während die unbehandelten Pflanzen zu 100 % befallen waren. Anwendungsbeispiel 2 - Wirksamkeit gegen die Netzfleckenkrankheit der Gerste verursacht durch Pyrenophora teres bei 1 Tag protektiver AnwendungIn this test, the plants treated with 63 ppm of the compounds 1-1, 1-2, 1-3 or I-5 showed no infection, while the untreated plants were 100% infected. Example of use 2 - Efficacy against the barley net spot disease caused by Pyrenophora teres with 1 day of protective application
Blätter von in Töpfen gewachsenen Gerstenkeimlingen wurden mit wässriger Suspen- sion in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. 24 Stunden nach dem Antrocknen des Spritzbelages wurden die Versuchspflanzen mit einer wässrigen Sporensuspension von Pyrenophora [syn. Drechslera] teres, dem Erreger der Netzfleckenkrankheit inokuliert. Anschließend wurden die Versuchspflanzen im Gewächshaus bei Temperaturen zwischen 20 und 24°C und 95 bis 100 % relativer Luftfeuchtigkeit aufgestellt. Nach 6 Tagen wurde das Ausmaß der Krankheitsentwicklung visuell in % Befall der gesamten Blattfläche ermittelt.Leaves of barley seedlings grown in pots were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. 24 hours after the spray coating had dried on, the test plants were treated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net spot disease. The test plants were then placed in the greenhouse at temperatures between 20 and 24 ° C. and 95 to 100% relative atmospheric humidity. After 6 days, the extent of the development of the disease was determined visually in% of the total leaf area.
In diesem Test zeigten die mit 63 ppm der Verbindungen 1-1 , 1-2, 1-3, bzw. I-5 behandelten Pflanzen keinen Befall, während die unbehandelten Pflanzen zu 90 % befallen waren. In this test, the plants treated with 63 ppm of the compounds 1-1, 1-2, 1-3 and I-5 showed no infection, while the untreated plants were 90% infected.

Claims

Patentansprücheclaims
1. 6-(2,4,6-Trifluorphenyl)-triazolopyrimidine der Formel I1. 6- (2,4,6-trifluorophenyl) triazolopyrimidines of the formula I.
in der die Substituenten folgende Bedeutung haben: in which the substituents have the following meaning:
R1 d-Cβ-Alkyl, d-C8-Halogenalkyl, C3-C8-Cycloalkyl, C3-C8-Halogencyclo- alkyl, C2-C8-Alkenyl, C2-C8-Halogenalkenyl, C3-C6-Cycloalkenyl, C3-C6- Halogencycloalkenyl, C2-C8-Alkinyl, C2-C8-Halogenalkinyl oder Phenyl, Naphthyl, oder ein fünf- oder sechsgliedriger gesättigter, partiell ungesättigter oder aromatischer Heterocyclus, enthaltend ein bis vier Heteroatome aus der Gruppe O, N oder S,R 1 d-Cβ-alkyl, dC 8 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 haloalkenyl, C 3 - C 6 -Cycloalkenyl, C 3 -C 6 - halocycloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S,
R2 Wasserstoff oder eine der bei R1 genannten Gruppen,R 2 is hydrogen or one of the groups mentioned for R 1 ,
R1 und R2 können auch zusammen mit dem Stickstoffatom, an das sie gebunden sind, ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bilden, welches über N gebunden ist und ein weiteres Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, Ci-Ce-Alkyl, d-C6-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, d-C6-Alkoxy, Cι-C6-Halogenalkoxy, C3-C6-Alkenyloxy, C3-Cβ-Halogenalkenyloxy, d-C6-Alkylen und Oxy-C C3- alkylenoxy tragen kann; R1 und/oder R2 können eine bis vier gleiche oder verschiedene Gruppen Ra tragen:R 1 and R 2 together with the nitrogen atom to which they are attached can also form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contain a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, Ci-Ce-alkyl, dC 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, dC 6 -alkoxy, C 6 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C β -haloalkenyloxy, dC 6 alkylene and oxy-C C 3 - alkyleneoxy can carry; R 1 and / or R 2 can carry one to four identical or different groups R a :
Ra Halogen, Cyano, Nitro, Hydroxy, d-C6-Alkyl, d-Ce-Halogenalkyl, d-C8-Alkylcarbonyl, C3-Cβ-Cycloalkyl, d-Cβ-Alkoxy, d-C6-Halogen- alkoxy, d-C6-Alkoxycarbonyl, d-Cβ-Alkylthio, Cι-Cβ-Alkylamino, Di- d-C6-alkylamino, C2-C6-Alkenyl, C2-Ce-Alkenyloxy, C3-C6-Alkinyloxy, Oxy-d-C3-alkylenoxy, C3-C6-Cycloalkyl, Phenyl, Naphthyl, fünf- oder sechsgliedriger gesättigter, partiell ungesättigter oder aromatischer Heterocyclus, enthaltend ein bis vier Heteroatome aus der Gruppe O, N oder S, wobei diese aliphatischen, alicyclischen oder aromatischen Gruppen ihrerseits partiell oder vollständig halogeniert sein können;R a halogen, cyano, nitro, hydroxy, dC 6 -alkyl, dC e -haloalkyl, dC 8 -alkylcarbonyl, C 3 -C β -cycloalkyl, dC β -alkoxy, dC 6 -haloalkoxy, dC 6 -alkoxycarbonyl, d-Cβ-alkylthio, -C-C β -alkylamino, di- dC 6 -alkylamino, C 2 -C 6 -alkenyl, C 2 -C e -alkenoxy, C 3 -C 6 -alkynyloxy, oxy-dC 3 -alkyleneoxy , C 3 -C 6 cycloalkyl, phenyl, naphthyl, five- or six-membered saturated, partially unsaturated or aromatic heterocycle, containing one to four heteroatoms from the group O, N or S, these aliphatic, alicyclic or aromatic groups can in turn be partially or completely halogenated;
X Cyano, d-C4-Alkoxy, C3-C -Alkenyloxy, C1-C2-Halogenalkoxy oder C3-C4- Halogenalkenyloxy.X cyano, dC 4 alkoxy, C 3 -C alkenyloxy, C 1 -C 2 haloalkoxy or C 3 -C 4 haloalkenyloxy.
2. Verbindungen der Formel I gemäß Anspruch 1 , in der X Cyano bedeutet.2. Compounds of formula I according to claim 1, in which X is cyano.
3. Verbindungen der Formel I gemäß Anspruch 1 , in der X Methoxy bedeutet.3. Compounds of formula I according to claim 1, in which X is methoxy.
4. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 3, in der R1 und R2 folgende Bedeutung haben:4. Compounds of formula I according to one of claims 1 to 3, in which R 1 and R 2 have the following meaning:
R1 CH(CH3)-CH2CH3 , CH(CH3)-CH(CH3)2 , CH(CH3)-C(CH3)3 , CH(CH3)-CF3 , CH2C(CH3)=CH2 ,CH2CH=CH2 , Cyclopentyl , Cyclohexyl;R 1 CH (CH 3 ) -CH 2 CH 3 , CH (CH 3 ) -CH (CH 3 ) 2 , CH (CH 3 ) -C (CH 3 ) 3 , CH (CH 3 ) -CF 3 , CH 2 C (CH 3 ) = CH 2 , CH 2 CH = CH 2 , cyclopentyl, cyclohexyl;
R2 Wasserstoff oder Methyl; oderR 2 is hydrogen or methyl; or
R1 und R2 bilden gemeinsam -(CH2)2CH(CH3)(CH2)2-, -(CH2)2CH(CF3)(CH2)2- R 1 and R 2 together form - (CH 2 ) 2 CH (CH 3 ) (CH 2 ) 2 -, - (CH 2 ) 2 CH (CF 3 ) (CH 2 ) 2 -
5. Verbindungen der Formel 1.1:5. Compounds of the formula 1.1:
in der G C2-C6-Alkyl, Cι-C4-Alkoxymethyl oder C3-C6-Cycloalkyl; R2 Wasserstoff oder Methyl; und X Cyano, Methoxy oder Ethoxy bedeuten. in the GC 2 -C 6 alkyl, -CC 4 alkoxymethyl or C 3 -C 6 cycloalkyl; R 2 is hydrogen or methyl; and X is cyano, methoxy or ethoxy.
Verbindungen der Formel I.2.Compounds of the formula I.2.
in der Y für Wasserstoff oder d-C -Alkyl und X für Cyano, Methoxy oder Ethoxy steht. Verbindungen der Formel 1.3 in which Y is hydrogen or dC -alkyl and X is cyano, methoxy or ethoxy. Compounds of the formula 1.3
in der in the
D zusammen mit dem Stickstoffatom ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bildet, welches über N gebunden ist und ein weiteres Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, d-C4-Alkyl, d-C4-Alkoxy und C C2-Halogenalkyl tragen kann; undD together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, dC 4 - Can carry alkyl, dC 4 alkoxy and CC 2 haloalkyl; and
X Cyano, Methoxy oder Ethoxy bedeuten.X is cyano, methoxy or ethoxy.
8. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1 , durch Umsetzung von 5-Halogen-6-(2,4,6-trifluo henyl)-triazolopyrimidinen der Formel II8. A process for the preparation of the compounds of the formula I according to claim 1, by reacting 5-halo-6- (2,4,6-trifluorohenyl) triazolopyrimidines of the formula II
in der Hai für ein Halogenatom steht, mit Verbindungen der Formel III M-X IM in der M für ein Ammonium-, Tetraalkylammonium- oder Alkali- oder Erdalkalimetall-Kation steht und X die Bedeutung gemäß Anspruch 1 hat. in the shark represents a halogen atom, with compounds of the formula III MX IM in which M represents an ammonium, tetraalkylammonium or alkali metal or alkaline earth metal cation and X has the meaning according to claim 1.
9. Mittel, enthaltend einen festen oder flüssigen Trägerstoff und eine Verbindung der Formel I gemäß Anspruch 1.9. Agent containing a solid or liquid carrier and a compound of formula I according to claim 1.
10. Saatgut, enthaltend eine Verbindung der Formel I gemäß Anspruch 1 in einer Menge von 1 bis 1000 g/100 kg10. Seed containing a compound of formula I according to claim 1 in an amount of 1 to 1000 g / 100 kg
11. Verfahren zur Bekämpfung von pflanzenpathogenen Schadpilzen, dadurch ge- kennzeichnet, dass man die Pilze oder die vor Pilzbefall zu schützenden Materialien, Pflanzen, den Boden oder Saatgüter mit einer wirksamen Menge einer Verbindung der Formel I gemäß Anspruch 1 behandelt. 11. A method for controlling phytopathogenic harmful fungi, characterized in that the fungi or the materials, plants, soil or seeds to be protected against fungal attack are treated with an effective amount of a compound of the formula I according to claim 1.
EP04797968A 2003-11-25 2004-11-18 6-(2,4,6-trifluorophenyl)-triazolopyrimidines, method for the production thereof, use thereof for controlling harmful fungi, and substances containing the same Withdrawn EP1689750A1 (en)

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US6255309B1 (en) * 1999-03-19 2001-07-03 American Cyanomid Co. Fungicidal trifluoromethylalkylamino-triazolopyrimidines
US6117876A (en) * 1997-04-14 2000-09-12 American Cyanamid Company Fungicidal trifluorophenyl-triazolopyrimidines
TWI252231B (en) * 1997-04-14 2006-04-01 American Cyanamid Co Fungicidal trifluorophenyl-triazolopyrimidines
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DE10218592A1 (en) * 2002-04-26 2003-11-06 Bayer Cropscience Ag triazolopyrimidines
BR0309637A (en) * 2002-05-03 2005-03-08 Basf Aktiengesellchaft Compost, process for preparing same, use of compost, and suitable agent and process for combating harmful fungi
KR20050119172A (en) * 2003-03-31 2005-12-20 바스프 악티엔게젤샤프트 7-alkenylamino-triazolopyrimidines, method for the production thereof and use thereof in controlling harmful fungi and substances containing said triazolopyrimidines
EP1613633A1 (en) * 2003-04-02 2006-01-11 Basf Aktiengesellschaft 7-alkinylamino-triazolopyrimidines, methods for the production and use thereof to combat harmful fungi and agents containing said compounds
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