EP1697373A1 - 6-(2,4,6-trihalophenyl)-triazolopyrimidines, method for their production and their use for combating pathogenic fungi, in addition to agents containing said substances - Google Patents

6-(2,4,6-trihalophenyl)-triazolopyrimidines, method for their production and their use for combating pathogenic fungi, in addition to agents containing said substances

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Publication number
EP1697373A1
EP1697373A1 EP04820434A EP04820434A EP1697373A1 EP 1697373 A1 EP1697373 A1 EP 1697373A1 EP 04820434 A EP04820434 A EP 04820434A EP 04820434 A EP04820434 A EP 04820434A EP 1697373 A1 EP1697373 A1 EP 1697373A1
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EP
European Patent Office
Prior art keywords
formula
compounds
alkyl
methyl
chlorine
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.)
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Application number
EP04820434A
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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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Publication of EP1697373A1 publication Critical patent/EP1697373A1/en
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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to 6- (2,4,6-trihalophenyl) 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 attached via N and contain one to three further heteroatoms from the group O, N and S as a ring member and / or one or more substituents from the group halogen, C ⁇ C 6 alkyl, C Ce haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, dCe alkoxy, dC 6 haloalkoxy, C 3 - C 6 alkenyloxy, C 3 -C 6 - haloalkenyloxy, (exo) -C 1 -C 3 -alkyleneoxy can carry 6 alkylene and oxy-C C;
  • R 1 and / or R 2 can carry one to four identical or different groups R a :
  • L ⁇ L 2 , L 3 independently of one another chlorine or fluorine, at least one group being chlorine;
  • X is cyano, dC 4 alkyl, dC 4 alkoxy, C 3 -C 4 alkenyloxy, CC 2 haloalkoxy or C 3 -C 4 haloalkenyloxy.
  • 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-trihalogenophenyl) triazolopyrimidines are generally known from FR-A 2 784 381.
  • 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 from the 5-halo-6- (2,4,6-trihalogenophenyl) triazolopyrimidines of the formula II known from FR-A 2 784 381 by reaction with compounds MX (formula III).
  • Compounds III represent depending on the The meaning of the group X to be introduced is 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; ammonium, tetraalkylammonium or alkali or alkaline earth metal salts are usually preferred for practical reasons.
  • 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, alcohols such as methanol or ethanol, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene or acetonitrile.
  • the 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines obtained in this way are converted with halogenating agents [HAL] under the conditions known from WO-A 94/20501 into the halogenopyrimidines of the formula VII, in which the shark represents a halogen atom , preferably a Bromine or a chlorine atom, in particular a chlorine atom.
  • a chlorinating or brominating agent such as phosphoroxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride is advantageously used as the halogenating agent [HAL].
  • This reaction is usually carried out at 0 ° C. to 150 ° C., preferably at 80 ° C. to 125 ° C. [cf. EP-A 770 615].
  • R 1 VII + H_N * ⁇ I (X alkyl)
  • R VIII The reaction of VII with amines VIII, where R 1 and R 2 are as defined in formula I, is advantageously at 0 ° C. to 70 ° C., preferably 10 ° C to 35 ° C carried out, preferably in the presence of an inert solvent such as ether, e.g. B.
  • dioxane diethyl ether or in particular tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [cf. WO-A 98/46608].
  • a base such as tertiary amines, for example triethylamine or inorganic amines, such as potassium carbonate, is preferred; Excess amine of the formula VIII can also serve as the base.
  • the subsequent saponification of the ester X takes place under generally customary conditions, depending on the various structural elements, the alkaline or acid saponification of the compounds X can be advantageous. Under the conditions of ester saponification, the decarboxylation to I can already take place in whole or in part.
  • the decarboxylation is usually carried out at from 20 ° C. to 180 ° C., preferably from 50 ° C. to 120 ° C., in an inert solvent, if appropriate in the presence of an acid.
  • Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid.
  • Suitable solvents are water, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.
  • intermediate and end products are in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or purified under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting.
  • isomer mixtures occur during the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (e.g. under the action of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.
  • Halogen fluorine, chlorine, bromine and iodine
  • Alkyl saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for example dC 6 alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1- Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl,, 2-dimethylpropyl, 1-methylpentyl, 2- Methylpentyl, 3-methylpentyl, 4-methylpentyI, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1- Ethylbutyl, 2-ethylbutyl,
  • Haloalkyl straight-chain or branched alkyl groups having 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-fluoro ethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2- T
  • 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, 2 -Pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2 - butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-prop
  • 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;
  • Alkynyl straight-chain or branched hydrocarbon groups with 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for example C 2 -C 6 -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2- Butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl 3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl
  • 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-tetrahydrofuranyI, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazothiazolidinyl, 4-isothiazolidinyl, 4-isothiazolidiazine Pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolid
  • 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom
  • 5-ring heteroaryl groups which in addition to carbon atoms can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, eg 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1, 3,4-triazol-2-yl;
  • 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinylI, 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-alkyl, C 2 -C 6 -alkenyl or d-Cs-haloalkyl.
  • Z 1 is hydrogen, fluorine or C ⁇ C 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 may be substituted by dC 4 alkylI.
  • 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.
  • GC 2 -C 6 alkyl especially ethyl, n- and i-propyl, n-, sec-, tert-butyl, and CC 4 - alkoxymethyl, especially ethoxymethyl, or C 3 -C 6 cycloalkyl, especially cyclopentyl or cyclohexyl ;
  • R 2 is hydrogen or methyl
  • X is as defined for formula I and in particular means 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
  • X is as defined for formula I and in particular 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 contain as a ring member and / or one or more substituents from the group halogen, CC 6 alkyl, d- C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, CC 6 - Alkoxy, CC 6 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -haloalkenyloxy, CC 6 -alkylene and oxy-C C 3 - alkyleneoxy can carry.
  • These compounds correspond in particular to formula I.3,
  • X is as defined for formula I and in particular means 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 4 alkyl or CC 4 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 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-haloalkyl by one or two groups , in particular by 3,5-dimethyl or 3,5-di- (trifluoromethyl).
  • R 2 is hydrogen or methyl; or R 1 and R 2 together - (CH 2 ) 2 CH (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 denotes methyl.
  • the compounds I are suitable as fungicides. They are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.
  • the compounds I are also suitable for combating harmful fungi such as Pacilomyces variotii in the protection of materials (for example wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds.
  • the application can take place both before and after the infection of the materials, plants or seeds by the fungi.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
  • 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 compound 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 rock powder (e.g. kaolins, clays, talc, chalk) and synthetic rock powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
  • natural rock powder e.g. kaolins, clays, talc, chalk
  • synthetic rock powder e.g. highly disperse silica, silicates
  • Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
  • mineral oil fractions from medium to high boiling points such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, e.g. Dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.
  • mineral oil fractions from medium to high boiling points such as kerosene or diesel oil
  • coal tar oils as well as oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated
  • 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). Examples of 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.
  • a compound according to the invention 20 parts by weight of a compound according to the invention are comminuted in a stirred ball mill to form a fine active ingredient suspension with the addition of dispersing and wetting agents and water or an organic solvent. Dilution in water results in a stable suspension of the active ingredient.
  • a compound according to the invention 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersing and wetting agents and produced as technical equipment (e.g. extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • technical equipment e.g. extrusion, spray tower, fluidized bed
  • 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. at dilution in water results in a stable dispersion or solution of the active ingredient.
  • a compound according to the invention 0.5 part by weight is ground finely and combined with 95.5% carriers.
  • Common processes are extrusion, spray drying or fluidized bed. This gives granules 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, old dispersions, pastes, dusts, sprinkling 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, old dispersions) by adding water.
  • emulsions, pastes or old 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 agent, tackifier, dispersant or emulsifier and possibly solvent 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
  • Oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, 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.
  • compositions according to the invention can also be present together with other active compounds which, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases.
  • Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl,
  • Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidine, guazatine, iminoctadine, spiroxamine, tridemorph • anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl,
  • Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,
  • Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazol, triazolazolone, triazolone, propiconone , Triticonazole,
  • Dicarboximides such as iprodione, myclozolin, procymidone, vinclozolin,
  • Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb, • Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamidite, dazonometone , Famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronil, nuarimol, probenazole, procinazid, pyrifenox, pyroquilone, quinoxyfen, silthiofam, thiaben- dazol, thifluzil, tricyclic acid, thiophanoline, thiophaniline, thiophanilanol Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride
  • Nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl
  • 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,
  • Sulfenic 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 as a stock solution with 25 mg of active ingredient, which was mixed with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent emulsifier was filled from 99 to 1 ad 10 ml. Then ad 100 ml was made up with water. This stock solution was diluted with the solvent-emulsifier / water mixture described to the active ingredient concentration given below.
  • Uniperol® EL wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
  • test plants Sprayed dripping wet. 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.
  • Example of use 2 Efficacy against the gray mold on paprika leaves caused by Botrytis cinerea in protective use
  • Pepper seedlings of the "Neusiedler Ideal Elite" variety after 2 to 3 leaves had developed well, were sprayed to runoff point with an aqueous suspension in the active compound concentration given below.
  • the treated plants were inoculated with a spore suspension of Botrytis cinerea, which contained 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution.
  • the test plants were then placed in a climatic chamber at 22 to 24 ° C, darkness and high air humidity. After 5 days, the extent of the fungal attack on the leaves could be determined visually in%.

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Abstract

The invention relates to 6-(2,4,6-trihalophenyl)-triazolopyrimidines of formula (I), in which the substituents are defined as follows: R<1> represents alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, cycloalkenyl, halocycloalkenyl, alkynyl, 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; R<2> represents hydrogen or one of the groups cited for R<1>; R<1> and R<2>, together with the nitrogen atom, to which they are bonded, can also form a five- or six-membered heterocyclyl or heteroaryl, which is bonded via N and can contain one to three additional heteroatoms from the groups O, N and S as a ring member; R<1> and/or R<2> can be substituted in accordance with the description; L<1>, L<2>, L<3> represent chlorine or fluorine, at least one group being chlorine; X represents cyano, alkyl, alkoxy, alkenyloxy, haloalkoxy or haloalkenyloxy. The invention also relates to methods for producing said compounds, to agents containing the latter and to their use for combating plant-pathogenic fungi.

Description

6-(2,4,6-Trihalogenphenyl)-triazolopyrimidine, Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung von Schadpilzen sowie sie enthaltende Mittel6- (2,4,6-Trihalogenphenyl) -triazolopyrimidines, processes for their preparation and their use for controlling harmful fungi, and agents containing them
Beschreibungdescription
Die vorliegende Erfindung betrifft 6-(2,4,6-Trihalogenphenyl)-triazolopyrimidine der Formel IThe present invention relates to 6- (2,4,6-trihalophenyl) triazolopyrimidines of the formula I.
in der die Substituenten folgende Bedeutung haben: in which the substituents have the following meaning:
R1 d-Cβ-Alkyl, CrCs-Halogenalkyl, C3-C8-Cycloalkyl, C3-C8-Halogencycloalkyl, C2-C8-Alkenyl, C2-C8-Halogenalkenyl, C3-C6-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 d-Cβ-alkyl, CrCs-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 up 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 bis drei weitere Heteroatome aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, CτC6-Alkyl, C C-e-Halogenalkyl, C2-C6-Alkenyl, C2-C6- Halogenalkenyl, d-C-e-Alkoxy, d-C6-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6- Halogenalkenyloxy, (exo)-C1-C6-Alkylen und Oxy-C 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 attached via N and contain one to three further heteroatoms from the group O, N and S as a ring member and / or one or more substituents from the group halogen, CτC 6 alkyl, C Ce haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, dCe alkoxy, dC 6 haloalkoxy, C 3 - C 6 alkenyloxy, C 3 -C 6 - haloalkenyloxy, (exo) -C 1 -C 3 -alkyleneoxy can carry 6 alkylene and oxy-C C;
R1 und/oder R2 können eine bis vier gleiche oder verschiedene Gruppen Ra tragen:R 1 and / or R 2 can carry one to four identical or different groups R a :
Ra Halogen, Cyano, Nitro, Hydroxy, CrCβ-Alkyl, d-Ce-Halogenalkyl, Cι-C6-Al- kylcarbonyl, C3-C6-CycIoalkyl, d-C-e-Alkoxy, d-C6-Halogenalkoxy, C C6- Alkoxycarbonyl, d-Ce-Alkylthio, d-C6-Alkylamino, Di-CrC6-alkylamino, C2-C8-Alkenyl, C2-C8-Halogenalkenyl, C2-C6-AlkenyIoxy, C2-C8-Alkinyl, C2-C8-Halogenalkinyl, C3-C6-Alkinyloxy, Oxy-d-C3-alkylenoxy, C3-C8- Cycloalkenyl, 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, ali- cyclischen oder aromatischen Gruppen ihrerseits partiell oder vollständig halogeniert sein können;R a halogen, cyano, nitro, hydroxy, C r Cβ-alkyl, d-Ce-haloalkyl, -C-C 6 -alkylcarbonyl, C 3 -C 6 -cycloalkyl, dCe-alkoxy, dC 6 -haloalkoxy, CC 6 - alkoxycarbonyl, d-Ce-alkylthio, dC 6 -alkylamino, di-CrC 6 -alkylamino, C 2 -C 8 -alkenyl, C 2 -C 8 -haloalkenyl, C 2 -C 6 -alkenyloxy, C 2 -C 8 Alkynyl, C 2 -C 8 -haloalkynyl, C 3 -C 6 -alkynyloxy, oxy-dC 3 -alkyleneoxy, C 3 -C 8 - cycloalkenyl, 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, ali- cyclic or aromatic groups in turn can be partially or completely halogenated;
L\ L2, L3 unabhängig voneinander Chlor oder Fluor, wobei mindestens eine Gruppe Chlor ist;L \ L 2 , L 3 independently of one another chlorine or fluorine, at least one group being chlorine;
X Cyano, d-C4-Alkyl, d-C4-Alkoxy, C3-C4-Alkenyloxy, C C2-Halogenalkoxy oder C3-C4-Halogenalkenyloxy.X is cyano, dC 4 alkyl, dC 4 alkoxy, C 3 -C 4 alkenyloxy, CC 2 haloalkoxy or C 3 -C 4 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-trihalogenphenyl)-triazolopyrimidine sind aus FR-A 2 784 381 all- gemein 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-trihalogenophenyl) triazolopyrimidines are generally known from FR-A 2 784 381. 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 l 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 FR-A 2 784 381 bekannten 5-Halogen-6-(2,4,6-trihaIogenphenyl)-triazolopyrimidinen der Formel II durch Umset- zung 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 üblicherweise Ammonium-, Tetraalkylammonium- oder Alkali- oder Erdalkalimetallsalze bevorzugt.The compounds according to the invention can be obtained in various ways. They are advantageously obtained from the 5-halo-6- (2,4,6-trihalogenophenyl) triazolopyrimidines of the formula II known from FR-A 2 784 381 by reaction with compounds MX (formula III). Compounds III represent depending on the The meaning of the group X to be introduced is 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; ammonium, tetraalkylammonium or alkali or alkaline earth metal salts are usually preferred for practical reasons.
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, Alkohole, wie Methanol oder Ethanol, halogenierte Kohlenwasserstoffe wie Dichlormethan und aromatische Kohlenwasserstoffe, wie Toluol oder Acetonitril.Suitable solvents include ethers such as dioxane, diethyl ether and, preferably tetrahydrofuran, alcohols such as methanol or ethanol, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene or acetonitrile.
Verbindungen der Formel I, in denen X für C1-C4-Alkyl steht, können vorteilhaft durch folgenden Syntheseweg erhalten werden:Compounds of the formula I in which X is C 1 -C 4 alkyl can advantageously be obtained by the following synthetic route:
Ausgehend von 2-Aminotriazol IV und Ketoestem V, wobei R d-C -AlkyI bedeutet und L1 bis L3 gemäß Formel I definiert sind, werden die 5-Alkyl-7-hydroxy-6-phenyItriazolo- pyrimidine VI erhalten. In Formeln V und VI steht X1 für d-C4-Alkyl. Durch Verwendung der leicht zugänglichen 2-Phenylacetessigestern (V mit X1=CH3) werden die 5-Methyl- 7-hydroxy-6-phenyltriazolopyrimidine erhalten, die einen bevorzugten Gegenstand der Erfindung darstellen [vgl. Chem. Pharm. Bull., 9, 801 , (1961)]. 2-Aminotriazol IV ist kommerziell erhältlich. Die Herstellung der Ausgangsverbindungen V erfolgt vorteilhaft unter den aus EP-A 10 02 788 beschrieben Bedingungen.Starting from 2-aminotriazole IV and keto ester V, where R dC denotes -AlkyI and L 1 to L 3 are defined according to formula I, the 5-alkyl-7-hydroxy-6-phenyItriazolo-pyrimidines VI are obtained. In formulas V and VI, X 1 represents dC 4 alkyl. By using the easily accessible 2-phenylacetoacetic esters (V with X 1 = CH 3 ), the 5-methyl-7-hydroxy-6-phenyltriazolopyrimidines are obtained, which are a preferred subject of the invention [cf. Chem. Pharm. Bull., 9, 801, (1961)]. 2-aminotriazole IV is commercially available. The starting compounds V are advantageously prepared under the conditions described in EP-A 10 02 788.
Die so erhaltenen 5-Alkyl-7-hydroxy-6-phenyltriazolopyrimidine werden mit Halogenie- rungs-mitteln [HAL] unter den aus WO-A 94/20501 bekannten Bedingungen in die Ha- logenpyrimidine der Formel VII überführt, in der Hai ein Halogenatom, bevorzugt ein Brom oder ein Chloratom, insbesondere ein Chloratom bedeutet. Als Halogenierungs- mittel [HAL] wird vorteilhaft ein Chlorierungs- oder Bromierungsmittel wie Phosphoro- xybromid, Phosphoroxychlorid, Thionylchlorid, Thionylbromid oder Sulfurylchlorid eingesetzt.The 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines obtained in this way are converted with halogenating agents [HAL] under the conditions known from WO-A 94/20501 into the halogenopyrimidines of the formula VII, in which the shark represents a halogen atom , preferably a Bromine or a chlorine atom, in particular a chlorine atom. A chlorinating or brominating agent such as phosphoroxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride is advantageously used as the halogenating agent [HAL].
Diese Umsetzung wird üblicherweise bei 0°C bis 150°C, bevorzugt bei 80°C bis 125°C, durchgeführt [vgl. EP-A 770 615]. R1 VII + H_N *~ I (X = Alkyl) R VIII Die Umsetzung von VII mit Aminen VIII, wobei R1 und R2 wie in Formel I definiert sind, wird vorteilhaft bei 0°C bis 70°C, bevorzugt 10°C bis 35°C durchgeführt, vorzugsweise in Anwesenheit eines inerten Lösungsmittels, wie Ether, z. B. Dioxan, Diethylether oder insbesondere Tetrahydrofuran, halogenierte Kohlenwasserstoffe, wie Dichlormethan und aromatische Kohlenwasserstoffe, wie beispielsweise Toluol [vgl. WO-A 98/46608].This reaction is usually carried out at 0 ° C. to 150 ° C., preferably at 80 ° C. to 125 ° C. [cf. EP-A 770 615]. R 1 VII + H_N * ~ I (X = alkyl) R VIII The reaction of VII with amines VIII, where R 1 and R 2 are as defined in formula I, is advantageously at 0 ° C. to 70 ° C., preferably 10 ° C to 35 ° C carried out, preferably in the presence of an inert solvent such as ether, e.g. B. dioxane, diethyl ether or in particular tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [cf. WO-A 98/46608].
Die Verwendung einer Base, wie tertiäre Amine, beispielsweise Triethylamin oder anorganische Amine, wie Kaliumcarbonat ist bevorzugt; auch überschüssiges Amin der Formel VIII kann als Base dienen.The use of a base, such as tertiary amines, for example triethylamine or inorganic amines, such as potassium carbonate, is preferred; Excess amine of the formula VIII can also serve as the base.
Verbindungen der Formel I, in derX Cι-C4-Alkyl bedeutet, können alternativ auch aus Verbindungen I, in der X Halogen, insbesondere Chlor, bedeutet und Malonaten der Formel IX hergestellt werden. In Formel IX bedeuten X" Wasserstoff oder C C3-Alkyl und R CτC4-Alkyl. Sie werden zu Verbindungen der Formel X umgesetzt und zu Verbindungen I decarboxyliert [vgl. US 5 994 360].Compounds of the formula I in which X is C 1 -C 4 -alkyl can alternatively also be prepared from compounds I in which X is halogen, in particular chlorine, and malonates of the formula IX can be prepared. In formula IX, X "denotes hydrogen or CC 3 -alkyl and R CτC 4 -alkyl. They are converted into compounds of the formula X and decarboxylated to give compounds I [cf. US Pat. No. 5,994,360].
Δ / H+ X *- I (X = CrC4-Alkyl) Die Malonate IX sind in der Literatur bekannt [J. Am. Chem. Soσ, Bd. 64, 2714 (1942); J. Org. Chem., Bd. 39, 2172 (1974); Helv. Chim. Acta, Bd. 61 , 1565 (1978)] oder können gemäß der zitierten Literatur hergestellt werden. Δ / H + X * - I (X = C r C 4 alkyl) The malonates IX are known in the literature [J. At the. Chem. Soσ, Vol. 64, 2714 (1942); J. Org. Chem., Vol. 39, 2172 (1974); Helv. Chim. Acta, Vol. 61, 1565 (1978)] or can be prepared according to the literature cited.
Die anschließende Verseifung des Esters X erfolgt unter allgemein üblichen Bedingungen, in Abhängigkeit der verschiedenen Strukturelemente kann die alkalische oder die saure Verseifung der Verbindungen X vorteilhaft sein. Unter den Bedingungen der Es- terverseifung kann die Decarboxylierung zu I bereits ganz oder teilweise erfolgen.The subsequent saponification of the ester X takes place under generally customary conditions, depending on the various structural elements, the alkaline or acid saponification of the compounds X can be advantageous. Under the conditions of ester saponification, the decarboxylation to I can already take place in whole or in part.
Die Decarboxylierung erfolgt üblicherweise bei Temperaturen von 20°C bis 180°C, vorzugsweise 50°C bis 120°C, in einem inerten Lösungsmittel, gegebenenfalls in Gegenwart einer Säure.The decarboxylation is usually carried out at from 20 ° C. to 180 ° C., preferably from 50 ° C. to 120 ° C., in an inert solvent, if appropriate in the presence of an acid.
Geeignete Säuren sind Salzsäure, Schwefelsäure, Phosphorsäure, Ameisensäure, Essigsäure, p-Toluolsulfonsäure. Geeignete Lösungsmittel sind Wasser, aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropyl- ether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butyl- methylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-ButanoI, sowie Dimethylsulfoxid, Dimethylformamid und Dimethylacetamid, besonders bevorzugt wird die Reaktion in Salzsäure oder Essigsäure durchgeführt. Es können auch Gemische der genannten Lösungsmittel verwendet werden.Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid. Suitable solvents are water, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert. -Butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol , as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably the reaction is carried out in hydrochloric acid or acetic acid. Mixtures of the solvents mentioned can also be used.
Verbindungen der Formel I, in denen X für d-C4-Alkyl steht, können auch durch Kupplung von 5-Halogentriazolopyrimidinen der Formel I, in der X Halogen bedeutet, mit metallorganischen Reagenzien der Formel XI erhalten werden. In einer Ausführungsform dieses Verfahrens erfolgt die Umsetzung unter Übergangsmetallkatalyse, wie Ni- oder Pd-Katalyse. l (X = Hal) + Mv(-X")y I (X = CrC4-Alkyl) XI In Formel XI steht M für ein Metallion der Wertigkeit Y, wie beispielsweise B, Zn oder Sn und X" für d-C3-Alkyl. Diese Reaktion kann beispielsweise analog folgender Methoden durchgeführt werden: J. Chem. Soc. Perkin Trans. 1 , 1187 (1994), ebenda 1 , 2345 (1996); WO-A 99/41255; Aust. J. Chem., Bd. 43, 733 (1990); J. Org. Chem., Bd. 43, 358 (1978); J. Chem. Soc. Chem. Commun. 866 (1979); Tetrahedron Lett., Bd. 34, 8267 (1993); ebenda, Bd. 33, 413 (1992). 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 er- höhter 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.Compounds of the formula I in which X is dC 4 -alkyl can also be obtained by coupling 5-halotriazolopyrimidines of the formula I in which X is halogen with organometallic reagents of the formula XI. In one embodiment of this process, the reaction takes place using transition metal catalysis, such as Ni or Pd catalysis. l (X = Hal) + Mv (-X ") y I (X = C r C 4 -alkyl) XI In formula XI, M stands for a metal ion of valence Y, such as B, Zn or Sn and X" for dC 3 alkyl. This reaction can be carried out, for example, analogously to the following methods: J. Chem. Soc. Perkin Trans. 1, 1187 (1994), ibid. 1, 2345 (1996); WO-A 99/41255; Aust. J. Chem., Vol. 43, 733 (1990); J. Org. Chem., Vol. 43, 358 (1978); J. Chem. Soc. Chem. Commun. 866 (1979); Tetrahedron Lett., Vol. 34, 8267 (1993); ibid., vol. 33, 413 (1992). The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products by chromatography. Some of the intermediate and end products are in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or purified under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting.
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-, Säureoder 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 occur during the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (e.g. under the action of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.
Bei den in den vorstehenden Formeln angegebenen Definitionen der Symbole wurden Sammelbegriffe verwendet, die allgemein repräsentativ für die folgenden Substituenten stehen:In the definitions of the symbols given in the formulas above, collective terms were used which are generally representative of the following substituents:
Halogen: Fluor, Chlor, Brom und Jod;Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: gesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 4, 6 oder 8 Kohlenstoffatomen, z.B. d-C6-Alkyl wie Methyl, Ethyl, Propyl, 1-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, ,2-Dimethylpropyl, 1 -Methyl pentyl, 2-Methylpentyl, 3-Methylpentyl, 4-MethylpentyI, 1 ,1-DimethyIbutyl, 1 ,2-Dimethylbutyl, 1 ,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dime- thylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1 ,1 ,2-Trimethylpropyi, 1 ,2,2-Tri- methylpropyl, 1-Ethyl-1-methylpropyl und 1-Ethyl-2-methyl propyl;Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for example dC 6 alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1- Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl,, 2-dimethylpropyl, 1-methylpentyl, 2- Methylpentyl, 3-methylpentyl, 4-methylpentyI, 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-trimethylpropyi, 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 C-ι-C2-HalogenalkyI wie Chlormethyl, Brommethyl, Dichlor- methyl, Trichlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyi, Chlordifluormethyl, 1-Chlorethyl, 1-Bromethyl, 1-FluorethyI, 2-Fluor- ethyl, 2,2-Difluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluorethyl, 2,2-Dichlor-2-fluorethyI, 2,2,2-Trichlorethyl, Pentafluorethyl oder 1 ,1 ,1 -Trifluorprop-2-yl;Haloalkyl: straight-chain or branched alkyl groups having 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-fluoro ethyl, 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-propenyI, 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- EthyI-1propenyl, 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-pentenyI, 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-butenyI, 2,3-Dimethyl-1 -butenyl, 2,3-Di- methyl-2-butenyl, 2,3-Dimethyi-3-butenyl, 3,3-Dimethyl-1 -butenyl, 3,3-Dimethyl-2-bu- tenyl, 1-Ethyl-1 -butenyl, 1-EthyI-2-butenyI, 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;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, 2 -Pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2 - butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2 -Dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl , 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3rd -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;
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;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 Kohle nstoffatomen und einer oder zwei Dreifachbindungen in beliebiger Position, z.B. C2-C6-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-DimethyI-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-MethyI-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4- pentinyi, 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- DimethyI-3-butinyl, 3,3-Dimethyl-l-butinyl, 1-Ethyl-2-butinyl, 1-Ethyl-3-butinyl, 2-Ethyl- 3-butinyl und 1-EthyI-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 6 -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2- Butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl 3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-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- butinyl, 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-TetrahydrofuranyI, 3-Tetrahydrofuranyl, 2-Tetrahydrothienyl, 3-Tetrahydrothienyl, 2-Pyrrolidinyl, 3-Pyrrolidinyl, 3-lsoxazolidinyl, 4-lsoxazolidinyl, 5-lsoxazolidinyl, 3-lsothiazolidinyl, 4-lsothiazolidinyI, 5-lsothiazolidinyl, 3-Pyrazolidinyl, 4-Pyrazolidinyl, 5-Pyrazolidinyl, 2-Oxazolidinyl, 4-Oxazolidinyl, 5-Oxazolidinyl, 2-Thia- zolidinyl, 4-Thiazolidinyl, 5-Thiazolidinyl, 2-Imidazolidinyl, 4-lmidazolidinyl, 2-Pyrrolin-2- yl, 2-Pyrrolin-3-yl, 3-Pyrrolin-2-yl, 3-Pyrrolin-3-yl, 2-Piperidinyl, 3-PiperidinyI, 4-Piperi- dinyl, 1 ,3-Dioxan-5-yl, 2-Tetrahydropyranyl, 4-TetrahydropyranyI, 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-tetrahydrofuranyI, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazothiazolidinyl, 4-isothiazolidinyl, 4-isothiazolidiazine 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-piperidinyI, 4-piperidinyl, 1, 3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyI, 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 Stickstoffatome und ein Schwefel- oder Sauerstoffatom als Ringglieder enthalten können, z.B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 2-Pyrrolyl, 3-Pyrrolyl, 3-PyrazolyI, 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 can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, eg 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1, 3,4-triazol-2-yl;
6-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-PyridazinyI, 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-pyridazinylI, 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; 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;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 ; 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-C -Alkyl, C2-C6-Alkenyl oder d-Cs-Halogenalkyl steht.Compounds I are preferred in which R 1 is dC-alkyl, C 2 -C 6 -alkenyl or d-Cs-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 CτC6-Fluoroalkyl, Z2 Wasserstoff oder Fluor, oder Z1 und Z2 bilden gemeinsam eine Doppelbindung; q 0 oder 1 ist; undZ 1 is hydrogen, fluorine or CτC 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
R3 Wasserstoff oder Methyl bedeuten.R 3 is hydrogen or methyl.
Außerdem werden Verbindungen I bevorzugt, in denen R1 für C3-C6-Cycloalkyl steht, welches durch d-C4-AlkyI substituiert sein kann.In addition, compounds I are preferred in which R 1 is C 3 -C 6 cycloalkyl, which may be substituted by dC 4 alkylI.
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 Chiralitäts- zentrum beinhalten, sind für diese Gruppen die (S)- Isomere bevorzugt. Im Fall halogenfreier 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.
Weiterhin werden Verbindungen der Formel I bevorzugt, in denen L1, L2 und L3 Chlor bedeuten. Eine bevorzugte Ausführungsform der Erfindung betrifft Verbindungen der Formel 1.1 :Furthermore, compounds of the formula I are preferred in which L 1 , L 2 and L 3 are chlorine. 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 C C4- Alkoxymethyl, insbesondere Ethoxymethyl, oder C3-C6-Cycioalkyl, insbesondere Cyclopentyl oder Cyclohexyl;GC 2 -C 6 alkyl, especially ethyl, n- and i-propyl, n-, sec-, tert-butyl, and CC 4 - alkoxymethyl, especially ethoxymethyl, or C 3 -C 6 cycloalkyl, especially cyclopentyl or cyclohexyl ;
R2 Wasserstoff oder Methyl; undR 2 is hydrogen or methyl; and
X wie für Formel I definiert ist und insbesondere Cyano, Methoxy oder Ethoxy bedeutet.X is as defined for formula I and in particular means 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 C C4-AIkyl, insbesondere für Methyl und Ethyl, und X wie für Formel I definiert ist und insbesondere für Cyano, Methoxy oder Ethoxy steht. in which Y is hydrogen or CC 4 -alkyl, in particular methyl and ethyl, and X is as defined for formula I and in particular 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, C C6-Alkyl, d- C6-Halogenalkyl, C2-C6-Alkenyl, C2-C6-HaIogenalkenyl, C C6-AIkoxy, C C6-Halo- genalkoxy, C3-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, C C6-Alkylen und Oxy-C 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 contain as a ring member and / or one or more substituents from the group halogen, CC 6 alkyl, d- C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, CC 6 - Alkoxy, CC 6 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -haloalkenyloxy, CC 6 -alkylene and oxy-C C 3 - alkyleneoxy can carry. These compounds correspond in particular to formula I.3,
in der 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, C C6-Alkyl, C C6-Halogen- alkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, d-C6-Alkoxy, C C6-Halogenalkoxy, C3-C6-AIkenyloxy, C3-C6-Halogenalkenyloxy, (exo)-C C6-Alkylen und Oxy-C C3- alkylenoxy tragen kann; und in the 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, CC 6 - Alkyl, CC 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, dC 6 -alkoxy, CC 6 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -haloalkenyloxy , (exo) -CC 6 -alkylene and oxy-C C 3 - alkyleneoxy can carry; and
X wie für Formel I definiert ist und insbesondere Cyano, Methoxy oder Ethoxy bedeutet.X is as defined for formula I and in particular means cyano, methoxy or ethoxy.
Besonders bevorzugt sind Verbindungen der Formel I.3, in der die Gruppen L\ L2 und L3 die folgenden Bedeutungen haben: L1 Chlor, L2 und L3 Fluor; L1 Fluor, L2 Chlor und L3 Fluor; L1 und L2 Fluor und L3 Chlor; oder L1 Chlor, L2 Fluor und L3 Chlor.Compounds of the formula I.3 in which the groups L \ L 2 and L 3 have the following meanings are particularly preferred: L 1 chlorine, L 2 and L 3 fluorine; L 1 fluorine, L 2 chlorine and L 3 fluorine; L 1 and L 2 fluorine and L 3 chlorine; or L 1 chlorine, L 2 fluorine and L 3 chlorine.
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-C4-Alkyl oder C C4-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 4 alkyl or CC 4 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 R 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-C - Halogenalkyl, insbesondere durch 3,5-Dimethyl oder 3,5-Di-(trifluormethyl) substituiert ist.Another preferred subject of the invention are compounds I in which R 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-haloalkyl by one or two groups , in particular 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 Methyl; 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 ) 2 CH (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. In einer anderen bevorzugten Ausgestaltung der Verbindungen der Formel I bedeutet X Methyl.Furthermore, compounds I are particularly preferred in which X is cyano, methoxy or ethoxy, in particular cyano or methoxy. In another preferred embodiment of the compounds of the formula I, X denotes methyl.
Insbesondere sind im Hinblick auf ihre Verwendung die in den folgenden Tabellen zu- sammengestellten 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.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 L1, L2 und L3 Chlor, 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 L 1 , L 2 and L 3 are chlorine, X is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one line of Table A.
Tabelle 2Table 2
Verbindungen der Formel I, in denen L1 Fluor, L2 und L3 Chlor, 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 L 1 is fluorine, L 2 and L 3 is chlorine, X is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one line of Table A.
Tabelle 3Table 3
Verbindungen der Formel I, in denen L1 Chlor, L2 Fluor und L3 Chlor, 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 L 1 is chlorine, L 2 is fluorine and L 3 is chlorine, X is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 4Table 4
Verbindungen der Formel I, in denen L1 und L2 Fluor und L3 Chlor, 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 L 1 and L 2 are fluorine and L 3 is chlorine, X is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 5Table 5
Verbindungen der Formel I, in denen L1 und L3 Fluor, L2 Chlor, 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 L 1 and L 3 are fluorine, L 2 is chlorine, X is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 6Table 6
Verbindungen der Formel I, in denen L1, L2 und L3 Chlor, X Methoxy bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 7Compounds of the formula I in which L 1 , L 2 and L 3 are chlorine, X is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A. Table 7
Verbindungen der Formel I, in denen L1 Fluor, L2 und L3 Chlor, 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 L 1 is fluorine, L 2 and L 3 is chlorine, X is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one line of Table A.
Tabelle 8Table 8
Verbindungen der Formel I, in denen L1 Chlor, L2 Fluor und L3 Chlor, 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 L 1 is chlorine, L 2 is fluorine and L 3 is chlorine, X is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 9Table 9
Verbindungen der Formel I, in denen L und L2 Fluor und L3 Chlor, 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 L and L 2 are fluorine and L 3 is chlorine, X is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 10Table 10
Verbindungen der Formel I, in denen L1 und L3 Fluor, L2 Chlor, 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 L 1 and L 3 are fluorine, L 2 is chlorine, X is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 11Table 11
Verbindungen der Formel I, in denen L1, L2 und L3 Chlor, 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 L 1 , L 2 and L 3 are chlorine, X is ethoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one line of Table A.
Tabelle 12Table 12
Verbindungen der Formel I, in denen L1 Fluor, L2 und L3 Chlor, 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 L 1 is fluorine, L 2 and L 3 is chlorine, X is ethoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one line of Table A.
Tabelle 13Table 13
Verbindungen der Formel I, in denen L1 Chlor, L2 Fluor und L3 Chlor, 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 L 1 is chlorine, L 2 is fluorine and L 3 is chlorine, X is ethoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 14Table 14
Verbindungen der Formel I, in denen L1 und L2 Fluor und L3 Chlor, X Ethoxy bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 15Compounds of the formula I in which L 1 and L 2 are fluorine and L 3 is chlorine, X is ethoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A. Table 15
Verbindungen der Formel I, in denen L1 und L3 Fluor, L2 Chlor, 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 L 1 and L 3 are fluorine, L 2 is chlorine, X is ethoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 16Table 16
Verbindungen der Formel I, in denen L1, L2 und L3 Chlor, X Methyl bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which L 1 , L 2 and L 3 are chlorine, X is methyl and the combination of R 1 and R 2 for a compound corresponds in each case to one line of Table A.
Tabelle 17Table 17
Verbindungen der Formel I, in denen L1 Fluor, L2 und L3 Chlor, X Methyl bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which L 1 is fluorine, L 2 and L 3 is chlorine, X is methyl and the combination of R 1 and R 2 for a compound corresponds in each case to one line of Table A.
Tabelle 18Table 18
Verbindungen der Formel I, in denen L1 Chlor, L2 Fluor und L3 Chlor, X Methyl bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which L 1 is chlorine, L 2 is fluorine and L 3 is chlorine, X is methyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 19Table 19
Verbindungen der Formel I, in denen L1 und L2 Fluor und L3 Chlor, X Methyl bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which L 1 and L 2 are fluorine and L 3 is chlorine, X is methyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 20Table 20
Verbindungen der Formel I, in denen L1 und L3 Fluor, L2 Chlor, X Methyl bedeutet und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which L 1 and L 3 are fluorine, L 2 is chlorine, X is methyl 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 hervorragende Wirksamkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten, Deuteromycθten, Oomyceten und Ba- 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 distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as 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.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.
Speziell eignen sie sich zur Bekämpfung folgender Pflanzenkrankheiten: • Alternaria-Aύen 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-Aάen 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-Arten 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-Arten an Getreide und Zuckerrohr, sowie Venturia-Aύen (Schorf) an Äpfeln und Birnen. 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. 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.They are particularly suitable for combating the following plant diseases: • Alternaria Aύen on vegetables and fruit, Bipolaris and Drechslera species on cereals, rice and lawn, Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, vegetables, Ornamental plants and vines, Erysiphe cichoracearum and Sphaerotheca fuliginea on gourd family, • Fusarium and Verticillium arums on various plants, Mycosphaerella species on cereals, bananas and peanuts, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Podpfara phosphaola on pods, Podfica vita • Pseudocercosporella herpotrichoides on wheat and barley, Pseudoperonospora species on hops and cucumbers, Puccinia species on cereals, Pyricularia oryzae on rice, Rhizoctonia species on cotton, rice and lawn, • Septoria tritici and Stagonospora nodorum on wheat, Uncinula necator on vines , Ustilago species on cereals and sugar cane, and Venturia-A -en (scab) on apples and pear s. The compounds I are also suitable for combating harmful fungi such as Pacilomyces variotii in the protection of materials (for example wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products. The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds. The application can take place both before and after the infection of the materials, plants or seeds by the fungi.
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.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.
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.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- währieisten.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 compound 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. Als oberflächenaktive Stoffe kommen Alkali-, Erdalkali-, Ammoniumsalze von Ligninsul- fonsäure, Naphthalinsulfonsäure, Phenolsulfonsäure, Dibutylnaphthalinsulfonsäure, Alkylarylsulfonate, Alkylsulfate, Alkylsulfonate, Fettalkohoisulfate, 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.- Carriers such as natural rock powder (e.g. kaolins, clays, talc, chalk) and synthetic rock powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose. Alkali metal, alkaline earth metal, 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 ether and condensation products with 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 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.For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions from medium to high boiling points, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, e.g. Dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.
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. Beispiele für Formulierungen sind: 1. Produkte zur Verdünnung in WasserThe formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum). Examples of formulations are: 1. Products for dilution in water
A 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.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 Emulsionen (EW, EO)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 einer Rührwerkskugelmühle zu einer feinen Wirkstoffsuspension zerkleinert. Bei der Verdünnung in Wasser ergibt sich eine stabile Suspension des Wirkstoffs.20 parts by weight of a compound according to the invention are comminuted in a stirred ball mill to form a fine active ingredient suspension with the addition of dispersing and wetting agents and water or an organic solvent. Dilution in water results in a stable suspension of the active ingredient.
F Wasserdispergierbare und wasserlösliche Granulate (WG, SG)F water-dispersible and water-soluble granules (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.50 parts by weight of a compound according to the invention are finely ground with the addition of dispersing and wetting agents and produced as technical equipment (e.g. extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
G 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 Wirkstoffs.G Water-dispersible and water-soluble powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. at dilution in water results in a stable dispersion or solution of the active ingredient.
2. Produkte für die Direktapplikation2. Products for direct application
H Stäube (DP)H dusts (DP)
5 Gew.Teile einer erfindungsgemäßen Verbindung werden fein gemahlen und mit 95 % feinteiligem Kaolin innig vermischt. Man erhält dadurch ein Stäubemittel.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, die Sprühtrocknung oder die Wirbelschicht. Man erhält dadurch ein Granulat für die Direktapplikation.0.5 part by weight of a compound according to the invention is ground finely and combined with 95.5% carriers. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.
J ULV- Lösungen (UL)J ULV solutions (UL)
10 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einem organischen Lösungsmittel z.B. Xylol gelöst. Dadurch erhält man ein Produkt für die Direktapplikation.10 parts by weight of a compound according to the invention are dissolved in an organic solvent e.g. Xylene dissolved. This gives you a product for direct application.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder Dispersionen, Emulsionen, Oldispersionen, 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 erfindungsgemäßen 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, old dispersions, pastes, dusts, sprinkling 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 netz- baren Pulvern (Spritzpulver, Oldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Oldispersionen können die Substanzen 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 even- tuell 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, old dispersions) by adding water. To prepare emulsions, pastes or old 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 agent, tackifier, dispersant or emulsifier and possibly solvent 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%. 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 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.
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.Oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, 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.In the use form as fungicides, the compositions according to the invention can also be present together with other active compounds which, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases.
Die folgende Liste von Fungiziden, mit denen die erfindungsgemäßen Verbindungen gemeinsam angewendet werden können, soll die Kombinationsmöglichkeiten erläutern, nicht aber einschränken: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 • Anilinopyrimidine wie Pyrimethanil, Mepanipyrim oder Cyrodinyl,Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidine, guazatine, iminoctadine, spiroxamine, tridemorph • 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, Enilconazol, Epoxiconazol, Fenbuconazol, Fluquiconazol, Flusilazol, Hexaco- nazol, Imazalil, Metconazol, Myclobutanil, Penconazol, Propiconazol, Prochloraz, Prothioconazol, Tebuconazol, Triadimefon, Triadimenol, Triflumizol, Triticonazol,Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazol, triazolazolone, triazolone, propiconone , Triticonazole,
• Dicarboximide wie Iprodion, Myclozolin, Procymidon, Vinclozolin,Dicarboximides such as iprodione, myclozolin, procymidone, vinclozolin,
• Dithiocarbamate wie Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propi- neb, 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, • Kupferfungizide wie Bordeaux Brühe, Kupferacetat, Kupferoxychlorid, basisches Kupfersulfat,• Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb, • Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamidite, dazonometone , Famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronil, nuarimol, probenazole, procinazid, pyrifenox, pyroquilone, quinoxyfen, silthiofam, thiaben- dazol, thifluzil, tricyclic acid, thiophanoline, thiophaniline, thiophanilanol Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate,
• Nitrophenylderivate, wie Binapacryl, Dinocap, Dinobuton, Nitrophthal-isopropyl• Nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl
• Phenylpyrrole wie Fenpiclonil oder Fludioxonil, • Schwefel• phenylpyrroles such as fenpiclonil or fludioxonil, • 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,Strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,
• Sulfensäurederivate wie Captafol, Captan, Dichlofluanid, Folpet, Tolylfluanid• Sulfenic acid derivatives such as Captafol, Captan, dichlofluanid, Folpet, Tolylfluanid
• Zimtsäureamide und Analoge wie Dimethomorph, Flumetover oder Flumorph.• Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.
Synthesebeispielesynthesis Examples
Die in den nachstehenden Synthesebeispielen wiedergegebenen Vorschriften können unter entsprechender Abwandlung der Ausgangsverbindungen zur Gewinnung weiterer Verbindungen I benutzt werden.The instructions given in the synthesis examples below can be used to obtain further compounds I with a corresponding modification of the starting compounds.
Beispiel 1 : Herstellung von 5-Cyano-6-(2,4,6-trichlorphenyl)-7-(4-methylpiperidinyl)- 1 ,2,4-triazolo[1 ,5a]pyrimidinExample 1: Preparation of 5-cyano-6- (2,4,6-trichlorophenyl) -7- (4-methylpiperidinyl) -1, 2,4-triazolo [1,5a] pyrimidine
Eine Lösung von 0,4 g (0,92 mmol) 5-Chlor-6-(2,4,6-trichorphenyl)-7-(4- methylpiperidinyl)-1 ,2,4-triazolo[1,5a]pyrimidin [vgl. US 6,242,451] und 1 ,2 g (4,6 rnmol) Tetrabutylammoniumcyanid in 3 ml Acetonitril wurden 5 Std. bei 60°C gerührt. Anschließend wurde das Lösungsmittel abdestilliert und der Rückstand mittels präpara- tiver MPLC über Kieselgel RP-18 mit Acetonitril-Wasser-Gemischen gereinigt. Man erhielt 0,2 g der Titelverbindung als farblosen Festkörper vom Fp. 177-179°C.A solution of 0.4 g (0.92 mmol) of 5-chloro-6- (2,4,6-trichorphenyl) -7- (4-methylpiperidinyl) -1, 2,4-triazolo [1,5a] pyrimidine [see. No. 6,242,451] and 1.2 g (4.6 mmol) of tetrabutylammonium cyanide in 3 ml of acetonitrile were stirred at 60 ° C. for 5 hours. The solvent was then distilled off and the residue was purified by means of preparative MPLC over silica gel RP-18 with acetonitrile / water mixtures. 0.2 g of the title compound was obtained as a colorless solid, mp. 177-179 ° C.
1H-NMR (CDCI3, δ in ppm): 8,55 (s, 1 H); 7,6 (s, 2H); 3,8 (m, 2H); 2,9 (m, 2H) 1 ,7 (m, 2H); 1 ,6 (m, 1H); 1 ,4 (m, 2H); 1 ,0 (d, 3H) 1 H NMR (CDCI 3 , δ in ppm): 8.55 (s, 1 H); 7.6 (s. 2H); 3.8 (m. 2H); 2.9 (m, 2H) 1.7 (m, 2H); 1.6 (m, 1H); 1.4 (m, 2H); 1, 0 (d, 3H)
Beispiel 2: Herstellung von 5-Methoxy-6-(2,4,6-trichlorphenyl)-7-(4-methylpiperidinyl)- 1 ,2,4-triazolo[1 ,5a]pyrimidinExample 2: Preparation of 5-methoxy-6- (2,4,6-trichlorophenyl) -7- (4-methylpiperidinyl) -1, 2,4-triazolo [1,5a] pyrimidine
Eine Lösung von 0,2 g (0,46 mmol) 5-Chlor-6-(2,4,6-trichorphenyl)-7-(4- methylpiperidinyl)-1 ,2,4-triazolo[1 ,5a]pyrimidin [vgl. US 6,242,451] in 3 ml Methanol wurde mit 1 g 30 %iger Natriummethylat-Lsg. versetzt und ca. 2,5 Std. bei 60°C ge- rührt. Nach Entfernen des Lösungsmittels wurde der Rückstand mittels präparativer MPLC über Kieselgel RP-18 mit Acetonitril/Wasser-Gemischen gereinigt. Man erhielt 0,02 g der Titelverbindung als gelbes Harz.A solution of 0.2 g (0.46 mmol) of 5-chloro-6- (2,4,6-trichorphenyl) -7- (4-methylpiperidinyl) -1, 2,4-triazolo [1, 5a] pyrimidine [see. US 6,242,451] in 3 ml of methanol was mixed with 1 g of 30% sodium methylate solution. shifted and approx. 2.5 hours at 60 ° C stir. After the solvent had been removed, the residue was purified by preparative MPLC over RP-18 silica gel with acetonitrile / water mixtures. 0.02 g of the title compound was obtained as a yellow resin.
1H-NMR (CDCI3> δ in ppm): 8,25 (s, 1 H); 7,5 (s, 2H); 4,0 (s, 3H); 3,55 (d, breit, 2H); 2,8 (t, breit, 2H); 1 ,6 (d, breit, 2H); 1 ,5 (m, 1 H); 1 ,25-1 ,4 (m, 2H); 0,95 (d, 3H) 1 H NMR (CDCI 3> δ in ppm): 8.25 (s, 1 H); 7.5 (s, 2H); 4.0 (s, 3H); 3.55 (d, broad, 2H); 2.8 (t, broad, 2H); 1, 6 (d, broad, 2H); 1.5 (m, 1H); 1.25-1.4 (m, 2H); 0.95 (d, 3H)
Beispiele für die Wirkung gegen SchadpilzeExamples 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 als eine Stammlösung aufbereitet mit 25 mg Wirkstoff, welcher mit einem Gemisch aus Aceton und/oder DMSO und dem Emulgator Uniperol® EL (Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxylierter Alkylpheno- le) im Volumen-Verhältnis Lösungsmittel-Emulgator von 99 zu 1 ad 10 ml aufgefüllt wurde. Anschließend wurde ad 100 ml mit Wasser aufgefüllt. Diese Stammlösung wurde mit dem beschriebenen Lösungsmittel-Emulgator-Wasser Gemisch zu der unten angegeben Wirkstoffkonzentration verdünnt.The active ingredients were prepared as a stock solution with 25 mg of active ingredient, which was mixed with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent emulsifier was filled from 99 to 1 ad 10 ml. Then ad 100 ml was made up with water. This stock solution was diluted with the solvent-emulsifier / water mixture described to the active ingredient concentration given below.
Anwendungsbeispiel 1 - Wirksamkeit gegen die Netzfleckenkrankheit der Gerste verursacht durch Pyrenophora teres bei protektiver AnwendungExample of use 1 - Efficacy against the network spot disease of the barley caused by Pyrenophora teres in protective use
Blätter von in Töpfen gewachsenen Gerstenkeimlingen der Sorte "Hanna" wurden mit wässriger Suspension in der unten angegebenen Wirkstoffkonzentration bis zurLeaves of barley seedlings of the "Hanna" variety grown in pots were treated with an aqueous suspension in the active ingredient concentration given below to the
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.Sprayed dripping wet. 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 250 ppm der Verbindung von Beispiel 1 behandelten Pflanzen etwa 1 % Befall, während die unbehandelten Pflanzen zu 90 % befallen waren. Anwendungsbeispiel 2 - Wirksamkeit gegen den Grauschimmel an Paprikablättern verursacht durch Botrytis cinerea bei protektiver AnwendungIn this test, the plants treated with 250 ppm of the compound from Example 1 showed approximately 1% infection, while the untreated plants were 90% infected. Example of use 2 - Efficacy against the gray mold on paprika leaves caused by Botrytis cinerea in protective use
Paprikasämlinge der Sorte "Neusiedler Ideal Elite" wurden, nachdem sich 2 bis 3 Blätter gut entwickelt hatten, mit einer wässrigen Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. Am nächsten Tag wurden die behandelten Pflanzen mit einer Sporensuspension von Botrytis cinerea, die 1 ,7 x 106 Sporen/ml in einer 2 %igen wässrigen Biomalzlösung enthielt, inokuliert. Anschließend wurden die Versuchspflanzen in eine Klimakammer mit 22 bis 24°C, Dunkelheit und hoher Luftfeuchtigkeit gestellt. Nach 5 Tagen konnte das Ausmaß des Pilzbefalls auf den Blättern visuell in % ermittelt werden.Pepper seedlings of the "Neusiedler Ideal Elite" variety, after 2 to 3 leaves had developed well, were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea, which contained 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution. The test plants were then placed in a climatic chamber at 22 to 24 ° C, darkness and high air humidity. After 5 days, the extent of the fungal attack on the leaves could be determined visually in%.
In diesem Test zeigten die mit 250 ppm der Verbindung von Beispiel 1 behandelten Pflanzen etwa 7 % Befall, während die unbehandelten Pflanzen zu 100 % befallen wa- ren. In this test, the plants treated with 250 ppm of the compound from Example 1 showed about 7% infection, while the untreated plants were 100% infected.

Claims

Patentansprücheclaims
1. 6-(2,4,6-Trihalogenphenyl)-triazolopyrimidine der Formel I1. 6- (2,4,6-trihalophenyl) triazolopyrimidines of the formula I.
in der die Substituenten folgende Bedeutung haben: in which the substituents have the following meaning:
R1 d-C8-Alkyl, CrC8-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 dC 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 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 which contains one up 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 bis drei weitere Heteroatome aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, d-C6-Alkyl, d-C6-Halo- genalkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, d-C6-Alkoxy, C C6-Halo- genalkoxy, C3-C6-AlkenyIoxy, C3-C6-HalogenaIkenyloxy, (exo)-C C6- Alkylen und Oxy-d-C3-alkyIenoxy 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 attached via N and contain one to three further heteroatoms from the group O, N and S as a ring member and / or one or more substituents from the group halogen, dC 6 alkyl, dC 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, dC 6 alkoxy, CC 6 halo genalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -halogenalkenyloxy, (exo) -CC 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 :
Ra Halogen, Cyano, Nitro, Hydroxy, C C6-Alkyl, d-C6-Halogenalkyl, d-C6-Alkylcarbonyl, C3-C6-Cycloalkyl, C C6-Alkoxy, d-C6-Halogen- alkoxy, d-C6-Alkoxycarbonyl, d-C6-Alkylthio, CrC6-Alkylamino, Di- CrCδ-alkylamino, C2-C8-Alkenyl, C2-C8-Halogenalkenyl, C2-C6- Alkenyloxy, C2-C8-Alkinyl, C2-C8-Halogenalkinyl, C3-C6-Alkinyloxy, Oxy-Cι-C3-aIkylenoxy, C3-C8-Cycloalkenyl, Phenyl, Naphthyl, fünf- oder sechsgliedriger gesättigter, partiell ungesättigter oder aromati- scher 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, CC 6 -alkyl, dC 6 -haloalkyl, dC 6 -alkylcarbonyl, C 3 -C 6 -cycloalkyl, CC 6 -alkoxy, dC 6 -haloalkoxy, dC 6 -alkoxycarbonyl, dC 6 alkylthio, CrC 6 alkylamino, diCrC δ alkylamino, C 2 -C 8 alkenyl, C 2 -C 8 haloalkenyl, C 2 -C 6 alkenyloxy, C 2 -C 8 alkynyl, C 2 -C 8 -haloalkynyl, C 3 -C 6 -alkynyloxy, oxy-Cι-C 3 -alkyleneoxy, C 3 -C 8 -cycloalkenyl, 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 being aliphatic, alicyclic or aromatic groups can in turn be partially or completely halogenated;
L1, L2, L3 unabhängig voneinander Chlor oder Fluor, wobei mindestens eine Gruppe Chlor ist;L 1 , L 2 , L 3 independently of one another chlorine or fluorine, at least one group being chlorine;
X Cyano, C C -Alkyl, C-ι-C4-Alkoxy, C3-C4-Alkenyloxy, C C2-Halogenalkoxy oder C3-C4-Halogenalkenyloxy.X is cyano, CC alkyl, C-ι-C 4 alkoxy, C 3 -C 4 alkenyloxy, CC 2 -haloalkoxy or C 3 -C 4 haloalkenyloxy.
2. Verbindungen der Formel I gemäß Anspruch 1 , in der X Cyano, C C4-Alkoxy, C3-C -Alkenyloxy, d-C2-Halogenalkoxy oder C3-C -Halogenalkenyloxy bedeutet.2. Compounds of formula I according to claim 1, in which X is cyano, CC 4 alkoxy, C 3 -C alkenyloxy, dC 2 haloalkoxy or C 3 -C haloalkenyloxy.
3. Verbindungen der Formel I gemäß Anspruch 1 oder 2, in der X Cyano bedeutet.3. Compounds of formula I according to claim 1 or 2, in which X is cyano.
4. Verbindungen der Formel I gemäß Anspruch 1 , in der X Methyl bedeutet.4. Compounds of formula I according to claim 1, in which X is methyl.
5. Verbindungen der Formel I gemäß Anspruch 1 oder 2, in der X Methoxy bedeutet.5. Compounds of formula I according to claim 1 or 2, in which X is methoxy.
6. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 5, in der R1 und R2 folgende Bedeutung haben:6. Compounds of formula I according to one of claims 1 to 5, in which R 1 and R 2 have the following meaning:
R1 CH(CH3)-CH2CH3 , CH(CH3)-CH(CH3)2 , CH(CH3)-C(CH3) , 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 ), CH (CH 3 ) -CF 3 , CH 2 C (CH 3 ) = CH 2 , CH 2 CH = CH 2 , cyclopentyl, cyclohexyl;
R Wasserstoff oder Methyl; oderR is hydrogen or methyl; or
R1 und R2 bilden gemeinsam -(CH2)2CH(CH3)(CH2)2-, -(CH2)2CH(CF3)(CH2)2- oder -(CH2)20(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 - or - (CH 2 ) 2 0 (CH 2 ) 2 -.
Verbindungen der Formel 1.1 :Compounds of formula 1.1:
in der G C2-C6-Alkyl, C C4-Alkoxymethyl oder C3-C6-Cycloalkyl; R2 Wasserstoff oder Methyl; und X Cyano, Methyl, Methoxy oder Ethoxy bedeutet und L1, L2 und L3 die Bedeutung gemäß Anspruch 1 haben. in the GC 2 -C 6 alkyl, CC 4 alkoxymethyl or C 3 -C 6 cycloalkyl; R 2 is hydrogen or methyl; and X represents cyano, methyl, methoxy or ethoxy and L 1 , L 2 and L 3 have the meaning according to claim 1.
Verbindungen der Formel I.2Compounds of the formula I.2
in der Y für Wasserstoff oder d-C4-Alkyl und X für Cyano, Methyl, Methoxy oder Ethoxy steht und L1, L2 und L3 die Bedeutung gemäß Anspruch 1 haben. in which Y is hydrogen or dC 4 alkyl and X is cyano, methyl, methoxy or ethoxy and L 1 , L 2 and L 3 have the meaning according to claim 1.
Verbindungen der Formel I.3,Compounds of the 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 Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, d-C6-Alkyl, d-C6-HalogenalkyI, C2-C6-AIkenyl, C2-C6-Halogenalkenyl, d-C6-Alkoxy, d-C6-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, (exo)- d-C-e-Alkylen und Oxy-d-C3-alkylenoxy tragen kann; und X Cyano, Methyl, Methoxy oder Ethoxy bedeuten 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 6 - Alkyl, dC 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, dC 6 -alkoxy, dC 6 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -haloalkenyloxy, ( exo) - can carry dCe-alkylene and oxy-dC 3 -alkyleneoxy; and X is cyano, methyl, methoxy or ethoxy and
L1, L2 und L3 die Bedeutung gemäß Anspruch 1 haben.L 1 , L 2 and L 3 have the meaning according to claim 1.
10. Verbindungen der Formel I.3 gemäß Anspruch 9, in denen L1 Chlor, L2 und L3 Fluor; L1 Fluor, L2 Chlor und L3 Fluor; L1 und L2 Fluor und L3 Chlor; oder L1 Chlor, L2 Fluor und L3 Chlor bedeuten.10. Compounds of formula I.3 according to claim 9, in which L 1 is chlorine, L 2 and L 3 fluorine; L 1 fluorine, L 2 chlorine and L 3 fluorine; L 1 and L 2 fluorine and L 3 chlorine; or L 1 is chlorine, L 2 is fluorine and L 3 is chlorine.
11. Verbindungen der Formeln 1, 1.1 , 1.2 und I.3 gemäß einem der Ansprüche 1 bis 9, in denen L\ L2 und L3 Chlor bedeuten. 11. Compounds of formulas 1, 1.1, 1.2 and I.3 according to one of claims 1 to 9, in which L \ L 2 and L 3 are chlorine.
12. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 2, durch Umsetzung von 5-Halogen-6-(2,4,6-trifluorphenyl)-triazolopyrimidinen der Formel II12. A process for the preparation of the compounds of the formula I according to claim 2, by reacting 5-halo-6- (2,4,6-trifluorophenyl) triazolopyrimidines of the formula II
in der Hai für ein Halogenatom steht, mit Verbindungen der Formel III M-X III in der M für ein Ammonium-, Tetraalkylammonium- oder Alkali- oder Erdalkalimetall-Kation steht und X die Bedeutung gemäß Anspruch 2 hat. in the shark represents a halogen atom, with compounds of the formula III MX III in which M represents an ammonium, tetraalkylammonium or alkali metal or alkaline earth metal cation and X has the meaning according to claim 2.
13. Verfahren zur Herstellung von Verbindungen der Formel I gemäß Anspruch 1 , in der X d-C4-Alkyl bedeutet, durch Umsetzung von 2-Aminotriazol der Formel IV mit Ketoestem der Formel V,13. A process for the preparation of compounds of the formula I according to claim 1, in which X is dC 4 -alkyl, by reacting 2-aminotriazole of the formula IV with ketoester of formula V,
in der R und X1 unabhängig voneinander C C4-Alkyl bedeuten und L1, L2 und L3 gemäß Anspruch 1 definiert sind, zu 5-Alkyl-7-hydroxy-6-phenyltriazoIopyri- midinen der Formel VI, in which R and X 1 independently of one another are CC 4 alkyl and L 1 , L 2 and L 3 are defined according to claim 1, to give 5-alkyl-7-hydroxy-6-phenyltriazoIopyrimidinen of formula VI,
Halogenierung von VI mit Halogenierungsmitteln zu Halogenpyrimidinen der Formel VII, Halogenation of VI with halogenating agents to give halopyrimidines of the formula VII,
in der Hai für ein Halogenatom steht, und Umsetzung von VII mit Aminen der Formel VIII, R1 H-N VIII 2 R2 in der R1 und R2 die Bedeutung wie in Formel I haben. in the shark represents a halogen atom, and reaction of VII with amines of the formula VIII, R 1 HN VIII 2 R 2 in which R 1 and R 2 have the meaning as in formula I.
14. Mittel, enthaltend einen festen oder flüssigen Trägerstoff und eine Verbindung der Formel I gemäß Anspruch 1 oder 2.14. Agent containing a solid or liquid carrier and a compound of formula I according to claim 1 or 2.
15. Saatgut, enthaltend eine Verbindung der Formel I gemäß Anspruch 1 oder 2 in einer Menge von 1 bis 1000 g/100 kg.15. Seed containing a compound of formula I according to claim 1 or 2 in an amount of 1 to 1000 g / 100 kg.
16. Verfahren zur Bekämpfung von pflanzenpathogenen Schadpilzen, dadurch gekennzeichnet, dass man die Pilze oder die vor Pilzbefall zu schützenden Materialien, Pflanzen, den Boden oder Saatgüter mit einer wirksamen Menge einer Ver- bindung der Formel I gemäß Anspruch 1 oder 2 behandelt. 16. 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 or 2.
EP04820434A 2003-12-17 2004-12-14 6-(2,4,6-trihalophenyl)-triazolopyrimidines, method for their production and their use for combating pathogenic fungi, in addition to agents containing said substances Withdrawn EP1697373A1 (en)

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US6242451B1 (en) * 1998-09-25 2001-06-05 Klaus-Juergen Pees Fungicidal trihalophenyl-triazolopyrimidines
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US20040162428A1 (en) * 2001-07-18 2004-08-19 Tormo I Blasco Jordi 6-(2,6-difluorophenyl)-triazolopyrimidines as fungicides
US7038047B2 (en) * 2001-07-18 2006-05-02 Basf Aktiengesellschaft Substituted 6-(2-methoxyphenyl) triazolopyrimides as fungicides
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