EP1732927A2 - 6-(2-fluorophenyl)-triazolopyrimidines, method for producing them, their use for controlling parasitic fungi and agents containing the same - Google Patents

6-(2-fluorophenyl)-triazolopyrimidines, method for producing them, their use for controlling parasitic fungi and agents containing the same

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Publication number
EP1732927A2
EP1732927A2 EP05716387A EP05716387A EP1732927A2 EP 1732927 A2 EP1732927 A2 EP 1732927A2 EP 05716387 A EP05716387 A EP 05716387A EP 05716387 A EP05716387 A EP 05716387A EP 1732927 A2 EP1732927 A2 EP 1732927A2
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EP
European Patent Office
Prior art keywords
formula
methyl
compounds
alkyl
triazolo
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
EP05716387A
Other languages
German (de)
French (fr)
Inventor
Carsten Blettner
Markus Gewehr
Wassilios Grammenos
Thomas Grote
Udo HÜNGER
Bernd Müller
Matthias NIEDENBRÜCK
Joachim Rheinheimer
Peter Schäfer
Frank Schieweck
Anja Schwögler
Oliver Wagner
Michael Rack
Barbara Nave
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 EP1732927A2 publication Critical patent/EP1732927A2/en
Withdrawn legal-status Critical Current

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Classifications

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

Definitions

  • the present invention relates to 6- (2-fluorophenyl) triazolopyrimidines of the formula I.
  • RC 4 -C 8 -AIRyl C -C 8 -halogenoalkyl, C 3 -C 6 -cycloalkyl, substituted by at least one group R a , C 3 -C 8 -halo-cycloalkyl, C 3 -C 6 -cycloalkyl-C C 6 - alkyl, C 5 -C 8 alkenyl, C 2 -C 8 - .
  • Haloalkenyl C 3 -C 6 cycloalkenyl, C 3 -C 6 halocycloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic Heterocycle containing one to four heteroatoms from the group O, N or S,
  • R 2 is hydrogen, CC 3 alkyl or one of the groups mentioned for R 1 ,
  • R 1 and R 2 also together with the nitrogen atom to which they are attached form a five- to eight-membered saturated or partially unsaturated heterocyclyl or five- or six-membered heteroaryl which is bonded via N and one to three further heteroatoms from the group O, N and S as ring member and / or one or more substituents from the group halogen, C ⁇ -C 6 -alkyl, C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 1 -C 6 -alkoxy, d-Ce-haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -haloalkenyloxy, (exo) -CC 6 -alkylene and oxy-C 3 -C -alkyleneoxy can carry, where Piperidin-1-yl, which is unsubstituted or substituted by one or more methyl groups, remains excluded;
  • R 1 and / or R 2 can carry one to four identical or different groups R a :
  • R a halogen, cyano, nitro, hydroxy, Ci-Ce-alkyl, CC 6 -haloalkyl, dC 6 -AI- alkylcarbonyl, C 3 -C 6 -cycloalkyl, C ⁇ -C 6 -alkoxy, d-Ce-haloalkoxy, C r C 6 - alkoxycarbonyl, CC 6 -alkylthio, -C-C 6 -alkylamino, di-C C 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-C C 3 alkyleneoxy, C 3 -C 8 cycloalkenyl, phenyl, naphthyl,
  • L 2 is hydrogen, if L 1 is fluorine, additionally fluorine;
  • the invention relates to a process for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.
  • 5-alkyl-6-halophenyl-triazolopyrimidines are generally known from US Pat. No. 5,994,360.
  • 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 publication by the specific combination of the substitution in the 5-position and the substitution of the 6-phenyl group with 7-amino groups 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.
  • Compounds of the formula I can advantageously be obtained by the following synthetic route:
  • the 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines IV are obtained.
  • X represents dC 4 alkyl.
  • the starting compounds III are advantageously prepared under the conditions described in EP-A 1002788.
  • the 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines IV are reacted with halogenating agents [HAL] under the conditions described above to give the 7-halotriazolopyrimidines of the formula V, in which Y represents a halogen atom.
  • Chlorination or bromination agents such as phosphorus oxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride are preferably used.
  • the reaction can be carried out in bulk or in the presence of a solvent. Usual reaction temperatures are from 0 to 150 ° C or preferably from 80 to 125 ° C.
  • reaction of V with amines VI is advantageously carried out at 0 ° C. to 70 ° C., preferably 10 ° C. to 35 ° C., preferably in the presence of an inert solvent, such as ether, e.g. B. dioxane, diethyl ether or in particular tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [cf. WO-A 98/46608].
  • ether e.g. B. dioxane, diethyl ether or in particular tetrahydrofuran
  • halogenated hydrocarbons such as dichloromethane
  • 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 VI can also serve as the base.
  • the subsequent saponification of the ester IX takes place under generally customary conditions, depending on the various structural elements, the alkaline or acid saponification of the compounds IX can be advantageous.
  • 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, optionally in the presence of an acid, which can also serve as a solvent.
  • 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.
  • the reaction mixtures are usually worked up, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products chromatographically.
  • the intermediate and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are freed or purified from volatile components under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting. If individual compounds I are not accessible in the ways described above, they can be prepared by derivatizing other compounds I.
  • 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-methyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1.1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, hexyl, 1,1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-dimethylIbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-eth
  • Haloalkyl straight-chain or branched alkyl groups with 1 to 2, 4, 6 or 8 carbon atoms (as mentioned above), it being possible for part or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above: in particular C 1 -C 4 -haloalkyl such as chloromethyl, Bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-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, 2nd -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-butenyl, 1,1
  • Haloalkenyl unsaturated, straight-chain or branched hydrocarbon radicals with
  • 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,
  • 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, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2 -Pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 4-oxazolidinyl , 5-oxazolidinyl, 2-thiazolidinyl, 4-thi
  • 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, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4- Oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 1, 3,4-triazol-2-yl;
  • 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;
  • Oxyalkyleneoxy divalent unbranched chains of 1 to 3 CH 2 groups, both valences being bound to the skeleton via an oxygen atom, for example OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O;
  • the scope of the present invention includes the (R) and (S) isomers and the racemates of compounds of the formula I which have chiral centers.
  • Z 1 is hydrogen, fluorine or dC 6 fluoroalkyl
  • Z 2 , Z 3 is hydrogen or fluorine, or Z 1 and Z 2 together form a double bond
  • q is 1, 2 or 3; and R 3 is hydrogen or methyl.
  • R 1 is C 4 -C 8 alkyl or C 4 -C 8 haloalkyl.
  • compounds I are preferred in which R 1 3 -C 6 cycloalkyl or C 3 -C 8 -halocycloalkyl or C 6 -C substituted by at least one group R a C - C cycloalkyl-C -alkyl.
  • R 1 is C 3 -C 6 cycloalkyl, which is substituted by CC alkyl, in particular methyl, are particularly preferred.
  • R 1 and / or R 2 contain haloalkyl or haloalkenyl groups with a chiral center, the (S) isomers are preferred for these groups.
  • the (R) -configured isomers are preferred.
  • a preferred embodiment of the invention relates to compounds of the formula 1.1:
  • GC 2 -C 6 alkyl especially ethyl, n- and i-propyl, n-, sec-, tert-butyl, and dC - alkoxymethyl, especially ethoxymethyl, or C 3 -C 6 cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl; and R 2 is hydrogen or methyl; mean.
  • Another preferred embodiment of the invention relates to compounds of the formula I.2.
  • Y is C 2 -C 4 alkyl, in particular ethyl and propyl.
  • 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, dC 6 -alkyl, d-Ce-haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -halogenalkenyl, dC 6 -alkoxy , d-Ce-haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, CC 6 alkylene and oxy-C C 3 - alkyleneoxy can wear.
  • These compounds correspond in particular to formula I.3,
  • D together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, dC 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) -dC 6 -alkylene and oxy-C r C 3 - alkyleneoxy can carry; mean.
  • Compounds of the formula I are particularly preferred, in particular those of the formula I.3 in which the groups L and L 2 have the following meanings: L 1 and L 2 fluorine,
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a morpholinyl or thiomorpholinyl ring, in particular a ring which may be halogenated by one to three groups, dC 4 -alkyl or dC 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 morpholinyl or a pyrrolidinyl ring, in particular a pyrrolidinyl ring, are particularly preferred.
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a pyrazole ring which may be halogen, CC 4 alkyl or dC through one or two groups - Haloalkyl, in particular substituted by 3,5-dimethyl or 3,5-di (trifluoromethyl).
  • R 2 is hydrogen or methyl; or
  • R 1 and R 2 together mean - (CH 2 ) 2 CH (CF 3 ) (CH 2 ) 2- or - (CH 2 ) 2 O (CH 2 ) 2 -.
  • the compounds I are suitable as fungicides. They are characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as foliar, stain and soil fungicides.
  • the compounds I are also suitable for combating harmful fungi such as Pacilomyces variot 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, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants.
  • solvents / auxiliaries water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example petroleum fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma -Butryolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters.
  • aromatic solvents for example Solvesso products, xylene
  • paraffins for example petroleum fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclohexanone, gamma -But
  • solvent mixtures can also be used, - Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg 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 stone powder eg kaolins, clays, talc, chalk
  • synthetic stone powder eg 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.
  • Water-dispersible and water-soluble granules 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersants and wetting agents and are prepared as water-dispersible or water-soluble granules by means of technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution in water results in a stable dispersion or solution of the active ingredient.
  • Water-dispersible and water-soluble powders 75 parts by weight of a compound according to the invention are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. 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, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring.
  • the application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates composed of an active substance, wetting 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 cyprodinil,
  • Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,
  • Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazol, penocolazolol, myocazolol, myocazolol, myclazol, myclazol, myclazol, myocazolol, myclazol, myclazol, myclazol, myclazol, myclazol, myclazol, myclazol, myclazol, myclazol, myclazol , Tetraconazole, tri-dimefon, triadimenol, triflumizole, triticonazole,
  • Dicarboximides such as iprodione, myclozolin, procymidone, vinclozolin,
  • Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb,
  • Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronazolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, nuquin Pyroquilon, quinoxyfen, silthofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforins, Copper fungicides such as
  • Nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl
  • Phenylpyrroles such as fenpiclonil or fludioxonil, sulfur,
  • fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamide, cymoxanil, diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, namimzone, fluazi, fluazi, fluazi Fosetyl aluminum, phosphorous acid, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, penthiopyrad, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide,
  • strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, cresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, • sulfenoic acid derivatives such as captafol, captan, dichlofluanfluanid, folpet, tolpet, tolpet
  • Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.
  • Example 1a 5-chloro-6- (2,4,6-trifluorophenyl) -7- (2-methyl-pyrrolidin-1-yl) -1, 2,4-triazolo [1,5a] pyrimidine
  • Example 2a methyl 2- (2,4,6-trifluorophenyI) acetoacetate
  • reaction mixture was mixed with 450 ml of ammonium chloride solution. and conc. Acidified hydrochloric acid. After dilution with methyl t-butyl ether (MtBE), the organic phase was diluted with dil. acid and NaHCO 3 solution. washed, then dried and freed from solvent. The residue was fractionated. 34.5 g of the title compound were obtained as a light yellow liquid.
  • MtBE methyl t-butyl ether
  • Example 2d 5-methyl-6- (2,4,6-trifluorophenyl) -7- (R-1, 2-dimethylprop-1-yl) -1, 2,4-tri-azolo [1, 5a] pyrimidine
  • Phenyl substitution two diastereomers are present, which can differ in the physical data.
  • the active ingredients were prepared as a stock solution with 25 mg 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.
  • 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 containing 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution. The test plants were then placed in a climatic chamber with 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%.
  • the plants treated with 250 ppm of the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 or I-8 showed a maximum of 1% infection, while the untreated plants were 90% infected.
  • Leaves of cucumber seedlings grown in pots were sprayed in the cotyledon stage with an aqueous suspension in the active ingredient concentration given below to runoff. 3 days after the application, the plants were inoculated with an aqueous spore suspension of cucumber mehite (Sphaerotheca fuliginea). The plants were then cultivated in a greenhouse at temperatures between 20 and 24 ° C. and 60 to 80% relative atmospheric humidity for 7 days. The extent of mildew development was then determined visually in% of the cotyledon area.

Abstract

The invention relates to the 6-(2-fluorophenyl)-triazolopyrimidines of formula (I), wherein the substituents are defined as follows: R1 represents C4-C8 alkyl, C4-C8 halogen alkyl, substituted C3-C8 cycloalkyl, C3-C8 halogen cycloalkyl, C5-C8 alkenyl, C2-C8 halogen alkenyl, C3-C6 cycloalkenyl, C3-C6 halogen cycloalkenyl, C2-C8 alkinyl, C2-C8 halogen alkinyl or phenyl, naphthyl, or a five-membered or six-membered saturated, partially unsaturated or aromatic heterocycle comprising one to four heteroatoms from the group including O, N or S; R2 represents hydrogen, C1-C3 alkyl or one of the groups mentioned for R1, R1 and R2, together with the nitrogen atom to which they are bound, may form a five-membered or six-membered heterocyclyl or heteroaryl which is bound via N, and may contain one to three additional heteroatoms from the group including O, N and S as a ring member, whereby piperidino-1-yl which is optionally substituted by methyl groups is exempt; R1 and/or R2 may be substituted according to the description; L1 represents chlorine or fluorine; L2 represents hydrogen, if L1 represents fluorine, L2 additionally represents fluorine; X represents alkyl. The invention also relates to a method for producing the aforementioned compounds, to agents containing them and to their use for controlling phytopathogenic parasitic fungi.

Description

6-(2-Fluorphenyl)-triazoIopyrimidine, Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung von Schadpilzen sowie sie enthaltende Mittel6- (2-fluorophenyl) -triazoIopyrimidines, processes for their preparation and their use for controlling harmful fungi, and agents containing them
Beschreibungdescription
Die vorliegende Erfindung betrifft 6-(2-Fluorphenyl)-triazolopyrimidine der Formel IThe present invention relates to 6- (2-fluorophenyl) triazolopyrimidines of the formula I.
in der die Substituenten folgende Bedeutung haben: in which the substituents have the following meaning:
R C4-C8-AIRyl, C -C8-HaIogenalkyl, durch mindestens eine Gruppe Ra substituiertes C3-C6-CycloalkyI, C3-C8-Halogencycloalkyl, C3-C6-Cycloalkyl-C C6-alkyl, C5-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,RC 4 -C 8 -AIRyl, C -C 8 -halogenoalkyl, C 3 -C 6 -cycloalkyl, substituted by at least one group R a , C 3 -C 8 -halo-cycloalkyl, C 3 -C 6 -cycloalkyl-C C 6 - alkyl, C 5 -C 8 alkenyl, C 2 -C 8 - . Haloalkenyl, C 3 -C 6 cycloalkenyl, C 3 -C 6 halocycloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic Heterocycle containing one to four heteroatoms from the group O, N or S,
R2 Wasserstoff, C C3-Alkyl oder eine der bei R1 genannten Gruppen,R 2 is hydrogen, CC 3 alkyl or one of the groups mentioned for R 1 ,
R1 und R2 körinen auch zusammen mit dem Stickstoffatom, an das sie gebunden sind, ein fünf- bis achtgliedriges gesättigtes oder teilweise ungesättigtes Heterocyclyl oder fünf- oder sechsgliednges 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, Cι-C6-Alkyl, Cι-C6-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, Cι-C6-Alkoxy, d-Ce-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, (exo)-C C6-Alkylen und Oxy-Cι-C3-alkylenoxy tragen kann, wobei Piperidin-1-yl, welches unsubstituiert oder durch eine oder mehrere Methylgruppen substituiert ist, ausgenommen bleibt;R 1 and R 2 also together with the nitrogen atom to which they are attached form a five- to eight-membered saturated or partially unsaturated heterocyclyl or five- or six-membered heteroaryl which is bonded via N and one to three further heteroatoms from the group O, N and S as ring member and / or one or more substituents from the group halogen, Cι-C 6 -alkyl, C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 1 -C 6 -alkoxy, d-Ce-haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -haloalkenyloxy, (exo) -CC 6 -alkylene and oxy-C 3 -C -alkyleneoxy can carry, where Piperidin-1-yl, which is unsubstituted or substituted by one or more methyl groups, remains excluded;
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, Ci-Ce-Alkyl, C C6-Halogenalkyl, d-C6-AI- kylcarbonyl, C3-C6-Cycloalkyl, Cι-C6-Alkoxy, d-Ce-Halogenalkoxy, CrC6- Alkoxycarbonyl, C C6-Alkylthio, Cι-C6-Alkylamino, Di-C C6-alkylamino, C2-C8-Alkenyl, C2-C8-HalogenaIkenyl, C2-C6-Alkenyloxy, C2-C8-Alkinyl, C2-C8-Halogenalkinyl, C3-C6-Alkinyloxy, Oxy-C 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, Ci-Ce-alkyl, CC 6 -haloalkyl, dC 6 -AI- alkylcarbonyl, C 3 -C 6 -cycloalkyl, Cι-C 6 -alkoxy, d-Ce-haloalkoxy, C r C 6 - alkoxycarbonyl, CC 6 -alkylthio, -C-C 6 -alkylamino, di-C C 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-C C 3 alkyleneoxy, C 3 -C 8 cycloalkenyl, phenyl, naphthyl, five- or six-membered saturated, partially unsaturated or aromatic heterocycle, containing one up to four heteroatoms from the group O, N or S, where these aliphatic, alicyclic or aromatic groups can in turn be partially or completely halogenated;
L1 Chlor oder Fluor;L 1 chlorine or fluorine;
L2 Wasserstoff, wenn L1 Fluor bedeutet, zusätzlich Fluor;L 2 is hydrogen, if L 1 is fluorine, additionally fluorine;
X d-C4-Alkyl.X dC 4 alkyl.
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-Alkyl-6-halogenphenyl-triazolopyrimidine sind aus US 5 994360 allgemein bekannt. Triazolopyrimidine mit optisch aktiven Aminosubstituenten in 7-Position werden in WO 02/38565 allgemein vorgeschlagen.5-alkyl-6-halophenyl-triazolopyrimidines are generally known from US Pat. No. 5,994,360. 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 vorgenann- ten Schrift beschriebenen durch die spezifische Kombination der Substitution in der 5-Position und der Substitution der 6-Phenylgruppe mit 7-Aminogruppen des Triazolo- pyrimidin-Gerüstes.The compounds according to the invention differ from those described in the abovementioned publication by the specific combination of the substitution in the 5-position and the substitution of the 6-phenyl group with 7-amino groups of the triazolopyrimidine skeleton.
Die Verbindungen der Formel I weisen eine gegenüber den bekannten Verbindungen erhöhte Wirksamkeit, bzw. ein verbreitertes Wirkungsspektrum gegen Schadpilze auf. Die erfindungsgemäßen Verbindungen können auf verschiedenen Wegen erhalten werden. Verbindungen der Formel I können vorteilhaft durch folgenden Syntheseweg erhalten werden: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. Compounds of the formula I can advantageously be obtained by the following synthetic route:
Ausgehend von 5-Amino-1 ,2,4-triazol der Formel II und Ketoestern III werden die 5-Alkyl-7-hydroxy-6-phenyltriazolopyrimidine IV erhalten. In Formeln III und IV steht X für d-C4-Alkyl. Durch Verwendung der leicht zugänglichen 2-Phenylacetessigestern (III mitX1=CH3) werden die 5-MethyI-7-hydroxy-6-phenyltriazolopyrimidine erhalten [vgl. Chem. Pharm. Bull., 9, 801, (1961)]. Die Herstellung der Ausgangsverbindungen III erfolgt vorteilhaft unter den aus EP-A 1002788 beschrieben Bedingungen.Starting from 5-amino-1, 2,4-triazole of the formula II and keto esters III, the 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines IV are obtained. In formulas III and IV, X represents dC 4 alkyl. The 5-methyl-7-hydroxy-6-phenyltriazolopyrimidines are obtained by using the easily accessible 2-phenylacetoacetic esters (III with X 1 = CH 3 ) [cf. Chem. Pharm. Bull., 9, 801, (1961)]. The starting compounds III are advantageously prepared under the conditions described in EP-A 1002788.
Die Verbindungen der Formel IV sind neu. Bevorzugte Zwischenprodukte sindThe compounds of formula IV are new. Preferred intermediates are
5-Methyl-6-(2-chlor-6-fluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ol; 5-Methyl-6-(2,6-difluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ol; und 5-Methyl-6-(2,4,6-trifluor-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ol.5-methyl-6- (2-chloro-6-fluorophenyl) - [1, 2,4] triazolo [1, 5-a] pyrimidin-7-ol; 5-methyl-6- (2,6-difluorophenyl) - [1, 2,4] triazolo [1, 5-a] pyrimidin-7-ol; and 5-methyl-6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-ol.
Die 5-Alkyl-7-hydroxy-6-phenyltriazolopyrimidine IV werden mit Halogenierungsmitteln [HAL] unter den weiter oben beschriebenen Bedingungen zu den 7-Halo- genotriazolopyrimidinen der Formel V umgesetzt, in der Y für ein Halogenatom steht. Bevorzugt werden Chlorierungs- oder Bromierungsmittel wie Phosphoroxybromid, Phosphoroxychlorid, Thionylchlorid, Thionylbromid oder Sulfurylchlorid eingesetzt. Die Umsetzung kann in Substanz oder in Gegenwart eines Lösungsmittels durchgeführt werden. Übliche Reaktionstemperaturen betragen von 0 bis 150°C oder vorzugsweise von 80 bis 125°C.The 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines IV are reacted with halogenating agents [HAL] under the conditions described above to give the 7-halotriazolopyrimidines of the formula V, in which Y represents a halogen atom. Chlorination or bromination agents such as phosphorus oxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride are preferably used. The reaction can be carried out in bulk or in the presence of a solvent. Usual reaction temperatures are from 0 to 150 ° C or preferably from 80 to 125 ° C.
Die Verbindungen der Formel V sind neu. Bevorzugte Zwischenprodukte sindThe compounds of formula V are new. Preferred intermediates are
7-Chlor-5-methyl-6-(2-chlor-6-fluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin;7-chloro-5-methyl-6- (2-chloro-6-fluorophenyl) - [1, 2,4] triazolo [1, 5-a] pyrimidine;
7-Brom-5-methyl-6-(2-chlor-6-fluor-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin;7-bromo-5-methyl-6- (2-chloro-6-fluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine;
7-Chlor-5-methyl-6-(2,6-difluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin;7-chloro-5-methyl-6- (2,6-difluorophenyl) - [1, 2,4] triazolo [1, 5-a] pyrimidine;
7-Brom-5-methyl-6-(2,6-difluor-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin;7-bromo-5-methyl-6- (2,6-difluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine;
7-Chlor-5-methyl-6-(2,4,6-trifluor-phenyl)-[1 ,2,4]triazolo[1 ,5-ajpyrimidin; und 7-Brom-5-methyl-6-(2,4,6-trifluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin. (X = Alkyl) 7-chloro-5-methyl-6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1, 5-ajpyrimidine; and 7-bromo-5-methyl-6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1, 5-a] pyrimidine. (X = alkyl)
Die Umsetzung von V mit Aminen VI 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 Koh- lenwasserstoffe, wie Dichlormethan und aromatische Kohlenwasserstoffe, wie beispielsweise Toluol [vgl. WO-A 98/46608].The reaction of V with amines VI is advantageously carried out at 0 ° C. to 70 ° C., preferably 10 ° C. to 35 ° C., preferably in the presence of an inert solvent, such as ether, e.g. B. dioxane, diethyl ether or in particular tetrahydrofuran, halogenated 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 VI 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 VI can also serve as the base.
Verbindungen der Formel I können alternativ auch aus 5-Halogen-triazolopyrimidinen der Formel VII, in der X Halogen, insbesondere Chlor, bedeutet und Malonaten der Formel VIII hergestellt werden. In Formel VIII bedeuten X1 Wasserstoff oder d-C3- Alkyl und R CrC4-Alkyl. Sie werden zu Verbindungen der Formel IX umgesetzt und zu Verbindungen I decarboxyliert [vgl. US 5 994360].Compounds of the formula I can alternatively also be prepared from 5-halogenotriazolopyrimidines of the formula VII, in which X is halogen, in particular chlorine, and malonates of the formula VIII. In formula VIII, X 1 is hydrogen or dC 3 alkyl and RC r C 4 alkyl. They are converted into compounds of the formula IX and decarboxylated to give compounds I [cf. US 5 994360].
Δ / H+ IX I (X = CrC4-Alkyl) Die Malonate VIII sind in der Literatur bekannt [J. Am. Chem. Soc, 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 + IX I (X = C r C 4 alkyl) The malonates VIII are known in the literature [J. At the. Chem. Soc, Vol. 64, 2714 (1942); J. Org. Chem., Vol. 39, 2172 (1974); Helv. Chim. Acta, Vol. 61, 1565 (1978)] or can be prepared according to the literature cited.
Die anschließende Verseifung des Esters IX erfolgt unter allgemein üblichen Bedin- gungen, in Abhängigkeit der verschiedenen Strukturelemente kann die alkalische oder die saure Verseifung der Verbindungen IX vorteilhaft sein. Unter den Bedingungen der Esterverseifung kann die Decarboxylierung zu I bereits ganz oder teilweise erfolgen. 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, welche auch als Lösungsmittel dienen kann.The subsequent saponification of the ester IX takes place under generally customary conditions, depending on the various structural elements, the alkaline or acid saponification of the compounds IX can be advantageous. Under the conditions of ester hydrolysis, 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, optionally in the presence of an acid, which can also serve as a solvent.
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.-Butanol, 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 VII sind allgemein aus EP-A 550 113 oder WO 98/46608 bekannt oder können analog der dort beschriebenen Methoden erhalten werden.Compounds of the formula VII are generally known from EP-A 550 113 or WO 98/46608 or can be obtained analogously to the methods described there.
Verbindungen der Formel I können auch durch Kupplung von 5-Halogentriazolo- pyrimidinen der Formel VII mit metallόr'gänischen Reagenzien der Formel X erhalten werden. In einer Ausführungsform dieses Verfahrens erfolgt die Umsetzung unter Ü- bergangsmetallkatalyse, wie Ni- oder Pd-Katalyse. VII + Mv(-X2)y *■ | X In Formel X steht M für ein Metallion der Wertigkeit Y, wie beispielsweise B, Zn oder Sn und X2 für CrC3-AlkyI. 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).Compounds of the formula I can also be obtained by coupling 5-halotriazolo-pyrimidines of the formula VII with metallic reagents of the formula X. In one embodiment of this process, the conversion takes place using transition metal catalysis, such as Ni or Pd catalysis. VII + Mv (-X 2 ) y * ■ | X In formula X, M stands for a metal ion of valence Y, such as B, Zn or Sn, and X 2 for C r C 3 alkylI. 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. 34: 8267 (1993); ibid., vol. 33, 413 (1992).
Die Reaktionsgemische werden in üblicherweise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenenfalls chromatographische Reinigung der Rohprodukte. Die Zwischen- und Endprodukte fallen z.T. in Form farbloser oder schwach bräunlicher, zäher Öle an, die unter vermindertem Druck und bei mäßig erhöhter Temperatur von flüchtigen Anteilen befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren erfolgen. Sofern einzelne Verbindungen I nicht auf den voranstehend beschriebenen Wegen zugänglich sind, können sie durch Derivatisierung anderer Verbindungen I hergestellt werden.The reaction mixtures are usually worked up, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products chromatographically. The intermediate and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are freed or purified from volatile components under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting. If individual compounds I are not accessible in the ways described above, they can be prepared by derivatizing other compounds I.
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-MethyIethyl, Butyl, 1-Methyl-propyl, 2-Methyl propyl, 1,1-Dimethylethyl, Pentyl, 1-Methylbutyl, 2-Me- thylbutyl, 3-Methylbutyl, 2,2-Di-methylpropyI, 1 -Ethyl propyl, Hexyl, 1,1-Dimethylpropyl, 1 ,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1 ,2-DimethyIbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dime- thylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethyl propyl, 1,2,2-Tri- methylpropyl, 1-Ethyl-1-methylpropyI und 1-Ethyl-2-methylpropyl;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-methyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1.1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, hexyl, 1,1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-dimethylIbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyI 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 Halogenatpme wie vorstehend genannt ersetzt sein können: insbesondere Cι-C -Halogenalkyl wie Chlormethyl, Brommethyl, Dichlor- methyl, Trichlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, 1-Chlorethyl, 1-Bromethyl, 1-Fluorethyl, 2-Fluor- ethyl, 2,2-Difluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluorethyl, 2,2-Dichlor-2-fluorethyl, 2,2,2-Trichlorethyl, Pentafluorethyl oder 1,1,1 -Trifluorprop-2-yl;Haloalkyl: straight-chain or branched alkyl groups with 1 to 2, 4, 6 or 8 carbon atoms (as mentioned above), it being possible for part or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above: in particular C 1 -C 4 -haloalkyl such as chloromethyl, Bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2- yl;
Alkenyl: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 4, 6, 8 oder 10 Kohlenstoffatomen und einer oder zwei Doppelbindungen in beliebiger Position, z.B. C2-C6-Alkenyl wie Ethenyl, 1 -Propenyl, 2-Propenyl, 1-Methylethenyl, 1-Butenyl, 2-Butenyl, 3-Butenyl, 1-Methyl-1 -propenyl, 2-Methyl-1 -propenyl, 1-Methyl-2- propenyl, 2-Methyl-2-propenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1-Me- thyl-1 -butenyl, 2-Methyl-1 -butenyl, 3-Methyl-1 -butenyl, 1-MethyI-2-butenyl, 2-Methyl-2- butenyl, 3-MethyI-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,Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl , 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2nd -Pentenyl, 3-pentenyl, 4-pentenyl, 1-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-butenyl, 1,1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1,2-dimethyl-2- propenyl,
1 -Ethyl-1 propenyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Methyl-1-pentenyl, 2-Methyl-1-pentenyl, 3-Methyl-1-pentenyl, 4-Methyl-1- pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2- pentenyl, 1-Methyl-3-pentenyl, 2-Methyl-3pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3- pentenyl, 1-MethyI-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4- pentenyl, 1,1-Dimethyl-2-butenyl, 1,1-DimethyI-3-butenyI, 1 ,2-DimethyI-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 und 1-Ethyl-2-methyl-2-propenyl;1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl , 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -Methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4 -pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl , 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl , 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl , 1-ethyl-1-butenyl, 1-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 mitHaloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals with
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; " '2 to 8 carbon atoms and one or two double bonds in any position (as mentioned above), in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine; " '
Alkinyl: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 4, 6 oder 8 Kohlenstoffatomen 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,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-propinyl, 1-Pentinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, 1-Methyl-2-butinyl, 1-Methyl-3-butinyl, 2-Methyl-3-butinyl, 3-Methyl-1-butinyl, 1,1-Dimethyl-2-propinyl, 1 -Ethyl-2-propinyl, 1-Hexinyl, 2-Hexinyl, 3-Hexinyl, 4-Ηexinyl, 5-Hexinyl, 1-Methyl-2- pentinyl, 1-MethyI-3-pentinyl, 1-Methyl-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4- pentinyl, 3-Methyl-1-pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-1-pentinyl, 4-Methyl-2- pentinyl, 1 ,1-Dimethyl-2-butinyl, 1,1-Dimethyl-3-butinyl, 1 ,2-Dimethyl-3-butinyl, 2,2- Dimethyl-3-butinyl, 3,3-Dimethyl-1-butinyl, 1-Ethyl-2-butinyl, 1-Ethyl-3-butinyl, 2-Ethyl- 3-butinyl und 1-Ethyl-1~methyl-2-propinyl;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-Ηexynyl, 5-hexynyl, 1-methyl-2- pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2- Dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1 ~ methyl-2- propynyl;
Cycloalkyl: mono- oder bicyclische, gesättigte Kohlenwasserstoffgruppen mit 3 bis 6 oder 8 Kohlenstoffringgliedern, z.B. C3-C8-CycloalkyI 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: 5- oder 6-gliedriges Heterocyclyl, enthaltend ein bis drei Stickstoffatome und/oder ein Sauerstoff- oder Schwefelatom oder ein oder zwei Sauerstoff- und/oder Schwefelatome, z.B. 2-Tetrahydrofuranyl, 3-Tetrahydrofuranyl, 2-Tetrahydrothienyl, 3-Tetrahydrothienyl, 2-Pyrrolidinyl, 3-PyrroIidinyl, 3-lsoxazolidinyl, 4-lsoxazolidinyl, 5-lsoxazolidinyl, 3-lsothiazolidinyl, 4-lsothiazolidinyl, 5-lsothiazolidinyl, 3-Pyrazolidinyl, 4-Pyrazolidinyl, 5-Pyrazolidinyl, 2-Oxazolidinyl, 4-Oxazolidinyl, 5-Oxazolidinyl, 2-Thia- zolidinyl, 4-Thiazolidinyl, 5-Thiazolidinyl, 2-lmidazoIidinyl, 4-lmidazoIidinyl, 2-Pyrrolin-2- yl, 2-Pyrrolin-3-yl, 3-Pyrrolin-2-yl, 3-Pyrrolin-3-yl, 2-Piperidinyl, 3-Piperidinyl, 4-Piperi- dinyl, 1,3-Dioxan-5-yl, 2-Tetrahydropyranyl, 4-Tetrahydropyranyl, 2-Tetrahydro- thienyl, 3-Hexahydropyridazinyl, 4-Hexahydropyridazinyl, 2-Hexahydropyrimidinyl, 4-Hexahydropyrimidinyl, 5-Hexahydropyrimidinyl und 2-Piperazinyl;five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S: 5- or 6-membered heterocyclyl containing one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2 -Pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 4-oxazolidinyl , 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl , 3-pyrrolin-3-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydro-thienyl, 3-hexahydropyridazinyl , 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl;
5-gliedriges Heteroaryl, enthaltend ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom: 5-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom als Ringglieder enthalten können, z.B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 1-Pyrrolyl, 2-Pyrrolyl, 3-Pyrrolyl, 1-Pyrazolyl, 3-Pyrazolyl, 4-Pyrazolyl, 5-Pyrazolyl, 2-Oxazolyl, 4-Oxazolyl, 5-Oxazolyl, 2-Thiazolyl, 4-Thiazolyl, 5-Thiazolyl, 1-lmidazolyl, 2-lmidazolyl, 4-lmidazolyl, 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, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4- Oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 1, 3,4-triazol-2-yl;
6-gliedriges Heteroaryl, enthaltend ein bis drei bzw. ein bis vier Stickstoffatome: 6-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis drei bzw. ein bis vier Stickstoffatome als Ringglieder enthalten können, z.B. 2-Pyridinyl, 3-Pyridinyl, 4-Pyridinyl, 3-Pyridazinyl, 4-Pyridazinyl, 2-Pyrimidinyl, 4-Pyrimidinyl, 5-Pyrimidinyl und 2-Pyrazinyl;6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;
Alkylen: gesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 4 oder 6 Kohlenstoffatomen, welche über eine Doppelbindung an das Gerüst gebunden sind, z. B. =CH2, =CH-CH3, =CH-CH2-CH3;Alkylene: saturated, straight-chain or branched hydrocarbon radicals with 1 to 4 or 6 carbon atoms, which are bonded to the skeleton via a double bond, e.g. B. = CH 2 , = CH-CH 3 , = CH-CH 2 -CH 3 ;
Oxyalkylenoxy: divalente unverzweigte Ketten aus 1 bis 3 CH2-Gruppen, wobei beide Valenzen über ein Sauerstoffatom an das Gerüst gebunden ist, z.B. OCH2O, OCH2CH2O und OCH2CH2CH2O;Oxyalkyleneoxy: divalent unbranched chains of 1 to 3 CH 2 groups, both valences being bound to the skeleton via an oxygen atom, for example OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O;
In dem Umfang der vorliegenden Erfindung sind die (R)- und (S)-Isomere und die Ra- zemate von Verbindungen der Formel I eingeschlossen, die chirale Zentren aufweisen.The scope of the present invention includes the (R) and (S) isomers and the racemates of compounds of the formula I which have chiral centers.
Im Hinblick auf ihre bestimmungsgemäße Verwendung der Triazolopyrimidine der Formel I sind die folgenden Bedeutungen der Substituenten, und zwar jeweils für sich allein oder in Kombination, besonders bevorzugt: Verbindungen I sind bevorzugt, in denen R1 für eine Gruppe A steht:With regard to their intended use of the triazolopyrimidines of the formula I, the following meanings of the substituents, in each case individually or in combination, are particularly preferred: Compounds I are preferred in which R 1 represents a group A:
worin wherein
Z1 Wasserstoff, Fluor oder d-C6-Fluoralkyl, Z2,Z3 Wasserstoff oder Fluor, oder Z1 und Z2 bilden gemeinsam eine Doppelbindung;Z 1 is hydrogen, fluorine or dC 6 fluoroalkyl, Z 2 , Z 3 is hydrogen or fluorine, or Z 1 and Z 2 together form a double bond;
q 1, 2 oder 3 ist; und R3 Wasserstoff oder Methyl bedeuten.q is 1, 2 or 3; and R 3 is hydrogen or methyl.
Daneben sind auch Verbindungen I bevorzugt, in denen R1 für C4-C8-Alkyl oder C4-C8- Halogenalkyl steht.In addition, compounds I are preferred in which R 1 is C 4 -C 8 alkyl or C 4 -C 8 haloalkyl.
Weiterhin sind Verbindungen I bevorzugt, in denen R1 für durch mindestens eine Gruppe Ra substituiertes C3-C6-Cycloalkyl oder C3-C8-Halogencycloalkyl oder C -C6- Cycloalkyl-C C6-alkyl steht.Furthermore, compounds I are preferred in which R 1 3 -C 6 cycloalkyl or C 3 -C 8 -halocycloalkyl or C 6 -C substituted by at least one group R a C - C cycloalkyl-C -alkyl. 6
Besonders bevorzugt sind Verbindungen I, in denen R1 für C3-C6-Cycloalkyl steht, wel- ches durch C C -Alkyl, insbesondere Methyl, substituiert ist.Compounds I in which R 1 is C 3 -C 6 cycloalkyl, which is substituted by CC alkyl, in particular methyl, are particularly preferred.
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.
Eine bevorzugte Ausführungsform der Erfindung betrifft Verbindungen der Formel 1.1:A preferred embodiment of the invention relates to compounds of the formula 1.1:
in der in the
G C2-C6-Alkyl, insbesondere Ethyl, n- und i-Propyl, n-, sek-, tert- Butyl, und d-C - Alkoxymethyl, insbesondere Ethoxymethyl, oder C3-C6-Cycloalkyl, insbesondere Cyclopropyl, Cyclopentyl oder Cyclohexyl; und R2 Wasserstoff oder Methyl; bedeuten.GC 2 -C 6 alkyl, especially ethyl, n- and i-propyl, n-, sec-, tert-butyl, and dC - alkoxymethyl, especially ethoxymethyl, or C 3 -C 6 cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl; and R 2 is hydrogen or methyl; mean.
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 C2-C4-Alkyl, insbesondere für Ethyl und Propyl steht. in which Y is C 2 -C 4 alkyl, in particular ethyl and propyl.
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, d-C6-Alkyl, d-Ce-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, d-C6-Alkoxy, d-Ce-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, C C6-AIkylen 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, dC 6 -alkyl, d-Ce-haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -halogenalkenyl, dC 6 -alkoxy , d-Ce-haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, CC 6 alkylene and oxy-C C 3 - alkyleneoxy can wear. These compounds correspond in particular to formula I.3,
in der in the
D zusammen mit dem Stickstoffatom ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bildet, welches über N gebunden ist und ein weiteres Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, d-C6-Alkyl, C C6-Halogen- alkyl, C2-C6-Alkenyl, C2-C6-HalogenaIkenyl, d-C6-Alkoxy, C C6-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, (exo)-d-C6-Alkylen und Oxy-CrC3- alkylenoxy tragen kann; bedeuten. Besonders bevorzugt sind Verbindungen der Formel I, insbesondere solche der Formel I.3, in der die Gruppen L und L2 die folgenden Bedeutungen haben: L1 und L2 Fluor,D together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as a ring member and / or one or more substituents from the group halogen, dC 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) -dC 6 -alkylene and oxy-C r C 3 - alkyleneoxy can carry; mean. Compounds of the formula I are particularly preferred, in particular those of the formula I.3 in which the groups L and L 2 have the following meanings: L 1 and L 2 fluorine,
L1 Fluor und L2 Wasserstoff; oder L1 Chlor.L 1 fluorine and L 2 hydrogen; or L 1 chlorine.
Weiterhin bevorzugt werden Verbindungen der Formel I.4,Compounds of the formula I.4 are also preferred,
in der die Variablen wie für Formel I definiert sind. in which the variables are as defined for Formula I.
Weiterhin werden Verbindungen I bevorzugt, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Morpholinyl- oder Thiomorpholinylring bilden, insbesondere einen Ring, der ggf. durch eine bis drei Gruppen Halogen, d-C4- Alkyl oder d-C4-Halogenalkyl substituiert ist. Besonders bevorzugt sind die Verbin- düngen, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Morpholinyl- oder einen Pyrrolidinylring, -insbesondere einen Pyrrolidinyl- ring, 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 morpholinyl or thiomorpholinyl ring, in particular a ring which may be halogenated by one to three groups, dC 4 -alkyl or dC 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 morpholinyl or a pyrrolidinyl ring, in particular a pyrrolidinyl ring, are particularly preferred.
Ein weiterer bevorzugter Gegenstand der Erfindung sind Verbindungen I, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Pyrazol- ring bilden, der ggf. durch eine oder zwei Gruppen Halogen, C C4-Alkyl oder d-C - Halogenalkyl, insbesondere durch 3,5-Dimethyl oder 3,5-Di-(trifluormethyI) substituiert ist.Another preferred subject of the invention are compounds I in which R 1 and R 2 together with the nitrogen atom to which they are attached form a pyrazole ring which may be halogen, CC 4 alkyl or dC through one or two groups - Haloalkyl, in particular substituted by 3,5-dimethyl or 3,5-di (trifluoromethyl).
Däneben sind auch Verbindungen der Formel I besonders bevorzugt, in denen R1 CH(CH3)-CH2CH3 , CH(CH3)-CH(CH3)2 , CH(CH3)-C(CH3)3 , CH(CH3)-CF3 , CH2C(CH3)=CH2 ,CH2CH=CH2; R2 Wasserstoff oder Methyl; oder R1 und R2 gemeinsam -(CH2)2CH(CF3)(CH2)2- oder -(CH2)2O(CH2)2- bedeuten.Compounds of the formula I are also 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 ; R 2 is hydrogen or methyl; or R 1 and R 2 together mean - (CH 2 ) 2 CH (CF 3 ) (CH 2 ) 2- or - (CH 2 ) 2 O (CH 2 ) 2 -.
Weiterhin werden Verbindungen I besonders bevorzugt, in denen X Methyl bedeutet.Furthermore, compounds I are particularly preferred in which X is methyl.
Insbesondere sind im Hinblick auf ihre Verwendung die in den folgenden Tabellen zusammengestellten Verbindungen I bevorzugt. Die in den Tabellen für einen Substituenten genannten Gruppen stellen außerdem für sich betrachtet, unabhängig von der Kombination, in der sie genannt sind, eine besonders bevorzugte Ausgestaltung des betreffenden Substituenten dar.In particular, in view of their use, the compounds I compiled in the tables below are preferred. The groups mentioned in the tables for a substituent are also considered independently of the The combination in which they are mentioned represents a particularly preferred embodiment of the substituent in question.
Tabelle 1Table 1
Verbindungen der Formel I, in denen L1 und L2 Fluor, 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, X is methyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 2Table 2
Verbindungen der Formel I, in denen L1 Chlor, L2 Wasserstoff, 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 hydrogen, X is methyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 3Table 3
Verbindungen der Formel I, in denen L1 Fluor und L2 Wasserstoff, 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 and L 2 is hydrogen, X is methyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle A - Verbindungen der FormelTable A - Compounds of Formula
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, Deuteromyceten, Oomyceten und Ba- sidiomyceten. Sie sind zum Teil systemisch wirksam und können im Pflanzenschutz als Blatt-, Beiz- und Bodenfungizide eingesetzt werden. The compounds I are suitable as fungicides. They are characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as foliar, stain and soil fungicides.
Besondere Bedeutung haben sie für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen wie Weizen, Roggen, Gerste, Hafer, Reis, Mais, Gras, Bananen, Baumwolle, Soja, Kaffee, Zuckerrohr, Wein, Obst- und Zierpflanzen und Gemü- sepflanzen wie Gurken, Bohnen, Tomaten, Kartoffeln und Kürbissen, 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 vegetable plants such as Cucumbers, beans, tomatoes, potatoes and pumpkins, as well as on the seeds of these plants.
Speziell eignen sie sich zur Bekämpfung folgender Pflanzenkrankheiten: Alternaria-Arten an Gemüse und Obst, • Bipolaris- und Drechslera-Arten an Getreide, Reis und Rasen, Blumeria graminis (echter Mehltau) an Getreide, Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Zierpflanzen und Reben, Erysiphe cichoracearum und Sphaerotheca fuliginea an Kürbisgewächsen, Fusarium- und Verticillium-Arten an verschiedenen Pflanzen, • Mycosphaerella-Arten an Getreide, Bananen und Erdnüssen, Phakopsora pachyrhizi und P. meibomiae an Soja, Phytophthora infestans an Kartoffeln und Tomaten, Plasmopara viticola an Reben, Podosphaera leucotricha an Äpfeln, • Pseudocercosporella herpotrichoides an Weizen und Gerste, Pseudoperonospora-Aήen an Hopfen und Gurken, Puccinia-Aήen an Getreide, Pyricυlaria oryzae an Reis, Rhizoctonia-Aήen an Baumwolle, Reis und Rasen, • Septoria tritici und Stagonospora nodorum an Weizen, Uncinula necatoran Reben, Ustilago-Arien an Getreide und Zuckerrohr, sowie Venft/r/a-Arten (Schorf) an Äpfeln und Birnen.They are particularly suitable for combating the following plant diseases: Alternaria species on vegetables and fruits, • Bipolaris and Drechslera species on cereals, rice and lawn, Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, vegetables, Ornamental plants and vines, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbitaceae, Fusarium and Verticillium species on various plants, • Mycosphaerella species on cereals, bananas and peanuts, Phakopsora pachyrhizi and P. meibomiae on soybeans, Phytophara and infestation viticola on vines, Podosphaera leucotricha on apples, • Pseudocercosporella herpotrichoides on wheat and barley, Pseudoperonospora Aaen on hops and cucumbers, Puccinia A Getreen on cereals, Pyricυlaria oryzae on rice, Rhizoctonia Aήen on cotton, rice and lawn, sepia, tritiani Stagonospora nodorum on wheat, Uncinula necatoran vines, Ustilago arias on cereals and sugar cane, see p owie Venft / r / a species (scab) on apples and pears.
Die Verbindungen I eignen sich außerdem zur Bekämpfung von Schadpilzen wie Pae- cilomyces variot 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.The compounds I are also suitable for combating harmful fungi such as Pacilomyces variot 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 Kubikmeter 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 gewährleisten.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 kommen dafür im wesentlichen in Betracht: - 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, - 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, Fettalkoholsulfate, Fettsäuren und sulfa- tierte Fettalkoholglykolether zum Einsatz, ferner Kondensationsprodukte von sulfonier- tem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphtalinsulfonsäure mit Phenol und Formaldehyd, Polyoxyethy- lenoctylphenolether, ethoxyliertes Isooctylphenol, Octylphenol, Nonylphenol, Alkylphe- nolpolyglykolether, Tributylphenylpolyglykolether, Tristerylphenylpolyglykolether, Alkyl- arylpolyetheralkohole, Alkohol- und Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether, ethoxyliertes Polyoxypropylen, Laurylalkoholpoly- glykoletheracetal, Sorbitester, Ligninsulfitablaugen und Methylcellulose in Betracht.The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. The following are essentially suitable as solvents / auxiliaries: water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example petroleum fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma -Butryolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used, - Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg 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, alkaline earth, and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated naphthalene naphthalene and sulfonated dehydrogenated naphthalene derivatives of sulfonated formaldehyde derivatives and sulfonated dehydrogenated naphthalenedaphthalene from sulfonates, as well as condensation products with sulfated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene ether and condensation products , Condensation products of naphthalene or of naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tri-butylphenyl polyglycol ether, trihylphenyl polyglycol ether, alkyl alcoholoxy ethoxylated alcohol, alkyl alcoholoxy ethoxylated alcohol , Laurylalkoholpolyglykoletheracetal, sorbitol ester, lignin sulfite 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- Iol, 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 Ge- treidemehl, 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.-%, vorzugsweise 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) 50 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von Disper- gier- und Netzmitteln fein gemahlen und mittels technischer Geräte (z.B. Extrusion, Sprühturm, Wirbelschicht) als wasserdispergierbare oder wasserlösliche Granulate hergestellt. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs.F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersants and wetting agents and are prepared as water-dispersible or water-soluble granules by means of technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution in water results in a stable dispersion or solution of the active ingredient.
G Wasserdispergierbare und wasserlösliche Pulver (WP, SP) 75 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von Disper- gier- und Netzmitteln sowie Kieselsäuregel in einer Rotor-Strator Mühle vermählen. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des 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, Öldispersionen, Pasten, Stäubemitteln, Streumitteln, Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der 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, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Wässrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netz- baren Pulvern (Spritzpulver, Öldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Öldispersionen 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, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates composed of an active substance, wetting 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 Cyprodinil,Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidine, guazatine, iminoctadine, spiroxamine, tridemorph • anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil,
• 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, Flutriafol, Hexaconazol, Imazalil, Ipconazol, Metconazol, Myclobutanil, Penconazol, Propico- nazol, Prochloraz, Prothioconazol, Simeconazol, Tebuconazol, Tetraconazol, Tria- dimefon, Triadimenol, Triflumizol, Triticonazol,Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazol, penocolazolol, myocazolol, myocazolol, myclazol, myclazol, myclazol, myocazolol, myclazol, myclazol, myclazol, myclazol, myclazol , Tetraconazole, tri-dimefon, triadimenol, triflumizole, 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,Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb,
• Heterocylische Verbindungen wie Anilazin, Benomyl, Boscalid, Carbendazim, Car- boxin, Oxycarboxin, Cyazofamid, Dazomet, Dithianon, Famoxadon, Fenamidon, Fenarimol, Fuberidazol, Flutolanil, Furametpyr, Isoprothiolan, Mepronil, Nuarimol, Picobenzamid, Probenazol, Proquinazid, Pyrifenox, Pyroquilon, Quinoxyfen, Silthio- fam, Thiabendazol, Thifluzamid, Thiophanat-methyl, Tiadinil, Tricyclazol, Triforine, • Kupferfungizide wie Bordeaux Brühe, Kupferacetat, Kupferoxychlorid, basisches Kupfersulfat,• Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronazolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, nuquin Pyroquilon, quinoxyfen, silthofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforins, 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, Diclomezin, Diclocymet, Diethofencarb, Edi- fenphos, Ethaboxam, Fenhexamid, Fentin-Acetat, Fenoxanil, Ferimzone, Fluazi- nam, Fosetyl, Fosetyl-Aluminium, Phosphorige Säure, Iprovalicarb, Hexachlorben- zol, Metrafenon, Pencycuron, Penthiopyrad, Propamocarb, Phthalid, Toloclofos- methyl, Quintozene, Zoxamid,• Other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamide, cymoxanil, diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, namimzone, fluazi, fluazi, fluazi Fosetyl aluminum, phosphorous acid, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, penthiopyrad, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide,
• Strobilurine wie Azoxystrobin, Dimoxystrobin, Enestroburin, Fluoxastrobin, Kreso- xim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin oder Trifloxystrobin, • Sulfensäurederivate wie Captafol, Captan, Dichlofluanid, Folpet, Tolylfluanid,• strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, cresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, • sulfenoic acid derivatives such as captafol, captan, dichlofluanfluanid, folpet, tolpet, tolpet
• 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 wurden unter entsprechender Abwandlung der Ausgangsverbindungen zur Gewinnung weiterer Verbindungen I benutzt. Die so erhaltenen Verbindungen sind in den anschließenden Tabellen mit physikalischen Angaben aufgeführt.The instructions given in the synthesis examples below were used with the appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the tables below with physical details.
Beispiel 1: Herstellung von 5-Methyl-6-(2,4,6-trifluorphenyl)-7-(2-methyl-pyrrolidin-1-yl)- 1 ,2,4-triazolo[1 ,5a]pyrimidinExample 1: Preparation of 5-methyl-6- (2,4,6-trifluorophenyl) -7- (2-methyl-pyrrolidin-1-yl) -1,4,4-triazolo [1,5a] pyrimidine
Beispiel 1a: 5-Chlor-6-(2,4,6-trifluorphenyl)-7-(2-methyl-pyrrolidin-1-yl)-1 ,2,4- triazolo[1 ,5a]pyrimidinExample 1a: 5-chloro-6- (2,4,6-trifluorophenyl) -7- (2-methyl-pyrrolidin-1-yl) -1, 2,4-triazolo [1,5a] pyrimidine
Eine Lösung von 0,2 g (0,63 mmol) 5,7-DichIor-6-(2,4,6-trifluorphenyl)-1 ,2,4-tri- azolo[1 ,5a]pyrimidin (vgl. WO 98/46607), 0,053 g (0,63 mmol) 2-Methylpyrrolidin und 0,064 g (0,63 mmol) Triethylamin in 5 ml Methylenchlorid wurden etwa 14 Std. bei 20- 25CC gerührt. Anschließend wurde die Reaktionsmischung mit verd. HCI-Lösung und Wasser gewaschen, dann getrocknet und vom Lösungsmittel befreit. Es blieben 0,2 g der Titelverbindung als farblose Kristallmasse vom Fp 151-152°C zurück.A solution of 0.2 g (0.63 mmol) 5,7-dichloro-6- (2,4,6-trifluorophenyl) -1, 2,4-tri-azolo [1,5a] pyrimidine (cf. WO 98/46607), 0.053 g (0.63 mmol) of 2-methylpyrrolidine and 0.064 g (0.63 mmol) of triethylamine in 5 ml of methylene chloride were stirred at 20-25 ° C. for about 14 hours. The reaction mixture was then washed with dil. HCl solution and water, then dried and freed from the solvent. There remained 0.2 g of the title compound as a colorless crystal mass of mp 151-152 ° C.
1H-NMR (CDCIa, δ in ppm): 8,35 (s, 1H); 6,75-6,9 (m, 2H); 5,15 (m, 1H); 3,2 (m, 1H); 3,05 (m, 1H); 2,3 (m, 1H); 1,75-1,95 (m, 2H); 1,5 (m, 1H); 1,5 (d, 3H) Beispiel 1 b: 5-(Dimethylmalon-2-yl)-6-(2,4,6-trifluorphenyl)-7-(2-methyl-pyrrolidin-1-yl)- 1 ,2,4-triazolo[1 ,5a]pyrimidin 1 H NMR (CDCIa, δ in ppm): 8.35 (s, 1H); 6.75-6.9 (m, 2H); 5.15 (m. 1H); 3.2 (m, 1H); 3.05 (m, 1H); 2.3 (m, 1H); 1.75-1.95 (m, 2H); 1.5 (m, 1H); 1.5 (d, 3H) Example 1 b: 5- (Dimethylmalon-2-yl) -6- (2,4,6-trifluorophenyl) -7- (2-methyl-pyrrolidin-1-yl) -1, 2,4-triazolo [1, 5a] pyrimidine
Eine Lösung von 1 g (2,7 mmol) des 5-Chlor-triazolopyrimidins aus Beispiel 1a und 1 g (6,5 mmol) Natrium-dimethylmalonat in 7 ml Acetonitril wurden 4 Stunden bei 70-80°C und anschließend etwa 2,5 Tage bei 20-25°C gerührt. Der dabei entstandene Niederschlag wurde abfiltriert, dann in Methylenchlorid und verdünnter Salzsäure aufgenommen. Man trennte die organische Phase ab und extrahierte die wässerige noch zweimal mit Methylenchlorid. Die vereinigten organischen Phasen wurden getrocknet und vom Lösungsmittel befreit. Es blieben 0,6 g der Titelverbindung als gelbes Öl zurück.A solution of 1 g (2.7 mmol) of the 5-chloro-triazolopyrimidine from Example 1a and 1 g (6.5 mmol) of sodium dimethylmalonate in 7 ml of acetonitrile were 4 hours at 70-80 ° C and then about 2, Stirred for 5 days at 20-25 ° C. The resulting precipitate was filtered off, then taken up in methylene chloride and dilute hydrochloric acid. The organic phase was separated off and the aqueous phase was extracted twice more with methylene chloride. The combined organic phases were dried and freed from the solvent. 0.6 g of the title compound remained as a yellow oil.
1H-NMR (CDCI3, δ in ppm): 8,4 (s, 1H); 6,9 (t, 1H); 6,8 (t, 1H); 5,1 (m, 1H); 4,65 (s, 1H); 3,8 (s, 6H); 3,15 (m, 1H); 3,0 (m, 1H); 2,25 (m, 1H); 1,7-1,95 (m, 2H); 1,45 (m, 1H); 1,1 (d, 3H) 1 H NMR (CDCI3, δ in ppm): 8.4 (s, 1H); 6.9 (t, 1H); 6.8 (t, 1H); 5.1 (m, 1H); 4.65 (s, 1H); 3.8 (s, 6H); 3.15 (m. 1H); 3.0 (m, 1H); 2.25 (m, 1H); 1.7-1.95 (m, 2H); 1.45 (m, 1H); 1.1 (d, 3H)
Beispiel 1 c: 5-Methyl-6-(2,4,6-trifluorphenyl)-7-(2-methyl-pyrrolidin-1-yl)-1 ,2,4- triazolo[1 ,5a]pyrimidinExample 1 c: 5-Methyl-6- (2,4,6-trifluorophenyl) -7- (2-methyl-pyrrolidin-1-yl) -1, 2,4-triazolo [1,5a] pyrimidine
0,6 g (1 ,7 mmol) der Verbindung aus Beispiel 1 b in 3 ml konz. Salzsäure wurden 3 Std. refluxiert. Nach Abkühlen auf 20-25°C wurde die Reaktionsmischung mit Methylenchlorid extrahiert. Die vereinigten organischen Phasen wurden getrocknet und vom Lösungsmittel befreit. Nach Chromatographie an Kieselgel RP-18 (Acetonitril/Wasser- Gemischen) erhielt man 0,13 g der Titelverbindung als farblosen Festkörper vom Fp 90 bis 93°C.0.6 g (1.7 mmol) of the compound from Example 1 b in 3 ml of conc. Hydrochloric acid was refluxed for 3 hours. After cooling to 20-25 ° C, the reaction mixture was extracted with methylene chloride. The combined organic phases were dried and freed from the solvent. After chromatography on silica gel RP-18 (acetonitrile / water mixtures), 0.13 g of the title compound was obtained as a colorless solid, mp 90 to 93 ° C.
1H-NMR (CDCI3, δ in ppm): 8,35 (s, 1H); 6,75-6,9 (m, 2H); 5,0 (m, 1H); 3,0-3,2 (m, 2H); 2,3 (s, 3H); 2,25 (m, 1H); 1,75-1,95 (m, 2H); 1,45 (m, 1H); 1,1 (d, 3H) 1 H NMR (CDCI 3 , δ in ppm): 8.35 (s, 1H); 6.75-6.9 (m, 2H); 5.0 (m, 1H); 3.0-3.2 (m, 2H); 2.3 (s, 3H); 2.25 (m, 1H); 1.75-1.95 (m, 2H); 1.45 (m, 1H); 1.1 (d, 3H)
Beispiel 2: Herstellung von 5-Methyl-6-(2,4,6-trifluorphenyl)-7-(R-1,2-dimethylprop-1- yl)-1 ,2,4-triazolo[1 ,5a]pyrimidin [I-7]Example 2: Preparation of 5-methyl-6- (2,4,6-trifluorophenyl) -7- (R-1,2-dimethylprop-1-yl) -1, 2,4-triazolo [1,5a] pyrimidine [I-7]
Beispiel 2a: 2-(2,4,6-TrifluorphenyI)-acetessigsäure-methylesterExample 2a: methyl 2- (2,4,6-trifluorophenyI) acetoacetate
Eine Lösung von 76 g (0,47 mol) Hexamethyldisiiazan in 440 ml Tetrahydrofuran (THF) wurden bei -40 bis -20°C mit 294 ml (0,47 mol) n-Butyllithium-Lsg. (1 ,6 m in Hexan) versetzt. Anschließend wurden bei -70°C 48,85 g (0,25 mol) 2,4,6- Trifluorphenylessigester, gelöst in 44 ml THF, zugetropft. Man rührte 2 Std. bei -70°C und ließ während etwa 14 Std. auf 20 bis 25°C erwärmen. Dann wurde die Reaktionsmischung mit 450 ml Ammoniumchlorid-Lsg. und konz. Salzsäure angesäuert. Nach Verdünnen mit Methyl-t-butylether (MtBE) wurde die organische Phase mit verd. Salz- säure und NaHCO3-Lsg. gewaschen, dann getrocknet und vom Lösungsmittel befreit. Der Rückstand wurde fraktioniert. Man erhielt 34,5 g der Titelverbindung als hellgelbe Flüssigkeit.A solution of 76 g (0.47 mol) of hexamethyldisiiazane in 440 ml of tetrahydrofuran (THF) was at -40 to -20 ° C with 294 ml (0.47 mol) of n-butyllithium solution. (1.6 m in hexane). 48.85 g (0.25 mol) of 2,4,6-trifluorophenylacetate, dissolved in 44 ml of THF, were then added dropwise at -70.degree. The mixture was stirred at -70 ° C. for 2 hours and allowed to warm to 20 to 25 ° C. over the course of 14 hours. Then the reaction mixture was mixed with 450 ml of ammonium chloride solution. and conc. Acidified hydrochloric acid. After dilution with methyl t-butyl ether (MtBE), the organic phase was diluted with dil. acid and NaHCO 3 solution. washed, then dried and freed from solvent. The residue was fractionated. 34.5 g of the title compound were obtained as a light yellow liquid.
1H-NMR (CDCI3,tf in ppm): 13,2 (s, 1H); 6,7 (t, 2H); 3,7 (s, 3H); 2,9 (s, 3H) 1 H NMR (CDCI 3 , tf in ppm): 13.2 (s, 1H); 6.7 (t. 2H); 3.7 (s. 3H); 2.9 (s, 3H)
Beispiel 2b: 5-Methyl-6-(2,4,6-trifluorphenyl)-7-hydroxy-1 ,2,4-triazolo[1 ,5a]pyrimidinExample 2b: 5-methyl-6- (2,4,6-trifluorophenyl) -7-hydroxy-1, 2,4-triazolo [1,5a] pyrimidine
Eine Lösung von 34 g (0,134 mol) 2-(2,4,6-Trifluorphenyl)-acetessigsäure-methylester aus Beispiel 2a und 11 ,4 g (0,135 mol) Aminotriazol in 150 ml Essigsäure wurden 24 Std. auf 120°C (Badtemperatur) erhitzt. Anschließend wurde die Essigsäure abdestilliert. Der Rückstand kristallisierte und wurde in Diisopropylether digeriert. Man erhielt 16 g (ca. 50%ig) der Titelverbindung als farblosen Festkörper, der ohne weitere Reinigung weiter umgesetzt wurde.A solution of 34 g (0.134 mol) of methyl 2- (2,4,6-trifluorophenyl) acetoacetate from Examples 2a and 11, 4 g (0.135 mol) of aminotriazole in 150 ml of acetic acid were heated to 120 ° C. for 24 hours ( Bath temperature) heated. The acetic acid was then distilled off. The residue crystallized and was digested in diisopropyl ether. 16 g (about 50% strength) of the title compound were obtained as a colorless solid which was reacted further without further purification.
1H-NMR (DMSO-d6,£ in ppm): 8,35 (s,1H); 7,35 (t,2H); 2,2 (s, 3H) 1 H NMR (DMSO-d 6 , £ in ppm): 8.35 (s, 1H); 7.35 (t. 2H); 2.2 (s, 3H)
Beispiel 2c: 5-Methyl-6-(2,4,6-trifluorphenyl)-7-chlor-1 ,2,4-triazolo[1 ,5a]pyrimidinExample 2c: 5-methyl-6- (2,4,6-trifluorophenyl) -7-chloro-1, 2,4-triazolo [1,5a] pyrimidine
16 g (ca. 50 %ig) des Triazolopyrimidins aus Beispiel 2b in 50 ml Phosphoroxychlorid wurden 8 Std. refluxiert. Dann destillierte man das überschüssige Phosphoroxychlori- dab, löste den Rückstand in Methylenchlorid und rührte die organische Phase etwa 30 min mit Wasser. Anschließend wurde die organische Phase abgetrennt, mit Cyclohe- xan/Essigester Gemisch verdünnt über Kieselgel filtriert, dann vom Lösungsmittel be- freit. Es blieben 6,6 g der Titelverbindung als farbloser Festkörper zurück.16 g (about 50% strength) of the triazolopyrimidine from Example 2b in 50 ml of phosphorus oxychloride were refluxed for 8 hours. The excess phosphorus oxychloride was then distilled, the residue was dissolved in methylene chloride and the organic phase was stirred with water for about 30 min. The organic phase was then separated off, diluted with cyclohexane / ethyl acetate mixture, filtered through silica gel and then freed from the solvent. There remained 6.6 g of the title compound as a colorless solid.
1H-NMR (CDCI3,£ in ppm): 8,55 (s, 1H); 6,95 (t, 2H); 2,55 (s, 3H) 1 H NMR (CDCI 3 , £ in ppm): 8.55 (s, 1H); 6.95 (t. 2H); 2.55 (s, 3H)
Beispiel 2d: 5-Methyl-6-(2,4,6-trifluorphenyl)-7-(R-1 ,2-dimethylprop-1-yl)-1 ,2,4-tri- azolo[1 ,5a]pyrimidinExample 2d: 5-methyl-6- (2,4,6-trifluorophenyl) -7- (R-1, 2-dimethylprop-1-yl) -1, 2,4-tri-azolo [1, 5a] pyrimidine
Eine Lösung von 0,5 g (1 ,7 mmol) des 7-Chlortriazolopyrimidins aus Beispiel 2c, 0,2 g (2,5 mmol) R-1 ,2-Dimethylpropylamin und 0,3 g (3 mmol) Triethylamin in 5 ml Methylenchlorid wurde etwa 14 Std. bei 20 bis 25CC gerührt. Anschließend wurde die Reak- tionsmischung mit Wasser gewaschen und vom Lösungsmittel befreit. Man reinigte den Rückstand mittels präparativer MPLC mit Acetonitril/Wasser 60:40 über Kieselgel-RP 18. Aus dem Eluat erhielt man nach Abdestillieren des Lösungsmittels 0,4 g der Titelverbindung als farblose Kristallmasse vom Fp 113-115°C. 1H-NMR (CDCI3, J in ppm): 8,3 (s, 1H); 6,85 (t, 2H); 6,1 (d, breit, 1H); 3,1 (m, 1H); 2,3 (s, 3H); 1,6 (m, 1H); 1,05 (d, 3H); 0,8 (d, 6H)A solution of 0.5 g (1.7 mmol) of the 7-chlorotriazolopyrimidine from Example 2c, 0.2 g (2.5 mmol) of R-1, 2-dimethylpropylamine and 0.3 g (3 mmol) of triethylamine in 5 ml of methylene chloride was stirred at 20 to 25 ° C. for about 14 hours. The reaction mixture was then washed with water and freed from the solvent. The residue was purified by means of preparative MPLC with acetonitrile / water 60:40 over silica gel RP 18. From the eluate, after distilling off the solvent, 0.4 g of the title compound was obtained as a colorless crystal mass of mp 113-115 ° C. 1 H NMR (CDCI 3 , J in ppm): 8.3 (s, 1H); 6.85 (t. 2H); 6.1 (d, broad, 1H); 3.1 (m. 1H); 2.3 (s, 3H); 1.6 (m, 1H); 1.05 (d. 3H); 0.8 (d, 6H)
Tabelle I - Verbindungen der Formel ITable I - Compounds of Formula I.
Phenylsubstitution zwei Diastereomeren vorliegen, die sich in den physikalischen Daten unterscheiden können. Phenyl substitution two diastereomers are present, which can differ in the physical data.
Beispiele für die Wirkung gegen SchadpilzeExamples of the action against harmful fungi
Die fungizide Wirkung der Verbindungen der Formel l 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. Anwendungsbeispiel 1 - Wirksamkeit gegen den Grauschimmel an Paprikablättern verursacht durch Botrytis cinerea bei protektiver AnwendungThe active ingredients were prepared as a stock solution with 25 mg 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. Example of use 1 - 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 Luftfeuch- tigkeit 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 containing 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution. The test plants were then placed in a climatic chamber with 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 Verbindungen 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, bzw. I-8 behandelten Pflanzen maximal 1% Befall, während die unbehandelten Pflan- zen zu 90% befallen waren.In this test, the plants treated with 250 ppm of the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 or I-8 showed a maximum of 1% infection, while the untreated plants were 90% infected.
Anwendungsbeispiel 2 - Wirksamkeit gegen Mehltau an Gurkenblättern verursacht durch Sphaerotheca fuliginea bei 3 Tage protektiver AnwendungExample of use 2 - Effectiveness against mildew on cucumber leaves caused by Sphaerotheca fuliginea after 3 days of protective use
Blätter von in Töpfen gewachsenen Gurkenkeimlingen wurden im Keimblattstadium mit wässriger Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. 3 Tage nach der Applikation wurden die Pflanzen mit einer wässrigen Sporensuspension des Gurkenmehitaus (Sphaerotheca fuliginea) inokuliert. Anschließend wurden die Pflanzen im Gewächshaus bei Temperaturen zwischen 20 und 24CC und 60 bis 80 % relativer Luftfeuchtigkeit für 7 Tage kultiviert. Dann wurde das Ausmaß der Mehltauentwicklung visuell in %-Befall der Keimblattfläche ermittelt.Leaves of cucumber seedlings grown in pots were sprayed in the cotyledon stage with an aqueous suspension in the active ingredient concentration given below to runoff. 3 days after the application, the plants were inoculated with an aqueous spore suspension of cucumber mehite (Sphaerotheca fuliginea). The plants were then cultivated in a greenhouse at temperatures between 20 and 24 ° C. and 60 to 80% relative atmospheric humidity for 7 days. The extent of mildew development was then determined visually in% of the cotyledon area.
In diesem Test zeigten die mit 250 ppm der Verbindungen I-3, bzw. I-4 behandelten Pflanzen keinen Befall, während die unbehandelten Pflanzen zu 100% befallen waren. In this test, the plants treated with 250 ppm of the compounds I-3 or I-4 showed no infection, while the untreated plants were 100% infected.

Claims

Patentansprüche claims
1. 6-Phenyl-triazolopyrimidine der Formel1. 6-phenyl-triazolopyrimidines of the formula
in der die Substituenten folgende Bedeutung haben: in which the substituents have the following meaning:
R1 C4-C8-Alkyl, C4-C8-HalogenalkyI, durch mindestens eine Gruppe Ra substituiertes C3-C6-Cycloalkyl, C3-C8-Halogencycloalkyl, C3-C6-Cycloalkyl-C C4- alkyl, C5-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, R2 Wasserstoff, CrC3-Akyl oder eine der bei R1 genannten Gruppen,R 1 is C 4 -C 8 alkyl, C 4 -C 8 -HalogenalkyI, by at least one group R a substituted C 3 -C 6 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 6 -cycloalkyl-C C 4 - alkyl, C 5 -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 -Halogenalkynyl 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 is hydrogen, CrC 3 -alkyl or one of those mentioned in R 1 Groups,
R1 und R2 können auch zusammen mit dem Stickstoffatom, an das sie gebunden sind, ein fünf- bis achtgliedriges gesättigtes oder teilweise ungesättigtes Heterocyclyl oder fünf- oder sechsgliedriges Heteroaryl bilden, wel- ches über N gebunden ist und ein bis drei weitere Heteroatome aus der Gruppe O, N und S als Ringgiied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, d-Cβ-Alkyl, d-C6-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, CrC6-Alkoxy, d-C6-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6-HalogenalkenyIoxy, (exo)-C C6-Alkylen und Oxy- d-C3-alkylenoxy tragen kann, wobei Piperidin-1-yl, welches unsubstituiert oder durch eine oder mehrere Methylgruppen substituiert ist, ausgenommen bleibt; 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- to eight-membered saturated or partially unsaturated heterocyclyl or five- or six-membered heteroaryl which is bonded via N and one to three further heteroatoms contain the group O, N and S as a ring member and / or one or more substituents from the group halogen, d-Cβ-alkyl, dC 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, CrC 6 -alkoxy, dC 6 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -halogenalkenyIoxy, (exo) -CC 6 -alkylene and oxy-dC 3 -alkyleneoxy can carry, where piperidin-1-yl, which is unsubstituted or substituted by one or more methyl groups; 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, C C6-HaIogenalkyl, d- C-e-Alkylcarbonyl, C3-C6-CycloalkyI, d-C-e-Alkoxy, C C6-Halogenalk- oxy, C C6-Alkoxycarbonyl, C C6-Alkylthio, C C6-Alkylamino, Di-C Ce-alkylamino, C2-C8-Alkenyl, C2-C8-Halogenalkenyl, C2-C6-Alkenyl- oxy, C2-C8-Alkinyl, C2-C8-Halogenalkinyl, C3-C6-Alkinyloxy, Oxy-Cr C3-aIkylenoxy, 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, alicyclischen oder aromatischen Gruppen ihrerseits partiell oder vollständig halogeniert sein können;R a halogen, cyano, nitro, hydroxy, CC 6 -alkyl, CC 6 -halogenoalkyl, d- Ce-alkylcarbonyl, C 3 -C 6 -cycloalkyI, dCe-alkoxy, CC 6 -haloalkoxy-oxy, CC 6 -alkoxycarbonyl, CC 6 alkylthio, CC 6 alkylamino, di-C Ce alkylamino, C 2 -C 8 alkenyl, C 2 -C 8 haloalkenyl, C 2 -C 6 alkenyl- oxy, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl, C 3 -C 6 alkynyloxy, oxy-C r 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, where these aliphatic, alicyclic or aromatic groups can in turn be partially or completely halogenated;
L1 Chlor oder Fluor; L2 Wasserstoff, wenn L1 Fluor bedeutet, zusätzlich Fluor;L 1 chlorine or fluorine; L 2 is hydrogen, if L 1 is fluorine, additionally fluorine;
X d-C4-Alkyl.X dC 4 alkyl.
2. Verbindungen der Formel I gemäß Anspruch 1, in der L1 und L2 Fluor bedeuten.2. Compounds of formula I according to claim 1, in which L 1 and L 2 are fluorine.
3. Verbindungen der Formel I gemäß Anspruch 1 , in der L1 Fluor und L2 Wasserstoff bedeuten.3. Compounds of formula I according to claim 1, in which L 1 is fluorine and L 2 is hydrogen.
4. Verbindungen der Formel I gemäß Anspruch 1 , in der L1 Chlor bedeutet.4. Compounds of formula I according to claim 1, in which L 1 is chlorine.
5. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 4, in der R1 und R2 gemeinsam einen Pyrrolidinring bilden, der eine bis vier gleiche oder verschiedene Gruppen Ra tragen kann.5. Compounds of formula I according to any one of claims 1 to 4, in which R 1 and R 2 together form a pyrrolidine ring which can carry one to four identical or different groups R a .
6. Verbindungen der Formel 1.1:6. Compounds of the formula 1.1:
in der G C2-C6-Alkyl, C C4-Alkoxymethyl oder C3-C6-Cycloalkyi; R2 Wasserstoff oder Methyl; und L1 und L2 die Bedeutung gemäß einem der Ansprüche 1 bis 4 haben. in the GC 2 -C 6 alkyl, CC 4 alkoxymethyl or C 3 -C 6 cycloalkyl; R 2 is hydrogen or methyl; and L 1 and L 2 have the meaning according to one of claims 1 to 4.
7. Verbindungen der Formel 1.2,7. Compounds of the formula 1.2,
in der Y für C2-C6-Alkyl und L1 und L2 die Bedeutung gemäß einem der Ansprüche 1 bis 4 haben. in which Y for C 2 -C 6 alkyl and L 1 and L 2 have the meaning according to one of claims 1 to 4.
8. Verbindungen der Formel I.3,8. Compounds of the formula I.3,
in der D zusammen mit dem Stickstoffatom ein fünf- oder sechsgliedriges gesättigtes oder teilweise ungesättigtes 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-Halogenalkyl, C2-C6- Alkenyl, C2-C6-Halogenalkenyl, Cι-C6-Alkoxy, C C6-HaIogenalkoxy, C3-C6- Alkenyloxy, C3-C6-Halogenalkenyloxy, (exo)-d-C6-Alkylen und Oxy-d-C3- alkylenoxy tragen kann; wobei Piperidin-1-yl, welches unsubstituiert oder durch eine oder mehrere Methylgruppen substituiert ist, ausgenommen bleibt; und in which D together with the nitrogen atom forms a five- or six-membered saturated or partially unsaturated 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, C 6 alkyl, dC 6 haloalkyl, C 2 -C 6 - alkenyl, C 2 -C 6 haloalkenyl, Cι-C6 alkoxy, CC 6 -HaIogenalkoxy, C 3 -C 6 - alkenyloxy, C 3 -C 6 haloalkenyloxy, (exo) -dC 6 alkylene and oxy-dC 3 - alkyleneoxy can carry; with the exception of piperidin-1-yl which is unsubstituted or substituted by one or more methyl groups; and
L1 und L2 die Bedeutung gemäß einem der Ansprüche 1 bis 4 haben.L 1 and L 2 have the meaning according to one of claims 1 to 4.
9. Verbindungen der Formeln I gemäß Anspruch 1 , wobei die Variablen folgende Bedeutung haben: L1,L2 Fluor, L3 Wasserstoff; X Methyl; und L1,L2 Chlor, L3 Wasserstoff; X Methyl.9. Compounds of formula I according to claim 1, wherein the variables have the following meaning: L 1 , L 2 fluorine, L 3 hydrogen; X methyl; and L 1 , L 2 chlorine, L 3 hydrogen; X methyl.
10. Verfahren zur Herstellung der Verbindungen der Formel I gemäß einem der An- sprüche 1 bis 4, durch Umsetzung von 5-Amino1 ,2,4-triazol der Formel II mit Ketoestern der Formel III10. Process for the preparation of the compounds of the formula I according to one of claims 1 to 4, by reaction of 5-amino1, 2,4-triazole of the formula II with keto esters of formula III
in der R für d-C4-Alkyl steht, zu 7-Hydroxytriazolopyrimidinen der Formel IV, in which R represents dC 4 -alkyl, to 7-hydroxytriazolopyrimidines of the formula IV,
welche mit Halogenierungsmitteln in die entsprechenden 7-Halogentriazolo- pyrimidinen der Formel V which with halogenating agents in the corresponding 7-halotriazolo-pyrimidines of formula V
übergeführt werden, und Verbindungen V mit Aminen der Formel VI are transferred, and compounds V with amines of the formula VI
^N-H VI zu Verbindungen der Formel I umgesetzt werden.^ N-H VI to be converted into compounds of formula I.
11. Verbindungen der Formeln IV und V: 5-Methyl-6-(2-chlor-6-fluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ol; 7-Chlor-5-methyl-6-(2-chlor-6-fluor-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin; 7-Brom-5-methyl-6-(2-chIor-6-fluor-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin; 5-Methyl-6-(2,6-difluor-phenyl)-[1,2I4]triazolo[1,5-a]pyrimidin-7-ol; 7-Chior-5-methyl-6-(2,6-difluor-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin; 7-Brom-5-methyl-6-(2,6-difluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin; 5-Methyl-6-(2,4>6-trifluor-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ol; 7-Chlor-5-methyl-6-(2I4I6-trifluor-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin; 7-Brom-5-methyl-6-(2,4I6-trifluor-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidin.11. Compounds of the formulas IV and V: 5-methyl-6- (2-chloro-6-fluorophenyl) - [1, 2,4] triazolo [1, 5-a] pyrimidin-7-ol; 7-chloro-5-methyl-6- (2-chloro-6-fluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine; 7-bromo-5-methyl-6- (2-chloro-6-fluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine; 5-methyl-6- (2,6-difluorophenyl) - [1.2 I 4] triazolo [1,5-a] pyrimidin-7-ol; 7-chloro-5-methyl-6- (2,6-difluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine; 7-bromo-5-methyl-6- (2,6-difluorophenyl) - [1, 2,4] triazolo [1, 5-a] pyrimidine; 5-methyl-6- (2,4 > 6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-ol; 7-chloro-5-methyl-6- (2 I 4 I 6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine; 7-bromo-5-methyl-6- (2.4 I 6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine.
12. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1 , durch Umsetzung von 5-Halogentriazolopyrimidinen der Formel VII mit Malonaten der Formel VIII,12. A process for the preparation of the compounds of the formula I according to claim 1, by reaction of 5-halotriazolopyrimidines of the formula VII with malonates of formula VIII,
in der X1 Wasserstoff oder d-C3-Alkyl und R C C4-Alkyl bedeuten, zu Verbindungen der Formel IX in which X 1 is hydrogen or dC 3 alkyl and RCC 4 alkyl, to compounds of formula IX
die nach Decarboxylierung Verbindungen der Formel I ergeben. which give compounds of formula I after decarboxylation.
13. Mittel, enthaltend einen festen oder flüssigen Trägerstoff und eine Verbindung der Formel I gemäß Anspruch 1.13. Agent containing a solid or liquid carrier and a compound of formula I according to claim 1.
14. Saatgut, enthaltend eine Verbindung der Formel I gemäß Anspruch 1 in einer Menge von 1 bis 1000 g/100 kg14. Seed containing a compound of formula I according to claim 1 in an amount of 1 to 1000 g / 100 kg
15. 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 Verbindung der Formel I gemäß Anspruch 1 behandelt. 15. A method for controlling phytopathogenic harmful fungi, characterized in that the fungi or the materials, plants, the soil or seeds to be protected against fungal attack are treated with an effective amount of a compound of the formula I according to claim 1.
EP05716387A 2004-03-30 2005-03-26 6-(2-fluorophenyl)-triazolopyrimidines, method for producing them, their use for controlling parasitic fungi and agents containing the same Withdrawn EP1732927A2 (en)

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