Classifications

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

Definitions

• the present invention relates to 6- (2,3,6-trifluorophenyl) triazolopyrimidines of the formula I.
• R 2 is hydrogen or one of the groups mentioned for R 1 ,
• R 1 and R 2 together with the nitrogen atom to which they are attached can also form a five- or six-membered heterocyclyl or heteroaryl which is attached via N and contain one to three further heteroatoms from the group O, N and S as a ring member and / or one or more substituents from the group halogen, C r C 6 alkyl, C -haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 - haloalkenyl, CC 6 alkoxy, d-Ce-haloalkoxy , C 3 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, (exo) -CC 6 alkylene and oxy-C C 3 alkyleneoxy can carry;
• R 1 and / or R 2 can carry one to four identical or different groups R a :
• 5-Halogen-6- (2 I 3,6-trifluorophenyl) thazolopyrimidines are generally known from EP-A 945 453.
• 5-cyano- and 5-alkoxy-triazolopyrimidines are disclosed in WO 02/083677.
• Triazolopyrimidines with optically active amino substituents in the 7-position are generally proposed in WO 02/38565.
• the present invention is based on the object of providing compounds with improved activity and / or broadened activity spectrum.
• the compounds according to the invention differ from those described in the abovementioned document by the substitution in the 5-position of the triazolopyrimidine skeleton.
• the compounds of the formula I have an increased activity or a broader spectrum of activity against harmful fungi than the known compounds.
• the compounds according to the invention can be obtained in various ways. They are advantageously obtained starting from the 5-halo-6- (2,3,6-trifluorophenyl) triazolopyrimidines of the formula II known from EP-A 945 453 by reaction with compounds MX (formula III). Depending on the meaning of the group X to be introduced, compounds III represent an inorganic cyanide or an alkoxylate. The reaction is advantageously carried out in the presence of an inert solvent.
• the cation M in formula III is of little importance; for practical reasons, Ammonium, tetraalkylammonium or alkali or alkaline earth metal salts are preferred.
• the reaction temperature is usually from 0 to 120 ° C., preferably from 10 to 40 ° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].
• R 2 is hydrogen
• a removable protective group is advantageously introduced before reaction with III [cf. Greene, Protective Groups in Organic Chemistry, J. Willey & Sons, (1981)].
• Suitable solvents include ethers such as dioxane, diethyl ether and, preferably tetrahydrofuran, alcohols such as methanol or ethanol, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene or acetonitrile.
• halogenating agents [HAL] are converted with halogenating agents [HAL] under the conditions known from WO-A 94/20501 into the halogenopyrimidines of the formula VII, in which the shark represents a halogen atom , preferably a bromine or a chlorine atom, in particular a chlorine atom.
• a halogenating agent [HAL] is advantageously a chlorinating or brominating agent such as phosphorus xybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride used.
• This reaction is usually carried out at 0 ° C. to 150 ° C., preferably at 80 ° C. to 125 ° C. [cf. EP-A 770 615].
• R 1 VII + HN , 2 * "I (X alkyl)
• R VIII The reaction of VII with amines VIII, where R 1 and R 2 are as defined in formula I, is advantageously at 0 ° C to 70 ° C, preferably 10 ° C to 35 ° C, preferably in the presence of an inert solvent such as ether, e.g.
• dioxane diethyl ether or in particular tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [see WO-A 98 / 46608].
• a base such as tertiary amines, for example triethylamine or inorganic amines, such as potassium carbonate, is preferred; Excess amine of the formula VIII can also serve as the base.
• the malonates IX 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.
• the subsequent saponification of the ester X takes place under generally customary conditions, depending on the various structural elements, the alkaline or acid saponification of the compounds X can be advantageous. Under the conditions of ester saponification, the decarboxylation to I can already take place in whole or in part.
• the decarboxylation is usually carried out at from 20 ° C. to 180 ° C., preferably from 50 ° C. to 120 ° C., in an inert solvent, if appropriate in the presence of an acid.
• Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid.
• Suitable solvents are water, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.
• reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products by chromatography.
• the intermediate and end products are partly in the form of colorless or slightly brownish, viscous oils, which are produced under reduced pressure and with moderate volatile components are removed or cleaned at high temperatures. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting.
• Alkyl saturated, straight-chain or branched hydrocarbon radicals with 1 to 4, 6 or 8 carbon atoms, for example dC 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, -dimethylethyl , Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl , 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethyl
• Haloalkyl straight-chain or branched alkyl groups with 1 to 2, 4, 6 or 8 carbon atoms (as mentioned above), in which case the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above: in particular dC 2 haloalkyl, such as chloromethyl, bromomethyl , Dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fiuoroethyl, 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, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1 -butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl , 3-methyl-3-butenyl, 1, 1-dimethyl-2-propeny
• Alkynyl straight-chain or branched hydrocarbon groups with 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for example C 2 -C 6 -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl , 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3 -butinyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -Methyl-2-
• 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; 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 e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isoliazolidiazolidinyl Pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2-
• 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom
• 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members can, e.g.
• 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-pyridinyI, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyI, 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;
• R 1 is CC 4 alkyl, C 2 -C 6 alkenyl or dC 8 haloalkyl.
• R 1 represents a group A: FF (CH, 2) 'q - CHR - AZ' Z in which
• Z 1 is hydrogen, fluorine or dC 6 fluoroalkyl
• Z 2 is hydrogen or fluorine, or Z 1 and Z 2 together form a double bond
• q is 0 or 1
• R 3 is hydrogen or methyl.
• R 1 is C 3 -C 6 cycloalkyl, which can be substituted by C 1 -C 4 alkyl.
• R 1 and / or R 2 contain haloalkyl or haloalkenyl groups with a chiral center, the (S) isomers are preferred for these groups.
• the (R) -configured isomers are preferred.
• GC 2 -C 6 alkyl especially ethyl, n- and i-propyl, n-, sec-, partially butyl, and CC 4 - alkoxymethyl, especially ethoxymethyl, or C 3 -C 6 cycloalkyl, especially cyclopentyl or cyclohexyl ;
• R 2 is hydrogen or methyl;
• X are defined according to formula I, in particular mean cyano, methoxy or ethoxy.
• Another preferred embodiment of the invention relates to compounds of the formula I.2.
• Y is hydrogen or dC 4 -alkyl, in particular methyl and ethyl
• X are defined according to formula I, in particular cyano, methoxy or ethoxy.
• 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 -halo-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, Ci-Ce-alkoxy, CC 6 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 - Haloalkenyloxy, (exo) -dC 6 -alkylene and oxy-C C 3 - alkyleneoxy can carry; and X are defined according to formula I, in particular mean cyano, methoxy or ethoxy.
• R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidinyl, morpholinyl or thimorpholinyl ring, in particular a piperidinyl ring which may be halogenated by one to three groups, CC 4 alkyl or C r C 4 haloalkyl is substituted.
• the compounds in which R 1 and R 2 together with the nitrogen atom to which they are attached form a 4-methylpiperidine ring are particularly preferred.
• R 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 ,
• R 2 is hydrogen or methyl; or R 1 and R 2 together - (CH 2 ) 2 CH (CH 3 ) (CH 2 ) 2 -, - (CH 2 ) 2 CH (CF 3 ) (CH 2 ) 2 - or - (CH 2 ) 2 O (CH 2 ) 2 - mean.
• compounds I are particularly preferred in which X is cyano, methoxy or ethoxy, in particular cyano or methoxy.
• X is -CC alkyl, in particular methyl.
• 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 leaf and soil fungicides.
• 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 comminuted in a stirred ball mill to form a fine active ingredient suspension with the addition of dispersing and wetting agents and water or an organic solvent. Dilution in water results in a stable suspension of the active ingredient.
• a compound according to the invention 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersing and wetting agents and produced as technical equipment (e.g. extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
• technical equipment e.g. extrusion, spray tower, fluidized bed
• 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.
• Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
• emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
• concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.
• the active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
• 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.
• Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, • Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph
• Antibiotics such as cycloheximide, griseofuivin, kasugamycin, natamycin, polyoxin or streptomycin,
• Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb,
• Phenylpyrroles such as fenpiclonil or fludioxonil
• the active ingredients were prepared as a stock solution with 25 mg of active ingredient, which was mixed with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent emulsifier was filled from 99 to 1 ad 10 ml. Then ad 100 ml was made up with water. This stock solution was diluted with the solvent-emulsifier / water mixture described to the active ingredient concentration given below.
• Uniperol® EL wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
• Leaves of "Hanna” barley seedlings grown in pots were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. 24 hours after the spray coating had dried on, the test plants were treated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of reticulum. The test plants were then placed in the greenhouse at temperatures between 20 and 24 ° C. and 95 to 100% relative atmospheric humidity. After 6 days, the extent of the development of the disease was determined visually in% of the total leaf area.
• Pepper seedlings of the "Neusiedler Ideal Elite" variety after 2 to 3 leaves had developed well, were sprayed to runoff point with an aqueous suspension in the active compound concentration given below.
• the treated plants were inoculated with a spore suspension of Botrytis cinerea, which contained 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution.
• the test plants were then placed in a climatic chamber at 22 to 24 ° C, darkness and high air humidity. After 5 days, the extent of the fungal attack on the leaves could be determined visually in%.

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• Organic Chemistry (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Catching Or Destruction (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Plural Heterocyclic Compounds (AREA)

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