Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
  • A61P31/10—Antimycotics
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P35/00—Antineoplastic agents
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/55—Acids; Esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/61—Halogen atoms or nitro radicals

Definitions

• the present invention relates to new pyrazolopyrimidines, several ner processes for their preparation and their use in combating undesired microorganisms.
• the invention also relates to new intermediate products. their manufacture.
• Rl represents optionally substituted alkyl, optionally substituted alkyl, optionally substituted alkynyl, optionally substituted cycloalkyl or optionally substituted heterocyclyl,
• R 2 represents hydrogen or alkyl
• Rl and R2 together with the nitrogen atom to which they are attached form an optionally substituted heterocyclic 's ring are,
• R 3 represents optionally substituted 'heterocyclyl
• R 4 represents hydrogen or alkyl
• X for halogen, cyano, ⁇ itro, alkyl, optionally substituted alkenyl, optionally substituted alkynyl, hydroxyalkyl, alkoxyalkyl, haloacyl, cycloalkyl, formyl, thiocarbamoyl, alkoxycarbonyl, alkylcarbonyl, hydroxyiminoalkyl, alkoximinoalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl . or alkylaminocarbonyl, found.
• the compounds according to the invention can optionally be present as mixtures of various possible isomeric forms, in particular of stereoisomers, such as E and Z, threo and erythro and optical isomers, but optionally also in the form of tautomers. If R ⁇ is unequally substituted on both atoms which are adjacent to the binding site, the compounds in question can exist in a special form of stereoisomerism, namely as atropisomers.
• R 3 , R 4 and shark have the meanings given above, fürl for halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl,.
• Rl and R 2 have the meanings given above, if appropriate in the presence of a ner diluent, if appropriate in the presence of a catalyst and if appropriate in the presence of an acid acceptor,
• R ⁇ R 2 , R 3 , R 4 and Hai have the meanings given above, either ⁇ ) with diisobutyl aluminum hydride in the presence of aqueous ammonium chloride solution and in the presence of an organic ner thinner, or. ß) with Grignard compounds of the formula
• R 5 represents alkyl
• X 2 represents chlorine or bromine, in the presence of a diluent and, if appropriate, in the presence of a catalyst,
• R6 represents hydrogen or alkyl
• R 7 represents hydrogen or alkyl, in the presence of a diluent and optionally in the presence of a catalyst, the _Am no compounds of the formula (V) also being able to be used in the form of their acid addition salts,
• R 8 represents hydrogen or optionally substituted alkyl, in the presence of a base and in Gregenwart a diluent, or
• R 9 represents alkyl
• X 3 represents chlorine, bro iodine or the radical R 9 0-S0 2 -0-,
• RIO represents hydrogen or optionally substituted alkyl
• R 11 represents alkyl
• X 4 represents chlorine or a radical of the formula - o - C - R 11 , II o in the presence of a catalyst and in the presence of a ner diluent.
• the pyrazolopyrimidines of the formula (I) are very suitable for controlling unwanted microorganisms. Above all, they show a strong fungicidal activity and can be used both in crop protection and in material protection.
• the pyrazolopyrimidines of the formula (I) according to the invention have a significantly better microbicidal activity than the constitutionally most similar, previously known substances of the same activity.
• the compounds of formula (f) according to the invention can, if appropriate, as mixtures of various possible isomeric forms, in particular of stereoisomers, such as E and Z, threo and erythro, and optical isomers, such as R and S isomers or atropisomers, but if appropriate also of tautomers.
• the compounds of the formula (I) have acidic or basic properties and can form salts. If the compounds of the formula ⁇ !) Carry hydroxyl, carboxy or other groups which induce acidic properties, these compounds can be reacted with bases to form salts.
• bases are, for example, hydroxides, carbonates, hydrogen carbonates of the alkali and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, ammonia, primary, secondary and tertiary amines with (-C4) -alkyl radicals and mono-, di- and Trialkanolamines of (C 1 -C 4 -alkanols.
• acids are, for example, mineral acids, such as salt, Sulfuric and phosphoric acid, organic acids such as acetic acid or oxalic acid and acidic salts such as NaHSC.4 and KHSO4
• the salts thus obtainable also have fungicidal and microbicidal properties.
• the invention also relates to the salt-like derivatives formed from compounds of the formula ⁇ ) by reaction with basic or acidic compounds, and to the N-oxides which can be prepared by customary oxygenation methods.
• heterocyclyl stands for saturated or unsaturated, aromatic or non-aromatic, ring-shaped compounds with 3 to 8 ring members in which at least one ring member is a hetero atom, that is to say an atom other than carbon. If the ring contains several heteroatoms, these can be the same or different. Heteroatoms are preferably oxygen, nitrogen or sulfur. If the ring contains several oxygen atoms, these are not directly adjacent. If appropriate, the ring-shaped compounds together with other carbocyclic or heterocyclic, fused or bridged rings together form a polycyclic ring system. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems.
• the pyrazolopyrimidines according to the invention are generally defined by the formula (I).
• Preferred substances of the formula (I) are those in dsne-n- - - - - -
• Rl stands for alkyl with 1 to 6 carbon atoms, which can be substituted one to five times, in the same way: or can be differently substituted by halogen, cyano, hydroxy, alkoxy with 1 to 4 carbon atoms and / or cycloalkyl with 3 to 6 carbon atoms, or
• IV stands for alkenyl with 2 to 6 carbon atoms, which can be substituted once to three times, in the same way: or differently, by halogen, cyano, hydroxy, alkoxy with 1 " to 4 carbon atoms and / or cycloalkyl with 3 to 6 carbon atoms, or
• Rl represents alkynyl having 3 to 6 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by halogen, cyano, alkoxy having 1 to 4 carbon atoms and / or cycloalkyl having 3 to 6 carbon atoms, or
• R * stands for cycloalkyl with 3 to 6 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by halogen and / or alkyl having 1 to 4 carbon atoms, or
• R represents saturated or unsaturated heterocyclyl with 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, it being possible for the heterocyclyl to be mono- or disubstituted by halogen, alkyl having 1 to 4 carbon atoms, cyano, nitro and / or cycloalkyl with 3 to 6 carbon atoms,
• R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms
• R! and R 2 together with the nitrogen atom to which they are attached represent a saturated or unsaturated heterocyclic ring with 3 to 6 ring members, the heterocycle being another nitrogen, oxygen or sulfur atom as a ring member can contain and where the heterocycle can be substituted up to three times by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 9 fluorine and / or chlorine atoms,
• R 3 represents saturated or unsaturated heterocyclyl with 5 or 6 ring members and 1 to ⁇ heteroatoms, such as oxygen, nitrogen and / or sulfur, it being possible for the heterocyclyl to be monosubstituted to tetrasubstituted by identical or different means
• Haloalkyl or haloalkoxy each having 1 to 3 carbon atoms and 1 to 1 halogen atoms
• R 4 represents hydrogen or alkyl having 1 to 4 carbon atoms
• X for cyano, fluorine, chlorine, bromine, iodine, nitro, formyl, haloalkyl with 1 to 6 carbon atoms and 1 to 9 fluorine, chlorine and / or bromine atoms, alkyl with 1 to 4 carbon atoms, alkenyl with 2 to 6 carbon atoms, by carboxy , Methoxycarbonyl or ethoxycarbonyl substituted alkenyl having 2 to 5 carbon atoms.
• alkynyl with 2 to 6 carbon atoms alkynyl with 2 to 5 carbon atoms substituted by carboxy, methoxycarbonyl or ethoxycarbonyl, hydroxyalkyl with 1 to 4 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the Alkyl part, cycloalkyl with 3 to 6 carbon atoms, thiocarbamoyl, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, alkylcarbonyl with 1 to 4 carbon atoms in the alkyl part, hydroximinoalkyl with 1 to 4 carbon atoms in the alkyl part, alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 up to 4 carbon atoms in the alkyl part, alkylthio with -1 to 4 carbon atoms, alkylsulf
• R 2 represents hydrogen, methyl, ethyl or propyl, or
• R and R 2 together with the nitrogen atom to which they are attached represent pyrrolidinyl, piperidinyl, morpholinyl, thiomopholinyl, piperazinyl, 3,6-dihydro-l (2H) -pipericimyl or tetrahydro-l (2H) -pyridazinyl, where these radicals can be substituted by 1 to 3 fluoratoins, 1 to 3 methyl groups and / or trifluoromethyl, or
• R ' represents hydrogen or methyl
• R represents methyl, ethyl, fluorine, chlorine or trifluoromethyl
• m stands for the numbers 0, 1, 2 or 3, where R "stands for identical or different radicals if m stands for 2 or 3,
• R '" stands for methyl, ethyl, fluorine, chlorine or trifluoromethyl and n stands for the numbers 0, 1, 2 or 3, where R"' stands for identical or different radicals if n stands for 2 or 3,
• R 3 represents pyridyl which is linked in the 2- or 4-position and can be mono- to tetrasubstituted, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, Methoximinomcthyl, methoximinoethyl and / or trifluoromethyl, or
• R 3 represents pyrimidyl which is linked in the 2- or 4-position and can be mono- to trisubstituted, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, Methoximinomethyl, methoximinoethyl and / or trifluoromethyl, or
• R 3 represents thienyl which is linked in the 2- or 3-position and can be mono- to trisubstituted, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, Methoximinimethyl, methoximinoethyl and / or trifluoromethyl, or
• R 3 represents thiazolyl, which is linked in the 2-, 4- or 5-position and can be mono- to z-substituted, identical or different, by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, Hydroximinomethyl, hydroximinoethyl, _methoximinimethyl, methoximinoethyl and / or trifluoromethyl,
• R 4 represents hydrogen, methyl, ethyl, propyl or isopropyl
• X for cyano, fluorine, chlorine, bromine, iodine, nitro, formyl, trifluoromethyl, difluoromethyl, methyl, ethyl, cyclopropyl, thiocarbamoyl, methoxycarbonyl, methylcarbonyl, ethylcarbonyl, hydroximinomethyl, methoximinomethyl, methylthio, methylsulfinyl methyls ⁇ lfonyl, methylaminocarbonyl, hydroxymethyl -yl, methoxymethyl, ethoxymethyl or 1-methoxy-eth.yl, or X for a residue of the formula
• radical definitions can be combined with one another in any way.
• individual definitions can be omitted.
• Formula (IT) provides a general definition of the halopyrazolopyrimidines required as starting materials for carrying out process (a) according to the invention.
• R 3 , R ⁇ and Hai preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the compounds of the formula (I) according to the invention.
• ⁇ l preferably represents fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
• ⁇ l preferably represents cyano, fluorine, chlorine, bromine, iodine, nitro, haloalkyl with 1 to 6 carbon atoms and 1 to 9 fluorine, chlorine and / or bromine atoms, alkyl with 1 to 4 carbon atoms, formyl, cycloalkyl with 3 to 6 Carbon atoms, thioearbamoyl, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, alkylcarbonyl with 1 to 4 carbon atoms in the alkyl part, alkylthio with 1 to 4 carbon atoms, alkylsulfinyl with 1 to 4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms or for alkylaminocarbonyl with 1 to 4 carbon atoms in the alkyl part.
• ⁇ l particularly preferably represents cyano, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, difluoromethyl, methyl, ethyl, formyl, cyclopropyl, thioearbamoyl, methoxycarbonyl, methylcarbonyl, methylthio, ethylcarbonyl, methylsulfinyl, methylsulfonyl, methylaminocarbonyl, 1,2 -Dibromopropyl or 1,2-dibromobutyl.
• halogen pyrazolopyrimidines of the formula (H) are new. These substances are also suitable for controlling unwanted microorganisms.
• halopyrazolopyrimidines of the formula (II) can be prepared
• R 3 and R ⁇ have the meanings given above, and
• R represents halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, thioearbamoyl, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl, with halogenating agents, if appropriate in the presence of a diluent, or
• R 3 and R ⁇ have the meanings given above, reacted with phosphorus oxychloride in the presence of dimethylformnamide and optionally after-reaction with the addition of phosphorus pentachloride.
• Formula (X) provides a general definition of the hydroxy-pyrazolopyrimidines required as starting materials for carrying out process (f) according to the invention.
• R 3 and R 4 preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the compounds of the formulas (I) according to the invention.
• R preferably represents cyano, fluorine, chlorine, bromine, iodine, nitro, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 fluorine, chlorine and / or bromine atoms, cycloalkyl having 3 to 6 carbon atoms , Thioearbamoyl, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, alkylthio with 1 to 4 carbon atoms, alkylsulfinyl with 1 to 4 carbon atoms, alkylsulfonyl with 1 " to 4 carbon atoms or for alkylaminocarbonyl with 1 to 4 carbon atoms in the alkyl part.
• R particularly preferably represents cyano, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, difluoromethyl, chloromethyl, methyl, ethyl, cyclopropyl, thioearbamoyl, methoxycarbonyl, methylthio, methylsulfinyl, methylsulfonyl or ethylaminocarbonyl.
• hydroxy-pyrazolopyrimidines of the formula (X) are also not yet known. They can be made by
• R 3 has the meaning given above and
• R 12 represents alkyl having 1 to 4 carbon atoms
• Formula (XII) provides a general definition of the heterocyclylmalonic esters required as starting materials for carrying out process (h) according to the invention.
• R 3 preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention.
• R * 2 preferably represents methyl or ethyl.
• heterocyclylmalonic esters of the formula (XU) are known (cf. DE 38 20 538-A, WO 01-11 965 and WO 99-32464);
• R * 2 has the meaning given above and
• R 13 represents halogen or haloalkyl.
• R 12 has the meaning given above
• R 14 "represents halogen or haloalkyl
• R 15 and R 1 ⁇ are independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy.
• the pyridylmalonic esters of the formula (XH-a) can be prepared by
• R 13 has the meaning given above and
• Y 2 represents halogen, with malon esters of the formula
• R 12 has the meaning given above
• halopyridines required as starting materials for carrying out process (i) according to the invention are generally defined by the formula (XTV).
• R preferably represents fluorine, chlorine or trifluoromethyl.
• Y 2 preferably represents chlorine or bromine.
• halopyridines of the formula (XIV) are known synthetic chemicals.
• the pyrimidylmalonic esters of the formula (Xll-b) can be prepared by
• R * 4 , R * 5 and R 1 ⁇ have the meanings given above and
• Y 3 represents halogen
• R * 2 has the meaning given above
• Formula (XVI) provides a general definition of the halopyrimidines required as starting materials for carrying out process (j) according to the invention.
• R 14 preferably represents fluorine, chlorine or trifluoromethyl.
• R 15 and R ⁇ are also preferably independently of one another hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy.
• Y 3 preferably represents chlorine or bromine.
• the halopyrimidines of the formula (XVI) are known and can be prepared by known methods (cf. J. Chem. Soc. 1955, 3478, 3481).
• Formula (XIH) provides a general definition of the aminopyrazoles required as reaction components for carrying out process (h) according to the invention.
• R ⁇ preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention.
• R preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the hydroxy-pyrazolopyrimidines of the formula (X).
• aminopyrazoles of the formula (XIII) are known or can be prepared by known methods.
• Suitable halogenating agents for carrying out process (f) are all components which are customary for the replacement of hydroxyl groups by halogen.
• Phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, thionyl bromide or mixtures thereof are preferably usable.
• the corresponding fluorine compounds of the formula (H) can be prepared from the chlorine or bromine compounds by reaction with potassium fluoride.
• Process (g) is suitable for the preparation of halopyrazolopyridines of the formula
• R 3 and R 4 have the meanings given above.
• Formula (XI) provides a general definition of the hydroxy-pyrazolopyrimidines required as starting materials in carrying out process (g).
• R 3 and R ⁇ preferably have those meanings which have already been given as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• the hydroxy-pyrazolopyrimidines of the formula (XI) can be prepared by process (h) by using aminopyrazoles of the formula (XHI) in which R represents hydrogen.
• Process (g) is carried out under the conditions of Vilsmeier formylation with the aid of phosphorus oxychloride in the presence of dimethylformamide.
• Phosphorus pentachloride can also be added as a chlorinating agent.
• reaction temperatures can be varied within a substantial range when carrying out process (g). In general, temperatures between -10 ° C and + J50 ° C, preferably between 0 ° C and 120 ° C.
• OAE formula (XI) is generally 2 to 5 mol of dimethylformamide, 5 to 15 mol phosphorus oxychloride clilorid and optionally 0 to 2 moles Phospliorpentachlorid a.
• the work-up takes place according to usual methods.
• Formula (HI) provides a general definition of the amines which are further required as starting materials for carrying out process (a) according to the invention.
• R * and R ⁇ preferably have those meanings which have already been given as preferred for R * and R 2 in connection with the description of the compounds of the formula (I) according to the invention.
• the amines of the formula (IH) are known or can be prepared by known methods.
• Suitable diluents for carrying out process (a) according to the invention are all customary, inert organic solvents.
• Halogenated hydrocarbons such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane, can preferably be used;
• Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxian, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;
• Nitriles such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile;
• Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-
• Suitable acid acceptors in carrying out process (a) according to the invention are all inorganic or organic bases customary for such reactions.
• Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates such as, for example, sodium hydride, sodium amide, lithium diisopropylamide, sodium methylate, sodium ethylate, potassium tert-butoxide, are preferably usable , Sodium hydroxide, potassium hydroxide, sodium acetate, potassium hydroxide, calcium acetate, sodium carbonate, Potassium carbonate, potassium bicarbonate and sodium bicarbonate, and also ammonium compounds such as ammonium hydroxide, ammonium acetate and ammonium carbonate, as well as tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N
• Suitable catalysts for carrying out process (a) according to the invention are all reaction accelerators customary for such reactions. Fluorides such as sodium fluoride, potassium fluoride or ammonium fluoride can preferably be used.
• reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 0 ° C and 80 ° C.
• Formula (Ia) provides a general definition of the pyrazolopyrimidines required as starting materials when carrying out process (b) according to the invention.
• R, R 2 , R 3 , R 4 and shark preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• the pyrazolopyrimidines of the formula (Ia) are substances according to the invention which can be prepared by process (a) according to the invention.
• Suitable diluents for carrying out the process (b, variant) according to the invention are all customary inert, organic solvents.
• Aliphatic or aromatic, optionally halogenated hydrocarbons, such as toluene, dichloromethane, chloroform or carbon tetrachloride, can preferably be used.
• reaction temperatures can be varied within a certain range when carrying out the process (b, / ariante ⁇ ). In general, temperatures between -80 ° C and + 20 ° C, preferably between -60 ° C and + 10 ° C.
• yrazolopyrimidine of the formula (Ia) is generally employed in an equivalent amount or else an excess shot, preferably 1.1 to 1.2 mol of di-isobutyl aluminum hydride and then adds an excess of aqueous ammonium chloride solution.
• the processing takes place according to usual methods. The general procedure is to acidify the reaction mixture, separate the organic phase, extract the aqueous phase with a water-immiscible organic solvent, wash the combined organic phases, dry and concentrate under reduced pressure.
• Formula (IV) provides a general definition of the Grignard compounds required as reaction components when carrying out process (b, variant ⁇ ) according to the invention.
• R ⁇ preferably represents alkyl having 1 to 4 carbon atoms, particularly preferably methyl or ethyl.
• X 2 preferably represents bromine.
• Suitable catalysts for carrying out the process according to the invention are all reaction accelerators customary for such Grignard reactions. Examples include potassium iodide and iodine.
• Suitable diluents for carrying out the process (b, variant ⁇ ) according to the invention are all inert organic solvents which are customary for such reactions.
• Ethers such as diethyl ether, dioxane or tetrahydrofuran, and also aromatic hydrocarbons, such as toluene, and also mixtures of ethers and aromatic hydrocarbons, such as toluene / tetrahydrofuran, can preferably be used.
• reaction temperatures can be varied within a certain range when carrying out the process (b, variant ⁇ ). In general, temperatures between -20 ° C and + 100 ° C, preferably between 0 ° C and 80 ° C.
• Formula (Ib) provides a general definition of the pyrazolopyrimidines required as starting materials when carrying out process (c) according to the invention.
• IV, R 2 , R 3 , R 4 and shark preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• R ⁇ preferably represents hydrogen or alkyl having 1 to 4 carbon atoms, particularly preferably hydrogen, methyl or ethyl.
• the pyrazolopyrimidines of the formula (Ib) are substances according to the invention which can be prepared by process (b) according to the invention.
• Formula (V) provides a general definition of the amino compounds required as reaction components when carrying out process (c, variant ⁇ ) according to the invention.
• R 7 preferably represents hydrogen or alkyl having 1 to 4 carbon atoms, particularly preferably hydrogen, methyl or ethyl.
• reaction components are acid addition salts, preferably hydrogen chloride addition salts of amino compounds of the formula (V).
• Suitable diluents for carrying out the process (c, variant ⁇ ) are all customary inert, organic solvents. Alcohols such as methanol, ethanol, n-propanol or isopropanol can preferably be used.
• Suitable catalysts for carrying out the process (c, variant) according to the invention are all reaction accelerators customary for such reactions.
• Acidic or basic catalysts such as e.g. the weakly basic ion exchanger commercially available under the name Amberlyst A-21®.
• reaction temperatures can be varied within a certain range when carrying out the process (c, variant ⁇ ). In general, temperatures between 0 ° C and 80 ° C, preferably between 10 ° C and 60 ° C.
• pyrazolopyrimidine of the formula (Ib) is generally employed in an equivalent amount or in excess, preferably between 1.1 and 1.5 mol of the amino compound of the formula (V) or an acid addition salt thereof.
• the processing takes place according to usual methods. The general procedure is to filter the reaction mixture, if appropriate, then to concentrate and to purify it.
• Formula (VI) provides a general definition of the triphenylphosphonium salts required as reaction components when carrying out the process (c, variant ⁇ ).
• Ph stands for phenyl.
• R 8 preferably represents hydrogen or alkyl having 1 to 4 carbon atoms, it being possible for the alkyl radicals to be substituted by carboxyl, methoxycarbonyl or ethoxycarbonyl.
• R 8 particularly preferably represents hydrogen, methyl or Ethyl, where the latter two radicals can be substituted by carboxyl, methoxycarbonyl or ethoxycarbonyl.
• triphenylphosphonium salts of the formula (VI) are known or can be prepared by known methods.
• Suitable bases for carrying out the process according to the invention are all deprotonating agents customary for such Wittig reactions.
• Butyl lithium can preferably be used.
• Suitable diluents for carrying out the process according to the invention are all organic solvents customary for such Wittig reactions.
• Ethers such as dioxane or tetrahydrofuran can preferably be used.
• reaction temperatures can be varied within a certain range when carrying out the process (c, variant ⁇ ). Generally one works at temperatures between -78 ° C and + 30 ° C.
• Formula (VIT) provides a general definition of the alkylating agents required as reaction components when carrying out process (c, variant ⁇ ).
• R ⁇ preferably represents alkyl having 1 to 4 carbon atoms, particularly preferably methyl or ethyl.
• X 3 preferably represents chlorine, bromine, iodine or the radical R 9 -0-S ⁇ 2-0-, where R ⁇ has the meanings given above.
• the alkylating agents of the formula (VII) are known or can be prepared by known methods.
• di-isobutyl aluminum hydride is used as the reducing agent in the first stage when carrying out the process (c, variant ⁇ ) in the first stage, the procedure is expediently carried out under the conditions already associated with the description of the method (b, variant ⁇ ) were mentioned.
• sodium borohydride is used as the reducing agent in carrying out the process (c, variant ⁇ ) in the first stage, alcohols, preferably methanol, ethanol or isopropanol, are generally used as diluents.
• reaction temperatures can be varied within a certain range. In general, temperatures between 0 ° C and 70 ° C, preferably between 0 ° C and 50 ° C.
• all customary acid binders are suitable as bases.
• Alkali metal hydrides, alcoholates and carbonates such as sodium hydride, sodium methylate, potassium tert-butoxide, sodium carbonate, potassium carbonate or lithium carbonate, can preferably be used.
• Carrying out the second stage of the process according to the invention takes into account all customary, inert organic solvents.
• Ethers such as dioxane or tetrahydrofuran, and also nitriles, such as acetonitrile, can preferably be used.
• the temperatures can be varied within a relatively wide range. In general, temperatures between 0 ° C and 100 ° C, preferably between 20 ° C and 80 ° C.
• the pyrazolopyrimidines required as starting materials when carrying out process (d) according to the invention are generally described by the formula (Id).
• IV, R 2 , R 3 , R 4 and shark preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• R 10 preferably represents hydrogen or alkyl having 1 to 4 carbon atoms, particularly preferably hydrogen, methyl, ethyl or propyl, where the three last-mentioned radicals can each be substituted by carboxyl, methoxycarbonyl or ethoxycarbonyl.
• the pyrazolopyrimidines of the formula (Id) are substances according to the invention which can be prepared by process (a) according to the invention.
• the pyrazolopyrimidines can be produced by
• Suitable strong bases for carrying out process (d) according to the invention are preferably alkali metal alcoholates, sodium methylate and potassium tert-butoxide being mentioned as examples.
• Suitable diluents for carrying out process (d) according to the invention are all inert organic solvents which are customary for such reactions.
• Alcohols such as methanol or ethanol, and nitriles, such as acetonitrile, can preferably be used.
• the temperatures can be varied within a certain range. In general, temperatures between -10 ° C and + 80 ° C, preferably between 0 ° C and 60 ° C.
• the pyrazolopyrimidines of the formula (NUT) are known or can be prepared by known methods (cf. PCT / EP 03/05 159).
• Formula (IX) provides a general definition of the acyl derivatives required as reaction components when carrying out process (e).
• R 1 * preferably represents alkyl having 1 to 4 carbon atoms, particularly preferably methyl, ethyl or n-propyl.
• X 4 is preferably chlorine or a radical of the formula - Q - Q - R 1 1 wherein R 11 in turn '' IIO the previously mentioned meaning.
• acyl derivatives of the formula (IX) are known or can be prepared by known methods.
• Suitable catalysts for carrying out process (e) according to the invention are all reaction accelerators which are customary in such Friedel-Crafts reactions.
• Metal chlorides such as aluminum trichloride or iron (_H) chloride, can preferably be used.
• Suitable diluents for carrying out process (e) according to the invention are all inert organic solvents which are customary for such reactions.
• Ethers such as diethyl ether, dioxane or tetrahydrofuran can preferably be used.
• the temperatures can be varied within a certain range. In general, temperatures between -20 ° C and + 20 ° C, preferably between -10 ° C and + 10 ° C.
• Suitable diluents for carrying out process (f) according to the invention are all solvents customary for such halogenations.
• Halogenated aliphatic or aromatic hydrocarbons such as chlorobenzene, can preferably be used.
• the halogenating agent itself for example phosphorus oxychloride or a mixture of halogenating agents, can also act as the diluent.
• the temperatures can also be varied within a substantial range when carrying out process (f). In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.
• hydroxy-pyrazolo-pyrimidine of the formula (X) is generally reacted with an excess of halogenating agent.
• the processing is carried out according to customary methods.
• Suitable diluents for carrying out process (h) are all inert organic solvents which are customary for such reactions.
• Alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol and tert-butanol can preferably be used.
• Suitable acid binders for carrying out process (h) are all inorganic and organic bases customary for such reactions.
• Tertiary amines such as tributylamine or pyridine, can preferably be used. A in excess can also act as a diluent.
• the temperatures can be varied within a wide range when carrying out process (h). In general, temperatures between 20 ° C and 200 ° C, preferably between 50 ° C and 180 ° C.
• heterocyclylmalonic esters of the formula (XU) and aminopyrazole of the formula (XEQ) are generally reacted in equivalent amounts. However, it is also possible to use one or the other component in an excess. The processing takes place according to usual methods.
• Suitable diluents for carrying out processes (i) and (j) are all customary, inert organic solvents.
• Halogenated hydrocarbons such as, for example, chlorobenzene, dichloro-benzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane, can preferably be used;
• Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1,2-diethoxyethane or anisole;
• Nitrites such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile;
• Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide
• Suitable acid acceptors for carrying out processes (i) and (j) according to the invention are all customary inorganic or organic bases.
• Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, lithium diisopropylamide, sodium methylate, sodium ethylate, potassium, are preferably usable.
• reaction temperatures may also be in the implementation of the methods (i) and Q) according to the invention m a larger area can be varied. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 0 ° C and 80 ° C.
• the methods according to the invention are generally carried out under atmospheric pressure. However, it is also possible to work under increased pressure.
• the substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.
• Fungicides can be used to control crop protection against Plasmo iophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
• Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
• Xanthomonas species such as, for example, Xanthomonas campestris pv. Oryzae;
• Pseudomonas species such as, for example, Pseudomonas syringae pv. Lachrymans;
• Erwinia species such as, for example, Erwinia amylovora;
• Pythium species such as, for example, Pythium ultimum
• Phytophthora species such as, for example, Phytophthora infestans
• Pseudoperonospora species such as, for example, Pseudoperonospora humuli or
• Plasmopara species such as, for example, Plasmopara viticola
• Bremia species such as, for example, Bremia lactucae
• Peronospora species such as, for example, Peronospora pisi or P. brassicae;
• Erysiphe species such as, for example, Erysiphe graminis
• Sphaerotheca species such as, for example, Sphaerotheca fuliginea
• Podosphaera species such as, for example, Podosphaera leucotricha
• Venturia species such as, for example, Venturia inaequalis
• Pyrenophora species such as, for example, Pyrenophora teres or P. gra inea
• Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
• Cochliobolus species such as, for example, Cochliobolus sativus
• Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
• Uromyces species such as, for example, Uromyces appendiculatus
• Pu.ccinia species such as, for example, Puccinia recondita
• Sclerotinia species such as, for example, Sclerotinia sclerotiorum
• Tilletia species such as, for example, Tilletia caries
• Ustilago species such as, for example, Ustilago nuda or Ustilago avenae;
• Pellicularia species such as, for example, Pellicularia sasakii;
• Pyricularia species such as, for example, Pyricularia oryzae
• Fusarium species such as, for example, Fusarium culmorum
• Botiytis species such as, for example, Botrytis cinerea
• Septoria species such as, for example, Septoria nodorum
• Leptosphaeria species such as, for example, Leptosphaeria nodorum;
• Cercospora species such as, for example, Cercospora canescens
• Alternaria species such as, for example, Altemaria brassicae;
• Pseudocercosporella species such as, for example, Pseudocercosporella he otrichoides.
• the active compounds according to the invention also have a very good strengthening effect in plants. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms.
• Plant-strengthening (resistance-inducing) substances are to be understood in the present context as substances which are able to stimulate the defense system of plants in such a way that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesired microorganisms.
• Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and niren.
• the substances according to the invention can thus be used to protect plants against attack by the pests mentioned within a certain period of time after the treatment.
• the period within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days after the treatment of plants with the active compounds.
• the fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.
• the active compounds according to the invention can be used with particularly good success in combating cereal diseases, for example against Erysiphe species, for diseases in wine, fruit and vegetable cultivation, for example against Botrytis, Venturia, Sphaerotheca and Podosphaera species ,
• the active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.
• the active compounds according to the invention can also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds.
• plants and parts of plants can be treated.
• Plants are understood here to mean all plants and plant populations, such as desired and undesirable wild plants or crop plants (including naturally occurring crop plants).
• Cultivated plants can be plants which are obtained by conventional breeding and optimization methods or by biotechnological and Genetic engineering methods or combinations of these methods can be obtained, including the transgenic plants and including the plant varieties that can be protected or not protected by plant breeders' rights.
• Plant parts are to be understood to mean all above-ground and underground parts and organs of the plants, such as shoots, leaves, flowers and roots, where Leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes are listed as examples such as vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
• the treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary treatment methods, for example by dipping, spraying, evaporating, atomizing, scattering, spreading and in the case of propagation material, in particular seeds single or multi-layer wrapping.
• the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
• technical materials are understood to mean non-living materials that have been prepared for use in technology.
• technical materials which are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be attacked or decomposed by microorganisms
• parts of production plants for example cooling water circuits, may also be mentioned which can be impaired by the multiplication of microorganisms.
• industrial materials are preferably adhesives, sizes, paper and board, leather, wood, "paints, cooling lubricants and heat-transfer liquids particularly preferably wood.
• Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials.
• the active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
• Microorganisms of the following genera may be mentioned, for example:
• Alternaria such as Alternaria tenuis
• Aspergillus such as Aspergillus niger
• Chaetomium like Chaetomium globosum
• Coniophora such as Coniophora puetana
• Lentinus such as Lentinus tigrinus
• Penicillium such as Penicillium glaucum
• Polyporus such as Polyporus versicolor
• Aureobasidium such as Aureobasidium pullulans
• Sclerophoma such as Sclerophoma pityophila, Trichoderma, like Trichoderma viride,
• Escherichia such as Escherichia coli
• Pseudomonas such as Pseudomonas aeruginosa
• Staphylococcus such as Staphylococcus aureus.
• the active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV -Cold and warm mist formulations.
• formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
• extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
• surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
• organic solvents can, for example, also be used as auxiliary solvents.
• aromatics such as xylene, toluene or alkylnaphthalenes
• chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
• aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions
• alcohols such as butanol or glycol and their ethers and esters
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
• strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
• Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.
• Solid carrier materials come into question: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates.
• Solid carriers for granules are possible: e.g.
• Suitable emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates.
• Possible dispersants are: eg lignin sulfite waste liquor and methyl cellulose.
• Adhesives such as cafboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
• Other additives can be mineral and vegetable oils.
• Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
• the formulations generally contain between 0J and 95 percent by weight of active compound, preferably between 0.5 and 90%.
• the active compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of activity or to prevent the development of resistance.
• fungicides bactericides
• acaricides nematicides or insecticides
• synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
• Dagger G debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; Diclomezine; dicloran; diethofencarb; Difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; Diniconazole-M; dinocap; diphenylamines; Dipyrithione; Ditalimfos; dithianon; dodine; Drazoxolon;
• edifenphos epoxiconazole; ethaboxam; ethirimol; etridiazole;
• famoxadone fenamidone; Fenapanil; fenarimol; Fenbuconazole; fenfuram; Fenhexamrid; Fenitropan; Fenoxanil; - fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; Flubenzimine; fludioxonil; flumetover; flumorph; fluoromides; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; Fosetyl-Al; Fosetyl-sodiixm; fuberidazole; furalaxyl; furametpyr; Furcarbanil; Furmecyclox;
• hnazalil hnibenconazole
• Iminoctadine triacetate Iminoctadine tris (albesil; Iodocarb; Ipconazole; Iprobefos; Iprodione; Iprovalicarb; Irumamycin; Isoprothiolane; Isovaledione;
• mancozeb maneb; Meferimzone; mepanipyrim; mepronil; metalaxyl; Metalaxyl-M; Metconazole; methasulfocarb; Methfuroxam; metiram; metominostrobin; Metsulfovax; mildiomycin; myclobutanil; myclozoline;
• natamycin natamycin; nicobifen; Nitro Thal-isopropyl; Novifluxnuron; nuarimol;
• tebuconazole tecloftalam; Tecnazene; Tetcyclacis; tetraconazole; thiabendazole; Thicyofen; Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; Triazbutil; triazoxide; Tricyclamide; Tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; Uniconazole;
• copper salts and preparations such as Bordeaux mixture; copper; Copper naphthenate; copper oxychloride; Copper sulfate; Cufraneb; copper; mancopper; Oxine-copper.
• Eflusilanate Emamectin, Emamectin-benzoate, Ernpenthrin (IR-isomer), Endosulfan, Entomothora spp.
• EPN Esfenvalerate
• Ethiofencarb Ethiprole
• Ethionj Ethoprophos Etofenprox
• Etox-azole Etrimfos
• Fenamiphos Fenazaquin, Fenbutatin oxide, Fenfluthrin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fensulfothion, Fenthion, Fentrifanil, Fenronilypyridone, Fenronilypyrate, Fenvalyryp, Fluazuron, flubenzimine, flubrocythrinate, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufen- prox, Flumethrin, Flupyrazofos, Flutenzin (Flufenzine), Fluvalinate, Fonofos, Formetanate, Formothion, Fosmethilan, Fosthiazate, Fubfenprox (Fluproxyf
• Halofenozide HCH, HCN-801, Heptenophos, Hexaflumuron, Hexythiazox, Hydra-methylnone, Hydroprene,
• IKA-2002 hnidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobefos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin,
• Mecarbam Mesulfenfos, Metaldehyde, Metam-sodium, Methacrifos, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoprene, Methoxychlor, Methoxyfenozide, Metolcarb, Metoxadiazone, MilevinephinI, Mevincinin MKB, Mevincinin MK5 MON-45700, Monocrotophos. Moxidectin, MTI-800,
• NC-104 NC-170, NC-184, NC-194, NC-196, Niclosamide, Nicotine, Nitenpyram, Nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, Novaluron, Noviflumuron,
• Paecilomyces fumosoroseus Parathion-methyl, Parathion (-ethyl), Permethrin (eis, tirans-), Petroleum, PH-6045, Phenothrin (lR-trans isomer), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphocarb, Phoxim, Piperonyl butöxide, Pirimicarb, Pirimiphos-methyl, Pirimiphos-ethyl, Prallethrin, Profenofos, Promecarb, Propaphos, Pfopargite, Propetamphos, Propoxur, Prothiofos, Prothoate, Protrifenbute, Pymetrozine, Pyraclofos, Pyridaphridyl, Pyridaphridyl, Pyridaphridyl, Pyridmetyl , Pyrimidifen, pyriproxyfen,
• the compounds of the formula (I) according to the invention also have very good antimycotic effects. They have a very broad antimycotic activity spectrum in particular against dermatophytes and yeasts, molds and diphasic fungi (for example against Candida species such as Candida albicans, Candida glabrata), and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, microsporon species such as microsporon canis and audouinii.
• Candida species such as Candida albicans, Candida glabrata
• Epidermophyton floccosum Aspergillus species such as Aspergillus niger and Aspergillus fumigatus
• Trichophyton species such as Trichophyton mentagrophytes
• microsporon species such as microsporon canis and audouinii.
• the list of these fungi is in no way
• an effective amount of one or more compounds of formula (I) or pharmaceutically acceptable salts thereof can be administered.
• the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, spoiling, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
• the application rates can be varied within a wide range depending on the type of application.
• the active compound application rates are generally between 0J and 10,000 g / ha, preferably between 10 and 1,000 g / ha.
• the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed.
• the active compound application rates are generally between 0J and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
• all plants and their parts can be treated according to the invention.
• wild plant species and plant varieties and their parts obtained by conventional biological breeding methods, such as crossing or protoplast fusion are treated.
• transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms) and their parts are treated.
• the term “parts” or “parts of plants” or “parts of plants” was explained above.
• Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention.
• Plant cultivars are understood to mean plants with new properties (“traits”) which have been grown by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, breeds, bio- and genotypes. Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, nutrition), the treatment according to the invention can also cause superadditive (“synergistic”) effects.
• the preferred transgenic plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous valuable properties (“traits”).
• traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the
• Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or vire n and an increased tolerance of the plants to certain herbicidal active ingredients.
• transgenic plants the important crop plants such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, R-aps and fruit plants (with the fruits apples, pears, citrus fruits and grapes) are mentioned ", where corn, Soybeans, potatoes, cotton, tobacco and rapeseed are particularly emphasized.
• the properties (“traits”) are particularly emphasized as the plants' increased defense against insects, arachnids, namatodes and snails by means of toxins which arise in the plants, in particular those which are caused by the genetic Bacillus thuringiensis material (e.g.
• Bt plants The increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins are also particularly emphasized as properties (“traits”).
• SAR systemic acquired resistance
• systemin phytoalexins
• elicitors and resistance genes and correspondingly expressed proteins and toxins are also particularly emphasized as properties (“traits”).
• trait are also particularly emphasized the increased tolerance of the plants to certain herbicidal active ingredients, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg" PAT "gene).
• herbicidal active ingredients for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg” PAT “gene).
• the each the Genes imparting the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants.
• Examples of “Bt plants” are corn varieties, cotton varieties, soy varieties and potato fries which are marketed under the trade names YIELD GARD® (eg corn, cotton, Soy), KnockOut® (e.g. corn), StarLink® (e.g.
• herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties which are marketed under the trade names Roundup Ready® (tolerance against glyphosate, e.g. maize, cotton, soybeans), Liberty Link® (tolerance against phosphinotricin, e.g. rape), IMI® ( Tolerance to imidazolinones) and STS® (tolerance to sulfonylureas such as corn) are sold.
• the herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties sold under the name Clearfield E. (for example maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").
• the plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention.
• the preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment should be particularly emphasized. with the compounds or mixtures specifically listed in the present text.
• the filtrate is dried over sodium sulfate and then filtered again.
• 1.48 g (30.34% of theory) of 5,7-dichloro-3-cyano-6- (t_hien-3-yl) -pyrazolo- [1,5-a] pyrimidine are obtained in the form of a solid.
• a mixture of 56 mmol of 5,7-dihydroxy-6- (5-chloropyrirnidin-4-yl) pyrazolo [l, 5-a] pyrimidine and 560 mmol of phosphorus oxychloride is stirred at 30 ° C. for 30 minutes, then to 0 Cooled and then added dropwise with 85 mmol of dimethylformamide with stirring. After the addition has ended, the reaction mixture is first stirred at room temperature for 12 hours and then heated under reflux for 6 hours. The reaction mixture is then treated with 56 mmol phosphorus penta- chloride added and heated under reflux for a further 12 hours. After cooling to room temperature, the reaction mixture is concentrated under reduced pressure and then poured onto ice water.
• Solvent 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkyl aryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
• the plants are then placed in the greenhouse at approximately 21.degree. C. and a relative atmospheric humidity of approximately 90%.
• Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
• Botrytis test (bean) / protective
• Solvent 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkyl aryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
• Solvent 50 parts by weight of N, N-dimethylacetamide.
• Emulsifier 1 part by weight of alkyl aryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
• the plants are then placed in the greenhouse at a temperature of approx. 20 ° C. and a relative atmospheric humidity of 80% in order to promote the development of rust pustules-
• Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
• Solvent 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkyl aryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
• Emulsifier alkylaryl polyglycol ether
• each of the preparation is pipetted into the wells of microtiter plates. After the solvent has evaporated, 200 ⁇ l each of a potato-dextrose medium is added to each of the S-avita, each having previously been mixed with the desired concentration of spores or mycelium of the microorganism to be tested. The resulting concentrations of active ingredient in the cavities are
• the resulting concentration of emulsifier is 300 ppm each.
• the microtiter plates are then moved up to 5 days on a shaker at a temperature of 22 ° C "3 until in the untreated control sufficient growth of the respective microorganism can be detected. ⁇
• the evaluation is carried out photometrically at a wavelength of 620 nm.
• the dose of active substance is calculated from the measurement data for the different concentrations, which leads to a 50% inhibition of fungal growth (ED50) compared to the untreated control.
• the E_D50 value of the compound according to the invention listed in Example 1 for Botrytis cinerea is at an active substance dose which is less than 10 ppm.

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• 2004
  • 2004-06-18 MX MXPA05013902A patent/MXPA05013902A/es not_active Application Discontinuation
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  • 2004-06-18 JP JP2006515995A patent/JP2007506665A/ja active Pending
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