Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/30—Halogen atoms or nitro radicals
• • 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
  • 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
  • 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 new triazolopyrimidines, a process for their preparation and their use for controlling unwanted microorganisms.
• the invention also relates to new intermediates and processes for their production.
• R.1 stands for optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl or for optionally substituted heterocyclyl,
• R2 represents hydrogen, halogen, optionally substituted alkyl or optionally substituted cycloalkyl
• R3 represents optionally substituted heterocyclyl
• G represents oxygen or SO n , wherein
• n 0, 1 or 2
• X represents halogen, cyano, optionally substituted alkyl, optionally substituted
• Alkoxy optionally substituted alkylthio, optionally substituted alkylsulfinyl or optionally substituted alkylsulfonyl,
• R ⁇ and R ⁇ have the meanings given above,
• ⁇ i stands for halogen
• ⁇ i halogen
• R ⁇ ⁇ R ⁇ G andX 1 have the meanings given above,
• R 4 represents optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl or cyano and
• R- * represents optionally substituted alkyl
• the triazolopyrimidines of the formula (T) 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 triazolopyrimidines of the formula (!) According to the invention have a substantially better microbicidal activity than the constitutionally most similar, known substances of the same action.
• the compounds of the formula (I) according to the invention can optionally be in the form of mixtures of various possible isomeric forms, in particular stereoisomers, such as E and Z, threo and erythro and optical isomers such as R and S isomers or atropisomers. but if tautomers are also present. Both the pure stereoisomers and any mixtures of these isomers are the subject of this invention, even if only the compounds of the formula (T) are mentioned here in general.
• 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, furthermore ammonia, primary, secondary and tertiary amines with (C 1 -C 4) -alkyl radicals and mono-, di - And trialkanolamines of (-C-C4) alkanols.
• acids are, for example, mineral acids, such as salt, sulfuric and phosphoric acid, organic acids, such as acetic acid or oxalic acid, and acid salts, such as aHSÜ4 and KHSO4.
• the salts obtainable in this way also have fungicidal and microbicidal properties.
• the invention also relates to the salt-like derivatives formed from compounds of the formula (I) 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 further 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 triazolopyrimidines according to the invention are generally defined by the formula (I).
• Preferred substances of the formula (I) are those in which
• Rl stands for alkyl with 1 to 6 'carbon atoms, which can be monosubstituted to quintuple, identical or differently substituted by halogen, cyano, hydroxy, alkoxy with 1 to 4 carbon atoms and / or cycloalkyl with 3 to 6 carbon atoms, or R stands for alkenyl with 2 to 6 carbon atoms, which can be monosubstituted to triple, identical or differently substituted 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
• Rl stands for cycloalkyl with 3 to 6 carbon atoms, which can be monosubstituted to trisubstituted, identical or different, by halogen and / or alkyl having 1 to 4 carbon atoms, or
• R * stands for 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 and / or cycloalkyl with 3 to 6 carbon atoms,
• R2 for hydrogen, fluorine, chlorine, bromine, iodine, alkyl with 1 to 4 carbon atoms, halogeno alkyl with 1 to 4 carbon atoms and 1 to 9 halogen atoms or for cycloalkyl with
• R stands for saturated or unsaturated heterocyclyl with 5 or 6 ring members and 1 to 4 heteroatoms, such as oxygen, nitrogen and / or sulfur, it being possible for the heterocyclyl to be monosubstituted to tetrasubstituted, identically or differently, by
• Haloalkyl or haloalkoxy each having 1 to 3 carbon atoms and 1 to 7 halogen atoms
• G represents oxygen or SO n ,
• n 0, 1 or 2
• X for fluorine, chlorine, bromine, cyano, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to
• R ⁇ represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, l-trifluoromethyl-2,2,2-trifluoroethyl or heptafluoroisopropyl,
• 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 , Methoximino-methyl, methoximinoethyl and / or trifluoromethyl, or
• R ⁇ stands for 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, Methoximino-methyl, methoximinoethyl and / or trifluoromethyl, or
• R ⁇ stands for 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, Me- thyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximino-methyl, methoximinoethyl and / or trifluoromethyl, or
• R 3 represents thiazolyl which is linked in the 2-, 4- or 5-position and can be mono- or disubstituted, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl , Methoximinomethyl, methoximinoethyl and / or trifluoromethyl,
• G oxygen or sulfur
• X represents fluorine, chlorine, bromine, cyano, methyl, methoxy or methylthio.
• radical definitions can be combined with one another in any way.
• individual definitions can be omitted.
• Formula (U) provides a general definition of the dihalotriazolo-pyrimidines required as starting materials when carrying out process (a) according to the invention.
• R ⁇ and R ⁇ 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 (! According to the invention.
• Y * preferably represents fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
• the dihalotriazolopyrimidines of the formula (U) are new. These substances are also suitable for controlling unwanted microorganisms.
• the dihalotriazolopyrimidines can be prepared by:
• R 2 and R 3 have the meaning given above
• halogenating agents optionally in the presence of a diluent.
• Formula (VT) provides a general definition of the dihydroxytriazolopyrimidines required as starting materials in carrying out process (b).
• 2 and R ⁇ preferably have those meanings which have already been given preference for these radicals in connection with the description of the substances of the formula (!) According to the invention.
• the dihydroxy-triazolopyrimidines of the formula (VI) are also not yet known. They can be made by
• R ⁇ has the meaning given above and
• R6 represents alkyl having 1 to 4 carbon atoms
• R ⁇ has the meaning given above
• Formula (VH) provides a general definition of the heterocyclylmalonic esters required as starting materials for carrying out process (c) according to the invention.
• R3 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> stands for methyl or ethyl.
• heterocyclylmalonic esters of the formula (VE) are known (cf. DE 38 20 538-A, WO 01-11 965 and WO 99-32464).
• R ° has the meaning given above and
• R? represents halogen or haloalkyl.
• R ° has the meaning given above
• R ° represents halogen or haloalkyl
• R9 and R10 are independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy.
• the pyridylmalonic esters of the formula (VTI-a) can be prepared by
• R 6 has the meaning given above
• Formula (IX) provides a general definition of the halopyridines required as starting materials for carrying out process (d) according to the invention.
• R ⁇ is preferably fluorine, chlorine or trifluoromethyl.
• Y ⁇ preferably represents chlorine or bromine.
• halopyridines of the formula (IX) are known synthetic chemicals.
• the malonic esters of the formula (X) which are furthermore required as starting materials for carrying out the process (d) according to the invention are likewise known synthetic chemicals.
• the pyrimidylmalonic esters of the formula (NH-b) can be prepared by
• R °, R ° and R * 0 have the meanings given above and
• R ° has the meaning given above, if appropriate in the presence of a diluent, if appropriate in the presence of a copper salt and if appropriate in the presence of an acid acceptor.
• Formula (XI) provides a general definition of the halopyrimidines required as starting materials for carrying out process (e) according to the invention.
• R ° preferably represents fluorine, chlorine or trifluoromethyl.
• R ° and R ⁇ ⁇ are also preferably independently of one another hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy.
• ⁇ 3 preferably represents chlorine or bromine.
• the halopyrimidines of the formula (XI) are known and can be prepared by known methods (cf. J. Chem. Soc. 1955, 3478, 3481).
• Formula (VIJ) provides a general definition of the aminotriazoles required as reaction components for carrying out process (c) according to the invention.
• R ⁇ preferably has the some meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (!) According to the invention.
• aminotriazoles of the formula (VTJI) are known or can be prepared by known methods (cf. DE-A 10 121 162).
• Suitable halogenating agents for carrying out process (b) 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 (JJ) can be prepared from the chlorine or bromine compounds by reaction with potassium fluoride.
• Formula (S) provides a general definition of the compounds required as reaction components when carrying out process (a) according to the invention.
• R and G preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these radicals.
• the compounds of the formula (JE) are known or can be prepared by known methods.
• Formula (Ia) provides a general definition of the triazolopyrimidines required as starting materials in carrying out the second stage of process (a) according to the invention.
• Rl, R ⁇ , R3 and G preferably have those meanings which have already been mentioned for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• X preferably represents fluorine, choir or bromine.
• Formula (IV) provides a general definition of the compounds required as reaction components when carrying out the second stage of the process (a, variant ⁇ ).
• R 4 preferably represents cyano, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, alkylsulfinyl having 1 to 4 carbon atoms or alkylsulfonyl having 1 to 4 carbon atoms.
• Me is also preferably sodium or potassium.
• R 4 particularly preferably represents cyano, methoxy or methylthio. Me also particularly preferably stands for sodium or potassium.
• the compounds of the formula (TV) are known.
• Formula (V) provides a general definition of the Grignard compounds required as reaction components when carrying out the second stage of the process (a, variant ⁇ ).
• R $ preferably represents alkyl having 1 to 4 carbon atoms, particularly preferably methyl.
• Shark is both preferably and particularly preferably chlorine or bromine.
• the Grignard compounds of the formula (V) are known or can be prepared by known methods, conveniently oriented 'e immediately before use for the further synthesis.
• Suitable diluents for carrying out the first stage of 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-arnyl ether, dioxane, tetrahydrofuran, 1,2- Dimethoxyethane, 1,2-diethoxyethane or anisole;
• Nitriles such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile;
• Arnides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl
• Suitable acid acceptors for carrying out the first stage of 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 acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate, and also ammonium compounds such as ammonium hydroxide, ammonium acetate and ammonium carbonate, and also tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimin , N, N-dimethylbenzylamine, pyridine, N-
• Suitable catalysts for carrying out the first stage of 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 the first stage of process (a) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 0 ° C and 80 ° C.
• 1 mol of dihalotriazolo-pyrimidine of the formula (ET) is generally used in 1 to 10 mol, preferably 1 to 1 mol
• reaction temperatures can be varied within a substantial range. In general, temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C.
• triazolopyrimidine of the formula (Ia) is reacted with an equivalent amount or with an excess of a compound of the formula (TV).
• the processing takes place according to usual methods.
• reaction temperatures can be varied within a certain range when carrying out the second stage of the process (a, variant ⁇ ); In general, temperatures between -20 ° C and 80 ° C, preferably between 0 ° C and 60 ° C.
• triazolopyrimidine of the formula (Ia) is reacted with an equivalent amount or else with an excess of the Grignard compound of the formula (V).
• the processing is again carried out using customary methods.
• Suitable diluents for carrying out process (b) 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 e.g. Phosphorus oxychloride or a mixture of halogenating agents act.
• temperatures can also be varied within a substantial range when carrying out process (b) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.
• dihydroxytriazole pyrimidine of the formula (VI) is generally reacted with an excess of halogenating agent.
• the processing takes place according to usual methods.
• Suitable diluents for carrying out process (c) according to the invention 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, are preferably usable.
• Suitable acid binders for carrying out process (c) according to the invention are all inorganic and organic bases which are customary for such reactions.
• Tertiary amines such as tributylamine or pyridine can preferably be used. Amine used in excess can also act as a diluent.
• temperatures can be varied within a substantial range when carrying out process (c) according to the invention. In general, temperatures between 20 ° C and 200 ° C, preferably between 50 ° C and 180 ° C.
• heterocyclylmalonic esters of the formula (VIT) and aminotriazole of the formula (VHT) 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 (d) and (e) 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, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;
• Nitriles such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile;
• Arnides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl
• the copper salts which can be used in carrying out processes (d) and (e) according to the invention are customary copper salts. Copper (I) chloride or copper (I) bromide can preferably be used.
• Suitable acid acceptors for carrying out processes (d) and (e) according to the invention are in each case all of the customary inorganic or organic bases.
• 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.
• DABCO Diazabicyclooctane
• DBN diazabicyclonones
• DBU diazabicycloundecene
• reaction temperatures can also be varied within a substantial range when carrying out processes (d) and (e) according to the invention. 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 protect plants against Plasmodiophoromycetes, 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. graminea
• 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
• Puccinia 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
• Botrytis 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, Alternaria brassicae;
• Pseudocercosporella species such as, for example, Pseudocercosporella herpotrichoides.
• 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 viruses.
• the substances according to the invention can therefore be used to protect plants from attack by the named pathogens within a certain period of time after the treatment.
• the period of time within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days, after the plants have been treated with the active compounds.
• the active compounds according to the invention can be used with particularly good success for 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 , deploy.
• 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, if appropriate in certain concentrations and application rates, also as herbicides, for influencing plant growth, and for animal pest control. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds.
• Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
• Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be 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, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes.
• the plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
• the treatment according to the invention of the plants and parts of plants with the active compounds takes place directly or by acting on their surroundings, living space or storage space according to the usual treatment methods, e.g. by dipping, spraying, evaporating, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by means of single- or multi-layer coating.
• 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 facilities for example cooling water circuits, which can be impaired by the multiplication of microorganisms, may also be mentioned.
• technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer fluids, particularly preferably wood.
• the active compounds according to the invention preferably act against fungi, in particular molds, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
• Microorganisms of the following genera may be mentioned, for example:
• Altemaria 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.
• extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers
• 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.
• 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 dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
• Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also 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 0.1 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 broaden the activity spectrum or to prevent the development of resistance.
• fungicides bactericides
• acaricides nematicides or insecticides
• synergistic effects are obtained, ie the effectiveness of the Mixing 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; fenhexamid; Fenipropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; Flubenzimine; fludioxonil; flumetover; flumorph; fluoromides; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; Fosetyl-Al; Fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; Furcarbanil; Furmecyclox;
• imazalil Imibenconazole; I-minoctadine triacetate; Ininoctadine tris (albesil; iodocarb; ipconazole; ipprobefos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione;
• mancozeb maneb; Meferimzone; mepanipyrim; mepronil; metalaxyl; Metalaxyl-M; Met conazoles; methasulfocarb; Methfuroxam; metiram; metominostrobin; Metsulfovax; mildiomycin; myclobutanil; myclozoline;
• natamycin natamycin
• nicobifen Nitro Thal-isopropyl
• Noviflumuron nuarimol
• tebuconazole tecloftalam; Tecnazene; Tetcyclacis; tetraconazole; thiabendazole; Thicyofen; Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofos-methyl; tolylfluanid; Triadimephone; triadimenol; Triazbutil; triazoxide; Tricyclamide; Tricyclazole; tridemorph; Trifloxystrobin; triflumizole; triforine; triticonazole;
• copper salts and preparations such as Bordeaux mixture; copper; Copper naphthenate; copper oxychloride; Copper sulfate; Cufraneb; copper; mancopper; Oxine-copper.
• DDT deltamethrin, Demeton-S-methyl, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Diazinone, Dichlofenthion, Dichlorvos, Dicofol, Dicrotophos, Dicyclanil, Diflubenzuron, Dimethoate, Dimethylvinphoc, Diap, Dinaputonononononoton, Dinobutonon, Dinobuton, Dinobuton, disobunon Docusat-sodium, Dofenapyn, DOWCO-439,
• Halofenozide HCH, HCN-801, Heptenophos, Hexaflumuron, Hexythiazox, Hydra-methylnone, Hydroprene,
• Mecarbam Mesulfenfos, Metaldehyde, Metam-sodium, Methacrifos, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoprene, Methoxychlor, Methoxyfenozide, Metolcarb, Metoxadiazone, M ⁇ be- distrus- 245, Mevbephosinin, M ⁇ bephincinin, M ⁇ be- mephinine, M ⁇ bephincinin, M ⁇ be- mephincinin, Mübbe- mephinine, M ⁇ be- mephincinin, Mevbe- phinine, M ⁇ be MON-45700, Monocrotophos, Moxidectin, MTT-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, trans-), Petroleum, PH-6045, Phenothrin (lR-trans isomer), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphocarb, Phoxim, Piperonyl butoxide, Pirimicarb, Piri iphos-methyl, Pirimiphos-ethyl, Prallethrin, Profenofos, Promecarb, Propaphos, Propargite, Propetamphos, Propoxur, Prothiofos, Prothoate, Protrifenbute, Pymetrozine, Pyraclhrinyl, Pyreshrhrumyl, Pyreshrophenyl, Pyreshrophenyl, Pyresulfuryl, Pyresulfuryl, Pyreshrophenyl Pyrid
• insecticidally active plant extracts nematodes, fungi or viruses.
• preparations containing insecticidally active plant extracts, nematodes, fungi or viruses are also possible.
• active compounds such as herbicides or with fertilizers and growth regulators, safeners or semiochemicals, is also possible.
• the compounds of the formula (T) according to the invention also have very good antimycotic effects. They have a very broad spectrum of antimycological effects, especially against dermatophytes and shoot fungi, mold and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) as well as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumus Species like Trichophyton mentagrophytes, Microsporon species like Microsporon canis and audouinii.
• Candida species such as Candida albicans, Candida glabrata
• Epidermophyton floccosum Aspergillus species such as Aspergillus niger and Aspergillus fumus Species like Trichophyton mentagrophytes
• Microsporon species like Microsporon canis and audouinii.
• the list of these fungi in no way represents a limitation of the detectable mycotic
• the compounds of the formula (I) according to the invention are furthermore suitable for suppressing the growth of tumor cells in humans and mammals. This is based on an interaction of the compounds according to the invention with tubulin and microtubules and by promoting microtubule polymerization.
• 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, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume method 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 substantial range, depending on the type of application.
• the active compound application rates are generally between 0.1 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 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
• all plants and their parts can be treated the.
• wild plant species or plant species and their parts obtained by conventional biological breeding methods, such as crossing or protoplast fusion are treated.
• transgenic plants and plant varieties 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 cultivated by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, breeds, bio- and genotypes.
• the treatment according to the invention can also result in superadditive (“synergistic”) effects an increase in the effect of the substances and agents which can be used according to the invention, 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 storability and / or workability of the harvested products possible, which go beyond the expected effects.
• superadditive an increase in the effect of the substances and agents which can be used according to the invention, 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 storability and / or workability of the harvested products possible, which go beyond the expected 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”). Examples of such properties 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 ripeness, higher harvest yields, higher quality and / or higher nutritional value of the crop products, higher storability and / or workability of the Other 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 viruses as well as an increased tolerance of the plants to certain herbicidal active ingredients.
• Cereals wheat, rice
• corn, soybeans, potatoes, cotton, tobacco, rapeseed and fruit plants with the fruits apples, pears, citrus fruits and grapes
• corn, soybeans, potatoes, cotton, tobacco and rapeseed being particularly emphasized.
• the traits are particularly emphasized as the increased defense of the plants against insects, arachnids, namatodes and snails by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (eg by the genes Cry ⁇ A (a) , CryIA (b), CryIA (c), CryHA, CrylllA, CryIIEB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter referred to as "Bt plants”).
• Bacillus thuringiensis eg by the genes Cry ⁇ A (a) , CryIA (b), CryIA (c), CryHA, CrylllA, CryIIEB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations
• Trans are also used the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors as well as resistance genes and correspondingly expressed proteins and toxins are particularly emphasized.
• SAR systemic acquired resistance
• the properties (“traits”) which are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example hnidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene).
• the genes which impart the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants.
• Bt plants are maize varieties, cotton varieties, soy varieties and potato varieties that are marketed under the trade names YTELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucoton® (cotton) and NewLeaf® (potato).
• herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties that are marketed under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g.
• rapeseed rapeseed
• IMI® tolerance to Imidazolinone
• STS® tolerance to sulfonylureas such as maize
• the herbicide-resistant plants include the varieties marketed under the name Clearfield® (eg 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 (!) 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 with the compounds or mixtures specifically listed in the present text should be particularly emphasized.
• a mixture of 2.0 g (10.74 mmol) of 2-thienylmalonic acid and 1.33 g (10.74 mmol) of 3-amino-5-cyclopropyl-l, 2,4-triazole is stirred at room temperature inside 41.13 g (286 mmol) of phosphorus oxychloride were added in the course of 2 minutes.
• the mixture is then heated to 90 ° C. for 18 hours and then cooled to room temperature.
• the reaction mixture is poured into 250 ml of ice water and the resulting suspension is stirred for 1 hour. It is suctioned off and washed with 50 ml of water.
• the filtrate is dried over sodium sulfate and then filtered again.
• the tributylamine is covered canted and the 6- (3-trifluorme yl-pyrid-2-yl) - [l, 2,4-triazolo [l, 5-a-pyrimidine-5,7-diol (yield: about 8 g, 60% purity) obtained without further cleaning used in the next reaction step.
• 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.
• 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.
• 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 approx. 21 ° C and a relative humidity of approx. 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.
• Example 2 shows an efficiency of over 90% at an application rate of 100 g / ha.
• Emulsifier alkylaryl polyglycol ether
• the resulting concentration of emulsifier is 300 ppm each.
• the microtiter plates are then agitated for 3 to 5 days on a shaker at a temperature of 22 ° C until sufficient growth of the respective microorganism can be determined in the untreated control.
• the evaluation is carried out photometrically at a wavelength of 620 n.
• the dose of active ingredient is calculated from the measurement data for the various concentrations, which leads to a 50% inhibition of fungal growth (ED50) compared to the untreated control.
• the ED5Q value of the compounds according to the invention listed in Examples 1 and 2 for Botrytis cinerea is at an active ingredient dose which is less than 10 ppm.

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• 2003
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• 2004
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