EP1856121A1 - 5,6-dialkyl-7-amino-azolopyrimidines, leur procede de production, leur utilisation pour lutter contre les champignons nuisibles et les produits les contenant - Google Patents

5,6-dialkyl-7-amino-azolopyrimidines, leur procede de production, leur utilisation pour lutter contre les champignons nuisibles et les produits les contenant

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Publication number
EP1856121A1
EP1856121A1 EP06724905A EP06724905A EP1856121A1 EP 1856121 A1 EP1856121 A1 EP 1856121A1 EP 06724905 A EP06724905 A EP 06724905A EP 06724905 A EP06724905 A EP 06724905A EP 1856121 A1 EP1856121 A1 EP 1856121A1
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EP
European Patent Office
Prior art keywords
formula
compounds
alkyl
alkoxy
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06724905A
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German (de)
English (en)
Inventor
Peter Schäfer
Udo HÜNGER
Maria Scherer
Harald Köhle
Helmut Schiffer
Thomas Grote
Jochen Dietz
Wassilios Grammenos
Jan Klaas Lohmann
Bernd Müller
Joachim Rheinheimer
Frank Schieweck
Anja Schwögler
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BASF SE
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BASF SE
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Publication of EP1856121A1 publication Critical patent/EP1856121A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • R 1 is C 2 -C 12 -alkenyl or C 2 -C 12 -alkynyl, where the carbon chains are unsubstituted or carry one to three identical or different groups R a and / or R b ; or d-Cu-alkyl, C- ⁇ -Ci2-alkoxy-Ci-Ci2-alkyl, C 1 -C 6 alkoxy-C 2 -C 2 -alkenyl or C 6 - alkoxy-C2-Ci2-alkynyl, wherein the carbon chains carry one to three identical or different groups R a ;
  • R a is halogen, cyano, nitro, hydroxy, C 1 -C 6 -alkylthio, C 3 -C 12 -alkenyloxy, C 3 -C 12 -alkynyloxy, NR 11 R 12 , or
  • R b may carry C3-C6-cycloalkyl one to four identical or different groups;
  • R b is C 1 -C 4 -alkyl, cyano, nitro, hydroxy, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, C 3 -
  • Ce-alkenyloxy, C 3 -C 6 -alkynyloxy and NR 11 R 12 R 11 , R 12 is hydrogen or C 1 -C 6 -alkyl; wherein the carbon chains of the groups R a may in turn be halogenated;
  • R 2 Ci-Ci2-alkyl, Ci-C 2 alkoxy-Ci-Ci 2 -alkyl, C 2 -C 2 -alkenyl or C 2 -Ci2-alkynyl, wherein the carbon chains c by one to three groups R may be substituted :
  • R c is halogen, cyano, nitro, hydroxy, C 1 -C 6 -alkoxy, C- ⁇ -C6 alkylthio, C3-C 12 -
  • A is N or CH
  • R 3 CH 3 when A is CH additionally hydrogen.
  • the invention relates to processes for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.
  • GB 1 148 629 generally suggests 5,6-dialkyl-7-amino-triazolo- and -pyrazolopyrimidines.
  • EP-A 141 317 discloses individual fungicidally active 5,6-dialkyl-7-amino-triazolo- and -pyrazolopyrimidines. However, their effect is in many cases unsatisfactory. On this basis, the object of the present invention is to provide compounds with improved activity and / or broadened spectrum of activity.
  • the compounds of formula I differ from those of the abovementioned publications by the specific embodiment of the substituent in the 6-position of the azolopyrimidine skeleton, which represents a haloalkyl group or an unsaturated aliphatic group.
  • the compounds of the formula I have an over the known compounds increased activity against harmful fungi.
  • the compounds of the invention can be obtained in various ways.
  • the compounds according to the invention are obtained by reacting substituted ⁇ -ketoesters of the formula II with an aminoazole of the formula III to give 7-hydroxyazolopyrimidines of the formula IV.
  • the variables in formulas II and IV have the meanings as for formula I and the group R in formula II means CrC 4 -
  • reaction of the substituted .beta.-keto esters of the formula II with the aminoazoles of the formula III can be carried out in the presence or absence of solvents. It is advantageous to use those solvents to which the starting materials are largely inert and in which they are completely or partially soluble.
  • the solvents used are, in particular, alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, amides such as dimethylformamide, diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanoic acids such as formic acid, Acetic acid, propionic acid or bases, such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metals.
  • alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers
  • aromatic hydrocarbons such as toluene, benzene or mesitylene
  • amides such as dimethylformamide, diethylformamide, di
  • metal hydrides organometallic compounds, in particular alkali metal alkyls, alkylmagnesium halides and alkali metal and alkaline earth metal alkoxides and dimethoxy magnesium, and also organic bases, for example tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethyl-aminopyridine and bicyclic amines and mixtures of these solvents with water in question.
  • Suitable catalysts are bases, as mentioned above, or acids, such as sulfonic acids or mineral acids.
  • the reaction is particularly preferably carried out without a solvent or in chlorobenzene, xylene, dimethyl sulfoxide, N-methylpyrrolidone.
  • Particularly preferred bases are tertiary amines such as triisopropylamine, tributylamine, N-methylmorpholine or N-methylpiperidine.
  • the temperatures are between 50 and 300 0 C, preferably at 50 to 180 ° C when operating in solution [cp. EP-A 770 615; Adv. Het. Chem. Vol. 57, p. 81ff. (1993)].
  • the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
  • the condensation products of the formula IV thus obtained are usually precipitated from the reaction solutions in pure form and are, after washing with the same solvent or with water and subsequent drying with halogenating agents, in particular chlorinating or brominating agents, the compounds of the formula V in the US Pat Hal is chlorine or bromine, in particular chlorine, reacted.
  • the reaction with chlorinating agents such as phosphorus oxychloride, thionyl onylchlorid or sulfuryl chloride is preferably carried out at 50 ° C to 150 0 C, preferably in excess phosphorus oxytrichloride at reflux temperature. After evaporation of the excess Phosphoroxitrichlorids the residue is treated with ice water optionally with the addition of a water-immiscible solvent.
  • the organic from the overall dry phase is optionally isolated after evaporation of the inert solvent chlorination is generally very pure and is then reacted with ammonia in inert solvents at 100 0 C to 200 0 C to give the 7-aminoazolo [1, 5-a] - Implemented pyrimidines.
  • the reaction is preferably carried out with 1 to 10 molar excess of ammonia under pressure of 1 to 100 bar.
  • the new 7-amino-azolo [1, 5-a] -pyrimidines are optionally isolated after evaporation of the solvent by trituration in water as crystalline compounds.
  • the ⁇ -keto esters of formula II can be prepared as in Organic Synthesis Coli. Vol. 1, p. 248, or are commercially available.
  • the intermediates of formula V are new.
  • novel compounds of the formula I can be obtained by reacting substituted acyl cyanides of the formula VI, in which R 1 and R 2 have the meanings indicated above, with an aminoazole of the formula III.
  • the reaction can be carried out in the presence or absence of solvents. It is advantageous to use those solvents to which the starting materials are largely inert and in which they are completely or partially soluble.
  • the solvents used are, in particular, alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, amides such as dimethylformamide, diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanoic acids such as formic acid, Acetic acid, propionic acid or bases, as mentioned above, and mixtures of these solvents with water in question.
  • the reaction temperatures are between 50 and 300 ° C, preferably at 50 to 150 ° C, when working in solution.
  • the new 7-amino-azolo [1, 5-a] -pyrimidines are optionally isolated after evaporation of the solvent or dilution with water as crystalline compounds.
  • substituted alkyl cyanides of the formula VI required for the preparation of the 7-amino-azolo [1,5-a] -pyrimidines are known in some cases or can be prepared by known methods from alkyl cyanides and carboxylic acid esters with strong bases, e.g. Alkali hydrides, alkali metal alcoholates, alkali metal amides or metal alkyls, are prepared (see: J. Amer., Chem. Soc., Vol. 73, (1951) p. 3766).
  • the halogenation is usually carried out at temperatures of from 0 ° C. to 200 ° C., preferably from 20 ° C. to 110 ° C., in an inert organic solvent in the presence of a free-radical initiator (for example dibenzoyl peroxide or azobisisobutyronitrile or under UV light). Irradiation, eg with a Hg vapor lamp) or an acid [cf. Synthetic Reagents, Vol. 2, pp. 1-63, Wiley, New York (1974)].
  • the reactants are generally reacted in equimolar amounts with each other. It may be advantageous for the yield to use the halogenating agent in an excess based on VII.
  • halogenating agent there are used, for example, elemental halogens (e.g., CI 2, Br 2, J 2), N-bromo-succinimide, N-chloro-succinimide or dibromodimethylhydrantoin.
  • elemental halogens e.g., CI 2, Br 2, J 2
  • N-bromo-succinimide N-chloro-succinimide or dibromodimethylhydrantoin.
  • the halogenating agents are generally used in equimolar amounts, in excess or, if appropriate, as solvents.
  • azolopyrimidines of the formula VII required for the preparation of the compounds I described above are known in some cases or can be prepared by known methods [cf. EP-A 141 317].
  • Halogen fluorine, chlorine, bromine and iodine, in particular fluorine or chlorine;
  • Alkyl saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or 10 carbon atoms, for example C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1 , 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methyl pentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- Dimethylbutyl, 1-ethylbutyl, 2-eth
  • Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in any position, e.g. C2-C6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1 Methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3 Methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl 3-Bu- tenyl, 1,1-di
  • Alkoxyalkyl saturated, straight-chain or mono-, di- or tri-branched hydrocarbon chain which is interrupted by an oxygen atom, for.
  • C5-C 12 - alkoxyalkyl hydrocarbon chain as hereinbefore described having 5 to 12 carbon atoms which may be interrupted by an oxygen atom at any position, such as propoxy-ethyl, butoxy-ethyl, pentoxy-ethyl, hexyloxy-ethyl, heptyloxy-ethyl , Octyloxyethyl, nonyloxyethyl, 3- (3-ethyl-hexyloxy) -ethyl, 3- (2,4,4-trimethyl-pentyloxy) -ethyl, 3- (1-ethyl-3-methyl-butoxy) -ethyl, ethoxy-propyl, propoxy-propyl, butoxy-propyl, pentoxy-propyl, hexyloxy
  • Haloalkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and one or two double bonds in any position (as mentioned above), wherein in these groups, the hydrogen atoms partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine could be;
  • Alkynyl straight-chain or branched hydrocarbon groups having 2 to 4, 6, 8 or 10 carbon atoms and one or two triple bonds in any position, for example C 2 -C 6 alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2 Butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl 3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl , 1-methyl-2-pentynyl
  • Cycloalkyl mono- or bicyclic saturated hydrocarbon groups having 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
  • azolopyrimidines of the formula I are the following meanings of the substituents, in each case alone or in combination, particularly preferably:
  • R 1 represents an unbranched or mono-, di-, tri- or poly-branched haloalkyl group.
  • R 1 is C 1 -C 14 -haloalkyl, C 1 -C 12 -haloalkoxy-C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy-C 1 -C 12 -haloalkyl, C 2 -C 12 -haloalkenyl or C 2 -C 12 -alkoxyalkyl Ci2-haloalkynyl, which groups one or two halo have logen atoms.
  • d-Cg-haloalkoxy-propyl and d-Cg-alkoxy-halopropyl groups are preferred.
  • R 1 represents a group C 1 -C 14 Haloalkenyl or C 2 -C 12 -haloalkynyl, which groups contain a halogen atom, preferably the halogen atom is present on the ⁇ -terminal carbon atom.
  • R 1 is a group (CH 2 ) n CF 3 or CH (CH 3 ) (CH 2 ) m CF 3, in which n is a number from 0 to 13 and m is a number from 0 to 11 , stands.
  • R 1 is chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2 , 2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-di-fluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl , Pentafluoroethyl, 1,1,1-trifluoroprop-2-yl, 1-chloropropyl, 1-fluoropropyl, 3-chloropropyl, 3-fluoropropyl, 3,
  • R 1 is C 2 -C 12 -alkenyl or C 2 -C 12 -alkynyl, where the carbon chains are unsubstituted or carry one to three identical or different groups R a and / or R b .
  • Compounds I are particularly preferred in which carbon chains of R 1 and R 2 together have not more than 14 carbon atoms.
  • R 2 is methyl, ethyl, n-propyl or n-butyl, preferably methyl or ethyl, in particular ethyl.
  • Halogen atoms in the groups R 1 and / or R 2 are preferably on the ⁇ -carbon atom.
  • Cyano groups in R 1 and / or R 2 are preferably on the terminal carbon atom.
  • One embodiment of the compounds according to the invention relates to compounds I in which A corresponds to CH Formula 1.1:
  • the compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes, in particular from the class of the Oomycetes. They are in part systemically effective and can be used in crop protection as foliar and soil fungicides. They are particularly important for the control of a variety of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers. Beans, tomatoes, potatoes and cucurbits, as well as the seeds of these plants.
  • Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines
  • Cercospora species on corn, soybeans, rice and sugar beet e.g., C. beticula on sugar beet
  • Cochliobolus species on corn, cereals, rice e.g., Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice
  • Gibberella species on cereals and rice e.g., Gibberella fujikuroiau rice
  • Mycosphaerella species on cereals, bananas and peanuts (M. graminicolä ax ⁇
  • Rhizoctonia species e.g., R. solanf
  • Sclerotinia species e.g., 5. sclerotiorum
  • oilseed rape e.g., 5. sclerotiorum
  • fungi from the class Oomycetes, such as Peronospora species, Phytophthora species, Plasmopara viticola and Pseudoper ⁇ nospora species.
  • the compounds I are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
  • harmful fungi ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sciophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., P / e ⁇ / - rotus spp., Poria spp., Serpula spp.
  • Tyromyces spp. Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and zygomycetes such as Mucor spp., moreover, in the protective material, the following yeasts: Candida spp. and Saccharomyces cerevisae.
  • the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients.
  • the application can be done both before and after the infection of the materials, plants or seeds by the fungi.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.
  • the application rates in the application in crop protection depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.
  • active ingredient in general, amounts of active ingredient of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of seed are needed.
  • the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.
  • the compounds of the formula I can be present in various crystal modifications, which may differ in their biological activity. They are also the subject of the present invention.
  • the compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants.
  • Suitable solvents / auxiliaries are essentially:
  • aromatic solvents eg Solvesso products, xylene
  • paraffins eg petroleum fractions
  • alcohols eg methanol, butanol, pentanol, benzyl alcohol
  • ketones eg cyclohexanone, gamma-butyrolactone
  • pyrrolidones NMP, NOP
  • Acetates glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters.
  • solvent mixtures can also be used
  • Excipients such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin liquors and methyl cellulose.
  • ground natural minerals e.g., kaolins, clays, talc, chalk
  • ground synthetic minerals e.g., fumed silica, silicates
  • Emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin liquors and methyl cellulose.
  • Suitable surface-active substances are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfonated Furthermore, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylpheny
  • mineral oil fractions of medium to high boiling point such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.
  • mineral oil fractions of medium to high boiling point such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivative
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
  • Granules e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers.
  • Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground
  • the formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • formulations are: 1. Products for dilution in water
  • a Water-soluble concentrates (SL, LS)
  • the active compounds 20 parts by weight are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • a dispersant e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • the active ingredient content is 20% by weight
  • the active compounds 25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion.
  • the formulation has an active ingredient content of 25% by weight.
  • E Suspensions 20 parts by weight of the active compounds are comminuted with the addition of 10 parts by weight of dispersing and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to give a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.
  • the active ingredient content in the formulation is 20% by weight.
  • Water-dispersible and water-soluble granules 50 parts by weight of the active compounds are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the formulation has an active ingredient content of 50% by weight.
  • Water-dispersible and water-soluble powders 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the active ingredient content of the formulation is 75% by weight.
  • H Gel Formulations In a ball mill 20 parts by weight of the active ingredients, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent are used. mulling agent to a fine suspension. Dilution with water results in a stable suspension with 20% by weight active ingredient content.
  • 0.5 parts by weight of the active ingredients are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.
  • LS water-soluble concentrates
  • FS suspensions
  • DS dusts
  • WS water-dispersible and water-soluble powders
  • ES emulsions
  • EC emulsifiable concentrates
  • gel formulations GF
  • the active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, litter, granules by spraying, misting, dusting, scattering or pouring.
  • the forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • the substances, as such or dissolved in an oil or solvent can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier.
  • wetter, tackifier, dispersant or emulsifier it is also possible to prepare wetting, adhesion, dispersing or emulsifying agents from effective substance and solvent or oil concentrates are prepared which are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume
  • wetting agents To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
  • adjuvants in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ® ; Alcohol alkoxylates, eg. As Atplus 245 ®, Atplus MBA 1303 ®, Plurafac LF 300 ® and Lutensol ON 30 ®; EO-PO block polymers, eg. B. Pluro- nic RPE 2035 ® and Genapol B ®; Alcohol ethoxylates, eg. As Lutensol XP 80 ®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ®.
  • organically modified polysiloxanes eg Break Thru S 240 ®
  • Alcohol alkoxylates eg. As Atplus 245 ®, Atplus MBA 1303 ®, Plurafac LF 300 ® and Lutensol ON 30 ®
  • EO-PO block polymers eg. B. Pluro
  • agents according to the invention may also be present in the form of use as fungicides together with other active substances, e.g. with herbicides, insecticides,
  • Growth regulators fungicides or with fertilizers.
  • the compounds I or the agents containing them with one or more further active compounds, in particular fungicides, for example, in many cases, the spectrum of activity can be broadened or development of resistance can be prevented. In many cases, synergistic effects are obtained.
  • Azoxystrobin dimoxystrobin, enestroburine, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-Chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) -carbamic acid methyl ester, 2- (ortho- (2,5-dimethylphenyl-oxymethylene) -phenyl) -3- methoxy-methyl acrylate; carboxamides
  • Carboxylic acid anilides Benalaxyl, Benodanil, Boscalid, Carboxin, Mepronil, Fenfuram, Fenhexamid, Flutolanil, Furametpyr, Metalaxyl, Ofurace, Oxadixyl, Oxycarboxin, Penthiopyrad, Thifluzamide, Tiadinil, 4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid - (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazol-5-carboxylic acid
  • Benzoic acid amides flumetover, fluopicolide (picobenzamide), zoxamide;
  • bitertanol bromuconazoles, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetracona - zole, triadimenol, triadimefon, triticonazole;
  • - imidazoles cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole;
  • Benzimidazoles benomyl, carbendazim, fuberidazole, thiabendazole; - Other: Ethaboxam, Etridiazole, Hymexazole;
  • Pyridines fluazinam, pyrifenox, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine; Pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil;
  • Morpholines aldimorph, dodemorph, fenpropimorph, tridemorph;
  • Dicarboximides iprodione, procymidone, vinclozolin;
  • fungicides - guanidines dodine, iminoctadine, guazatine;
  • Organometallic compounds fentin salts
  • Sulfur-containing heterocyclyl compounds isoprothiolanes, dithianone;
  • Organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and their salts;
  • Organochlorine compounds thiophanates methyl, chlorothalonil, dichlofluanid, toluylfluanid, flusulfamides, phthalides, hexachlorobenzene, pencycuron, quintozene;
  • Nitrophenyl derivatives binapacryl, dinocap, dinobuton;
  • the active compounds were prepared as a stock solution with 25 mg of active ingredient with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent-emulsifier of 99 was made up to 1 ad 10 ml. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.
  • Uniperol® EL wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
  • the active ingredients were formulated separately as stock solution with a concentration of 10,000 ppm in DMSO.
  • the stock solution is pipetted into a microtiter plate (MTP) and diluted with an aqueous malt-based mushroom nutrient medium to the stated active substance concentration. This was followed by the addition of an aqueous spore suspension of Pyricularia oryzae.
  • MTP microtiter plate
  • the plates were placed in a steam-saturated chamber at temperatures of 18 ° C. With an absorption photometer, the MTPs were measured at 405 nm on the 7th day after inoculation.
  • the measured parameters were compared with the growth of the active substance-free control variant and the fungus-free and active ingredient-free blank value in order to determine the relative growth in% of the pathogens in the individual active substances.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

L'invention concerne des 5,6-dialkyl-7-amino-azolopyrimidines de la formule (I) où les substituants ont la signification suivante: R1 représente halogenalkyle, halogenalcoxyalkyle, alcoxyhalogenalkyle, alcényle, halogenalcényle, alkinyle ou halogenalkinyle; R2 représente alkyle, alcoxyalkyle, alcényle ou alkinyle; R1 et/ou R2 pouvant être substitués conformément à la description; A représente N ou CH et R3 représente CH3 et, si A représente CH, hydrogène. L'invention concerne un procédé et des produits intermédiaires pour la production de ces composés, les produits les contenant et leur utilisation pour lutter contre les champignons nuisibles phytopathogènes.
EP06724905A 2005-03-01 2006-03-01 5,6-dialkyl-7-amino-azolopyrimidines, leur procede de production, leur utilisation pour lutter contre les champignons nuisibles et les produits les contenant Withdrawn EP1856121A1 (fr)

Applications Claiming Priority (2)

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DE102005009884 2005-03-01
PCT/EP2006/060365 WO2006092414A1 (fr) 2005-03-01 2006-03-01 5,6-dialkyl-7-amino-azolopyrimidines, leur procede de production, leur utilisation pour lutter contre les champignons nuisibles et les produits les contenant

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EP1856121A1 true EP1856121A1 (fr) 2007-11-21

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US (1) US20080188493A1 (fr)
EP (1) EP1856121A1 (fr)
JP (1) JP2008531653A (fr)
CN (1) CN101133059A (fr)
TW (1) TW200714602A (fr)
WO (1) WO2006092414A1 (fr)

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JP5457198B2 (ja) * 2007-01-19 2014-04-02 ビーエーエスエフ ソシエタス・ヨーロピア １−メチルピラゾール−４−イルカルボン酸アニリド類とアゾロピリミジニルアミン類の殺菌剤混合物
KR20090105974A (ko) * 2007-01-30 2009-10-07 바스프 에스이 아졸로피리미디닐아민 유도체 및 살곤충제 기재의 살충 혼합물
WO2008092836A2 (fr) * 2007-01-30 2008-08-07 Basf Se Procédé d'amélioration de la santé des plantes
CN101720327A (zh) * 2007-04-30 2010-06-02 雅培制药有限公司 二酰甘油o-酰基转移酶1型酶的抑制剂
EP2324710A1 (fr) 2007-09-20 2011-05-25 Basf Se Combinaisons comprenant une souche fongicide et au moins un fongicide additionnel

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DE3338292A1 (de) * 1983-10-21 1985-05-02 Basf Ag, 6700 Ludwigshafen 7-amino-azolo(1,5-a)-pyrimidine und diese enthaltende fungizide
DE3533050A1 (de) * 1985-09-17 1987-03-26 Basf Ag 7-amino-azolo(1,5-a)pyrimidine, verfahren zu ihrer herstellung und diese enthaltende fungizide, bzw. deren verwendung als fungizide
JPH04307543A (ja) * 1991-04-04 1992-10-29 Konica Corp 新規な写真用カプラー
RU2147584C1 (ru) * 1995-10-27 2000-04-20 Американ Цианамид Компани Способ получения дигалоидазолопиримидинов и способ получения дигидроксиазолопиримидинов
JPH1143434A (ja) * 1997-05-30 1999-02-16 Pola Chem Ind Inc カリウムチャンネル開口薬
KR20060130719A (ko) * 2004-03-10 2006-12-19 바스프 악티엔게젤샤프트 5,6-디히드로카르빌-7-아미노-트리아졸로피리미딘, 그의제조 방법, 그의 병원성 진균류 방제를 위한 용도 및 상기화합물을 포함하는 제제
CN1930166B (zh) * 2004-03-10 2011-05-25 巴斯福股份公司 5,6-二烷基-7-氨基三唑并嘧啶、其制备方法及其在防治致病性真菌中的用途以及包含这些化合物的组合物
US20080207455A1 (en) * 2005-03-01 2008-08-28 Basf Aktingesellschaft 5,6-Dialkyl-7-Aminoazolopyrimidines, Their Preparation and Their Use for Controlling Harmful Fungi, and Compositions Comprising These Compounds

Non-Patent Citations (1)

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Title
See references of WO2006092414A1 *

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WO2006092414A1 (fr) 2006-09-08
TW200714602A (en) 2007-04-16
JP2008531653A (ja) 2008-08-14
CN101133059A (zh) 2008-02-27
US20080188493A1 (en) 2008-08-07

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