WO1994029281A1 - Cyclobutylazoles - Google Patents

Cyclobutylazoles Download PDF

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Publication number
WO1994029281A1
WO1994029281A1 PCT/EP1994/001692 EP9401692W WO9429281A1 WO 1994029281 A1 WO1994029281 A1 WO 1994029281A1 EP 9401692 W EP9401692 W EP 9401692W WO 9429281 A1 WO9429281 A1 WO 9429281A1
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WO
WIPO (PCT)
Prior art keywords
carbon atoms
chain
straight
branched
alkyl
Prior art date
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PCT/EP1994/001692
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German (de)
English (en)
Inventor
Hans-Ludwig Elbe
Ralf Tiemann
Stefan Dutzmann
Heinz-Wilhelm Dehne
Gerd Hänssler
Original Assignee
Bayer Aktiengesellschaft
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Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to JP7501253A priority Critical patent/JPH08511010A/ja
Priority to EP94918373A priority patent/EP0702676A1/fr
Priority to AU69715/94A priority patent/AU6971594A/en
Publication of WO1994029281A1 publication Critical patent/WO1994029281A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the invention relates to new cyclobutylazoles, a process for their preparation and their use as pesticides in crop protection and in the protective material.
  • R represents in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or aryl,
  • Z represents a carbonyl group or a -CH (OH) group
  • the substances according to the invention have a much better fungicidal activity than 2,2-dimethyl-1- (4-methylphenyl) -4- (1,2,4-triazol-1-yl) -heptan-3-one and the l- (4-chlorophenyl) -2,2-dimethyl-4- (l, 2,4-triazol-l-yl) -heptan-3-one, which are constitutionally similar, known active substances of the same direction of action.
  • the new cyclobutylazoles of formula (I) are also interesting intermediates for the production of other crop protection agents.
  • those substances of the formula (I), in which a keto group is present will be converted by "Uia ⁇ etzung on the carbonyl function in oximes, oxime ethers, hydrazones and ketals.
  • Those compounds of the formula (I) containing a CH (OH) -Group can be converted into corresponding ether, acyl or carbamoyl derivatives by reaction on the hydroxy group.
  • the cyclobutylazoles according to the invention are generally defined by the formula (I).
  • X represents a nitrogen atom or a CH group.
  • Z represents a carbonyl group or a CH (OH) group.
  • R preferably represents straight-chain or branched alkyl having 1 to 12
  • Alkyl part straight-chain or branched alkoximinoalkyl with 1 to 8 carbon atoms in the alkoxy part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched hydroximinoalkyl with 1 to 8 carbon atoms, straight-chain or branched cyanoalkyl with 1 to 8 carbon atoms in the alkyl part, straight-chain or branched
  • R also preferably represents cycloalkylalkyl optionally having from one to five times, identical or different, substituted by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms, or optionally having from one to five times, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms, substituted cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part.
  • R further preferably represents aryl having 6 to 10 carbon atoms
  • R furthermore particularly preferably represents cycloalkyl having 3 to 6 carbon atoms substituted by fluorine, chlorine, bromine and / or straight-chain or branched alkyl having 1 to 3 carbon atoms, the same or different.
  • R furthermore particularly preferably represents cycloalkylalkyl having 3 to 6
  • R furthermore particularly preferably represents aryl having 6 or 10 carbon atoms
  • the rest in the aryl part can be substituted by up to three times, in the same way or differently
  • Pentachlorethoxy trifluoromethylthio, difluoromethylthio, fluoromethylthio, difluorochloromethylthio, dichlorofluoromethylthio, difluoroethylthio, difluoro- bromomethylthio, trichloromethylthio, trifluoroethylthio, tetrafluoroethylthio, pentafluoroethylthio, Trifluorchlorethylthio, Trifluordichlorethylthio, penta- chloroethylthio, methylsulphinyl, trifluoromethylsulphinyl, Dichlorfluorme- thylsulfinyl, thylsulfinyl Difluorchlormethylsulfinyl, fluoromethylsulfinyl, Difiuorme-, Methylsulfonyl, trifluoromethylsul
  • straight-chain or branched alkyl having 1 to 7 carbon atoms straight-chain or branched alkenyl having 2 to 7 carbon atoms, straight-chain or branched alkynyl having 2 to 7 carbon atoms, straight-chain or branched methoxyalkyl, straight-chain or branched dimethoxyalkyl, straight-chain or branched trimethoxyalkyl, straight-chain or branched methylthioalkyl, straight-chain or branched dimethylthioalkyl, straight-chain or branched trimethylthioalkyl, straight-chain or branched methylsulfinylalkyl, straight-chain or branched methylsulfonylalkyl, straight-chain or branched hydroxyliminoalkyl or straight-chain methoximinoalkyl or straight-chain or branched methoximinoalkyl, straight-chain or branched in each case 3 to 6 carbon atoms in the
  • R also very particularly preferably represents dioxolanylalkyl
  • Dithiolanylalkyl, dioxanylalkyl or dithianylalkyl each having 1 to 3 carbon atoms in the straight-chain or branched alkyl part
  • cycloalkylalkyl in the cycloalkyl part which is optionally mono- to trisubstituted, identically or differently, by fluorine, chlorine, bromine and / or methyl and has 3 to 6 carbon atoms in the cycloalkyl part and 1 to 3 carbon atoms in the straight-chain or branched alkyl part.
  • R very particularly preferably represents phenyl, ⁇ -naphthyl or ⁇ -naphthyl, where each of these radicals can be substituted once to three times, in the same way or differently
  • Ar, Ar 1 and Ar 2 independently of one another represent phenyl, ⁇ -naphthyl or ⁇ -naphthyl, where each of these aryl radicals can be monosubstituted to trisubstituted, identical or different,
  • Difluorochloromethylthio dichlorofluoromethylthio, difluoroethylthio, difluoro- bromomethylthio, trichloromethylthio, Trifiuorethylthio, tetrafluoroethyl thio, pentafluoroethylthio, Trifluorchlorethylthio, Trifluordichlorethylthio, penta- chloroethylthio, methylsulphinyl, trifluoromethylsulphinyl, Dichlorfluorme- thylsulfinyl, Difluorchlormethylsulfinyl, fluoromethylsulfinyl, Difluorme- thylsulfinyl, methylsulfonyl, Trifiuormethylsulfonyl, sulfonyl Dichlorfluormethyl- , Difluorchlormethylsulfonyl
  • Y, Y 1 and Y 2 independently of one another for oxygen, sulfur, sulfinyl, sulfonyl or for one of the groups -CH 2 -; -O-CH 2 -; -CH 2 -O-;
  • n, p each represent 0 or 1 and
  • q, r and s each represent a number 0, 1 or 2.
  • Preferred compounds according to the invention are also addition products of acids and those cyclobutylazoles of the formula (I) in which the substituents tuenten R, X and Z have the meanings that have already been mentioned preferably for these substituents.
  • the acids that can be added preferably include hydrohalic acids, e.g. Hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, nitric acid, sulfuric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, sulfonic acids such as e.g. p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid and saccharin or thiosaccharin.
  • hydrohalic acids e.g. Hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, nitric acid, sulfuric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. Acetic acid, maleic acid,
  • preferred substances according to the invention are addition products from salts of metals of the II. To IV. Main and of I. and II. And IV. To VIII. Subgroup of the periodic table of the elements and those cyclobutylazoles of the formula (I) in which R, X and Z have the meanings which have preferably already been mentioned for these substituents.
  • Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred.
  • Anions of these salts are those which are derived from acids which lead to environmentally compatible addition products.
  • Particularly preferred such acids in this connection are the hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, nitric acid and sulfuric acid.
  • Formula (II) provides a general definition of the azolyl methyl ketones required as starting compounds for carrying out the process according to the invention.
  • R and X preferably represent those meanings which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.
  • the azolyl methyl ketones of the formula (II) are known or can be prepared by processes which are known in principle (cf. EP-OS 0 054 865).
  • 1,3-dihalopropane compounds which are further required as starting materials for carrying out the process according to the invention are represented by the formula (III) generally defined.
  • shark is preferably chlorine or bromine.
  • 1,3-Dihalopropane compounds of the formula (III) are generally known compounds of organic chemistry.
  • Inert organic solvents are suitable as diluents for carrying out the 1st stage of the process according to the invention.
  • Aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, are preferably usable.
  • Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethyl-acetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide or sulfoxides, such as dimethyl sulfoxide.
  • Alkaline earth or alkali metal hydrides are preferably usable,
  • Ammonium compounds such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
  • DABCO diazabicyclooctane
  • DBN diazabicyclononene
  • DBU diazabicycloundecene
  • the 1st stage of the process according to the invention can optionally also be carried out in a two-phase system, such as water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst.
  • suitable phase transfer catalysts are: tetra-butylammonium iodide, tetrabutylammomum bromide, tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-Ci 3 / C 15 -alkylarnmonium chloride, trimethyl-C 13 / C 15 -alkylammonium bromide, dibenzyl-dimethyl-ammonium-ammonium fat, dimethyl-C 12 / C 14 -alkyl-benzylammonium chloride, dimethyl-C 12 / C 14 -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, tri
  • reaction temperatures can be varied over a wide range when carrying out the 1st stage of the process according to the invention. In general, temperatures between 0 ° C and + 150 ° C, preferably at temperatures between 20 ° C and + 120 ° C.
  • the first stage of the process according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol, of 1,3-dihalopropane compound of the formula are generally employed per mol of azolyl methyl ketone of the formula (II) (III) and optionally 3.0 to 6.0 mol, preferably 2.0 to 3.0 mol, of an acid binder.
  • the reaction is carried out, worked up and isolated from the reaction products by customary methods.
  • the second stage of the process according to the invention is carried out in the presence of a suitable reducing agent.
  • a suitable reducing agent customary reducing agents which can be used for carbonyl group reduction are suitable.
  • Complex hydrides such as lithium aluminum hydride or sodium borohydride or also aluminum alcoholates, such as aluminum isopropylate, are preferably used.
  • Suitable diluents for carrying out the second stage of the process according to the invention are conventional organic solvents, depending on the reducing agent used.
  • Aliphatic, alicyclic or aromatic hydrocarbons such as, for example, gasoline, benzene, toluene, xylene, petroleum ether, hexane, cyclohexane, ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; or alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomers ethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
  • reaction temperatures can be varied over a wide range when carrying out the second stage of the process according to the invention. In general, depending on the reducing agent used, temperatures between -30 ° C. and + 150 ° C., preferably at temperatures between 0 ° C. and + 100 ° C.
  • the second stage of the process according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, of reducing agent are generally employed per mol of cyclobutylazole of the formula (Ia).
  • the reaction is carried out, worked up and isolated in each case by the reaction products using customary methods.
  • cyclobutylazoles of the formula (I) according to the invention can be converted into acid addition salts or metal salt complexes.
  • the acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and in a known manner, for example by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent.
  • metal salt complexes of the compounds of formula (I) preference is given to those salts of metals which have already been mentioned as preferred metal salts in connection with the description of the metal salt complexes according to the invention.
  • the metal salt complexes of the compounds of formula (I) can be obtained in a simple manner by conventional methods, e.g. by dissolving the metal salt in alcohol, e.g. Ethanol and adding to compounds of formula (I).
  • Metal salt complexes can be prepared in a known manner, e.g. by filtering, isolating and, if necessary, cleaning by recrystallization.
  • the end products of the formula (I) are purified using customary methods, for example by column chromatography or by recrystallization.
  • the characterization is carried out using the melting point or, in the case of non-crystallizing compounds, using the refractive index or proton nuclear magnetic resonance spectroscopy (1H-NMR).
  • the active compounds according to the invention have a strong action against pests and can be used to control unwanted harmful organisms.
  • the active ingredients are suitable for use as crop protection agents, in particular as fungicides in crop protection and in material protection.
  • Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • 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 Pseudoperonospora cubensis
  • Plasmopara species such as, for example, Plasmopara viticola
  • Peronospora species such as, for example, Peronospora pisi or Peronospora 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 Pyrenophora graminea (conidial form: Drechslera, synonym: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • 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 can be particularly successful in combating diseases in fruit and vegetable cultivation, such as, for example, against the pathogen of apple scab (Venturia inaequalis) or against the pathogen of cucumber mildew (Sphaerotheca fuliginea) or against the pathogen of apple mildew (Podosphaera leucotricha) or against the pathogen of the real vine mildew (Uncinula necator) or for combating Cereal diseases such as, for example, against the causative agent of broken wheat stalk (Pseudocercosporella herpotrichoides) or against the causative agent of powdery mildew (Erysiphe graminis) or against the causative agent of barley mesh spot disease (Pyrenophora teres) or against the causative agent of cotyledon weus (brown spot disease) sativus) or against the pathogen causing brown furs in wheat (Septoria nodorum) or against Fusa
  • the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
  • technical materials are to be understood as 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 adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked by microorganisms or can be decomposed.
  • parts of production plants for example cooling water circuits, may also be mentioned which can be impaired by the multiplication of microorganisms.
  • technical materials are preferably adhesives, glues, papers and cartons, 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 break down or change the technical materials.
  • the active compounds according to the invention preferably act against fungi, in particular mold, wood-staining and wood-destroying fungi (Basidiomycetes) and against mucus organisms and algae.
  • microorganisms of the following genera may be mentioned:
  • Alternaria such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureulomaid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid,
  • the active compounds can be converted into 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.
  • liquid solvents aromatics, such as xylene, toluene, 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 its ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl formamide or dimethyl sulfoxide, as well as water;
  • Liquefied gaseous extenders or carriers mean those 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 are suitable: for example natural rock powder
  • Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers, 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 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds can also be mixed with known fungicides, bactericides,
  • Acaricides, nematicides or insecticides can be used, for example To broaden the spectrum of activity or to prevent the development of resistance. In some cases, synergistic effects also occur, which means that the effectiveness of the mixtures is higher than the sum of the effectiveness of the individual components.
  • the following substances can be used as mixing partners.
  • Oxadixyl Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,
  • Fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
  • Fipronil fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb,
  • HCH Heptenophos, Hexafiumuron, Hexythiazox,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos,
  • Promecarb Propaphos, Propoxur, Prothiofos, Prothiophos, Prothoat, Pymetrozin,
  • Tebufenozid Tebufenpyrad
  • Tebupirimphos Teflubenzuron
  • Tefluthrin Temephos
  • the active compounds can be used as such, in the form of their formulations or in 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 customary manner, for example by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to prepare the active ingredient or the like Inject active ingredient into the soil yourself. The seeds of the plants can also be treated.
  • the application rate can be varied within a substantial range depending on the type of application.
  • the active substance concentrations in the treatment of parts of plants in the use forms are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.
  • amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
  • active ingredient concentrations are from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0 , 02% by weight required at the site of action.
  • microbicidal agents used to protect industrial materials generally contain the active compounds in an amount of 1 to 95% by weight, preferably 10 to 75% by weight.
  • the application concentrations of active substances according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected.
  • the optimal amount can be determined by test series.
  • the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.
  • the active compounds according to the invention can also be used in a mixture with other known active compounds when used in material protection.
  • the following active ingredients may be mentioned: benzyl alcohol mono- (poly) hemiformal and other formaldehyde-releasing compounds, benzimide azolyl methyl carbamates, tetramethyl thiuram disulfide, zinc salts of dialkyl dithiocarbamates, 2,4,5,6-tetrachloroisophthalonitrile, thiazolyl benzapto-2-benzoimidazole-benzolidazolido-benzolimidazol-benzapto-benzimidazol-benzapto-benzimidazol-benzapto-benzimidazol-benzapto-benzimidazol-2 -Thiocyanatomethylthiobenzthiazol, methylene bisthiocyanate, phenol derivatives such as 2-phenylphenol, (2,2'-dihydroxy-5,5'-dichloro) -dipheny
  • Emulsifier 0.25 parts 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 placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.
  • Evaluation is carried out 7 days after the inoculation.
  • Emulsifier 0.25 parts 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 placed in a greenhouse at a temperature of approx. 15 ° C and a relative humidity of approx. 80%.
  • Evaluation is carried out 10 days after the inoculation.
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • a part by weight of active compound is mixed with the stated amounts of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
  • the disease infestation is evaluated 5 to 8 days after the inoculation.
  • the substances according to the invention listed in Examples 2, 4, 6, 10 and 12 show an efficiency of 100% at an active ingredient concentration of 0.025% in the spray liquid, while the comparison substance (A) has no effect.
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • a part by weight of active compound is mixed with the stated amounts of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
  • the plants are then placed in a greenhouse at 25 ° C. and a relative atmospheric humidity of 100%.
  • the disease infestation is evaluated 4 days after the inoculation.
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • a 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 a greenhouse at 23 ° C to 24 ° C and a relative humidity of approx. 75%.
  • Evaluation is carried out 14 days after the inoculation.
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • a 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 a greenhouse at 23 ° C. and a relative humidity of approx. 70%.
  • Evaluation is carried out 10 days after the inoculation.
  • MIC minimum inhibitory concentrations
  • agar made from wort and peptone is mixed with active substances according to the invention in concentrations of 0.1 mg / 1 to 5,000 mg / 1. After the agar solidifies, it is contaminated with pure cultures of the test organisms listed in the table. After two weeks of storage at 28 ° C and 60 to 70% relative humidity, the MIC is determined. MIC is the lowest concentration of active ingredient at which no growth occurs due to the type of microbe used.
  • Example 14 shows a very good inhibitory effect on Penicillium brevicaule, Chaetomium globosum and Aspergillus niger.
  • an agar is prepared using malt extract and active ingredient formulations of certain concentrations are added. After the agar has solidified, inoculate with well overgrown cylindrical agar pieces which have a diameter of 5 mm. The treated agar preparations are left to stand at a temperature of 27 ° C. for 7 days and the diameter of the colonies formed is then measured. Untreated control plates serve as a reference, the determined values are expressed in percent. 0% means that there is no inhibitory effect, 100% means complete inhibition of growth.
  • Example 14 shows a 100% inhibitory effect on Coriolus versicolor at a concentration of 20 ppm.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Nouveaux cyclobutylazoles de formule (I) dans laquelle R désigne un alkyle, alcényle, alcinyle, cycloalkyle ou aryle, chacun d'eux étant éventuellement substitué, X désigne un atome d'azote ou un groupe CH, et Z désigne un groupe carbonyle ou un groupe -CH(OH)-, ainsi que leurs sels d'addition d'acide et leurs complexes avec des sels métalliques, procédé de fabrication de ces nouveaux produits et leur utilisation comme agents phytosanitaires dans la protection des végétaux et des matériaux.
PCT/EP1994/001692 1993-06-07 1994-05-25 Cyclobutylazoles WO1994029281A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP7501253A JPH08511010A (ja) 1993-06-07 1994-05-25 シクロブチルアゾール
EP94918373A EP0702676A1 (fr) 1993-06-07 1994-05-25 Cyclobutylazoles
AU69715/94A AU6971594A (en) 1993-06-07 1994-05-25 Cyclobutylazoles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934318916 DE4318916A1 (de) 1993-06-07 1993-06-07 Cyclobutylazole
DEP4318916.4 1993-06-07

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WO1994029281A1 true WO1994029281A1 (fr) 1994-12-22

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EP (1) EP0702676A1 (fr)
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AU (1) AU6971594A (fr)
DE (1) DE4318916A1 (fr)
WO (1) WO1994029281A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013062964A3 (fr) * 2011-10-24 2013-08-15 Abbvie Inc. Nouveaux modulateurs de trpv3
CN104254522A (zh) * 2011-10-24 2014-12-31 艾伯维公司 作为trpv3调节剂的甲醇衍生物
US9012651B2 (en) 2011-03-24 2015-04-21 Abbvie Inc. TRPV3 modulators
US9156788B2 (en) 2010-08-10 2015-10-13 Abbvie Inc. TRPV3 modulators

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19648888A1 (de) * 1996-11-26 1998-05-28 Remmers Bauchemie Gmbh Wasserverdünnbares Konzentrat für den Holzschutz

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054865A1 (fr) * 1980-12-20 1982-06-30 Bayer Ag 1-Azolyl-butan-2-ones substitués, procédé de leur préparation et leur application comme fongicides ainsi que comme intermédiaires
EP0237916A2 (fr) * 1986-03-15 1987-09-23 Hoechst Aktiengesellschaft Dérivés de cyclopropanes 1,1-disubstitués, leurs procédés de préparation et leur emploi comme antimycotiques, ou comme intermédiaires
EP0284702A1 (fr) * 1987-04-03 1988-10-05 Ciba-Geigy Ag Cyclobutanone substituée et procédé de préparation

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GB1508977A (en) * 1974-04-20 1978-04-26 Beecham Group Ltd Beta-lactam antibiotic from streptomyces clavuligerus
EP0026044B1 (fr) * 1979-08-24 1983-06-08 Beecham Group Plc Sel amine de l'acide clavulanique, sa préparation et son utilisation
ES2010143A6 (es) * 1989-03-01 1989-10-16 Pharma Mar S A Pharmar Un nuevo procedimiento de obtencion del acido z(2r,5r)-3-(2-hiadroxietiliden)-7- oxo-4-oxa-1-azabiciclo(3,2,0) -heptano-2-carboxilico y de sales estares farmaceutiacamente aceptables del mismo,a partir de caldos de fermentacion de streptomyces, sp.
AT399155B (de) * 1992-03-26 1995-03-27 Lek Tovarna Farmacevtskih Neue alkylendiammonium-diclavulanat-derivate, verfahren zu deren herstellung sowie deren verwendung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054865A1 (fr) * 1980-12-20 1982-06-30 Bayer Ag 1-Azolyl-butan-2-ones substitués, procédé de leur préparation et leur application comme fongicides ainsi que comme intermédiaires
EP0237916A2 (fr) * 1986-03-15 1987-09-23 Hoechst Aktiengesellschaft Dérivés de cyclopropanes 1,1-disubstitués, leurs procédés de préparation et leur emploi comme antimycotiques, ou comme intermédiaires
EP0284702A1 (fr) * 1987-04-03 1988-10-05 Ciba-Geigy Ag Cyclobutanone substituée et procédé de préparation

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9156788B2 (en) 2010-08-10 2015-10-13 Abbvie Inc. TRPV3 modulators
US9012651B2 (en) 2011-03-24 2015-04-21 Abbvie Inc. TRPV3 modulators
WO2013062964A3 (fr) * 2011-10-24 2013-08-15 Abbvie Inc. Nouveaux modulateurs de trpv3
US8772499B2 (en) 2011-10-24 2014-07-08 Abbvie Inc. TRPV3 modulators
US8772500B2 (en) 2011-10-24 2014-07-08 Abbvie Inc. TRPV3 modulators
CN104254522A (zh) * 2011-10-24 2014-12-31 艾伯维公司 作为trpv3调节剂的甲醇衍生物

Also Published As

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AU6971594A (en) 1995-01-03
JPH08511010A (ja) 1996-11-19
EP0702676A1 (fr) 1996-03-27
DE4318916A1 (de) 1994-12-08

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