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WO1997001547A1 - Derives de benzazole aux proprietes de microbiocides - Google Patents

Derives de benzazole aux proprietes de microbiocides Download PDF

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Publication number
WO1997001547A1
WO1997001547A1 PCT/EP1996/002610 EP9602610W WO9701547A1 WO 1997001547 A1 WO1997001547 A1 WO 1997001547A1 EP 9602610 W EP9602610 W EP 9602610W WO 9701547 A1 WO9701547 A1 WO 9701547A1
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WO
WIPO (PCT)
Prior art keywords
carbon atoms
chlorine
halogen
methyl
compounds
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.)
Ceased
Application number
PCT/EP1996/002610
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German (de)
English (en)
Inventor
Klaus Wagner
Udo Kraatz
Martin Kugler
Heinrich Schrage
Hermann Uhr
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Bayer AG
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Bayer AG
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Filing date
Publication date
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Priority to AU63563/96A priority Critical patent/AU6356396A/en
Publication of WO1997001547A1 publication Critical patent/WO1997001547A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/76—Sulfur atoms attached to a second hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • the present invention relates to new benzazole derivatives, a process for their preparation and their use as microbicides in crop protection and in
  • n 1 or 2
  • R 1 , R 2 , R 3 and R 4 individually independently of one another for hydrogen, halogen, cyano, nitro, in each case optionally substituted alkyl, cycloalkyl,
  • R 1 and R 2 or R 2 and R 3 or R 3 and R 4 together with the carbon atoms to which they are attached form a further, optionally substituted, carbocyclic or heterocyclic ring,
  • X represents hydrogen or halogen, found, the compound 6-chloro-2-difluoromethylsulfonylbenzthiazol is excluded.
  • hydrocarbon chains such as alkyl
  • the hydrocarbon chains are in each case straight-chain or branched, also in combination with heteroatoms, such as in alkoxy, alkylthio or alkylamino.
  • Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular chlorine or bromine.
  • Aryl is exemplary and preferably aromatic, mono or polycyclic hydrocarbon rings, e.g. Phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl.
  • Heterocyclyl is an example and preferably for saturated or unsaturated, as well as aromatic, ring-shaped compounds, in which at least one ring member is a heteroatom, i. H. is 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 appropriate, the ring-shaped compounds together with other carbocyclic or heterocyclic, fused or bridged rings together form a polycyclic ring system. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems.
  • Cycloalkyl is an example and preferably for saturated, carbocyclic, ring-shaped compounds which, if appropriate, form a polycyclic ring system with further carbocyclic, fused or bridged rings.
  • R 1 , R 2 , R 3 , R 4 , Q and X have the meanings given above,
  • the benzazoles of the formula (I) have very good microbicidal properties and can be used in material protection and in crop protection.
  • the compounds according to the invention can optionally be in the form of mixtures of various possible isomeric forms, in particular stereoisomers, such as e.g. optical isomers. Both the R and the S isomers and any mixtures of these isomers are claimed.
  • the invention preferably relates to compounds of the formula (I) in which
  • n 1 or 2
  • R 1 , R 2 , R 3 and R 4 individually independently of one another for hydrogen, fluorine, chlorine, bromine, cyano, nitro, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms, haloalkyl haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 8 carbon atoms and 1 to 5 identical or different halogen atoms, for each in the phenyl or heteroaryl part, if appropriate, simply to triple, identical or different by Ha ⁇ logenous, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different hal
  • Halogenalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 8 carbon atoms and 1 to 5 identical or different halogen atoms substituted, six-membered, aromatic ring, or
  • X represents hydrogen or halogen
  • the invention relates in particular to compounds of the formula (I) in which
  • n 1 or 2
  • R 1 , R 2 , R 3 and R 4 individually independently of one another for hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Cyclopropyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio ,
  • R 1 and R 2 or R 2 and R 3 or R 3 and R 4 together with the carbon atoms to which they are attached, for a further one, optionally by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-
  • R 1 and R 2 or R 2 and R 3 or R 3 and R 4 together for an optionally single to quadruple, identical or different, substituted by fluorine, chlorine, methyl, trifluoromethyl or ethyl alkylene chain with 3 or 4 links, in one or two (non-adjacent) carbon atoms can be replaced by oxygen atoms,
  • X represents hydrogen or bromine
  • Formula (II) provides a general definition of the thioethers required as starting materials for carrying out the process according to the invention.
  • R 1 , R 2 , R, R 4 , Q and X preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred were preferably given for R 1 , R 2 , R 3 , R 4 , Q and X.
  • the starting materials of the formula (II) are known and / or can be prepared by processes which are known per se (cf., for example, DE A 2334356).
  • the process according to the invention is carried out using an oxidizing agent.
  • Chloroperbenzoic acid potassium hydrogen persulfate, potassium peroxodisulfate, sodium perborate, sodium percarbonate or sodium peroxodisulfate, also also potassium permanganate, or sodium perrhenate, also also chlorous or hypochlorous acid or their metal salt solutions in water.
  • the process according to the invention is optionally carried out using a catalyst.
  • Salts of metals of IV., V. and VI. are preferred as catalysts.
  • the process according to the invention is optionally also 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: tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tributylmethylphosphonium bromide, trimethyl-C 13 / C ] 5- alkylammonium chloride, trimethyl-C 13 / C 15 -alkylammonium bromide, dibenzylmethyl sulfonate , Dimethyl-C 12 / C ] 4 -alkyl-benzylammonium chloride, dimethyl-C 12 / C 14 -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, methyl
  • Suitable diluents for carrying out the process according to the invention are all inert organic solvents.
  • This includes preferably aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane or trichloroethane; Ethers, such as diethyl ether,
  • Esters such as methyl acetate or ethyl acetate
  • Sulfoxides such as dimethyl sulfoxide
  • Sulfones such as sulfolane
  • Alcohols such as methanol, ethanol, n- or i-
  • reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.
  • n 1, 1 to 1.5 equivalents, preferably 1 to, are generally employed per mole of the thioether of the formula (II) 1.2 equivalents of oxidizing agent.
  • n 2 to 10 equivalents, preferably 2 to 5 equivalents, are generally employed per mole of the thioether of the formula (II) of oxidizing agent.
  • the process according to the invention is generally carried out under normal pressure. It is also possible, however, under increased or reduced pressure
  • the active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.
  • technical materials are to be understood as non-living materials that have been prepared for use in technology.
  • technical materials that are to be protected against microbial change or destruction by active substances according to the invention adhesives, glues, paper and cardboard, textiles, leather,
  • Production plants such as cooling water circuits, called by
  • technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and
  • Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials.
  • the active compounds or agents according to the invention preferably act against fungi, in particular mold, and against
  • 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 versucorum, Polyporusicol, Polyporusicol , Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus.
  • Alternaria such as Alternaria tenuis
  • Fungicidal agents in crop protection are used to combat plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Some pathogens of fungal diseases which fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
  • 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
  • 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 of the formula (I) can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances.
  • formulations or agents 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, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foaming 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, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foaming agents.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foaming agents.
  • organic solvents can, for example, also be used as auxiliary 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
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone
  • strongly polar solvents such as
  • liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; solid carriers are possible: e.g. 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.
  • emulsifying and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates,
  • Aryl sulfonates and protein hydrolyzates Possible dispersants are: e.g. Lignin sulfite 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 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, ferrocyanin and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese,
  • the effectiveness and the spectrum of activity of the active compounds of the formula (I) or the agents, precursors or very generally formulations which can be prepared therefrom can be increased if, if appropriate, further antimicrobial agents Compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients to increase the spectrum of action or to achieve special effects such as, for example, additional protection against insects are added. These mixtures can have a broader spectrum of activity than the compounds according to the invention.
  • Triazoles such as: Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole,
  • Fenchlorazole Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazole, Isozofos, Myclobutanil, Metconazole, Epoxyconazole, Paclobutrazol, Penconazole, Propioconazole, (+) - cis-l- (4-chlorophenyl) -2, (l -triazol-l-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.
  • Imidazoles such as:
  • Succinate dehydrogenase inhibitors such as:
  • Fenfuram furcarbanil, cyclafiuramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (moncut);
  • Naphthalene derivatives such as terbinafine, naftifine. Butenafine, 3-chloro-7- (2-aza-
  • Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;
  • Benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate methyl, thiabendazole or their salts; Morpholine derivatives, such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph, aldimorph, fenpropidine and their aryl sulfonic acid salts, such as, for example, p-toluene sulfonic acid and p-dodecylphenyl sulfonic acid;
  • Dithiocarbamates such as Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram;
  • Benzothiazoles such as 2-mercaptobenzothiazole
  • Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide
  • Boron compounds such as boric acid, boric acid esters, borax;
  • Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poly) hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide,
  • Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, ⁇ -bromocinnamaldehyde;
  • Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc;
  • quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride;
  • Iodine derivatives such as diiodomethyl p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodallyl alcohol, 3 -Bromine-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl-cyclohexyl carbamate, 3 Iodine-2-propynylphenyl carbamate; Phenol derivatives, such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol,
  • Microbicides with activated halogen group such as chloroacetamide, bronopol,
  • Bronidox tectamers such as 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxyacetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4 -dicyanobutane, ß- B rom-ß-nitrosty rol;
  • Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mri, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, 1-
  • Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
  • Metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate,
  • Oxides such as tributyltin oxide, Cu 2 O, CuO, ZnO;
  • Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;
  • Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;
  • N- (2-p-chlorobenzoylethyl) hexaminium chloride potassium N-hydroxymethyl-N'-methyl-dithiocarbamate, 2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride, Phenyl- (2-chloro-cyanovinyl) sulfone, phenyl- (1,2-dichloro-2-cyanovinyl) sulfone; Zeolites containing Ag, Zn or Cu alone or included in polymeric active substances.
  • Fthalides Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal -isopropyl, Nuarimol, Ofurace, Oxadiyl, Perflurazoate, Pencycuron, Phosdiphen, Pimaricin, Proponymone, Pyonoxone, Pyronoxin, Proamonoxyrin, Proamonoxyrin, Proconoxinone, Proamonoxin, Proamonoxin, Proamonoxin, Proamonoxin, Proamon, Pyronoxin Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide,
  • Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, ⁇ -l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, Chlo ⁇ yrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos , Dimethoate, Ethoate, Ethoprophos,
  • Etrimfos Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphone; Carbamates such as aldicarb, bendiocarb, ⁇ -2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxy carboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarbox;
  • Organosilicon compounds preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether, such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethylether or [(phenyl) -3- (3-phenoxyphenyl) -propyl] (dimethyl) -silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenylpropyl] dimethyl silane, silafluofen;
  • Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro- 2-trifluoro-methyl-vinyl) -cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;
  • Nitroimines and nitromethylenes such as imidacloprid, N - [(6-chloro-3-pyridyl) methyl-] N2-cyano-N 1 -methyl acetamide (NI-25);
  • Mephosfolan Mercurous, chloride, Metam, Metarthizin, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Pentometholone, Ometholone, Ometholone, Ometholone, Ometholone oils, phenothrin, phenthoates, phorates;
  • Fentin acetates metaldehydes, methiocarb.
  • Niclosamide thiodicarb, trimethacarb.
  • Herbicides acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfonon, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, benz
  • TCA metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide, monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadlorone, pentahlorophenone, oxyfluenthophenone petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodiamine, proglinazine, propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifarbi-carboxilonium, thifarbi-chloro-thioblimi, thifarbazoxi
  • the weight ratios of the active ingredients in these active ingredient combinations can be varied within relatively large ranges.
  • the active substance combinations preferably contain 0.1 to 99.9%, in particular 1 to 75%, particularly preferably 5 to 50% of the active substance, the rest being filled 100% by one or more of the above-mentioned mixing partners.
  • microbicidal agents or concentrates used to protect the industrial materials contain the active ingredient or combination of active ingredients in a concentration of 0.01 and 95% by weight, in particular 0.1 to 60% by weight.
  • the application concentrations of the active substances to be used or the active substance combinations 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 become.
  • 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 substances or agents according to the invention advantageously make it possible to replace the microbicidal agents available to date with more effective ones. They show good stability and advantageously have a broad spectrum of activity.
  • MIC Heram concentrations
  • Active ingredients according to the invention are added to an agar which is produced using malt extract in concentrations of 0.1 mg / l to 5,000 mg / l. After the agar solidifies, it is contaminated with pure cultures of the test organisms listed in Table 1. After 2 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, it is shown in Table 2 below.
  • the paint to be tested is coated on both sides on a suitable surface.
  • some of the test specimens are leached with running water (24 hours; 20 ° C) before the test for mold resistance; another part is treated with a warm fresh air flow (7 days; 40 ° C).
  • test specimens prepared in this way are placed on an agar culture medium. Test specimens and culture medium are contaminated with fungal spores. After 2 to 3 weeks
  • Fungus spores of the following molds which are known as paint destroyers or are often found on paints, are used for contamination:
  • Coatings are resistant to mold according to recipe A (even after leaching and
  • Wind tunnel exposure if they contain, for example, 0.6% (based on solids) of compound 9.

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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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne de nouveaux dérivés de benzazole, un procédé pour les produire et leur utilisation comme microbiocides dans la protection phytosanitaire et la protection des matériaux.
PCT/EP1996/002610 1995-06-28 1996-06-17 Derives de benzazole aux proprietes de microbiocides Ceased WO1997001547A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU63563/96A AU6356396A (en) 1995-06-28 1996-06-17 Benzazole derivatives with microbiocidal properties

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19523447.2 1995-06-28
DE1995123447 DE19523447A1 (de) 1995-06-28 1995-06-28 Benzazolderivate

Publications (1)

Publication Number Publication Date
WO1997001547A1 true WO1997001547A1 (fr) 1997-01-16

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ID=7765433

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/002610 Ceased WO1997001547A1 (fr) 1995-06-28 1996-06-17 Derives de benzazole aux proprietes de microbiocides

Country Status (3)

Country Link
AU (1) AU6356396A (fr)
DE (1) DE19523447A1 (fr)
WO (1) WO1997001547A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153653A (en) * 1963-01-11 1964-10-20 Du Pont 2-(polyfluoroaliphatic thio)-benzo-thiazoles and -benzoxazoles
DE2334356A1 (de) * 1973-07-06 1975-01-30 Hoechst Ag Substituierte benzthiazole
WO1994006783A1 (fr) * 1992-09-16 1994-03-31 Zeneca Limited Derives de benzoxazole et de benzothiazole

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153653A (en) * 1963-01-11 1964-10-20 Du Pont 2-(polyfluoroaliphatic thio)-benzo-thiazoles and -benzoxazoles
DE2334356A1 (de) * 1973-07-06 1975-01-30 Hoechst Ag Substituierte benzthiazole
WO1994006783A1 (fr) * 1992-09-16 1994-03-31 Zeneca Limited Derives de benzoxazole et de benzothiazole

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 72, no. 21, 25 May 1970, Columbus, Ohio, US; abstract no. 111455h, BUCKMAN,J.D. ET AL: "Microbiocidal organic thiocyanates /benzothiazoles" page 407; XP002015646 *
PAULUS,W.: "Microbiocides for material protection with special regard to the paint industry", FAERG LACK SCAND., vol. 38, no. 9, 1992, STOCKHOLM, pages 161 - 164,166, XP002016175 *

Also Published As

Publication number Publication date
DE19523447A1 (de) 1997-01-02
AU6356396A (en) 1997-01-30

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