WO1995014383A1 - Alkyl-n-pyrroles - Google Patents

Alkyl-n-pyrroles Download PDF

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Publication number
WO1995014383A1
WO1995014383A1 PCT/EP1994/003745 EP9403745W WO9514383A1 WO 1995014383 A1 WO1995014383 A1 WO 1995014383A1 EP 9403745 W EP9403745 W EP 9403745W WO 9514383 A1 WO9514383 A1 WO 9514383A1
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Prior art keywords
alkyl
compounds
chain
substituted
oxy
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PCT/EP1994/003745
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German (de)
French (fr)
Inventor
Lutz Heuer
Martin Kugler
Heinrich Schrage
Ralf Tiemann
Original Assignee
Bayer Aktiengesellschaft
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Publication date
Priority claimed from DE4416409A external-priority patent/DE4416409A1/en
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU81423/94A priority Critical patent/AU8142394A/en
Publication of WO1995014383A1 publication Critical patent/WO1995014383A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • C07D207/327—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • 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
    • 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 application relates to the use of branched, cyclic or substituted alkyl or alkyl-N-azoles in material protection as well as new and known S-alkyl-N-azoles and a process for their preparation.
  • branched-chain or substituted or unsaturated alkyl-N-azoles of the formula (I) have outstanding microbicidal activities from the large number of known agents with fungicidal, algicidal, bactericidal or biocidal properties.
  • azoles of the formula (I) have physical / chemical properties which prevent their use in paint, plastic, wood, in adhesives, glues, textiles, leather and coolants through undesirable interactions and / or discoloration and / or wash-out and / or evaporation to disturb.
  • R represents a branched, cyclic and / or substituted by C j -C 19 alkyl, C 2 -C 10 alkenyl and / or OR 1 and / or C (O) OR 1 alkyl chain or alkenyl chain with 5 to 20 carbon atoms, possibly by one or two
  • W, X, Y, Z independently of one another represent nitrogen or the group CR 2 , at least two standing for the group CR ", and in which
  • R 2 represents hydrogen or straight-chain or branched C j -C 10 alkyl
  • R 1 represents straight-chain or branched C j -C x 0 alkyl, C 2 -C 0 alkenyl or benzyl or cinnamyl which is monosubstituted to trisubstituted by methyl, chlorine and / or fluorine,
  • alkyl in the definitions of R, R 1 and R 2 represents straight-chain or branched alkyl, such as methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and their branched isomers.
  • alkenyl in the definitions of R, R 1 and R 2 stands for straight-chain or branched alkenyl with one or more double bonds, such as ethenyl, n-propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n -Octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl and their branched isomers.
  • R is a branched, cyclic or mono- to trisubstituted by C j -C 16 alkyl
  • W represents the groups CH or C- (C r C 10 ) -alkyl
  • Z, X represent nitrogen or the group CH
  • Y represents the group CH
  • R 1 represents C r C 6 alkyl.
  • R represents a branched or mono- to disubstituted or substituted by C 1 -C 3 alkyl, OR 1 and / or C (O) OR 1 groups in the ⁇ - or ⁇ -position alkyl chain or alkenyl chain with 9 to 12 carbon atoms, which may be by an oxygen atom is interrupted, or represents cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl which is mono-, di- or trisubstituted by C 4 -C 15 , OR 1 and / or COOR 1 ,
  • W represents CH, C-Me, C-Et or C-propyl
  • R 1 represents Me, Et, n-, i-Pr, n-, i-, s-, t-Bu or n-pentyl.
  • R 3 represents an n-alkyl chain with C 7 -C 14 carbon atoms substituted in the ⁇ -position by CC 9 -n-alkyl chain, or stands for a cyclohexyl or cyclopentyl substituted in the 2-, 3- or 4-position, the Substituent one
  • R 4 represents H or C r C 6 alkyl.
  • R 3 represents an n-alkyl chain with C 8 -C 12 carbon atoms substituted in the ⁇ -position by C to C 5 -n-alkyl chain, or stands for a cyclohexyl substituted in the 2- or 4-position, the substituent being a C 5 -C 12 alkyl or alkenyl group, and
  • R 4 represents H or C r C 4 alkyl.
  • R 3 represents an n-alkyl chain with C 9 -C n atoms substituted in the ⁇ -position by C j - to C 3 -n-alkyl chain, or a cyclohexyl substituted in the 2-position, the substituent being an alkyl or Represents alkenyl group with C 6 -C 12 , and
  • R 4 represents H or Me, Et, n-, i-Pr, n-, i-, s-, t-Bu or n-pentyl.
  • the new compounds of the formula (II) are prepared analogously to the known compounds of the formula I and as described below and in DE-2 442 706.
  • the active compounds of the formula (II) and the agents according to the invention have a strong microbicidal action and can be used practically to combat unwanted microorganisms.
  • the active compounds of the formula (II) and the agents according to the invention are suitable for protecting industrial 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 can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be attacked or decomposed by microorganisms .
  • parts of production plants for example cooling water circuits, may also be mentioned which can be impaired by the multiplication of microorganisms.
  • technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably paints.
  • 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 substances or agents according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
  • microorganisms of the following genera may be mentioned: 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, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Pechichomonas, such as Escherichiaiaosine, such as Escherichia, as well as like Staphylococcus aureus.
  • Alternaria such as Alternaria tenuis
  • Aspergillus such as Aspergillus niger
  • the active compounds of the formulas (I) and (II) can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances .
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, under pressure the liquefied gases and / or solid carriers, if appropriate 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
  • 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.
  • aromas 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 their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, and water
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide
  • Solid carrier materials are suitable: for example natural rock powders such as ka
  • 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 are used.
  • 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 are used.
  • the active compounds of the formula (II) and the compounds of the formula (I) are preferably used to protect paints against attack and destruction by undesired microorganisms.
  • painting is to be understood as meaning a coating made of paints on a substrate.
  • the paint may have penetrated more or less into the surface. It can consist of one or more layers and can be produced by processes such as brushing, spraying, dipping, flooding or similar processes.
  • Paints according to the invention therefore contain, in addition to at least one fungicidal active ingredient of the formula (I) and / or (II), generally customary paint components in, for example, liquid, pasty or powdery form, for example
  • Colorants such as pigments or dyes, preferably pigments.
  • examples include titanium dioxide, zinc oxide and iron oxide.
  • Binders such as, for example, oxidatively drying alkyd resins, vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers, plastic powders, novolaks, amino resins, polyester resins, epoxy resins, silicone resins, isocyanate resins, vinyl polymers and vinyl copolymers, water-borne polymers and acrylic copolymers and other copolymers used are preferred and acrylic copolymers and other copolymers used .
  • the paints may also contain the following additives
  • Fillers such as heavy spar, calcite, dolomite and talc,
  • Solvents such as alcohols, ketones, esters, glycol ethers and aliphatic and aromatic hydrocarbons,
  • thickening and thixotropic agents as well as thickening and thixotropic agents, dispersants and wetting agents, drying agents, skin-preventing agents, leveling agents, anti-foaming agents, corrosion inhibitors, UV absorbers, fragrances, antistatic agents, antifreeze agents.
  • paints or precursors for the production of paints may preferably be mentioned as paints or precursors for the production of paints:
  • Glues and adhesives based on the well-known animal, vegetable or synthetic raw materials.
  • Plastic dispersions such as latex dispersions or dispersions based on other polymers.
  • - Starch solutions, dispersions or slurries or other starch-based products such as pressure thickeners.
  • Slurries of other raw materials such as color pigments (eg iron oxide pigments, carbon black pigments, titanium dioxide pigments) or slurries of fillers such as kaolin or calcium carbonate.
  • Concrete additives for example based on molasses or lignin sulfonates. - bitumen emulsions.
  • Dispersion paints for the painting industry - coats and finishes.
  • the effectiveness and the spectrum of activity of the active compounds of the formulas (I) and (II) or the agents, precursors or very generally formulations which can be prepared therefrom is increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active compounds are used to enlarge the spectrum of effects or achieve special effects such as added protection against insects. These mixtures have a broader spectrum of activity than the compounds according to the invention.
  • Triazoles such as:
  • Imidazoles such as:
  • Succinate dehydrogenase inhibitors such as:
  • Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorofolpet; Captan, Captofol;
  • Benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonat-methyl, Thiabendazole or their salts; Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph,
  • Dodemorph, aldimorph, fenpropidine and their arylsulfonic acid salts such as e.g. p-
  • Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide
  • Boron compounds such as boric acid, boric acid ester, borax;
  • Formaldehyde and formaldehyde releasing compounds such as benzyl alcohol mono-
  • 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-iodine-2-propynyl alcohol, 4-chlorophenyl
  • Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali and alkaline earth metal salts;
  • Microbicides with activated halogen group such as chloroacetamide, bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-di
  • 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, copper fluorosilicate;
  • Oxides such as tributyltin oxide, Cu 2 O, CuO, ZnO;
  • Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates,
  • Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate; Quinolines such as 8-hydroxyquinoline and their Cu salts; Mucochloric acid, 5-hydroxy-2 (5H) furanone;
  • Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, ⁇ -l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, 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 Trichlorphon;
  • Carbamates such as aldicarb, bendiocarb, ⁇ -2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
  • Organosilicon compounds preferably dimethyl (phenyl) silyl-methyl-3-phenoxy-benzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) -silyl-methyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl (9- ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxypheny
  • 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-trif -methylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin; Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-lH-imidazol-2-amine (imidacloprid), N - [(6-ch
  • Fentin acetates metaldehydes, methiocarb.
  • Niclosamide thiodicarb, trimethacarb.
  • Algicide Coppersulfate, dichlororphen, Endothal, Fentinacetate, Quinoclamine.
  • the weight ratios of the active ingredients in these active ingredient combinations can be varied within relatively large ranges.
  • the active compound combinations preferably contain from 0.1 to 99.9%, in particular from 1 to 75%, particularly preferably from 5 to 50%, the rest being filled 100% by one or more of the above-mentioned mixing partners.
  • the present invention also relates to new, in particular aqueous and optionally organic, solvent-free and emulsifier-free microbicidal combinations of active ingredients of the alkyl-N-azoles of the formula (I) and quaternary ammonium fungicides.
  • the low water solubility of azoles limits their use in some areas of application such as Leather, water-based wood protection, disinfection, cooling water treatment, paper industry, metal processing, technical preservation of water-containing products are restricted or not possible.
  • Quaternary ammonium salts have long been known as broadly effective microbicides and find e.g. Use in disinfection and textile preservation.
  • Water-insoluble solvents are incompatible with aqueous products such as leather liquors, emulsion paints, cooling and process water, disinfectants.
  • water-soluble solvents would be suitable as solubilizers in aqueous systems. But if they get into the wastewater, they can cause ecological problems. In addition, solvents can interfere with the products to be protected.
  • emulsifiers Another way of imparting solvents for the production of water-based active ingredient formulations is to use emulsifiers.
  • highly water-insoluble compounds such as azoles
  • large amounts of emulsifier are generally required for this, which should be avoided for ecological reasons.
  • the effectiveness of microbicidal active ingredient can also be severely impaired by the use of emulsifiers.
  • the usability for certain systems can also be limited.
  • the object of the invention was therefore also to provide new, preferably water-based, solvent-free and emulsifier-free microbicidal active ingredient formulations based on azole fungicides; that can be easily diluted with water and thereby deliver storage-stable use solutions.
  • R 1 , R 2 , R 3 , R 4 are the same or different and each is unsubstituted or substituted, straight-chain or branched, saturated or unsaturated
  • Residues R 1 to R 4 at the quaternary center can optionally form a saturated or unsaturated 5-, 6- or 7-membered (heter) cycle with further heteroatoms and
  • X for an anion that promotes water solubility e.g. Halide, sulfate, alkyl sulfonate or optionally substituted aryl sulfonate.
  • aqueous solutions or emulsions can be prepared which have a particularly high microbicidal activity.
  • Such aqueous formulations avoid the aforementioned ecological and application-technical disadvantages of solvent-based or emulsifier-mediated formulations and in this respect represent a valuable enrichment of the prior art.
  • Preferred quaternary ammonium compounds are ammonium salts such as
  • Trimethylcocosammonium chloride called didecyldimethylammonium chloride.
  • C 12 -C 14 -Alkyl-benzyl-dimethylammonium chloride is particularly preferred.
  • the azole fungicides are in the form of their free base.
  • a combination of alkyl-N-azoles of the formula (I) and C 12 -C 14 -alkyl-benzyl-dimethylammonium chloride is very particularly preferred, preferably in combination with tebuconazole.
  • the weight ratios of the active substances in the active substance combinations can be varied within relatively large ranges.
  • the weight ratio of azole fungicide to quaternary ammonium fungicide is 1:99 to 99: 1, in particular 1:40 to 9: 1, particularly preferably 1:20 at 1: 1 and very particularly preferably 1:10 to 1: 2.
  • the active ingredients are incorporated individually or as a combination of active ingredients, for example in the form of powders, granules, pastes or concentrated solutions, suspensions or emulsions, by simple mixing in water and are then in the form of an aqueous suspension, solution or emulsion.
  • the aqueous solutions or emulsions preferably contain more than 20% by weight, in particular more than 40% by weight, of water and can be diluted with water to the application concentration as desired. It is of course also possible to incorporate the active substances or combination of active substances in the form of concentrates, solutions, suspensions, emulsions, powders, granules or pastes directly into the application agents in the amounts required for the application, for example by stirring.
  • microbicidal agents contain the active ingredient combination in a concentration of 0.001 to 95% by weight, in particular 0.01 to 60% by weight and, if appropriate, 0.001 to 30% by weight, in particular 0.01 to 20% by weight, very particularly 0.05 to 10% by weight of a suitable further fungicide, insecticide or another active ingredient.
  • 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.
  • 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.
  • 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 ( 1 H-NMR).
  • the active compounds are also suitable for use as crop protection agents, in particular as fungicides.
  • Fungicidal agents in crop protection are used to combat plasmo- diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi-diomycetes, 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 cubense;
  • 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
  • Drechslera (Conidial form: Drechslera, synonym: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechs ⁇ lera, 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 used with particularly good success for combating diseases in fruit and vegetable cultivation, such as, for example, against the pathogen causing tomato brown rot (Phytophthora infestans) or against the pathogen of apple scab (Venturia inaequalis) or for combating cereal diseases such as For example, against the pathogen of the powdery mildew (Erysiphe graminis) or against the pathogen of the barley net spot disease (Pyrenophora teres) or against the pathogen of the brown furs of the wheat (Leptosphaeria nodorum) or against fusarium species on cereals or for controlling rice diseases, such as can be used against the pathogen of the rice stain disease (Pyricularia oryzae).
  • the active compounds according to the invention have good in vitro activity.
  • 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 produced 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 foam-producing agents Means. 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 foam-producing agents Means.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-producing agents Means.
  • 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 their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, and water;
  • Liquefied gaseous extenders or carriers mean liquids which are at normal temperature and under normal conditions.
  • gaseous 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 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: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks;
  • Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyg
  • Adhesives such as carboxymethylceliulose, 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 ingredient, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In many cases, synergistic effects occur.
  • mixtures for example:
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil,
  • HCH heptenophos, hexaflumuron, hexythiazox, Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,
  • Methamidophos Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
  • Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M,, Primiphos A, Profenofos, Profenophos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothoat,
  • Tebufenozid Tebufenpyrad
  • Tebupirimphos Teflubenzuron
  • Tefluthrin Temephos
  • the active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil. The seeds of the plants can also be treated.
  • the active substance concentrations in the use forms can be varied within a wide range: they are generally mean between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
  • 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 of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.
  • the compounds 73 to 104 are prepared in an analogous manner from the primary alcohols extended with propylene oxide in a manner known from the literature; for this purpose, the alcohols are first reacted either with PBr 3 or with mesyl chloride and then, as mentioned above, with sodium imidazole to the final stage.
  • the 2-bromofatty acid esters are commercially available or can be produced according to the regulations of the Organic, German Publishing House of Sciences, Berlin 1990.
  • hexane oxide 50 g are kept at 140 ° C. for 4 h with 37.4 g of imidazole in 200 ml of DMF. After cooling, the DMF is evaporated off, taken up in methylene chloride, washed with water and distilled on a bulb tube.
  • precursor 196 7.0 g are mixed with 2.58 g of sodium hydride (60%) in 200 ml of DMF and stirred at 50 ° C. for 30 min. After adding 6.88 g of bromhexane, the mixture is stirred at 50 ° C. for 5 h, the volatile components are stripped off in vacuo and the residue is column-chromatographed using toluene as the eluent.
  • a solution B is prepared from 12.83 g imidazole, 8.55 g NaH (60% in oil) and 100 ml DMF, to which solution A is slowly added dropwise. After 22 hours at 40 ° C., the mixture is extracted with ethyl acetate and concentrated, and the residue is chromatographed on silica gel using toluene. 2.3 g of isomer mixture of the target compound are obtained. ⁇ H: 4.18 ppm, multiplet.
  • the 2-alkyl-cyclohexanols can be prepared analogously to the literature: Tietze / Eicher, Reactions and Syntheses, Thieme 1981; Attempts K-2a-b / C3-5; Preparation of the Schiff base from cycloalkyl ketone and cycloalkylamine, alkylation thereof, hydrolysis and reduction of the same.
  • Example II Analogously to Example I, only the 2.5 g azole fungicide according to Example 36 and 1.25 g tebuconazole are used. The solution obtained can be diluted with water as desired and has synergistic effects in accordance with Example A.
  • Example III Analogously to Example I, only the 5.0 g decylimidazole can be used.
  • agar which is produced using malt extract is mixed with active compounds according to the invention in concentrations of 0.1 mg / 1 to 5000 mg / 1. 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 substance to be tested for its fungicidal activity is incorporated in the desired concentration in the (dispersion) color using a dissolver.
  • the paint is then spread on both sides on a suitable surface.
  • test specimens are leached with running water (24 h; 20 ° C) before the test for mold resistance.
  • test specimens thus prepared are placed on an agar medium.
  • Test specimens and culture medium are contaminated with fungal spores. After storage for 1 to 3 weeks at 29 + 1 ° C and 80-90% rel. Humidity is sampled.
  • the paint is permanently mold-resistant if the test specimen remains free of fungi or if at most a slight edge infestation can be seen.
  • Fungus spores of the following nine molds which are known as paint destroyers or are often found on paints, are used for contamination:
  • Table V shows the active compound concentrations at which the paint test specimen remains free of fungi (concentrations based on the solids content of the emulsion paint) Table V

Abstract

The use of branched, cyclic or substituted alkyl or alkyl-N-pyrroles for the protection of materials is disclosed, as well as new and known S-alkyl-N-pyrroles and a process for preparing the same.

Description

Alkyl-N-azoleAlkyl-N-azoles
Die Anmeldung betrifft die Verwendung von verzweigten, cyclischen oder substitu¬ ierten Alkyl- oder Alkyl-N-azole im Materialschutz sowie neue und bekannte S-Al- kyl-N-azole und ein Verfahren zu ihrer Herstellung.The application relates to the use of branched, cyclic or substituted alkyl or alkyl-N-azoles in material protection as well as new and known S-alkyl-N-azoles and a process for their preparation.
Bekannt sind geradkettig alkylsubstituierte Imidazolderivate für den Einsatz im Materialschutz (DE-2.442.706). Ihre Wirkung auf im Materialschutz relevante Mikrooganismen ist in vielen Fällen nicht ausreichend.Straight-chain alkyl-substituted imidazole derivatives for use in material protection are known (DE-2,442,706). In many cases, their effect on microoganisms relevant in material protection is not sufficient.
Bekannt sind weiterhin einige verzweigtkettige und/oder ungesättigte Imidazol- derivate für den Einsatz als Synergisten für Insektizide im Pflanzenschutz (DE- 2.750.030 und DE-2.750.031). Ihre f ngizide Wirkung ist nicht beschrieben.Also known are some branched-chain and / or unsaturated imidazole derivatives for use as synergists for insecticides in crop protection (DE-2,750,030 and DE-2,750,031). Their fungicidal activity is not described.
Es wurde nun überraschenderweise gefunden, daß aus der Vielzahl bekannter Mittel mit fungiziden, algiziden, bakteriziden oder bioziden Eigenschaften die verzweigtkettigen oder substituierten oder ungesättigten Alkyl-N-azole der Formel (I) hervorragende mikrobizide Aktivitäten aufweisen. Darüber hinaus haben Azole der Formel (I) physikalisch/chemische Eigenschaften, die ihre Verwendung im Anstrich, Kunststoff, Holz, in Klebstoffen, Leimen, Textilien, Leder und Kühlschutzmitteln nicht durch unerwünschte Wechselwirkungen und/oder Verfärbungen und/oder Auswaschungen und/oder Abdampfen stören.It has now surprisingly been found that the branched-chain or substituted or unsaturated alkyl-N-azoles of the formula (I) have outstanding microbicidal activities from the large number of known agents with fungicidal, algicidal, bactericidal or biocidal properties. In addition, azoles of the formula (I) have physical / chemical properties which prevent their use in paint, plastic, wood, in adhesives, glues, textiles, leather and coolants through undesirable interactions and / or discoloration and / or wash-out and / or evaporation to disturb.
Gegenstand der Anmeldung sind mikrobizide Mittel zum Schutz von technischen Materialien, enthaltend mindestens eine Verbindung der Formel (I) W = XThe application relates to microbicidal agents for protecting industrial materials, comprising at least one compound of the formula (I) W = X
R-N (I)R-N (I)
Z=Y in welcherZ = Y in which
R für eine verzweigte, cyclische und/oder durch Cj-C19-Alkyl, C2-C10- Alkenyl und/oder OR1 und/oder C(O)OR1 substituierte Alkylkette oder Alkenylkette mit 5 bis 20 Kohlenstoffatomen steht, die gegebenenfalls durch ein oder zweiR represents a branched, cyclic and / or substituted by C j -C 19 alkyl, C 2 -C 10 alkenyl and / or OR 1 and / or C (O) OR 1 alkyl chain or alkenyl chain with 5 to 20 carbon atoms, possibly by one or two
Schwefel- oder Sauerstoffatome unterbrochen ist,Sulfur or oxygen atoms is interrupted,
W, X, Y, Z unabhängig voneinander für Stickstoff oder die Gruppe CR2 stehen, wobei mindestens zwei für die Gruppe CR" stehen, und worinW, X, Y, Z independently of one another represent nitrogen or the group CR 2 , at least two standing for the group CR ", and in which
R2 für Wasserstoff oder geradkettiges oder verzweigtes Cj-C10-Alkyl steht,R 2 represents hydrogen or straight-chain or branched C j -C 10 alkyl,
R1 für geradkettiges oder verzweigtes C j -C x 0- Alkyl, C2-C 0- Alkenyl oder für einfach bis dreifach durch Methyl, Chlor und/oder Fluor substituiertes Benzyl oder Cinnamyl steht,R 1 represents straight-chain or branched C j -C x 0 alkyl, C 2 -C 0 alkenyl or benzyl or cinnamyl which is monosubstituted to trisubstituted by methyl, chlorine and / or fluorine,
zum Schutz von technischen Materialien.to protect technical materials.
Alkyl steht im folgenden in den Definitionen von R, R1 und R2 für geradkettiges oder verzweigtes Alkyl, wie Methyl, n-Ethyl, n-Propyl, n-Butyl, n-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Pentadecyl und deren verzweigte Isomeren.In the following, alkyl in the definitions of R, R 1 and R 2 represents straight-chain or branched alkyl, such as methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and their branched isomers.
Alkenyl steht im folgenden in den Definitionen von R, R1 und R2 für geradkettiges oder verzweigtes Alkenyl mit einer oder mehreren Doppelbindungen, wie Ethenyl, n- Propenyl, n-Butenyl, n-Pentenyl, n-Hexenyl, n-Heptenyl, n-Octenyl, n-Nonenyl, n- Decenyl, n-Undecenyl, n-Dodecenyl, n-Tridecenyl, n-Tetradecenyl, n-Pentadecenyl und deren verzweigten Isomeren.In the following, alkenyl in the definitions of R, R 1 and R 2 stands for straight-chain or branched alkenyl with one or more double bonds, such as ethenyl, n-propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n -Octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl and their branched isomers.
Bevorzugt sind Mittel, enthaltend Verbindungen der Formel (I), in welcherAgents containing compounds of the formula (I) are preferred in which
R für eine verzweigte, cyclische oder einfach bis dreifach durch Cj-C16-Alkyl,R is a branched, cyclic or mono- to trisubstituted by C j -C 16 alkyl,
C2-C6-Alkenyl, OR1 und/oder C(O)OR! Gruppen substituierte Alkylkette oder Alkenylkette mit 5 bis 14 Kohlenstoffatomen steht, die gegebenenfalls durch ein Sauerstoffatom unterbrochen ist,C 2 -C 6 alkenyl, OR 1 and / or C (O) OR ! Groups substituted alkyl chain or alkenyl chain with 5 to 14 carbon atoms, which is optionally interrupted by an oxygen atom,
W für die Gruppen CH oder C-(CrC10)-Alkyl steht,W represents the groups CH or C- (C r C 10 ) -alkyl,
Z, X für Stickstoff oder die Gruppe CH stehen, undZ, X represent nitrogen or the group CH, and
Y für die Gruppe CH steht, undY represents the group CH, and
R1 für CrC6-Alkyl steht.R 1 represents C r C 6 alkyl.
Besonders bevorzugt sind Mittel, enthaltend Verbindungen der Formel (I),Agents containing compounds of the formula (I) are particularly preferred
in welcherin which
R für eine verzweigte oder einfach bis zweifach durch C1-C3 -Alkyl, OR1 und/oder C(O)OR1 Gruppen in α- oder ß-Position substituierte Alkylkette oder Alkenylkette mit 9 bis 12 Kohlenstoffatomen steht, die gegebenenfalls durch ein Sauerstoffatom unterbrochen ist, oder für einfach, zweifach oder dreifach durch C4-C15, OR1 und/oder COOR1 substituiertes Cyclopentyl, Cyclohexyl, Cycloheptyl oder Cyclooctyl steht,R represents a branched or mono- to disubstituted or substituted by C 1 -C 3 alkyl, OR 1 and / or C (O) OR 1 groups in the α- or β-position alkyl chain or alkenyl chain with 9 to 12 carbon atoms, which may be by an oxygen atom is interrupted, or represents cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl which is mono-, di- or trisubstituted by C 4 -C 15 , OR 1 and / or COOR 1 ,
W für CH, C-Me, C-Et oder C-Propyl steht,W represents CH, C-Me, C-Et or C-propyl,
Z, Y für CH stehen,Z, Y stand for CH,
X für Stickstoff steht, undX represents nitrogen, and
R1 für Me, Et, n-, i-Pr, n-, i-, s-, t-Bu oder n-Pentyl steht.R 1 represents Me, Et, n-, i-Pr, n-, i-, s-, t-Bu or n-pentyl.
Gegenstand der Anmeldung sind weiterhin neue Verbindungen der Formel (II) FCThe application also relates to new compounds of the formula (II) FC
(II)(II)
R3-N ' NR 3 -N ' N
in welcherin which
R3 für eine in α-Position durch C C9-n-Alkylkette substituierte n-Alkylkette mit C7-C14-Kohlenstoffatomen steht, oder für ein in 2-, 3- oder 4-Position substituiertes Cyclohexyl oder Cyclopentyl steht, wobei der Substituent eineR 3 represents an n-alkyl chain with C 7 -C 14 carbon atoms substituted in the α-position by CC 9 -n-alkyl chain, or stands for a cyclohexyl or cyclopentyl substituted in the 2-, 3- or 4-position, the Substituent one
C4-C15- Alkyl- oder Alkenylgruppe darstellt, undRepresents C 4 -C 15 alkyl or alkenyl group, and
R4 für H oder CrC6-Alkyl steht.R 4 represents H or C r C 6 alkyl.
Bevorzugt sind Verbindungen der Formel (II),Compounds of the formula (II) are preferred
in welcherin which
R3 für eine in α-Position durch C bis C5-n- Alkylkette substituierte n-Alkylkette mit C8-C12-Kohlenstoffatomen steht, oder für ein in 2- oder 4-Position substituiertes Cyclohexyl steht, wobei der Substituent eine C5-C12-Alkyl- oder Alkenylgruppe darstellt, undR 3 represents an n-alkyl chain with C 8 -C 12 carbon atoms substituted in the α-position by C to C 5 -n-alkyl chain, or stands for a cyclohexyl substituted in the 2- or 4-position, the substituent being a C 5 -C 12 alkyl or alkenyl group, and
R4 für H oder CrC4-Alkyl steht.R 4 represents H or C r C 4 alkyl.
Besonders bevorzugt sind Verbindungen der Formel (II),Compounds of the formula (II) are particularly preferred
in welcherin which
R3 für eine in α-Position durch Cj- bis C3-n-Alkylkette substituierte n-Alkylkette mit C9-Cn-Atomen steht, oder eine in 2-Position substituiertes Cyclohexyl steht, wobei der Substituent eine Alkyl- oder Alkenylgruppe mit C6-C12 darstellt, undR 3 represents an n-alkyl chain with C 9 -C n atoms substituted in the α-position by C j - to C 3 -n-alkyl chain, or a cyclohexyl substituted in the 2-position, the substituent being an alkyl or Represents alkenyl group with C 6 -C 12 , and
R4 für H oder Me, Et, n-, i-Pr, n-, i-, s-, t-Bu oder n-Pentyl steht. Die neuen Verbindungen der Formel (II) werden in Analogie "zu den bekannten Verbindungen der Formel I und wie nachstehend und in der DE-2 442 706 beschrieben, hergestellt.R 4 represents H or Me, Et, n-, i-Pr, n-, i-, s-, t-Bu or n-pentyl. The new compounds of the formula (II) are prepared analogously to the known compounds of the formula I and as described below and in DE-2 442 706.
Die Wirkstoffe der Formel (II) und die erfindungsgemäßen Mittel weisen eine starke mikrobizide Wirkung auf und können zur Bekämpfung von unerwünschte Mikroorganismen praktisch eingesetzt werden. Die Wirkstoffe der Formel (II) und die erfindungsgemäßen Mittel sind zum Schutz von technischen Materialien gegen Befall und Zerstörung durch unerwünschte Mikroorganismen geeignet.The active compounds of the formula (II) and the agents according to the invention have a strong microbicidal action and can be used practically to combat unwanted microorganisms. The active compounds of the formula (II) and the agents according to the invention are suitable for protecting industrial materials against attack and destruction by undesired microorganisms.
Unter technischen Materialien sind im vorliegenden Zusammenhang nicht-lebende Materialien zu verstehen, die für die Verwendung in der Technik zubereitet worden sind. Beispielsweise können technische Materialien, die durch erfindungsgemäße Wirkstoffe vor mikrobieller Veränderung oder Zerstörung geschützt werden sollen, Klebstoffe, Leime, Papier und Karton, Textilien, Leder, Holz, Anstrichmittel und Kunststoffartikel, Kühlschmierstoffe und andere Materialien sein, die von Mikroorganismen befallen oder zersetzt werden können. Im Rahmen der zu schützenden Materialien seien auch Teile von Produktionsanlagen, beispielsweise Kühlwasserkreisläufe, genannt, die durch Vermehrung von Mikroorganismen beein¬ trächtigt werden können. Im Rahmen der vorliegenden Erfindung seien als technische Materialien vorzugsweise Klebstoffe, Leime, Papiere und Kartone, Leder, Holz, Anstrichmittel, Kühlschmiermittel und Wärmeübertragungsflüssigkeiten genannt, besonders bevorzugt Anstrichmittel.In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be attacked or decomposed by microorganisms . In the context of the materials to be protected, parts of production plants, for example cooling water circuits, may also be mentioned which can be impaired by the multiplication of microorganisms. Within the scope of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably paints.
Als Mikroorganismen, die einen Abbau oder eine Veränderung der technischen Materialien bewirken können, seien beispielsweise Bakterien, Pilze, Hefen, Algen und Schleimorganismen genannt. Vorzugsweise wirken die erfindungsgemäßen Wirk- Stoffe bzw. Mittel gegen Pilze, insbesondere Schimmelpilze, holzverfärbende und holzzerstörende Pilze (Basidiomyceten) sowie gegen Schleimorganismen und Algen.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 substances or agents according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
Es seien beispielsweise Mikroorganismen der folgenden Gattungen genannt: Alternaria, wie Alternaria tenuis, Aspergillus, wie Aspergillus niger, Chaetomium, wie Chaetomium globosum, Coniophora, wie Coniophora puetana, Lentinus, wie Lentinus tigrinus, Penicillium, wie Penicillium glaucum, Polyporus, wie Polyporus versicolor, Aureobasidium, wie Aureobasidium pullulans, Sclerophoma, wie Sclerophoma pityophila, Trichoderma, wie Trichoderma viride, Escherichia, wie Escherichia coli, Pseudomonas, wie Pseudomonas aeruginosa, Staphylococcus, wie Staphylococcus aureus.For example, 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, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Pechichomonas, such as Escherichiaiaosine, such as Escherichia, as well as like Staphylococcus aureus.
Die Wirkstoffe der Formel (I) und (II) können in Abhängigkeit von ihren jeweiligen physikalischen und/oder chemischen Eigenschaften in übliche Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate, Aerosole und Feinstverkapselungen in polymeren Stoffen.Depending on their respective physical and / or chemical properties, the active compounds of the formulas (I) and (II) can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances .
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehen¬ den verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwen¬ dung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermit¬ teln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel ver- wendet werden. Als flüssige Lösungsmittel kommen im wesentlichen infrage: Aroma- ten, wie Xylol, Toluol, Alkylnaphthaline, chlorierte Aromaten oder chlorierte alipha- tische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene, oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktio¬ nen, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lö¬ sungsmittel, wie Dimethylformamid oder Dimethylsulfoxid, sowie Wasser; mit ver¬ flüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten ge¬ meint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe kommen infrage: z.B. natürliche Gesteins¬ mehle, wie Kaoline, Tonerden, Talkum, Kreide, Quartz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate kommen infrage' z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier- und/oder schaumerzeugende Mittel kommen infrage: z.B. nicht ionogene und anionische Emulgatoren, wie Polyoxyethy- len-Fettsäureester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkylarylpolyglykolether, Alkyl sulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergier¬ mittel kommen infrage: z.B. Ligninsulfitablaugen und Methyl cellulose.These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, under pressure the liquefied gases and / or solid carriers, if appropriate 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. The following are essentially suitable as liquid solvents: aromas, 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 their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules come into question ' eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische, pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholi- pide, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.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.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocy- anblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyaninfarb- stoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.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 are used.
Bevorzugt werden die erfindungsgemäßen Wirkstoffe der Formel (II) und die Verbindungen der Formel (I) zum Schutz von Anstrichen gegen Befall und Zerstörung durch unerwünschte Mikroorganismen eingesetzt.The active compounds of the formula (II) and the compounds of the formula (I) are preferably used to protect paints against attack and destruction by undesired microorganisms.
Unter Anstrich ist im vorliegenden Zusammenhang eine aus Anstrichstoffen hergestellte Beschichtung auf einem Untergrund zu verstehen. Der Anstrich kann mehr oder weniger in den Untergrund eingedrungen sein. Er kann aus einer oder mehreren Schichten bestehen und durch Verfahren wie Streichen, Spritzen, Tauchen, Fluten oder ähnliche Verfahren hergestellt werden.In the present context, painting is to be understood as meaning a coating made of paints on a substrate. The paint may have penetrated more or less into the surface. It can consist of one or more layers and can be produced by processes such as brushing, spraying, dipping, flooding or similar processes.
Die Verbindungen der Formeln (I) und (II) werden in die Anstrichmittel oder in Vorprodukte zur Herstellung der Anstrichmittel nach üblichen Methoden, z.B. durch Vermischen der Wirkstoffe mit den anderen Komponenten, eingearbeitet. Erfindungsgemäße Anstrichmittel enthalten daher neben mindestens einem fungiziden Wirkstoff der Formel (I) und/oder (II) allgemein übliche Anstrichkomponenten in z.B. flüssiger, pastöser oder pulverförmiger Form wie z.B.The compounds of the formulas (I) and (II) are incorporated into the paints or into precursors for the preparation of the paints by customary methods, for example by mixing the active ingredients with the other components. Paints according to the invention therefore contain, in addition to at least one fungicidal active ingredient of the formula (I) and / or (II), generally customary paint components in, for example, liquid, pasty or powdery form, for example
Farbmittel, wie Pigmente oder Farbstoffe, bevorzugt Pigmente. Beispielsweise genannt sei Titandioxid, Zinkoxid und Eisenoxid.Colorants, such as pigments or dyes, preferably pigments. Examples include titanium dioxide, zinc oxide and iron oxide.
Bindemittel, wie beispielsweise oxidativ trocknende Alkydharze, Vinylpoly- merisate und Vinylcopolymerisate, Acrylpolymerisate und Acrylcopoly- merisate, Kunststoffpulver, Novolacke, Aminoharze, Polyesterharze, Epoxidharze, Silikonharze, Isocyanatharze bevorzugt sind Vinylpolymerisate und Vinylcopolymerisate, Acrylpolymerisate und Acrylcopolymerisate und andere in Wasser verdünnbaren Anstrichstoffen verwendbare Bindemittel.Binders, such as, for example, oxidatively drying alkyd resins, vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers, plastic powders, novolaks, amino resins, polyester resins, epoxy resins, silicone resins, isocyanate resins, vinyl polymers and vinyl copolymers, water-borne polymers and acrylic copolymers and other copolymers used are preferred and acrylic copolymers and other copolymers used .
Daneben enthalten die Anstriche gegebenenfalls folgende ZusatzstoffeThe paints may also contain the following additives
Füllstoffe, wie beispielsweise Schwerspat, Calcit, Dolomit und Talk,Fillers such as heavy spar, calcite, dolomite and talc,
Lösemittel, wie beispielsweise Alkohole, Ketone, Ester, Glykolether und aliphatische sowie aromatische Kohlenwasserstoffe,Solvents, such as alcohols, ketones, esters, glycol ethers and aliphatic and aromatic hydrocarbons,
sowie Verdickungs- und Thixotropiermittel, Dispergier-und Netzmittel, Trockenstoffe, Hautverhütungsmittel, Verlaufmittel, Antischaummittel, Korro¬ sionsinhibitoren, UV-Absorber, Duftstoffe, Antistatika, Frostschutzmittel.as well as thickening and thixotropic agents, dispersants and wetting agents, drying agents, skin-preventing agents, leveling agents, anti-foaming agents, corrosion inhibitors, UV absorbers, fragrances, antistatic agents, antifreeze agents.
Als Anstrichmittel bzw. Vorprodukte zur Herstellung von Anstrichmitteln seien vorzugsweise folgende genannt:The following may preferably be mentioned as paints or precursors for the production of paints:
Leime und Klebstoffe auf Basis der bekannten tierischen, pflanzlichen oder synthetischen Rohstoffe.Glues and adhesives based on the well-known animal, vegetable or synthetic raw materials.
Kunststoffdispersionen wie Latexdispersionen oder Dispersionen auf Basis anderer Polymere. - Stärkelösungen, -dispersionen oder -slurries oder andere auf Basis von Stärke hergestellte Produkte wie z.B. Druckverdicker. Slurries anderer Rohstoffe wie Farbpigmente (z.B. Eisenoxidpigmente, Rußpigmente, Titandioxidpigmente) oder Slurries von Füllstoffen wie Kaolin oder Calciumcarbonat.Plastic dispersions such as latex dispersions or dispersions based on other polymers. - Starch solutions, dispersions or slurries or other starch-based products such as pressure thickeners. Slurries of other raw materials such as color pigments (eg iron oxide pigments, carbon black pigments, titanium dioxide pigments) or slurries of fillers such as kaolin or calcium carbonate.
Betonadditive beispielsweise auf Basis von Melasse oder Ligninsulfonaten. - Bitumenemulsionen.Concrete additives, for example based on molasses or lignin sulfonates. - bitumen emulsions.
Vor- und Zwischenprodukte der chemischen Industrie, z.B. bei der Farbstoffproduktion und -lagerung. Tinten oder Tuschen.Preliminary and intermediate products of the chemical industry, e.g. in dye production and storage. Inks or inks.
Dispersionsfarben für die Anstrichindustrie. - Schichten und Appreturen.Dispersion paints for the painting industry. - coats and finishes.
Die Wirksamkeit und das Wirkungsspektrum der Wirkstoffe der Formeln (I) und (II) bzw. die daraus herstellbaren Mittel, Vorprodukte oder ganz allgemein Formulie¬ rungen wird erhöht, wenn gegebenenfalls weitere antimikrobiell wirksame Verbindungen, Fungizide, Bakterizide, Herbizide, Insektizide oder andere Wirkstoffe zur Vergrößerung des Wirkungsspektrums oder Erzielung besonderer Effekte wie z.B. des zusätzlichen Schutzes vor Insekten zugesetzt werden. Diese Mischungen besitzen ein breiteres Wirkungsspektrum als die erfindungsgemäßen Verbindungen.The effectiveness and the spectrum of activity of the active compounds of the formulas (I) and (II) or the agents, precursors or very generally formulations which can be prepared therefrom is increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active compounds are used to enlarge the spectrum of effects or achieve special effects such as added protection against insects. These mixtures have a broader spectrum of activity than the compounds according to the invention.
In vielen Fällen erhält man dabei synergistische Effekte, d.h. die Wirksamkeit der Mischung ist größer als die Wirksamkeit der Einzelkomponenten. Besonders günstige Mischungspartner sind z.B. die folgenden Verbindungen:In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components. Particularly favorable mix partners are e.g. the following connections:
Triazole wie:Triazoles such as:
Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazole, Isozofos, Myclobutanil, Metconazole, Epoxyconazole, Paclobutrazol, Penconazole, Propioconazole, (±)-cis- 1 -(4-chlorphenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-cy cloheptanol, Tetraconazole, Triadimefon, Triadimenol, Triapenthenol, Triflumizole, Triticonazole, Uniconazole sowie deren Metallsalze und Säureaddukte.Amitrole, azocyclotine, BAS 480F, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, metconazole, epoxyconazole, paclobutrazole () chlorphenyl) -2- (1 H- 1, 2,4-triazol- 1 -yl) -cy cloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.
Imidazole wie:Imidazoles such as:
Imazalil, Pefurazoate, Prochloraz, Triflumizole, 2-(l-tert-Butyl)-l-(2-chlorphenyl)-3- (l,2,4-triazol-l-yl)-propan-2-ol, Thiazolcarboxanilide wie 2',6'-Dibromo-2-methyl-4- trifluoromethoxy-4'-trifluoromethyl-l,3-thiazole-5-carboxanilide, l-Imidazolyl-l-(4'- chlorophenoxy)-3,3-dimethylbutan-2-on sowie deren Metallsalze und Säureaddukte.Imazalil, pefurazoate, prochloraz, triflumizole, 2- (l-tert-butyl) -l- (2-chlorophenyl) -3- (l, 2,4-triazol-l-yl) -propan-2-ol, thiazole carboxanilides such as 2 ', 6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide, l-imidazolyl-l- (4'- chlorophenoxy) -3,3-dimethylbutan-2-one and their metal salts and acid adducts.
Methyl(E)-2-[2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate, methyl(E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacryla- teξiethyl(E)-2-[2-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate; meti yl(E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate; methyl(E)-2-[2-[3-( yrimidin-2-yloxy)phenoxy]phenyl]-3-methoxyacryla__)ethyl(E)- 2-[2-[3-(5-me1_aylpyrimidin-2-yloxy)-phenoxy]phenyl]-3-methoxyacrylatepιethyl(E)- 2-[2-[3-(phenyl-sulfonyloxy)phenoxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[3- (4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-phenoxyphenyl]- 3-methoxyacrylate, methyl(E)-2-[2-(3,5-dimethylbenzoyl)pyrrol-l-yl]-3- methoxyacrylate, methyl(E)-2-[2-(3-methoxyphenoxy)phenyl]-.3-methoxyacrylate, methyl(E)-2-[2-(2-phenylethen-l-yl)-ρhenyl]-3-methoxyacrylatepιethyl(E)-2-[2-(3,5- dichlorophenoxy)pyridin-3-yl]-3-methoxyacrylate, methyl(E)-2-(2-(3-(l,l,2,2- tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate,methyl(E)-2-(2-[3-(alpha- hydroxybenzyl)phenoxy]phenyl)-3-methoxyacrylate, methyl(E)-2-(2-(4-phenoxy- pyridin-2-yloxy)phenyl)-3-methoxyacrylatemethyl(E)-2-[2-(3-n-propyloxyphenoxy)- phenyl]3-methoxyacrylate, methyl(E)-2-[2-(3-isopropyloxyphenoxy)phenyl]-3-meth- oxyacrylat«Jjethyl(E)-2-[2-[3-(2-fluorophenoxy)pehnoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3-ethoxyphenoxy)phenyl]-3-methoxyacrylatarιethyl(E)-2-[2-(4-tert.- butylpyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(3- cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylatajιethyl(E)-2-[2-(3-methylpyridin- 2-yloxymethyl)phenyl]-3-methoxyacrylategaethyl(E)-2-[2-[6-(2-methylphenoxy)pyri- midin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-(5-bromopyridin-2-yloxy- methyl)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3-(3-iodopyridin-2-yloxy)phen- oxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimi- din-4-yloxy]phenyl]-3-methoxyacrylate, (E ,(E)methyl-2-[2-(5,6-dimethylpyrazin-2- ylmethyloximinomethyl)phenyl]-3-methoxyacrylate(E)-methyl-2-{2-[6-(6-methylpy- ridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, (E),(E)methyl-2-{2-(3- methoxyphenyl)methyloximinomethyl]phenyl}-3-methoxyacrylat^E)methyl-2-{2-(6- (2-azidophenoxy)-pyrimidin-4-yloxy]phenyl}3-methoxyacrylate,(E),(E)methyl-2-{2- [6-phenylpyrimidin-4-yl)-methyloximinomethyl]phenyl}-3-methoxyacrylate, (E),(E)methyl-2-{2-[(4-chlorophenyl)-methyloximinomethyl]phenyl } -3 -methoxyacry- late, (E)methyl-2-{2-[6-(2-n-propylphenoxy)-l,3,5-triazin-4-yloxy]phenyl}-3-methoxy- acrylate, (E),(E)methyl-2-{2-[(3-nitrophenyl)methyloximinomethyl]phenyl}-3-meth- oxyacrylate;Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylates, methyl (E) -2- [2- [6- (2-thioamidophenoxy) pyrimidine- 4-yloxy] phenyl] -3-methoxyacrylate ethyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates ; methyl (E) -2- [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates ; methyl (E) -2- [2- [3- (yrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacryla __) ethyl (E) - 2- [2- [3- (5-me1_aylpyrimidin-2-yloxy ) -phenoxy] phenyl] -3-methoxyacrylatepιethyl (E) - 2- [2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- ( 4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dimethylbenzoyl) pyrrole-1 -yl] -3- methoxyacrylate, methyl (E) -2- [2- (3-methoxyphenoxy) phenyl] -. 3-methoxyacrylate, methyl (E) -2- [2- (2-phenylethen-l-yl) -ρhenyl] -3-methoxyacrylatepιethyl (E) -2- [2- (3,5- dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl (E) -2- (2- (3- (l, 1,2,2-tetrafluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate, methyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate, methyl (E) -2 - (2- (4-phenoxy-pyridin-2-yloxy) phenyl) -3-methoxyacrylate methyl (E) -2- [2- (3-n-propyloxyphenoxy) phenyl] 3-methoxyacrylate, methyl (E) -2 - [2- (3-isopropyloxyphenoxy) phenyl] -3-meth-oxyacrylate «Jjethyl (E) -2- [2- [3- (2-fluorophenoxy) pehnoxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- (3-ethoxyphenoxy) phenyl] -3-methoxyacrylatarethyl (E) -2- [2- (4-tert-butylpyridin-2-yloxy ) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (3-cyanophenoxy) phenoxy] phenyl] -3-methoxyacrylataethyl (E) -2- [2- (3-methylpyridine-2- yloxymethyl) phenyl] -3-methoxyacrylate ethyl (E) -2- [2- [6- (2-methylphenoxy) pyriminin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (5-bromopyridin-2-yloxy-methyl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxyacrylate , methyl (E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidine-4-yloxy] phenyl] -3-methoxyacrylate, (E, (E) methyl-2- [2 - (5,6-Dimethylpyrazin-2-ylmethyloximinomethyl) phenyl] -3-methoxyacrylate (E) -methyl-2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] phenyl } -3-methoxyacrylates, (E), (E) methyl-2- {2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate ^ E) methyl-2- {2- (6- (2-azidophenoxy ) -pyrimidin-4-yloxy] phenyl} 3-methoxyacrylate, (E), (E) methyl-2- {2- [6-phe nylpyrimidin-4-yl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E), (E) methyl-2- {2 - [(4-chlorophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E ) methyl-2- {2- [6- (2-n-propylphenoxy) -1, 3,5-triazin-4-yloxy] phenyl} -3-methoxy-acrylate, (E), (E) methyl-2 - {2 - [(3-nitrophenyl) methyloximinomethyl] phenyl} -3-meth- oxyacrylates;
Succinat-Dehydrogenase Inhibitoren wie:Succinate dehydrogenase inhibitors such as:
Fenfuram, Furcarbanil, Cyclafluramid, Furmecyclox, Seedvax, Metsulfovax, Pyro- carbolid, Oxycarboxin, Shirlan, Mebenil (Mepronil), Benodanil, Flutolanil (Moncut); Naphthalin-Derivate wie Terbinafine, Naftifine, Butenafine, 3-Chloro-7-(2-aza-2,7,7- trimethyl-oct-3-en-5-in);Fenfuram, furcarbanil, cyclafluramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (moncut); Naphthalene derivatives such as terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-in);
Sulfenamide wie Dichlofluanid, Tolylfluanid, Folpet, Fluorfölpet; Captan, Captofol;Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorofolpet; Captan, Captofol;
Benzimidazole wie Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonat- methyl, Thiabendazole oder deren Salze; Morpholinderivate wie Tridemorph, Fenpropimorph, Falimorph, Dimethomorph,Benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonat-methyl, Thiabendazole or their salts; Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph,
Dodemorph, Aldimorph, Fenpropidin und ihre arylsulfonsauren Salze, wie z.B. p-Dodemorph, aldimorph, fenpropidine and their arylsulfonic acid salts such as e.g. p-
Toluolsulfonsäure und p-Dodecylphenyl-sulfonsäure;Toluenesulfonic acid and p-dodecylphenyl sulfonic acid;
Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam,Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam,
Metiram, Thiram Zeneb, Ziram; Benzthiazole wie 2-Mercaptobenzothiazol;Metiram, Thiram Zeneb, Ziram; Benzothiazoles such as 2-mercaptobenzothiazole;
Benzamide wie 2,6-Dichloro-N-(4-trifluoromethylbenzyl)-benzamide;Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide;
Borverbindungen wie Borsäure, Borsäureester, Borax;Boron compounds such as boric acid, boric acid ester, borax;
Formaldehyd und Formaldehydabspaltende Verbindungen wie Benzylalkoholmono-Formaldehyde and formaldehyde releasing compounds such as benzyl alcohol mono-
(poly)-hemiformal, Oxazolidine, Hexa-hydro-S-triazine, N-Methylolchloracetamid, Paraformadehyd, Nitropyrin, Oxolinsäure, Tecloftalam;(poly) hemiformal, oxazolidine, hexa-hydro-S-triazine, N-methylolchloroacetamide, paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;
Tris-N-(cyclohexyldiazeniumdioxy)-aluminium,N-(Cyclo-hexyldiazeniumdioxy)-tri- butylzinn bzw. K-Salze, Bis-N-(cyclohexyldiazeniumdioxy)-kupfer;Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclo-hexyldiazeniumdioxy) tri-butyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper;
N-Methylisothiazolin-3-on,5-Chlor-N-methylisothiazolin-3-on,4,5-Dichloro-N-octyl- isothiazolin-3-on, N-Octyl-isothiazolin-3-on, 4,5-Trimethylen-isothiazolinone, 4,5- Benzisothiazolinone, N-Methylolchloracetamid;N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octyl-isothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5- Trimethylene-isothiazolinone, 4,5-benzisothiazolinone, N-methylolchloroacetamide;
Aldehyde wie Zimtaldehyd, Formaldehyd, Glutardialdehyd, ß-Bromzimtaldehyd;Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde;
Thiocyanate wie Thiocyanatomethylthiobenzothiazol, Methylenbisthiocyanat, usw; quartäre Ammoniumverbindungen wie Benzyldimethyltetradecylammoniumchlorid,Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc; quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride,
Benzyldimethyldodecylammoniumchlorid, Didecyldimethaylammoniumchlorid; lodderivate wie Diiodmethyl-p-tolylsulfon, 3-Iod-2-propinyl-alkohol, 4-Chlorphenyl-Benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride; Iodine derivatives such as diiodomethyl p-tolyl sulfone, 3-iodine-2-propynyl alcohol, 4-chlorophenyl
3-iodpropargylformal, 3-Brom-2,3-diiod-2-propenylethylcarbamat, 2,3,3-Triiodallyl- alkohol, 3-Brom-2,3-diiod-2-propenylalkohol, 3-Iod-2-propinyl-n-butylcarbamat, 3-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl alcohol n-butyl carbamate, 3-
Iod-2-propinyl-n-hexylcarbamat, 3-Iod-2-propinyl-cyclohexylcarbamat, 3-Iod-2-pro- pinyl-phenylcarbamat; Phenolderivate wie Tribromphenol, Tetrachlorphenol, 3-Methyl-4-chlorphenol, 3,5- Dimethyl-4-chlorphenol, Phenoxyethanol, Dichlorphen, o-Phenylphenol, m-Phenyl- phenol, p-Phenylphenol, 2-Benzyl-4-chlorphenol und deren Alkali- und Erdalkali¬ metallsalze; Mikrobizide mit aktivierter Halogengruppe wie Chloracetamid, Bronopol, Bronidox, Tectamer wie 2-Brom-2-nitro-l,3-propandiol, 2-Brom-4'-hydroxy-acetophenon, 2,2- Dibrom-3-nitril-propionamid, 1 ,2-Dibrom-2,4-dicyanobutan, ß-Brom-ß-nitrostyrol; Pyridine wie l-Hydroxy-2-pyridinthion (und ihre Na-, Fe-, Mn-, Zn-Salze), Tetrachlor-4-methylsulfonylpyridin, Pyrimethanol, Mepanipyrim, Dipyrithion, 1- Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(lH)-pyridin;Iodine-2-propynyl-n-hexylcarbamate, 3-iodine-2-propynylcyclohexylcarbamate, 3-iodine-2-propynylphenylcarbamate; Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali and alkaline earth metal salts; Microbicides with activated halogen group such as chloroacetamide, bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene; Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, 1-hydroxy-4-methyl-6- (2nd , 4,4-trimethylpentyl) -2 (1H) pyridine;
Metallseifen wie Zinn-, Kupfer-, Zinknaphtenat, -octoat, 2-ethylhexanoat, -oleat, -phosphat, -benzoat;Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
Metallsalze wie Kupferhydroxycarbonat, Natriumdichromat, Kaliumdichromat, Kaliumchromat, Kupfersulfat, Kupferchlorid, Kupferborat, Zinkfluorosilikat, Kupfer- fluorosilikat;Metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;
Oxide wie Tributylzinnoxid, Cu2O, CuO, ZnO;Oxides such as tributyltin oxide, Cu 2 O, CuO, ZnO;
Dialkyldithiocarbamate wie Na- und Zn-Salze von Dialkyldithiocarbamaten,Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates,
Tetramethylthiuramdisulfid, Kalium-N-methyl-dithiocarbamat;Tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;
Nitrilewie2,4,5,6-Tetrachlorisophthalodinitril,Dinatrium-cyano-dithioimidocarbamat; Chinoline wie 8-Hydroxychinolin und deren Cu-Salze; Mucochlorsäure, 5-Hydroxy-2(5H)-furanon;Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate; Quinolines such as 8-hydroxyquinoline and their Cu salts; Mucochloric acid, 5-hydroxy-2 (5H) furanone;
4,5-Dichlorodithiazolinon, 4,5-Benzdithiazolinon, 4,5-Trimethylendithiazolinon, 4,5- Dichlor-(3H)-l,2-dithiol-3-on, 3,5-Dimethyl-tetrahydro-l,3,5-fhiadiazin-2-thion, N-(2-p-Chlorbenzoylethyl)-hexaminiumchloridJvalium-N-hydroxymethyl-N'-methyl- dithiocarbamat,4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-dichloro- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetrahydro-l, 3, 5-fhiadiazin-2-thione, N- (2-p-chlorobenzoylethyl) hexaminium chloride Jvalium-N-hydroxymethyl-N'-methyldithiocarbamate,
2-Oxo-2-(4-hydroxy-phenyl)acethydroximsäure-chlorid,2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride,
Phenyl-(2-chlor-cyan-vinyl)sulfon,Phenyl- (2-chloro-cyano-vinyl) sulfone,
Phenyl-( 1 ,2-dichlor-2-cyan-vinyl)sulfon;Phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone;
Ag, Zn oder Cu-haltige Zeolithe allein oder eingeschlossen in polymere WirkstoffeZeolites containing Ag, Zn or Cu alone or included in polymeric active substances
Ganz besonders bevorzugt sind Mischungen mitMixtures with are very particularly preferred
Azaconazole, Bromuconazole, Cyproconazole, Dichlobutrazol, Diniconazole, Hexa- conazole, Metaconazole, Penconazole, Propiconazole, Tebuconazole, Methyl-(E)- methoximino[α-(o-tolyloxy)-o-tolyl)]acetate ethyl-(E)-2-{2-[6-(2-cyanphenoxy)-py- rimidin-4-yl-oxy]phenyl}-3-methoxyacrylat, Methfuroxam, Carboxin, Fenpiclonil, 4- (2,2-Difluoro-l,3-benzodioxol-4-yl)-lH-pyrrol-3-carbonitril, Butenafine, Imazalil, N- Methyl-isothiazolin-3-on, 5-Chlor-N-methylisothiazolin-3-on, N-Octylisothiazolin-3- on, Benzisothiazolinone, N-(2-Hydroxypropyl)-amino-methanol, Benzylalkohol- (hemi)-formal, Glutaraldehyd, Omadine, Dimethyldicarbonat, und/oder 3-Iodo-2-pro- pinyl-n-butylcarbamate.Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl- (E) - methoximino [α- (o-tolyloxy) -o-tolyl)] acetate ethyl- (E) - 2- {2- [6- (2-cyanophenoxy) -py-rimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4- (2,2-difluoro-l, 3-benzodioxol-4-yl) -lH-pyrrole-3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3- on, N-octylisothiazolin-3-one, benzisothiazolinone, N- (2-hydroxypropyl) amino-methanol, benzyl alcohol (hemi) formal, glutaraldehyde, omadine, dimethyl dicarbonate, and / or 3-iodo-2-propynyl -n-butyl carbamates.
Desweiteren werden auch gut wirksame Mischungen mit den folgenden Wirkstoffen hergestellt:Furthermore, well-effective mixtures with the following active ingredients are also produced:
Fungizide:Fungicides:
Acypetacs, 2-Aminobutane, Ampropylfos, Anilazine, Benalaxyl, Bupirimate, Chinomethionat, Chloroneb, Chlozolinate, Cymoxanil, Dazomet, Diclomezine, Dichloram, Diethofencarb, Dimethirimol, Diocab, Dithianon, Dodine, Drazoxolon, Edifenphos, Ethirimol, Etridiazole, Fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobenfos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadiyl, Perflur- azoate, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichlamide, Tricyclazole, Triforine, Vinclozolin.Acypetacs, 2-aminobutane, Ampropylfos, anilazine, benalaxyl, Bupirimate, chinomethionat, chloroneb, chlozolinate, cymoxanil, dazomet, Diclomezine, Dichloram, diethofencarb, dimethirimol, Diocab, dithianon, dodine, Drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Perateurolol, Nuarimurololimurolimolarimurololimarolimololimolurimololimolurimololimurolimolarolimolurimololimolurimololimurolimolurimololimolurimolurololimolurimololimolurimololimolurimololimolurimolurololimurolimolurimolololate Pencycuron, phosdiphen, pimaricin, piperalin, procymidone, propamocarb, propineb, pyrazophos, pyrifenox, pyroquilon, quintozene, tar oils, tecnazene, thicyofen, thiophanate-methyl, tolclofos-methyl, triazoxide, trichlamine, tricyzolinzole, tricyzolinzole.
Insektizide:Insecticides:
Phosphorsäureester wie Azinphos-ethyl, Azinphos-methyl, α-l(4-Chlorphenyl)-4-(O- ethyl, S-propyl)phosphoryloxy-pyrazol, Chlorpyrifos, 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 und Trichlorphon;Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, 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 Trichlorphon;
Carbamate wie Aldicarb, Bendiocarb, α-2-(l-Methylpropyl)-phenylmethylcarbamat, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur und Thiodicarb; Organosiliciumverbindungen,vorzugsweiseDimethyl(phenyl)silyl-methyl-3-phenoxy- benzylether wie Dimethyl-(4-ethoxyphenyl)-silylmethyl-3-phenoxybenzylether oder (Dimethylphenyl)-silyl-methyl-2-phenoxy-6-pyridylmethyletherwiez.B.Dimethyl-(9- ethoxy-phenyl)-silylmethyl-2-phenoxy-6-pyridylmethylether oder [(Phenyl)-3-(3- phenoxyphenyl)-propyl](dimethyl)-silane wie z.B. (4-Ethoxyphenyl)-[3-(4-fluoro-3- phenoxyphenyl-propyl]dimethyl-silan, Silafluofen;Carbamates such as aldicarb, bendiocarb, α-2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb; Organosilicon compounds, preferably dimethyl (phenyl) silyl-methyl-3-phenoxy-benzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) -silyl-methyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl (9- ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) -propyl] (dimethyl) -silanes such as (4-ethoxyphenyl) - [3- (4-fluoro -3-phenoxyphenyl-propyl] dimethyl silane, silafluofen;
Pyrethroide wie Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3- phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chlor-2-trifluor-methylvinyl)cyclopropan- carboxylat, Fenpropathrin, Fenfluthrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate, Permethrin, Resmethrin und Tralomethrin; Nitroimine und Nitromethylene wie l-[(6-Chlor-3-pyridinyl)-methyl]-4,5-dihydro-N- nitro-lH-imidazol-2-amin (Imidacloprid), N-[(6-Chlor-3-pyridyl)methyl-]N2-cyano- N^methylacetamide (NI-25);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-trif -methylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin; Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-lH-imidazol-2-amine (imidacloprid), N - [(6-chloro-3 -pyridyl) methyl-] N 2 -cyano- N ^ methylacetamide (NI-25);
Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethrins, Pyridaben, Pyridafenthion, Pyriproxyfen, Quinalphos, RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl- pyrimidin-5-yl-o-isopropyl-phosphorothiate, Thiocyclam, Thiofanox, Thiometon, Tralomethrin, Triflumuron, Trimethacarb, Vamidothion, Verticillium Lacanii, XMC, Xylylcarb, Benfuracarb, Bensultap, Bifenthrin, Bioallethrin, MERbioallethrin (S)- cyclopentenyl isomer, Bromophos, Bromophos-ethyl, Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionat, Chlordane, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha-cypermethrin, Cyophenothrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphon, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Esfenvalerate, Ethiofencarb, Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, IPSP, Isazofos, Isofenphos, Isoprothiolane, Isoxathion, Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous, Chloride, Metam, Metarthizium, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Omethoate, Oxydemeton-methyl, Pentachlorophenol, Petroleum oils, Phenothrin, Phenthoate, Phorate;Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethriproxyphid, Pyrethridafid, Pyrethridafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafide, RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl -phosphorothiate, thiocyclam, thiofanox, thiometone, tralomethrin, triflumuron, trimethacarb, vamidothion, verticillium lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioomerophenoz, bromine, cyclophone, bromophosphate, bromophosphate Calcium polysulfide, carbophenothione, cartap, quinomethionate, chlordane, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-cyfluthrin, alpha-cypermethrin, cyophene othrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Etobucarboxate, Ethenucarboxate, Ethfenucarboxate, Ethfenucarboxate, Ethfenucarboxate, Ethenucarboxate, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, IPSP, Isazofos, Isofenphos, Isoxathioniol, Isoprothiolane , Mephosfolan, Mercurous, Chloride, Metam, Metarthizin, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPeth-Methylophen, Oxophen, Oxotine, Nicotine, Nicotine Oxophenol Petroleum oils, phenothrin, phenthoates, phorates;
Molluscicide:Molluscicide:
Fentinacetate, Metaldehyde, Methiocarb. Niclosamide, Thiodicarb, Trimethacarb.Fentin acetates, metaldehydes, methiocarb. Niclosamide, thiodicarb, trimethacarb.
Algicide: Coppersulfate, Dichlororphen, Endothal, Fentinacetate, Quinoclamine.Algicide: Coppersulfate, dichlororphen, Endothal, Fentinacetate, Quinoclamine.
Herbicides:Herbicides:
acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, bensulfide, bentazone, benzofencap, benzthiazuron, bifenox, bilanafos, borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butamifos, fuenachlor, butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen, chloramben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone, clomeprop, clopyralid, cyanamide, cyanazine, dinoseb acetate, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluoroxypyr, cycloate, cycloxydim, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicamba, dichlorbenil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA- thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachlor, methabenzthiazuron, methazole, methoproptryne, methyldymron, methylisothiocyanate, metobromuron, fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, imazaquin, imazethapyr, ioxynil, isoprppalin, propyzamide, prosulfocab, pyrazolynate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate, quinclorac, quinmerac, quinocloamine, quizalofop, quzizalofop-P, S-23121, sethoxydim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA, metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide, monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, pentachlorophenol, pentaochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodiamine, proglinazine, propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifensulfüron, thiobencarb, thiocarbazil, tioclorim, tralkoxydim, tri-allate, triasulfuron, tribenzuron, triclopyr, tridiphane, trietazine, trifluralin, IBI-C4874 veraolate, propanil, propaquizafop, propazine, propham.acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, bensulfide, benzafthoxane, benzafone, benzafone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzafone, benzazone, benzazone benzax dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromynoxoxiloxyloxomiloxilyl, bromomoxililoxyl bromoboxane butamifos, fuenachlor, butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen, chloramben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone, clomeprop, clopyralid, cyanamide, cyanazine, dinoseb acetate, dinoterb, diphenamide, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop , flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluoroxypyr, cycloate, cycloxydim, 2,4-D, daimuron, dalapon, DB, desometham, 2.4 , desmetryn, dicamba, dichlorbenil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA- thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metachiazole meth , methoproptryne, methyldymron, methylisothiocyanate, metobromuron, fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, imazaquin, imazethapyr, ioxynil, isoprppalin, propabzamide, prosulfate pyrazolynate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate, quinclorac, quinmerac, quinocloamine, quizalofop, quzizalofop-P, S-23121, sethoxydim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfachloronuron, sulfometuronurol , metribzin, metsulfuron, molinate, monalide, monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pentulate chlorophenylphenolchlorophenylchlorophenylchlorophene, pentimethane phenylchlorophenol, pentamine chloride picloram, piperophos, pretilachlor, primisulfuron, prodiamine, proglinazine, propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifensulfüron, thiobenazim, trioxarbon, trioxarbon, thioxarbon, thioxarbon, thioxarbon, thioxarbon, thioxazarbil, thioxarbon, thioxarbon, thioxarbon, thioxarbon, thioxazarbil, tri triclopyr, tridiphane, trietazine, trifluralin, IBI-C4874 veraolate, propanil, propaquizafop, propazine, propham.
Die Gewichtsverhältnisse der Wirkstoffe in diesen Wirkstoffkombinationen können in relativ großen Bereichen variiert werden.The weight ratios of the active ingredients in these active ingredient combinations can be varied within relatively large ranges.
Vorzugsweise erhalten die Wirkstoffkombinationen den Wirkstoff zu 0,1 bis 99,9 %, insbesondere zu 1 bis 75 %, besonders bevorzugt 5 bis 50 %, wobei der Rest zu 100 % durch einen oder mehrere der obengenannten Mischungspartner ausgefüllt wird.The active compound combinations preferably contain from 0.1 to 99.9%, in particular from 1 to 75%, particularly preferably from 5 to 50%, the rest being filled 100% by one or more of the above-mentioned mixing partners.
Die vorliegende Erfindung betrifft zudem neue, insbesondere wäßrige und gegebe¬ nenfalls organisch-lösungsmittel- und emulgatorfreie mikrobizide Wirkstoffkombina¬ tionen der Alkyl-N-azole der Formel (I) und quartären Ammoniumfungiziden.The present invention also relates to new, in particular aqueous and optionally organic, solvent-free and emulsifier-free microbicidal combinations of active ingredients of the alkyl-N-azoles of the formula (I) and quaternary ammonium fungicides.
Die geringe Wasserlöslichkeit von Azolen begrenzt deren Einsatz in einigen Anwendungsgebieten wie z.B. Leder, wasserbasierter Holzschutz, Desinfektion, Kühlwasserbehandlung, Papierindustrie, Metallverarbeitung, technische Konservierung wasserhaltiger Produkte eingeschränkt oder nicht möglich.The low water solubility of azoles limits their use in some areas of application such as Leather, water-based wood protection, disinfection, cooling water treatment, paper industry, metal processing, technical preservation of water-containing products are restricted or not possible.
Quartäre Ammoniumsalze sind als breit wirksame Mikrobizide seit langem bekannt und finden z.B. Anwendung in der Desinfektion und Textilkonservierung.Quaternary ammonium salts have long been known as broadly effective microbicides and find e.g. Use in disinfection and textile preservation.
Zwar sind diese Wirkstoffe meistens gut wasserlöslich, neigen aber bei den Anwen- dungskonzentrationen zu starker Schaumbildung, die in vielen Einsatzfeldern stört. Außerdem können sie aufgrund ihrer kationenaktiven Eigenschaften mit anionischen Komponenten wie Seifen, Tensiden etc. reagieren. Dadurch kann ihr Eigenschaftsprofil negativ beeinflußt werden, bzw. können sie desaktiviert werden. Desweiteren ist bekannt, daß quartäre Ammoniumsalze durch die Anwesenheit von Eiweiß und Schmutz leicht desaktiviert werden.Although these active substances are mostly readily water-soluble, they tend to concentration too much foam, which is a nuisance in many fields of application. In addition, due to their cationic properties, they can react with anionic components such as soaps, surfactants, etc. This can have a negative effect on their property profile or they can be deactivated. It is also known that quaternary ammonium salts are easily deactivated by the presence of protein and dirt.
Für vielen Anwendungen in der Praxis des Material Schutzes ist es wünschenswert, die Wirkstoffe in flüssigen Formulierungen einzusetzen, die frei von organischen Lösemitteln sind oder in denen der entsprechende Lösemittelanteil drastisch reduziert ist.For many applications in the practice of material protection, it is desirable to use the active ingredients in liquid formulations which are free from organic solvents or in which the corresponding proportion of solvent is drastically reduced.
Wasserunlösliche Lösemittel sind inkompatibel mit wäßrigen Produkten wie Lederflotten, Dispersionsfarben, Kühl- und Prozeßwässern, Desinfektionsmitteln.Water-insoluble solvents are incompatible with aqueous products such as leather liquors, emulsion paints, cooling and process water, disinfectants.
Häufig sind auch die Anwender nicht auf die Handhabung von Produkten in Form von Lösungen in organischen Lösungsmitteln eingerichtet, da zur Aufbringung aus dem Lösungsmittel und zu dessen Rückgewinnung, die zur Vermeidung ökologischer Probleme unerläßlich ist, besondere Vorrichtungen erforderlich sind, die mit hohen Investitionskosten verbunden sind.Often, users are not equipped to handle products in the form of solutions in organic solvents either, since special devices are required to apply them from the solvent and to recover it, which is essential to avoid ecological problems, and these are associated with high investment costs .
Wasserlösliche Lösungsmittel wären als Lösungsvermittler in wäßrigen Systemen prinzipiell geeignet. Aber sie können, wenn sie ins Abwasser gelangen, ökologische Probleme hervorrufen. Zudem können Lösemittel sich in den zu schützenden Produkten störend bemerkbar machen.In principle, water-soluble solvents would be suitable as solubilizers in aqueous systems. But if they get into the wastewater, they can cause ecological problems. In addition, solvents can interfere with the products to be protected.
Eine weitere Möglichkeit der Lösevermittlung zur Herstellung wasserbasierter Wirkstofformulierungen besteht in der Verwendung von Emulgatoren. Bei stark wasserunlöslichen Verbindungen wie Azolen werden hierfür in der Regel große Emulgatormengen benötigt, was aus ökologischen Gründen vermieden werden soll. Ebenso kann die Wirksamkeit mikrobizider Wirkstoff stark durch die Verwendung von Emulgatoren beeinträchtigt werden. Ebenso kann die Einsetzbarkeit für bestimmte Systeme begrenzt sein.Another way of imparting solvents for the production of water-based active ingredient formulations is to use emulsifiers. In the case of highly water-insoluble compounds such as azoles, large amounts of emulsifier are generally required for this, which should be avoided for ecological reasons. The effectiveness of microbicidal active ingredient can also be severely impaired by the use of emulsifiers. The usability for certain systems can also be limited.
Aufgabe der Erfindung war daher auch die Bereitstellung neuer, vorzugsweise wasserbasierter, lösungsmittel- und emulgatorfreier mikrobizider Wirkstoff¬ formulierungen auf der Basis von Azolfungiziden; die sich einfach mit Wasser verdünnen lassen und dabei lagerstabile Gebrauchslösungen liefern.The object of the invention was therefore also to provide new, preferably water-based, solvent-free and emulsifier-free microbicidal active ingredient formulations based on azole fungicides; that can be easily diluted with water and thereby deliver storage-stable use solutions.
Es wurde nun überraschenderweise gefunden, daß durch die Kombination von mindestens einem der hier beschriebenen Azolfungizide in Form der freien Base und mindestens einem quartären Ammoniumfüngizid vorzugsweise der Formel (II)It has now surprisingly been found that the combination of at least one of the azole fungicides described here in the form of the free base and at least one quaternary ammonium fungicide preferably of the formula (II)
Figure imgf000020_0001
in welcher
Figure imgf000020_0001
in which
R1, R2, R3, R4 gleich oder verschieden sind und jeweils für unsubstituierte oder substituierte, geradkettige oder verzweigte, gesättigte oder ungesättigteR 1 , R 2 , R 3 , R 4 are the same or different and each is unsubstituted or substituted, straight-chain or branched, saturated or unsaturated
Alkylgruppen mit 1 bis 20 Kohlenstoffatomen im Arylteil und 1 bis 20 Kohlenstoffatomen im Arylteil und 1 bis 20 Kohlenstoffatomen im Alkylteil oder Arylgruppen mit 5 bis 10 Kohlenstoffatomen, sowie gegebenenfalls einfach oder mehrfach alkoxylierte Derivate hiervon; wobei als Substituenten Halogen, C1-C4-Alkyl, Cj-C4-Alkoxy in Frage kommen; und wobei 2 oder 3Alkyl groups with 1 to 20 carbon atoms in the aryl part and 1 to 20 carbon atoms in the aryl part and 1 to 20 carbon atoms in the alkyl part or aryl groups with 5 to 10 carbon atoms, and optionally single or multiple alkoxylated derivatives thereof; where halogen, C 1 -C 4 alkyl, C j -C 4 alkoxy are suitable as substituents; and where 2 or 3
Reste R1 bis R4 am quartären Zentram gegebenenfalls mit weiteren Heteroatomen einen gesättigten oder ungesättigten 5-, 6- oder 7-gliedrigen (Heter)cyclus bilden können undResidues R 1 to R 4 at the quaternary center can optionally form a saturated or unsaturated 5-, 6- or 7-membered (heter) cycle with further heteroatoms and
X für ein die Wasserlöslichkeit förderndes Anion wie z.B. Halogenid, Sulfat, Alkylsulfonat oder gegebenenfalls substituiertes Arylsulfonat.X for an anion that promotes water solubility, e.g. Halide, sulfate, alkyl sulfonate or optionally substituted aryl sulfonate.
steht,stands,
stabile wäßrige Lösungen oder Emulsionen hergestellt werden können, die eine besonders hohe mikrobizide Wirksamkeit aufweisen.stable aqueous solutions or emulsions can be prepared which have a particularly high microbicidal activity.
Derartige wäßrige Formulierungen vermeiden die vorgenannten ökologischen und anwendungstechnischen Nachteile lösemittelbasierter oder Emulgatorvermittelter Formulierungen und stellen insofern eine wertvolle Bereicherung des Standes der Technik dar.Such aqueous formulations avoid the aforementioned ecological and application-technical disadvantages of solvent-based or emulsifier-mediated formulations and in this respect represent a valuable enrichment of the prior art.
Als quartäre Ammoniumverbindungen seien vorzugsweise Ammoniumsalze wiePreferred quaternary ammonium compounds are ammonium salts such as
- C12-C]4-Alkyl-benzyl-dimethylammoniumchlorid- C 12 -C ] 4 alkyl benzyl dimethyl ammonium chloride
Trimethylcocosammoniumchlorid Didecyldimethylammoniumchlorid genannt.Trimethylcocosammonium chloride called didecyldimethylammonium chloride.
Besonders bevorzugt ist C12-C14-Alkyl-benzyl-dimethylammoniumchlorid.C 12 -C 14 -Alkyl-benzyl-dimethylammonium chloride is particularly preferred.
Die Azolfungizide liegen wie schon erwähnt in Form ihrer freien Base vor.As already mentioned, the azole fungicides are in the form of their free base.
Ganz besonders bevorzugt ist eine Kombination von Alkyl-N-azolen der Formel (I) und C12-C14-Alkyl-benzyl-dimethylammoniumchlorid, vorzugsweise in Kombination mit Tebuconazole.A combination of alkyl-N-azoles of the formula (I) and C 12 -C 14 -alkyl-benzyl-dimethylammonium chloride is very particularly preferred, preferably in combination with tebuconazole.
Die Gewichtsverhältnisse der Wirkstoffe in den Wirkstoffkombinationen können in relativ großen Bereichen variiert werden.The weight ratios of the active substances in the active substance combinations can be varied within relatively large ranges.
Sie sind im allgemeine abhängig von dem Einsatzgebiet und von den jeweils eingesetzten Azol- und quartären Ammoniumfungiziden. Diese Gewichtsverhältnisse können jedoch in Testreihen durch einfaches Mischen der Komponenten leicht festgestellt werden.They are generally dependent on the area of application and on the azole and quaternary ammonium fungicides used in each case. However, these weight ratios can easily be determined in test series by simply mixing the components.
Vorzugsweise beträgt das Gewichtsverhältnis von Azolfungizid zu quartärem Ammoniumfungizid 1:99 bis 99: 1, insbesondere 1:40 bis 9:1, besonders bevorzugt 1 :20 bei 1 :1 und ganz besonders bevorzugt 1:10 bis 1 :2. Zur Herstellung von wäßrigen Formulierungen werden die Wirkstoffe einzeln oder al s Wirkstoffkombination z.B. in Form von Pulvern, Granulaten, Pasten oder konzentrierten Lösungen, Suspensionen oder Emulsionen durch einfaches Mischen in Wasser eingearbeitet und liegen dann in Form einer wäßrigen Suspension, Lösung oder Emulsion vor. Die wäßrigen Lösungen bzw. Emulsionen enthalten vorzugsweise mehr als 20 Gew.-%, insbesondere mehr als 40 Gew.-% Wasser und können beliebig mit Wasser bis auf Anwendungskonzentration verdünnt werden. Es ist selbstverständlich auch möglich, die Wirkstoffe bzw. Wirkstoffkombination in Form von Konzentraten, Lösungen, Suspensionen, Emulsionen, Pulvern, Granulaten oder Pasten direkt in den für die Anwendung erforderlichen Mengen z.B. durch Rühren in die Anwendungsmittel einzuarbeiten.The weight ratio of azole fungicide to quaternary ammonium fungicide is 1:99 to 99: 1, in particular 1:40 to 9: 1, particularly preferably 1:20 at 1: 1 and very particularly preferably 1:10 to 1: 2. To prepare aqueous formulations, the active ingredients are incorporated individually or as a combination of active ingredients, for example in the form of powders, granules, pastes or concentrated solutions, suspensions or emulsions, by simple mixing in water and are then in the form of an aqueous suspension, solution or emulsion. The aqueous solutions or emulsions preferably contain more than 20% by weight, in particular more than 40% by weight, of water and can be diluted with water to the application concentration as desired. It is of course also possible to incorporate the active substances or combination of active substances in the form of concentrates, solutions, suspensions, emulsions, powders, granules or pastes directly into the application agents in the amounts required for the application, for example by stirring.
Die mikrobiziden Mittel enthalten die Wirkstoffkombination in einer Konzentration von 0,001 bis 95 Gew.-%, insbesondere 0,01 bis 60 Gew.-% und daneben gegebenenfalls 0,001 bis 30 Gew.-%, insbesondere 0,01 bis 20 Gew.-%, ganz besonders 0,05 bis 10 Gew.-% eines geeigneten weiteren Fungizides, Insektizides oder eines weiteren Wirkstoffes.The microbicidal agents contain the active ingredient combination in a concentration of 0.001 to 95% by weight, in particular 0.01 to 60% by weight and, if appropriate, 0.001 to 30% by weight, in particular 0.01 to 20% by weight, very particularly 0.05 to 10% by weight of a suitable further fungicide, insecticide or another active ingredient.
Die Anwendungskonzentrationen der zu verwendenden Wirkstoffe bzw. der Wirkstoffkombinationen richtet sich nach der Art und dem Vorkommen der zu bekämpfenden Mikroorganismen sowie nach der Zusammensetzung des zu schützen¬ den Materials. Die optimale Einsatzmenge kann durch Testreihen ermittelt werden. Im allgemeinen liegen die Anwendungskonzentrationen im Bereich von 0,001 bis 5 Gew.-%, vorzugsweise von 0,05 bis 1,0 Gew.-%, bezogen auf das zu schützende Material.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. In general, 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.
Die erfindungsgemäßen Wirkstoffe bzw. Mittel ermöglichen in vorteilhafter Weise, die bisher verfügbaren mikrobiziden Mittel durch effektivere zu ersetzen. Sie zeigen eine gute Stabilität und haben in vorteilhafter Weise ein breites Wirkungsspektrum.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.
Die Charakterisierung erfolgt mit Hilfe des Schmelzpunktes oder bei nicht kristalli¬ sierenden Verbindungen mit Hilfe des Brechungsindex oder der Protonen-Kernreso- nanzspektroskopie (1H-NMR).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 ( 1 H-NMR).
Desweiteren wurde gefunden, daß die Wirkstoffe auch für den Gebrauch als Pflanzenschutzmittel, insbesondere als Fungizide geeignet sind.Furthermore, it was found that the active compounds are also suitable for use as crop protection agents, in particular as fungicides.
Fungizide Mittel im Pflanzenschutz werden eingesetzt zur Bekämpfung von Plasmo- diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi- diomycetes, Deuteromycetes.Fungicidal agents in crop protection are used to combat plasmo- diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi-diomycetes, Deuteromycetes.
Beispielhaft aber nicht begrenzend seien einige Erreger von pilzlichen Krankheiten, die unter die oben aufgezählten Oberbegriffe fallen, genannt: Pythium-Arten, wie beispielsweise Pythium ultimum;Some pathogens of fungal diseases which come 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-Arten, wie beispielsweise Phytophthora infestans;Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora-Arten, wie beispielsweise Pseudoperonospora humuli oder Pseu- doperonospora cubense;Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubense;
Plasmopara-Arten, wie beispielsweise Plasmopara viticola; Peronospora- Arten, wie beispielsweise Peronospora pisi oder Peronospora brassicae;Plasmopara species, such as, for example, Plasmopara viticola; Peronospora species, such as, for example, Peronospora pisi or Peronospora brassicae;
Erysiphe-Arten, wie beispielsweise Erysiphe graminis;Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca-Arten, wie beispielsweise Sphaerotheca fuliginea;Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera-Arten, wie beispielsweise Podosphaera leucotricha;Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia-Arten, wie beispielsweise Venturia inaequalis; Pyrenophora- Arten, wie beispielweise Pyrenophora teres oder Pyrenophora gramineaVenturia species, such as, for example, Venturia inaequalis; Pyrenophora species, such as, for example, Pyrenophora teres or Pyrenophora graminea
(Konidienform: Drechslera, Synonym: Helminthosporium);(Conidial form: Drechslera, synonym: Helminthosporium);
Cochliobolus-Arten, wie beispielsweise Cochliobolus sativus (Konidienform: Drechs¬ lera, Synonym: Helminthosporium);Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechs¬ lera, synonym: Helminthosporium);
Uromyces-Arten, wie beispielsweise Uromyces appendiculatus; Puccinia-Arten, wie beispielsweise Puccinia recondita;Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccinia recondita;
Tilletia-Arten, wie beispielsweise Tilletia caries;Tilletia species, such as, for example, Tilletia caries;
Ustilago-Arten, wie beispielsweise Ustilago nuda oder Ustilago avenae;Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia-Arten, wie beispielsweise Pellicularia sasakii;Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia-Arten, wie beispielsweise Pyricularia oryzae; Fusarium-Arten, wie beispielsweise Fusarium culmorum;Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum;
Botrytis- Arten, wie beispielsweise Botrytis cinerea;Botrytis species, such as, for example, Botrytis cinerea;
Septoria- Arten, wie beispielsweise Septoria nodorum;Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria-Arten, wie beispielsweise Leptosphaeria nodorum;Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora-Arten, wie beispielsweise Cercospora canescens; Alternaria- Arten, wie beispielsweise Alternaria brassicae;Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella-Arten, wie beispielsweise Pseudocercosporella herpotrichoides.Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
Die gute Pflanzenverträglichkeit der Wirkstoffe in den zur Bekämpfung von Pflan¬ zenkrankheiten notwendigen Konzentrationen erlaubt eine Behandlung von oberirdi- sehen Pflanzenteilen, von Pflanz- und Saatgut und des Bodens.The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground see parts of plants, plant and seed, and soil.
Dabei können die erfindungsgemäßen Wirkstoffe mit besonders gutem Erfolg zur Be¬ kämpfung von Krankheiten im Obst- und Gemüseanbau, wie beispielsweise gegen den Erreger der Tomatenbraunfäule (Phytophthora infestans) oder gegen den Erreger des Apfelschorfes (Venturia inaequalis) oder zur Bekämpfung von Ge¬ treidekrankheiten wie beispielsweise gegen den Erreger des echten Getreidemehltaues (Erysiphe graminis) oder gegen den Erreger der Netzfleckenkrankheit der Gerste (Pyrenophora teres) oder gegen den Erreger der Braunspelzigkeit des Weizens (Leptosphaeria nodorum) oder gegen Fusariumarten an Getreide oder zur Be- kämpfung von Reiskrankheiten, wie beispielsweise gegen den Erreger der Reisflec¬ kenkrankheit (Pyricularia oryzae) eingesetzt werden. Daneben besitzen die erfin¬ dungsgemäßen Wirkstoffe eine gute in vitro-Wirksamkeit.The active compounds according to the invention can be used with particularly good success for combating diseases in fruit and vegetable cultivation, such as, for example, against the pathogen causing tomato brown rot (Phytophthora infestans) or against the pathogen of apple scab (Venturia inaequalis) or for combating cereal diseases such as For example, against the pathogen of the powdery mildew (Erysiphe graminis) or against the pathogen of the barley net spot disease (Pyrenophora teres) or against the pathogen of the brown furs of the wheat (Leptosphaeria nodorum) or against fusarium species on cereals or for controlling rice diseases, such as can be used against the pathogen of the rice stain disease (Pyricularia oryzae). In addition, the active compounds according to the invention have good in vitro activity.
Die Wirkstoffe können in Abhängigkeit von ihren jeweiligen physikalischen und/oder chemischen Eigenschaften in übliche Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate, Aerosole, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, sowie ULV-Kalt- und -Warmnebel-Formulierungen.Depending on their respective physical and / or chemical properties, 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.
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Disper¬ giermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfs¬ lösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentli- chen infrage: Aromaten, wie Xylol, Toluol, Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene, oder Methylenchlorid, aliphatsche Kohlenwasserstoffe, wie Cyclohexan oder Pa¬ raffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclo- hexanon, stark polare Lösungsmittel, wie Dimethylformamid oder Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Nor- maldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe kommen infrage: z.B. natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quartz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate kommen infrage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier- und/oder schaumerzeugende Mittel kommen infrage: z.B. nicht ionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäureester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkylarylpolyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen infrage: z.B. Ligninsulfitablaugen und Methyl cellulose.These formulations are produced 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 foam-producing agents Means. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as 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 their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are at normal temperature and under normal conditions. are gaseous 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 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: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: eg lignin sulfite waste liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylceliulose, natürliche und synthetische, pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phos- pholipide, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxymethylceliulose, 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.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferroc- yanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyanin- farbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.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.
Die Formulierungen enthalten im allgemeinenzwischen 0, 1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0, 1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Fungiziden, Bakteriziden, Akariziden, Nematiziden oder Insektiziden verwendet werden, um so z.B. das Wirkungsspektrum zu verbreitern oder Resistenzentwicklungen vorzubeugen. In vielen Fällen treten dabei synergistische Effekte auf. Für die Mischungen kommen beispielsweise infrage:The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In many cases, synergistic effects occur. For the mixtures, for example:
Fungizide:Fungicides:
2-Aminobutan;2-Anilino-4-methyl-6-cyclopropyl-pyrimidin;2',6'-Dibromo-2-methyl- 4,-trifluoromethoxy-4'-trifluoro-methyl-l,3-thizole-5-carboxanilid?,6-Dichloro-N-(4- trifluoromemylben_yl)benzan_ c(^)-2-Me1_aoxyimino-N-methyl-2-(2-phenoxyphenyl) acetamid; 8-Hydroxyquinolinsulfat; Methyl-(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin- 4-yloxy]phenyl}-3-methoxyacrylat; Methyl-(E)-methoximino [alpha-(o-tolyloxy)-o- tolyl] acetat; 2-Phenylphenol (OPP), Aldimo h, Ampropylfos, Anilazin, Azaconazol, Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4 , -trifluoromethoxy-4'-trifluoro-methyl-l, 3-thizole-5- carboxanilide?, 6-dichloro-N- (4-trifluoromemylben_yl) benzane_ c (^) - 2-Me1_aoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -otolyl] acetate; 2-phenylphenol (OPP), Aldimo h, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
Calciumpolysulfid, Captafol, Captan, Carbendazim, Carboxin, Chinomethionat (Quinomethionat), Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinat, Cufraneb, Cymoxanil, Cyproconazole, Cyprofüram, Dichlorophen, Diclobutrazol, Diclofluanid, Diclomezin, Dicloran, Diethofencarb, Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Dinocap, Diphenylamin, Dipyrithion, Ditalimfos, Dithianon, Dodin, Drazoxolon, Edifenphos, Epoxyconazole, Ethirimol, Etridiazol,Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofüram, dichlorophen, diclobutrazole, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, diclomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, diclomolanidol, dicloflomolonidol, diclofolomidol, diclofolomidol, diclozolidl , Dinocap, Diphenylamine, Dipyrithion, Ditalimfos, Dithianon, Dodin, Drazoxolon, Edifenphos, Epoxyconazole, Ethirimol, Etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropi¬ morph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl- Aluminium, Fthalide, Fuberidazol, Furalaxyl, Furmecyclox, Guazatine,Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropi¬ morph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolafolidol, Futin, Futin, Futin, Futin, Futin, Futin, Futin Furalaxyl, furmecyclox, guazatine,
Hexachlorobenzol, Hexaconazol, Hymexazol, Imazalil, Imibenconazol, Iminoctadin, Iprobenfos (IBP), Iprodion, Isoprothiolan, Kasugamycin, Kupfer-Zubereitungen, wie: Kupferhydroxid, Kupfernaphthenat, Kupferoxychlorid, Kupfersulfat, Kupferoxid, Oxin-Kupfer and Bordeaux-Mischung, Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel dimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,Hexachlorobenzene, Hexaconazole, Hymexazol, Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper per Man and Bordeaux , Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel dimethyldithiocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin
Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Probenazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazo- phos, Pyrifenox, Pyrimethanil, Pyroquilon, Quintozen (PCNB), Schwefel und Schwefel-Zubereitungen,Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyraphosphos, pyrifenox, pyrimethanil, pyroquilon, quintozen (PCNB) Sulfur and sulfur preparations,
Tebuconazol, Tecloftalam, Tecnazen, Tetraconazol, Thiabendazol, Thicyofen, Thio- phanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazol, Validamycin A, Vinclozolin, Zineb, ZiramTebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanat-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamid, tricyclazole, tridemorph, triflorolizolin, triflorolizolinol, triflorolizolinol, triflorolizolinol, triflorolizolinol, triflorolizolin, triflorolizolinol, triflorolizolinol, triflorolizolinol, triflorolizoline, triflorolizolinol, triflorolizolin, triflorolizolinol, triflorolizolinol, triflorolizolin, triflorolizoline, triflorolizolin, triflorolizol, z , Ziram
Bakterizide:Bactericides:
Bronopol, Dichlorophen, Nitrapyrin, Nickel Dimethyldithiocarbamat, Kasugamycin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insektizide / Akarizide / Nematizide:Insecticides / acaricides / nematicides:
Abamectin, Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb,Abamectin, abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,
Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, AzinphosAlphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos
M, Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfüracarb, Bensultap, Betacyluthrin, Bifenthrin,M, Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfüracarb, Bensultap, Betacyluthrin, Bifenthrin,
BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,
Butylpyridaben,Butyl pyridaben,
Cadusafos, Carbaryl, Carbofüran, Carbophenothion, Carbosulfan, Cartap, CGA 157Cadusafos, Carbaryl, Carbofüran, Carbophenothion, Carbosulfan, Cartap, CGA 157
419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocy- thrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin,419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhexatinhrin, Cyhalothrin
Cypermethrin, Cyromazin,Cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon,Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon,
Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat,Dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate,
Dimethylvinphos, Dioxathion, Disulfoton,Dimethylvinphos, dioxathione, disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho- prophos, Etofenprox, Etrimphos,Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etofenprox, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil,Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil,
Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate,Fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,
Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,
HCH, Heptenophos, Hexaflumuron, Hexythiazox, Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,HCH, heptenophos, hexaflumuron, hexythiazox, Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,
Lamda-cyhalothrin, Lufenuron,Lamda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyd, Methacrifos,Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos,
Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, NI 25, NitenpyramNaled, NC 184, NI 25, Nitenpyram
Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, ,Primiphos A, Profenofos, Profenophos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothoat,Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M,, Primiphos A, Profenofos, Profenophos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothoat,
Pymetrozin, Pyrachlophos, Pyraclofos, Pyraclophos, Pyradaphenthion, Pyresmethrin,Pymetrozine, pyrachlophos, pyraclofos, pyraclophos, pyradaphenthion, pyresmethrin,
Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,
Quinalphos,Quinalphos,
RH 5992, Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,RH 5992, Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos,Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos,
Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiome- thon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron,Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron,
Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, XMC, Xylylcarb, YI 5301 / 5302, Zetamethrin.Trichlorfon, triflumuron, trimethacarb, vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Herbiziden oder mit Düngemitteln und Wachstumsregulatoren ist möglich.A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus be¬ reiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Suspensionen, Spritz- pulver, Pasten, lösliche Pulver, Stäubemittel und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Verspritzen, Versprü¬ hen, Verstreuen, Verstäuben, Verschäumen, Bestreichen usw. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low- Volume- Verfahren auszubringen oder die Wirk¬ stoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. Es kann auch das Saatgut der Pflanzen behandelt werden.The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil. The seeds of the plants can also be treated.
Bei der Behandlung von Pflanzenteilen können die Wirkstoffkonzentrationen in den Anwendungsformen in einem größeren Bereich variiert werden: Sie liegen im allge- meinen zwischen 1 und 0,0001 Gew.-%, vorzugsweise zwischen 0,5 und 0,001 Gew.-%.When treating parts of plants, the active substance concentrations in the use forms can be varied within a wide range: they are generally mean between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 50 g je Kilogramm Saatgut, vorzugsweise 0,01 bis 10 g benötigt.In the seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
Bei der Behandlung des Bodens sind Wirkstoffkonzentrationen von 0,00001 bis 0,1 Gew.-%, vorzugsweise von 0,0001 bis 0,02 Gew.-% am Wirkungsort erforderlich.When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.
Die nachfolgenden Beispiele dienen zur Verdeutlichung der Erfindung. Die Erfindung ist nicht auf die Beispiele beschränkt. The following examples serve to illustrate the invention. The invention is not limited to the examples.
HersteUungsbeispieleMANUFACTURING EXAMPLES
Beispiel 1example 1
2-Dodecylimidazol2-dodecylimidazole
5,80 g Imidazol werden in 70 ml DMF vorgelegt und mit 2,56 g 80 %igem Natriumhydrid versetzt, 30 min lang bei 25°C gerührt und dann 25,0 g 2-Bromdecan (Aldrich, techn. 90 %ig) tropfenweise zugesetzt. Nach 5 h bei 100°C wird eingeengt, mit Methylenchlorid extrahiert und destilliert. Man erhält 6,51 g (32 %) vom Siedepunkt Kp0 j = 125-131 des Zielprodukts.5.80 g of imidazole are placed in 70 ml of DMF and mixed with 2.56 g of 80% sodium hydride, stirred for 30 minutes at 25 ° C. and then 25.0 g of 2-bromodecane (Aldrich, technical 90%) dropwise added. After 5 h at 100 ° C., the mixture is concentrated, extracted with methylene chloride and distilled. 6.51 g (32%) of the boiling point Kp 0 j = 125-131 of the target product are obtained.
In analoger Weise werden die in der nachfolgenden Tabelle aufgeführten Verbin- düngen hergestellt:The connections listed in the table below are produced in an analogous manner:
Figure imgf000030_0001
Figure imgf000030_0001
Typ A Typ B Typ C Typ DType A Type B Type C Type D
Die Verbindungen 73 bis 104 werden in analoger Weise aus den mit Propylenoxid verlängerten primären Alkoholen in literaturbekannter Weise hergestellt; die Alkohole werden dazu zuvor entweder mit PBr3 oder mit Mesylchlorid umgesetzt und dann wie o.g. mit Natriumimidazol zur Endstufe umgesetzt.The compounds 73 to 104 are prepared in an analogous manner from the primary alcohols extended with propylene oxide in a manner known from the literature; for this purpose, the alcohols are first reacted either with PBr 3 or with mesyl chloride and then, as mentioned above, with sodium imidazole to the final stage.
Die phs. Daten werden durch Kugelrohrdestillation beim angegebenen Dampfdruck oder durch 1H-NMR-Spektroskopie bestimmt. The phs. Data are determined by Kugelrohr distillation at the specified vapor pressure or by 1H NMR spectroscopy.
Tabelle 1Table 1
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
2 A 3-Octyl H2 A 3-octyl H
3 B 3-Octyl H3 B 3-octyl H
4 C 3-Octyl H δ = 3,804 C 3-octyl H δ = 3.80
5 D 3-Octyl H5 D 3-octyl H
6 A 2-Nonyl H6 A 2-nonyl H
7 B 2-Nonyl H7 B 2-nonyl H
8 C 2-Nonyl H Kp 125°C/0,5 mm8 C 2-nonyl H bp 125 ° C / 0.5 mm
9 D 2-Nonyl H9 D 2-nonyl H
10 A 2-Decyl H10 A 2-decyl H
11 B 2-Decyl H11 B 2-decyl H
12 C 2-Decyl H δ = 4,1012 C 2-decyl H δ = 4.10
13 D 2-Decyl H13 D 2-decyl H
14 C 2-Decyl Me14 C 2-Decyl Me
15 C 2-Decyl Et15 C 2-decyl Et
16 C 2-Decyl n-Pr16 C 2-decyl n-Pr
17 C 2-Decyl n-Bu17 C 2-decyl n-Bu
18 A 3-Undecyl H18 A 3-undecyl H
19 B 3-Undecyl H19 B 3-Undecyl H
20 C 3-Undecyl H δ = 3,8020 C 3-undecyl H δ = 3.80
21 D 3-Undecyl H21 D 3-undecyl H
22 C 3-Undecyl Me22 C 3-Undecyl Me
23 C 3-Undecyl Et23 C 3-Undecyl Et
24 C 3-Undecyl n-Pr24 C 3-Undecyl n-Pr
25 C 3-Undecyl n-Bu25 C 3-Undecyl n-Bu
26 A 4-Dodecyl H26 A 4-dodecyl H
27 B 4-Dodecyl H 3027 B 4-dodecyl H 30th
Tabelle 1 (Fortsetzung)Table 1 (continued)
Bsp - Typ R R2 phys. Nr. DatenExample - type RR 2 phys. No. Data
28 C 4-Dodecyl H δ = 3,9028 C 4-dodecyl H δ = 3.90
29 D 4-Dodecyl H29 D 4-dodecyl H
30 C 4-Dodecyl Me30 C 4-dodecyl Me
31 C 4-Dodecyl Et31 C 4-dodecyl Et
32 C 4-Dodecyl n-Pr32 C 4-dodecyl n-Pr
33 C 4-Dodecyl n-Bu33 C 4-dodecyl n-Bu
34 A 2-Undecyl H34 A 2-Undecyl H
35 B 2-Undecyl H35 B 2-Undecyl H
36 C 2-Undecyl H δ = 4,1136 C 2-undecyl H δ = 4.11
37 D 2-Undecyl H δ = 4,3637 D 2-undecyl H δ = 4.36
38 C 2-Undecyl Me38 C 2-Undecyl Me
39 C 2-Undecyl Et39 C 2-Undecyl Et
40 C 2-Undecyl n-Pr40 C 2-Undecyl n-Pr
41 C 2-Undecyl n-Bu41 C 2-Undecyl n-Bu
42 A 6, 10-Dimethyl-2-undecyl H42 A 6, 10-dimethyl-2-undecyl H
43 B 6, 10-Dimethyl-2-undecyl H43 B 6, 10-dimethyl-2-undecyl H
44 C 6, 10-Dimethyl-2-undecyl H δ = 4,1144 C 6, 10-dimethyl-2-undecyl H δ = 4.11
45 D 6, 10-Dimethyl-2-undecyl H45 D 6, 10-dimethyl-2-undecyl H
46 A 2-Dodecyl H46 A 2-dodecyl H
47 B 2-Dodecyl H47 B 2-dodecyl H
48 C 2-Dodecyl H Kp =48 C 2-dodecyl H Kp =
145°C/0,55 m m145 ° C / 0.55 m m
49 D 2-Dodecyl H Kp = 113°C/0,2 mm49 D 2-dodecyl H bp = 113 ° C / 0.2 mm
50 C 2-Dodecyl Me δ = 4,0750 C 2-dodecyl Me δ = 4.07
51 C 2-Dodecyl Et δ = 4,1051 C 2-dodecyl Et δ = 4.10
52 C 2-Dodecyl n-Pr52 C 2-dodecyl n-Pr
53 C 2-Dodecyl n-Bu 31 -53 C 2-dodecyl n-Bu 31 -
Tabelle 1 (Fortsetzung)Table 1 (continued)
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
54 A 3-Tridecyl H54 A 3-tridecyl H
55 B 3-Tridecyl H55 B 3-tridecyl H
56 C 3-Tridecyl H δ = 3,9056 C 3-tridecyl H δ = 3.90
57 D 3-Tridecyl H57 D 3-tridecyl H
58 C 3-Tridecyl Me58 C 3-tridecyl Me
59 C 3-Tridecyl Et59 C 3-tridecyl Et
60 C 3-Tridecyl n-Pr60 C 3-tridecyl n-Pr
61 C 3-Tridecyl n-Bu61 C 3-tridecyl n-Bu
62 A 2-Tridecyl H62 A 2-tridecyl H
63 B 2-Tridecyl H63 B 2-tridecyl H
64 C 2-Tridecyl H Kp 150°C/0,7 mm64 C 2-tridecyl H bp 150 ° C / 0.7 mm
65 D 2-Tridecyl H65 D 2-tridecyl H
66 C Cyclohexyl Cyclohexyl66 C cyclohexyl cyclohexyl
67 C Cyclooctyl H δ = 4,1967 C cyclooctyl H δ = 4.19
68 C Cyclododecyl H δ = 4,1868 C cyclododecyl H δ = 4.18
69 C Cyclododecyl Me69 C cyclododecyl Me
70 C Cyclododecyl Et70 C cyclododecyl Et
71 C Cyclododecyl n-Pr71 C cyclododecyl n-Pr
72 C Cyclododecyl n-Bu72 C cyclododecyl n-Bu
73 A 4-Oxo-2-undecyl H73 A 4-oxo-2-undecyl H
74 B 4-Oxo-2-undecyl H74 B 4-oxo-2-undecyl H
75 C 4-Oxo-2-undecyl H75 C 4-oxo-2-undecyl H
76 D 4-Oxo-2-undecyl H76 D 4-oxo-2-undecyl H
77 C 4-Oxo-2-undecyl Me77 C 4-oxo-2-undecyl Me
78 C 4-Oxo-2-undecyl Et78 C 4-oxo-2-undecyl Et
79 C 4-Oxo-2-undecyl n-Pr - 3279 C 4-oxo-2-undecyl n-Pr - 32
Tabelle 1 (Fortsetzung)Table 1 (continued)
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
80 C 4-Oxo-2-undecyl n-Bu80 C 4-oxo-2-undecyl n-Bu
81 A 4-0x0-3 -undecyl H81 A 4-0x0-3 -undecyl H
82 B 4-Oxo-3 -undecyl H82 B 4-oxo-3-undecyl H
83 C 4-Oxo-3 -undecyl H83 C 4-oxo-3-undecyl H
84 D 4-0x0-3 -undecyl H84 D 4-0x0-3 -undecyl H
85 C 4-Oxo-3 -undecyl Me85 C 4-oxo-3-undecyl Me
86 C 4-0x0-3 -undecyl Et86 C 4-0x0-3 -undecyl Et
87 C 4-Oxo-3 -undecyl n-Pr87 C 4-oxo-3-undecyl n-Pr
88 C 4-Oxo-3 -undecyl n-Bu88 C 4-oxo-3-undecyl n-Bu
89 A 3-Oxo-2-undecyl H89 A 3-oxo-2-undecyl H
90 B 3-Oxo-2-undecyl H90 B 3-oxo-2-undecyl H
91 C 3 -Oxo-2-undecyl H91 C 3 -Oxo-2-undecyl H
92 D 3 -Oxo-2-undecy 1 H92 D 3 -Oxo-2-undecy 1 H
93 A 4-Oxo-3-dodecyl H93 A 4-oxo-3-dodecyl H
94 B 4-0x0-3 -dodecyl H94 B 4-0x0-3 -dodecyl H
95 C 4-0x0-3 -dodecyl H95 C 4-0x0-3 -dodecyl H
96 D 4-Oxo-3 -dodecyl H96 D 4-oxo-3-dodecyl H
97 A 4-Oxo-2-dodecyl H97 A 4-oxo-2-dodecyl H
98 B 4-Oxo-2-dodecyl H98 B 4-oxo-2-dodecyl H
99 C 4-Oxo-2-dodecyl H99 C 4-oxo-2-dodecyl H
100 D 4-Oxo-2-dodecyl H100 D 4-oxo-2-dodecyl H
101 A 4-Oxo-2-decyl H101 A 4-oxo-2-decyl H
102 B 4-Oxo-2-decyl H102 B 4-oxo-2-decyl H
103 C 4-Oxo-2-decyl H103 C 4-oxo-2-decyl H
104 D 4-Oxo-2-decyl H Beispiel 105104 D 4-oxo-2-decyl H Example 105
2-Imidazolylheptansäureethylester2-Imidazolylheptanoic acid ethyl ester
2,86 g Imidazol werden in 120 ml DMF vorgelegt und mit 1,26 g Natriumhydrid (80 %ig) versetzt, 30 min lang bei 25°C gerührt und dann mit 10,0 g 2-Brom- heptansäureethylester versetzt. Nach 8 h bei 25°C wird auf Eis gegeben, mehrfach mit Methylenchlorid extrahiert und nach Phasentrennung, Trocknung und Verdampfen des Lösungsmittels der Rückstand mit Toluol/Ester säulenchromatographiert.2.86 g of imidazole are placed in 120 ml of DMF and mixed with 1.26 g of sodium hydride (80%), stirred for 30 minutes at 25 ° C. and then mixed with 10.0 g of 2-bromo-heptanoic acid ethyl ester. After 8 h at 25 ° C., the mixture is poured onto ice, extracted several times with methylene chloride and, after phase separation, drying and evaporation of the solvent, the residue is column chromatographed with toluene / ester.
Man erhält 7,51 g (80 % d.Th.) eines Öls. δH = 4,657.51 g (80% of theory) of an oil are obtained. δH = 4.65
Die 2-Bromfettsäureester sind kommerziell erhältlich oder nach Vorschriften des Organikums, Deutscher Verlag der Wissenschaften, Berlin 1990, herstellbar.The 2-bromofatty acid esters are commercially available or can be produced according to the regulations of the Organic, German Publishing House of Sciences, Berlin 1990.
Die folgende Tabelle enthält weitere, nach dieser Methode hergestellte Verbindungen. The following table contains other compounds made using this method.
Tabelle 2Table 2
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
106 A 2-Heptansäureethylester H106 A ethyl 2-heptanoate H
107 B 2-Heptansäureethylester H107 B ethyl 2-heptanoate H
108 C 2-Heptansäureethylester H δ = 4,65108 C 2-heptanoic acid ethyl ester H δ = 4.65
109 D 2-Heptansäureethylester H δ = 5,02109 D ethyl 2-heptanoate H δ = 5.02
110 A 2-Octansäureethylester H110 A ethyl 2-octanoate H
111 B 2-Octansäureethylester H111 B ethyl 2-octanoate H
112 C 2-Octansäureethylester H δ = 4,66112 C 2-octanoic acid ethyl ester H δ = 4.66
113 D 2-Octansäureethylester H δ = 5,01113 D ethyl 2-octanoate H δ = 5.01
114 A 2-Nonansäuremethylester H114 A 2-nonanoic acid methyl ester H
115 B 2-Nonansäuremethylester H115 B methyl 2-nonanoate H
116 C 2-Nonansäuremethylester H116 C 2-nonanoic acid methyl ester H
117 D 2-Nonansäuremethylester H117 D 2-nonanoic acid methyl ester H
118 C 2-Nonansäuremethylester Me118 C 2-nonanoic acid methyl ester Me
119 C 2-Nonansäuremethylester Et119 C 2-nonanoic acid methyl ester Et
120 C 2-Nonansäuremethylester n-Pr120 C 2-nonanoic acid methyl ester n-Pr
121 C 2-Nonansäuremethylester n-Bu121 C 2-nonanoic acid methyl ester n-Bu
122 A 2-Nonansäureethylester H122 A 2-nonanoic acid ethyl ester H
123 B 2-Nonansäureethylester H123 B ethyl 2-nonanoate H
124 C 2-Nonansäureethylester H124 C 2-nonanoic acid ethyl ester H
125 D 2-Nonansäureethylester H125 D 2-nonanoic acid ethyl ester H
126 C 2-Nonansäureethyl ester Me126 C 2-nonanoic acid ethyl ester Me
127 C 2-Nonansäureethy 1 ester Et127 C 2-Nonanoic acid ethyl 1 ester Et
128 C 2-Nonansäureethylester n-Pr128 C 2-nonanoic acid ethyl ester n-Pr
129 C 2-Nonansäureethylester n-Bu129 C 2-nonanoic acid ethyl ester n-Bu
130 A 2-Decansäuremethylester H130 A methyl 2-decanoate H
131 B 2-Decansäuremethylester H Tabelle 2 (Fortsetzung)131 B methyl 2-decanoate H Table 2 (continued)
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
132 C 2-Decansäuremethylester H132 C 2-decanoic acid methyl ester H
133 D 2-Decansäuremethylester H133 D methyl 2-decanoate H
134 C 2-Decansäuremethylester Me134 C 2-decanoic acid methyl ester Me
135 C 2-Decansäuremethylester Et135 C 2-decanoic acid methyl ester Et
136 C 2-Decansäuremethylester n-Pr136 C 2-decanoic acid methyl ester n-Pr
137 C 2-Decansäuremethylester n-Bu137 C 2-decanoic acid methyl ester n-Bu
138 A 2-Decansäureethylester H138 A ethyl 2-decanoate H
139 B 2-Decansäureethylester H139 B ethyl 2-decanoate H
140 C 2-Decansäureethylester H δ = 4,66140 C 2-decanoic acid ethyl ester H δ = 4.66
141 D 2-Decansäureethylester H δ = 5,01141 D ethyl 2-decanoate H δ = 5.01
142 C 2-Decansäureethylester Me142 C 2-Decanoic acid ethyl ester Me
143 C 2-Decansäureethylester Et143 C 2-decanoic acid ethyl ester Et
144 C 2-Decansäureethylester n-Pr144 C 2-decanoic acid ethyl ester n-Pr
145 C 2-Decansäureethylester n-Bu145 C 2-decanoic acid ethyl ester n-Bu
146 A 2-Undecansäuremethylester H146 A methyl 2-undecanoate H
147 B 2-Undecansäuremethylester H147 B methyl 2-undecanoate H
148 C 2-Undecansäuremethyl ester H148 C 2-Undecanoic acid methyl ester H
149 D 2-Undecansäuremethylester H149 D methyl 2-undecanoate H
150 C 2-Undecansäuremethy 1 ester Me150 C 2-undecanoic acid methyl 1 ester Me
151 C 2-Undecansäuremethylester Et151 C 2-undecanoic acid methyl ester Et
152 C 2-Undecansäuremethylester n-Pr152 C 2-undecanoic acid methyl ester n-Pr
153 C 2-Undecansäuremethylester n-Bu153 C 2-undecanoic acid methyl ester n-Bu
154 A 2-Undecansäureethylester H154 A 2-undecanoic acid ethyl ester H
155 B 2-Undecansäureethylester H155 B ethyl 2-undecanoate H
156 C 2-Undecansäureethylester H156 C 2-undecanoic acid ethyl ester H
157 D 2-Undecansäureethylester H 36157 D ethyl 2-undecanoate H 36
Tabelle 2 (Fortsetzung)Table 2 (continued)
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
158 C 2-Undecansäureethylester Me158 C 2-undecanoic acid ethyl ester Me
159 C 2-Undecansäureethylester Et159 C 2-undecanoic acid ethyl ester Et
160 c 2-Undecansäureethylester n-Pr160 c ethyl 2-undecanoate n-Pr
161 C 2-Undecansäureethylester n-Bu161 C 2-undecanoic acid ethyl ester n-Bu
162 A 2-Dodecansäuremethylester H162 A methyl 2-dodecanoate H
163 B 2-Dodecansäuremethylester H163 B methyl 2-dodecanoate H
164 C 2-Dodecansäuremethylester H164 C 2-dodecanoic acid methyl ester H
165 D 2-Dodecansäuremethylester H165 D methyl 2-dodecanoate H
166 C 2-Dodecansäuremethylester Me166 C 2-dodecanoic acid methyl ester Me
167 C 2-Dodecansäuremethylester Et167 C 2-dodecanoic acid methyl ester Et
168 C 2-Dodecansäuremethylester n-Pr168 C 2-dodecanoic acid methyl ester n-Pr
169 C 2-Dodecansäuremethylester n-Bu169 C 2-dodecanoic acid methyl ester n-Bu
170 A 2-Dodecansäureethylester H170 A ethyl 2-dodecanoate H
171 B 2-Dodecansäureethylester H171 B ethyl 2-dodecanoate H
172 C 2-Dodecansäureethylester H δ = 4,64172 C 2-dodecanoic acid ethyl ester H δ = 4.64
173 D 2-Dodecansäureethylester H Fp = 53°C173 D ethyl 2-dodecanoate H mp = 53 ° C
174 C 2-Dodecansäureethylester Me174 C 2-dodecanoic acid ethyl ester Me
175 C 2-Dodecansäureethylester Et175 C 2-Dodecanoic acid ethyl ester Et
176 C 2-Dodecansäureethylester n-Pr176 C 2-dodecanoic acid ethyl ester n-Pr
177 C 2-Dodecansäureethylester n-Bu177 C 2-dodecanoic acid ethyl ester n-Bu
178 A 2-Tridecansäureethylester H178 A ethyl 2-tridecanoate H
179 B 2-Tridecansäureethylester H179 B ethyl 2-tridecanoate H
180 C 2-Tridecansäureethylester H180 C 2-tridecanoic acid ethyl ester H
181 D 2-Tri decansäureethy 1 ester H181 D 2-tri decanoic acid ethyl 1 ester H
182 A 2-Tetradecansäureethylester H182 A ethyl 2-tetradecanoate H
183 B 2-Tetradecansäureethylester H183 B ethyl 2-tetradecanoate H
184 C 2-Tetradecansäureethy 1 ester H δ = 4,64184 C 2-tetradecanoic acid ethyl ester H δ = 4.64
185 D 2-Tetradecansäureethylester H Fp = 57°C Beispiel 196185 D ethyl 2-tetradecanoate H mp = 57 ° C Example 196
VorstufePrepress
1 -Imidazolyl-2-hy droxyhexan1-imidazolyl-2-hy droxyhexane
50 g Hexanoxid werden mit 37,4 g Imidazol in 200 ml DMF für 4 h bei 140°C gehalten. Nach Abkühlen wird das DMF abgedampft, mit Methylenchlorid aufgenommen, mit Wasser gewaschen und am Kugelrohr destilliert.50 g of hexane oxide are kept at 140 ° C. for 4 h with 37.4 g of imidazole in 200 ml of DMF. After cooling, the DMF is evaporated off, taken up in methylene chloride, washed with water and distilled on a bulb tube.
Kp0 2 = 170°C 61,1 g (73 %)Kp 0 2 = 170 ° C 61.1 g (73%)
In analoger Weise werden die Vorstufen für die in Tabelle 3 genannten Produkte hergestellt.The precursors for the products listed in Table 3 are prepared in an analogous manner.
l-Imidazolyl-2-(oxyhexyl)hexanl-imidazolyl-2- (oxyhexyl) hexane
7,0 g Vorstufe 196 werden mit 2,58 g Natriumhydrid (60 %) in 200 ml DMF versetzt und 30 min bei 50°C gerührt. Nach Zugabe von 6,88 g Bromhexan wird 5 h bei 50°C gerührt, die flüchtigen Komponenten im Vakuum abgezogen und der Rückstand mit Toluol als Laufmittel säulenchromatographiert.7.0 g of precursor 196 are mixed with 2.58 g of sodium hydride (60%) in 200 ml of DMF and stirred at 50 ° C. for 30 min. After adding 6.88 g of bromhexane, the mixture is stirred at 50 ° C. for 5 h, the volatile components are stripped off in vacuo and the residue is column-chromatographed using toluene as the eluent.
Man erhält 3,8 g (36 %) eines Öls. (SH = 3,90)3.8 g (36%) of an oil are obtained. (SH = 3.90)
In analoger Weise werden die Produkte der Tabelle 3 hergestellt:The products in Table 3 are produced in an analogous manner:
Figure imgf000039_0001
A/B ergeben sich aus den Difinitionen oben. Tabelle 3
Figure imgf000039_0001
A / B result from the definitions above. Table 3
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
197 A 2-(Oxyhexyl)hexan H197 A 2- (oxyhexyl) hexane H
198 B 2-(Oxyhexyl)hexan H198 B 2- (oxyhexyl) hexane H
199 C 2-(Oxyhexyl)hexan H δ = 3,90199 C 2- (oxyhexyl) hexane H δ = 3.90
200 D 2-(Oxyhexyl)hexan H200 D 2- (oxyhexyl) hexane H
201 A 2-(Oxy-4-chlorbenzyl)hexan H201 A 2- (oxy-4-chlorobenzyl) hexane H
202 B 2-(Oxy-4-chlorbenzyl)hexan H202 B 2- (oxy-4-chlorobenzyl) hexane H
203 C 2-(Oxy-4-chlorb enzyl)hexan H δ = 4,34203 C 2- (oxy-4-chlorobenzyl) hexane H δ = 4.34
204 D 2-(Oxy-4-chlorbenzyl)hexan H204 D 2- (oxy-4-chlorobenzyl) hexane H
205 A 2-(Oxy-2,6-dichlorbenzyl)hexan H205 A 2- (oxy-2,6-dichlorobenzyl) hexane H
206 B 2-(Oxy-2,6-dichlorbenzyl)hexan H206 B 2- (oxy-2,6-dichlorobenzyl) hexane H
207 C 2-(Oxy-2,6-dichlorbenzyl)hexan H δ = 4,74207 C 2- (oxy-2,6-dichlorobenzyl) hexane H δ = 4.74
208 D 2-(Oxy-2,6-dichlorbenzyl)hexan H208 D 2- (oxy-2,6-dichlorobenzyl) hexane H
209 A 2-(Oxy-2,4-dichlorbenzyl)hexan H209 A 2- (oxy-2,4-dichlorobenzyl) hexane H
210 B 2-(Oxy-2,4-dichlorbenzyl)hexan H210 B 2- (oxy-2,4-dichlorobenzyl) hexane H
211 C 2-(Oxy-2,4-dichlorbenzyl)hexan H δ = 4,52211 C 2- (oxy-2,4-dichlorobenzyl) hexane H δ = 4.52
212 D 2-(Oxy-2,4-dichlorbenzyl)hexan H212 D 2- (oxy-2,4-dichlorobenzyl) hexane H
213 A 2-(Oxy-cinnamyl)hexan H213 A 2- (oxy-cinnamyl) hexane H
214 B 2-(Oxy-cinnamyl)hexan H214 B 2- (oxy-cinnamyl) hexane H
215 C 2-(Oxy-cinnamyl)hexan H δ = 6,48215 C 2- (oxy-cinnamyl) hexane H δ = 6.48
216 D 2-(Oxy-cinnamyl)hexan H216 D 2- (oxy-cinnamyl) hexane H
217 A 2-(Oxy-4-chlorbenzyl)octan H217 A 2- (oxy-4-chlorobenzyl) octane H
218 B 2-(Oxy-4-chlorbenzyl)octan H218 B 2- (oxy-4-chlorobenzyl) octane H
219 C 2-(Oxy-4-chlorbenzyl)octan H δ = 4,37219 C 2- (oxy-4-chlorobenzyl) octane H δ = 4.37
220 D 2-(Oxy-4-chlorbenzyl)octan H220 D 2- (oxy-4-chlorobenzyl) octane H
221 C 2-(Oxy-4-chlorbenzyl)octan Me221 C 2- (oxy-4-chlorobenzyl) octane Me
222 c 2-(Oxy-4-chlorbenzyl)octan Et Tabelle 3 (Fortsetzung)222 c 2- (oxy-4-chlorobenzyl) octane Et Table 3 (continued)
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
223 C 2-(Oxy-4-chlorbenzyl)octan n-Pr223 C 2- (oxy-4-chlorobenzyl) octane n-Pr
224 C 2-(Oxy-4-chlorbenzyl)octan n-Bu224 C 2- (oxy-4-chlorobenzyl) octane n-Bu
225 A 2-(Oxy-2,4-dichlorbenzyl)octan H225 A 2- (oxy-2,4-dichlorobenzyl) octane H
226 B 2-(Oxy-2,4-dichlorbenzyl)octan H226 B 2- (oxy-2,4-dichlorobenzyl) octane H
227 C 2-(Oxy-2,4-dichlorbenzyl)octan H δ = 4,51227 C 2- (oxy-2,4-dichlorobenzyl) octane H δ = 4.51
228 D 2-(Oxy-2,4-dichlorbenzyl)octan H228 D 2- (oxy-2,4-dichlorobenzyl) octane H
229 C 2-(Oxy-2,4-dichlorbenzyl)octan Me229 C 2- (oxy-2,4-dichlorobenzyl) octane Me
230 C 2-(Oxy-2,4-dichlorbenzyl)octan Et230 C 2- (oxy-2,4-dichlorobenzyl) octane Et
231 C 2-(Oxy-2,4-dichlorbenzyl)octan n-Pr231 C 2- (oxy-2,4-dichlorobenzyl) octane n-Pr
232 C 2-(Oxy-2,4-dichlorbenzyl)octan n-Bu232 C 2- (oxy-2,4-dichlorobenzyl) octane n-Bu
233 A 2-(Oxy-2,6-dichlorbenzyl)octan H233 A 2- (oxy-2,6-dichlorobenzyl) octane H
234 B 2-(Oxy-2,6-dichlorbenzyl)octan H234 B 2- (oxy-2,6-dichlorobenzyl) octane H
235 C 2-(Oxy-2,6-dichlorbenzyl)octan H δ = 4,74235 C 2- (oxy-2,6-dichlorobenzyl) octane H δ = 4.74
236 D 2-(Oxy-2,6-dichlorbenzyl)octan H236 D 2- (oxy-2,6-dichlorobenzyl) octane H
237 C 2-(Oxy-2,6-dichlorbenzyl)octan Me237 C 2- (oxy-2,6-dichlorobenzyl) octane Me
238 C 2-(Oxy-2,6-dichlorbenzyl)octan Et238 C 2- (oxy-2,6-dichlorobenzyl) octane Et
239 C 2-(Oxy-2,6-dichlorbenzyl)octan n-Pr239 C 2- (oxy-2,6-dichlorobenzyl) octane n-Pr
240 C 2-(Oxy-2,6-dichlorbenzyl)octan n-Bu240 C 2- (oxy-2,6-dichlorobenzyl) octane n-Bu
241 A 2-(Oxy-cinnamyl)octan H241 A 2- (oxy-cinnamyl) octane H
242 B 2-(Oxy-cinnamyl)octan H242 B 2- (oxy-cinnamyl) octane H
243 C 2-(Oxy-cinnamyl)octan H δ = 6,49243 C 2- (oxy-cinnamyl) octane H δ = 6.49
244 D 2-(Oxy-cinnamyl)octan H244 D 2- (oxy-cinnamyl) octane H
245 A 2-(Oxy-methyl)decan H245 A 2- (oxymethyl) decane H
246 B 2-(Oxy-methyl)decan H246 B 2- (oxymethyl) decane H
247 C 2-(Oxy-methyl)decan H247 C 2- (oxymethyl) decane H
248 D 2-(Oxy-methyl)decan H Tabelle 3 (Fortsetzung)248 D 2- (oxymethyl) decane H Table 3 (continued)
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
249 C 2-(Oxy-methyl)decan Me249 C 2- (oxymethyl) decane Me
250 C 2-(Oxy-methyl)decan Et250 C 2- (oxymethyl) decane Et
251 C 2-(Oxy-methyl)decan n-Pr251 C 2- (oxymethyl) decane n-Pr
252 C 2-(Oxy-methyl)decan n-Bu252 C 2- (oxymethyl) decane n-Bu
253 A 2-(Oxy-ethyl)decan H253 A 2- (oxy-ethyl) decane H
254 B 2-(Oxy-ethyl)decan H254 B 2- (oxy-ethyl) decane H
255 C 2-(Oxy-ethyl)decan H255 C 2- (oxy-ethyl) decane H
256 D 2-(Oxy-ethyl)decan H256 D 2- (oxy-ethyl) decane H
257 C 2-(Oxy-ethyl)decan Me257 C 2- (oxy-ethyl) decane Me
258 C 2-(Oxy-ethyl)decan Et258 C 2- (oxy-ethyl) decane Et
259 C 2-(Oxy-ethyl)decan n-Pr259 C 2- (oxy-ethyl) decane n-Pr
260 C 2-(Oxy-ethyl)decan n-Bu260 C 2- (oxy-ethyl) decane n-Bu
261 A 2-(Oxy-methyl)dodecan H261 A 2- (oxymethyl) dodecane H
262 B 2-(Oxy-methyl)dodecan H262 B 2- (oxymethyl) dodecane H
263 C 2-(Oxy-methyl)dodecan H δ = 3,26263 C 2- (oxymethyl) dodecane H δ = 3.26
264 D 2-(Oxy-methyl)dodecan H264 D 2- (oxymethyl) dodecane H
265 C 2-(Oxy-methyl)dodecan Me265 C 2- (oxymethyl) dodecane Me
266 C 2-(Oxy-methyl)dodecan Et266 C 2- (oxymethyl) dodecane Et
267 C 2-(Oxy-methyl)dodecan n-Pr267 C 2- (oxymethyl) dodecane n-Pr
268 C 2-(Oxy-methyl)dodecan n-Bu268 C 2- (oxymethyl) dodecane n-Bu
269 A 2-(Oxy-ethyl)dodecan H269 A 2- (oxy-ethyl) dodecane H
270 B 2-(Oxy-ethyl)dodecan H270 B 2- (oxy-ethyl) dodecane H
271 C 2-(Oxy-ethyl)dodecan H δ = 4,01271 C 2- (oxy-ethyl) dodecane H δ = 4.01
272 D 2-(Oxy-ethyl)dodecan H272 D 2- (oxy-ethyl) dodecane H
273 C 2-(Oxy-ethyl)dodecan Me273 C 2- (oxy-ethyl) dodecane Me
274 C 2-(Oxy-ethyl)dodecan Et Tabelle 1274 C 2- (oxy-ethyl) dodecane Et Table 1
Bsp.- Typ R R2 phys.Example - type RR 2 phys.
Nr. DatenNo data
275 C 2-(Oxy-ethyl)dodecan n-Pr275 C 2- (oxy-ethyl) dodecane n-Pr
276 C 2-(Oxy-ethyl)dodecan n-Bu276 C 2- (oxy-ethyl) dodecane n-Bu
277 A 2-(Oxy-butyl)dodecan H277 A 2- (oxy-butyl) dodecane H
278 B 2-(Oxy-butyl)dodecan H278 B 2- (oxy-butyl) dodecane H
279 C 2-(Oxy-butyl)dodecan H δ = 4,01279 C 2- (oxy-butyl) dodecane H δ = 4.01
280 D 2-(Oxy-butyl)dodecan H280 D 2- (oxy-butyl) dodecane H
281 A 2-(Oxy-hexyl)dodecan H281 A 2- (oxyhexyl) dodecane H
282 B 2-(Oxy-hexyl)dodecan H282 B 2- (oxyhexyl) dodecane H
283 C 2-(Oxy-hexyl)dodecan H v = 1505 cm"1 283 C 2- (oxyhexyl) dodecane H v = 1505 cm "1
284 D 2-(Oxy-hexyl)dodecan H284 D 2- (oxyhexyl) dodecane H
285 A 2-(Oxy-4-chlorb enzy l)dodecan H285 A 2- (oxy-4-chlorobenzyl) dodecane H
286 B 2-(Oxy-4-chlorbenzyl)dodecan H286 B 2- (oxy-4-chlorobenzyl) dodecane H
287 C 2-(Oxy-4-chlorbenzyl)dodecan H δ = 4,37287 C 2- (oxy-4-chlorobenzyl) dodecane H δ = 4.37
288 D 2-(Oxy-4-chlorbenzyl)dodecan H288 D 2- (oxy-4-chlorobenzyl) dodecane H
289 A 2-(Oxy-2,6-dichlorbenzyl)dodecan H289 A 2- (oxy-2,6-dichlorobenzyl) dodecane H
290 B 2-(Oxy-2,6-dichlorbenzyl)dodecan H290 B 2- (oxy-2,6-dichlorobenzyl) dodecane H
291 C 2-(Oxy-2,6-dichlorbenzyl)dodecan H δ = 4,74291 C 2- (oxy-2,6-dichlorobenzyl) dodecane H δ = 4.74
292 D 2-(Oxy-2,6-dichlorbenzyl)dodecan H292 D 2- (oxy-2,6-dichlorobenzyl) dodecane H
293 A 2-(Oxy-2,4-dichlorbenzyl)dodecan H293 A 2- (oxy-2,4-dichlorobenzyl) dodecane H
294 B 2-(Oxy-2,4-dichlorbenzyl)dodecan H294 B 2- (oxy-2,4-dichlorobenzyl) dodecane H
295 C 2-(Oxy-2,4-di chl orb enzy 1 )dodecan H δ = 4,50295 C 2- (oxy-2,4-di chloro enzy 1) dodecane H δ = 4.50
296 D 2-(Oxy-2,4-dichlorbenzyl)dodecan H296 D 2- (oxy-2,4-dichlorobenzyl) dodecane H
297 A 2-(Oxy-cinnamyl)dodecan H297 A 2- (oxy-cinnamyl) dodecane H
298 B 2-(Oxy-cinnamyl)dodecan H298 B 2- (oxy-cinnamyl) dodecane H
299 C 2-(Oxy-cinnamyl)dodecan H δ = 6,48299 C 2- (oxy-cinnamyl) dodecane H δ = 6.48
300 D 2-(Oxy-cinnamyl)dodecan H Tabelle 4 (Die Herstellung der Verbindungen erfolgt analog DE-2.750.031)300 D 2- (oxy-cinnamyl) dodecane H Table 4 (The connections are made analogously to DE-2.750.031)
Figure imgf000044_0001
43
Figure imgf000044_0001
43
Tabelle 4 (Fortsetzung)Table 4 (continued)
Figure imgf000045_0001
Tabelle 4 (Fortsetzung)
Figure imgf000045_0001
Table 4 (continued)
Figure imgf000046_0001
Tabelle 4 (Fortsetzung)
Figure imgf000046_0001
Table 4 (continued)
Figure imgf000047_0001
Tabelle 4 (Fortsetzung)
Figure imgf000047_0001
Table 4 (continued)
Figure imgf000048_0001
Tabelle 4 (Fortsetzung)
Figure imgf000048_0001
Table 4 (continued)
Figure imgf000049_0001
Beispiel 351
Figure imgf000049_0001
Example 351
33,90 g Imidazol und 150 ml Dichlormethan werden bei 20°C mit 15,35 g Thionyl chlorid versetzt und 10 min gerührt. Man setzt 20 g Hendecanon (Undecanon-2) zu, rührt für eine Stunde, extrahiert mit Methylenchlorid/Wasser und trocknet die organische Phase. Nach Destillation am Kugelrohr bei 150°C/0,15 mm erhält man 17,5 g (68 % der Theorie) 2-Imidazolyl-undecan-2 als cis/trans-Gemisch.33.90 g imidazole and 150 ml dichloromethane are mixed at 20 ° C with 15.35 g thionyl chloride and stirred for 10 min. 20 g of Hendecanone (Undecanone-2) are added, the mixture is stirred for one hour, extracted with methylene chloride / water and the organic phase is dried. After distillation on a bulb tube at 150 ° C./0.15 mm, 17.5 g (68% of theory) of 2-imidazolyl-undecane-2 are obtained as a cis / trans mixture.
Auf gleiche Weise werden die in Tabelle 5 und 8 beschriebenen Verbindungen her¬ gestellt. The compounds described in Tables 5 and 8 are prepared in the same way.
Tabelle 5Table 5
Figure imgf000051_0001
Tabelle 5 - Fortsetzung
Figure imgf000051_0001
Table 5 - continued
Figure imgf000052_0001
Figure imgf000052_0001
Beispiel 370Example 370
29,41 g 2-Octylcyclohexanol in 100 ml Dichlormethan werden bei 5°C mit 18,77 g Triethylamin und dann 21,20 g Mesylchlorid versetzt, auf Rückfluß-Temperatur erhitzt und dann 6 Stunden gehalten. Nach Vertreiben des Lösungsmittels wird zwischen Wasser/Dichlormethan verteilt, die organische Phase getrocknet und eingeengt = Lösung A.29.41 g of 2-octylcyclohexanol in 100 ml of dichloromethane are mixed at 5 ° C with 18.77 g of triethylamine and then 21.20 g of mesyl chloride, heated to reflux temperature and then held for 6 hours. After the solvent has been driven off, the mixture is partitioned between water / dichloromethane, the organic phase is dried and concentrated = solution A.
Man bereitet sich aus 12,83 g Imidazol, 8,55 g NaH (60 % in Öl) und 100 ml DMF eine Lösung B, zu der langsam Lösung A zugetropft wird. Nach 22 Stunden 40°C wird mit Essigsäureethylester extrahiert, eingeengt und der Rückstand über eine Kieselgelsäure mit Toluol chromatographiert. Man erhält 2,3 g Isomerengemisch der Ziel Verbindung. δH: 4,18 ppm, Multiplett.A solution B is prepared from 12.83 g imidazole, 8.55 g NaH (60% in oil) and 100 ml DMF, to which solution A is slowly added dropwise. After 22 hours at 40 ° C., the mixture is extracted with ethyl acetate and concentrated, and the residue is chromatographed on silica gel using toluene. 2.3 g of isomer mixture of the target compound are obtained. δH: 4.18 ppm, multiplet.
Analog werden die in Tabelle 7 genannten Verbindungen erhalten. Die physi¬ kalischen Daten beziehen sich im Falle von NMR-Daten auf das Hauptisomere (> 50 % des Gemischs).The compounds mentioned in Table 7 are obtained analogously. In the case of NMR data, the physical data relate to the main isomer (> 50% of the mixture).
Vorstufen für Tabelle 7Precursors for table 7
Die Herstellung der 2-Alkyl-cyclohexanole gelingt analog der Literatur: Tietze/Eicher, Reaktionen und Synthesen, Thieme 1981; Versuche K-2a-b/C3-5; Herstellen der Schiffschen Base aus Cycloalkylketon und Cycloalkylamin, Alkylierung desselben, Hydrolyse und Reduktion desselben. The 2-alkyl-cyclohexanols can be prepared analogously to the literature: Tietze / Eicher, Reactions and Syntheses, Thieme 1981; Attempts K-2a-b / C3-5; Preparation of the Schiff base from cycloalkyl ketone and cycloalkylamine, alkylation thereof, hydrolysis and reduction of the same.
Tabelle 6, Phys. Daten der Vorstufen für Tabelle 7Table 6, Phys. Prepress data for Table 7
Figure imgf000054_0001
Figure imgf000054_0001
Tabelle 7Table 7
Figure imgf000055_0001
Tabelle 7 - Fortsetzung
Figure imgf000055_0001
Table 7 - continued
Figure imgf000056_0001
Figure imgf000056_0001
Tabelle 8Table 8
Figure imgf000057_0001
Tabelle 8 - Fortsetzung
Figure imgf000057_0001
Table 8 - continued
Figure imgf000058_0001
Figure imgf000058_0001
FormulierungsbeispieleFormulation examples
I) In 7,5 ml Wasser werden 7,5 g C12-C14-Alkyl-Benzyl-dimethylammonium- chlorid gelöst und 5 g Azolfungizid gemäß Beispiel 36 zugefügt und solange bei 25°C gerührt, bis eine klare Lösung entstanden ist. Die Lösung ist beliebig mit Wasser verdünnbar, ohne das eine zweite Phase beobachtet werden kann (Mikroemulsion).I) 7.5 g of C 12 -C 14 -alkyl-benzyl-dimethylammonium chloride are dissolved in 7.5 ml of water and 5 g of azole fungicide are added as in Example 36 and the mixture is stirred at 25 ° C. until a clear solution has formed. The solution can be diluted with water as required without a second phase being observed (microemulsion).
II) Analog Beispiel I nur das 2,5 g Azolfungizid gemäß Beispiel 36 und 1,25 g Tebuconazole verwendet werden. Die erhaltene Lösung ist beliebig mit Wasser verdünnbar und zeigt in ihrer Wirkung gemäß Beispiel A synergistische Effekte.II) Analogously to Example I, only the 2.5 g azole fungicide according to Example 36 and 1.25 g tebuconazole are used. The solution obtained can be diluted with water as desired and has synergistic effects in accordance with Example A.
III) Analog Beispiel I nur das 5,0 g Decylimidazol verwendet werden. III) Analogously to Example I, only the 5.0 g decylimidazole can be used.
Anwendungsbeispiel:Example of use:
AnwendungsbeispielApplication example
A. Zum Nachweis der Wirksamkeit gegen Pilze werden die minimalen Hemm- Konzentrationen (MHK) von erfindungsgemäßen Mitteln bestimmt:A. To demonstrate the activity against fungi, the minimum inhibitory concentrations (MIC) of agents according to the invention are determined:
Ein Agar, der unter Verwendung von Malzextrakt hergestellt wird, wird mit erfindungsgemäßen Wirkstoffen in Konzentrationen von 0,1 mg/1 bis 5000 mg/1 versetzt. Nach Erstarren des Agars erfolgt Kontamination mit Reinkulturen der in der Tabelle 1 aufgeführten Testorganismen. Nach 2- wöchiger Lagerung bei 28°C und 60 bis 70 % relativer Luftfeuchtigkeit wird die MHK bestimmt. MHK ist die niedrigste Konzentration an Wirkstoff, bei der keinerlei Bewuchs durch die verwendete Mikrobenart erfolgt, sie ist in der nachstehenden Tabelle 2 angegeben. An agar which is produced using malt extract is mixed with active compounds according to the invention in concentrations of 0.1 mg / 1 to 5000 mg / 1. 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.
Tabelle ITable I
Minimale Hemmkonzentrationen (mg/1)Minimum inhibitory concentrations (mg / 1)
Figure imgf000061_0001
Figure imgf000061_0001
Tabelle IITable II
Minimale Hemmkonzentrationen (mg/1)Minimum inhibitory concentrations (mg / 1)
108 109 112 113108 109 112 113
Penicillium brevicaule <600 >600 <600 <600Penicillium brevicaule <600> 600 <600 <600
Chaetomium globosum <600 <600 <600 <600Chaetomium globosum <600 <600 <600 <600
Aspergillus niger >600 >600 >600 >600Aspergillus niger> 600> 600> 600> 600
140 141 172 173140 141 172 173
Penicillium brevicaule <600 <600 <600 <600Penicillium brevicaule <600 <600 <600 <600
Chaetomium globosum <600 <600 <600 <600Chaetomium globosum <600 <600 <600 <600
Aspergillus niger <600 >600 <600 >600Aspergillus niger <600> 600 <600> 600
184 185184 185
Penicillium brevicaule <600 >600Penicillium brevicaule <600> 600
Chaetomium globosum <600 <600Chaetomium globosum <600 <600
Aspergillus niger >600 >600 Tabelle mAspergillus niger>600> 600 Table m
Minimale Hemmkonzentrationen (mg/1)Minimum inhibitory concentrations (mg / 1)
199 203 207 211199 203 207 211
Penicillium brevicaule <400 <400 <400 <400Penicillium brevicaule <400 <400 <400 <400
Chaetomium globosum <400 <400 <400 <400Chaetomium globosum <400 <400 <400 <400
Aspergillus niger <400 >400 <400 <400Aspergillus niger <400> 400 <400 <400
215 227 235 243215 227 235 243
Penicillium brevicaule <400 >400 <400 <400Penicillium brevicaule <400> 400 <400 <400
Chaetomium globosum <400 <400 <400 <400Chaetomium globosum <400 <400 <400 <400
Aspergillus niger >400 >400 <400 >400Aspergillus niger> 400> 400 <400> 400
271 283 291271 283 291
Penicillium brevicaule <400 <400 <400Penicillium brevicaule <400 <400 <400
Chaetomium globosum <400 <400 <400Chaetomium globosum <400 <400 <400
Aspergillus niger <400 >400 >400Aspergillus niger <400> 400> 400
Tabelle ININ table
Minimale Hemmkonzentrationen (mg/1)Minimum inhibitory concentrations (mg / 1)
307 31 1 327 331307 31 1 327 331
Penicillium brevicaule <400 <400 <400 <400Penicillium brevicaule <400 <400 <400 <400
Chaetomium globosum <400 <400 <400 <400Chaetomium globosum <400 <400 <400 <400
Aspergillus niger <400 >400 <400 <400Aspergillus niger <400> 400 <400 <400
335 343 347335 343 347
Penicillium brevicaule <400 <400 <400Penicillium brevicaule <400 <400 <400
Chaetomium globosum <400 <400 <400Chaetomium globosum <400 <400 <400
Aspergillus niger >400 >400 <400 B. Prüfung der Schimmelfestigkeit von AnstrichenAspergillus niger>400> 400 <400 B. Testing the mold resistance of paints
Die auf ihre fungizide Wirksamkeit zu prüfende Substanz wird in der ge¬ wünschten Konzentration in die (Dispersions)-Farbe mittels eines Dissolvers eingearbeitet. Anschließend wird die Farbe beidseitig auf eine geeignete Unterlage gestrichen.The substance to be tested for its fungicidal activity is incorporated in the desired concentration in the (dispersion) color using a dissolver. The paint is then spread on both sides on a suitable surface.
Um praxisnahe Ergebnisse zu erhalten wird ein Teil der Prüflinge vor dem Test auf Schimmelfestigkeit mit fließendem Wasser (24 h; 20°C) ausgelaugt.In order to obtain practical results, some of the test specimens are leached with running water (24 h; 20 ° C) before the test for mold resistance.
Dieso vorbereitete Prüflinge werden auf einen Agar-Nährboden gelegt. Prüflinge und Nährboden werden mit Pilzsporen kontaminiert. Nach 1- bis 3- wöchiger Lagerung bei 29 + 1°C und 80-90 % rel. Luftfeuchte wird abge¬ mustert. Der Anstrich ist dauerhaft schimmelfest, wenn der Prüfling pilzfrei bleibt oder höchstens einen geringen Randbefall erkennen läßt.The test specimens thus prepared are placed on an agar medium. Test specimens and culture medium are contaminated with fungal spores. After storage for 1 to 3 weeks at 29 + 1 ° C and 80-90% rel. Humidity is sampled. The paint is permanently mold-resistant if the test specimen remains free of fungi or if at most a slight edge infestation can be seen.
Zur Kontamination werden Pilzsporen folgender neun Schimmelpilze verwendet, die als Anstrichzerstörer bekannt sind oder häufig auf Anstrichen angetroffen werden:Fungus spores of the following nine molds, which are known as paint destroyers or are often found on paints, are used for contamination:
1. Alternaria tenuis1. Alternaria tenuis
2. Aspergillus flavus2. Aspergillus flavus
3. Aspergillus niger3. Aspergillus niger
4. Aspergillus ustus 5. Cladosporium herbarum4. Aspergillus ustus 5. Cladosporium herbarum
6. Paecilomyces variotii6. Paecilomyces variotii
7. Penicillium citrinum7. Penicillium citrinum
8. Aureobasidium pullulans8. Aureobasidium pullulans
9. Stachybotrys atra Corda9. Stachybotrys atra Corda
Die folgende Tabelle V zeigt die Wirkstoffkonzentrationen, bei denen der An¬ strichprüfling pilzfrei bleibt (Konzentrationen bezogen auf Feststoffgehalt der Dispersionsfarbe) Tabelle VThe following Table V shows the active compound concentrations at which the paint test specimen remains free of fungi (concentrations based on the solids content of the emulsion paint) Table V
ohne Belastung nach Wässerungwithout stress after watering
Bekannt n-Octyl-N-imidazol 0,6 % > 2 '% n-Decyl-N-imidazol 2,0 % 2,0 % n-Dodecyl-N-imidazol >3 % >3 % n-Octyl-N-2-methyl- >3 % >3 % imidazol n-Decyl-N-triazol >3 % >3 % erfindungsgemäß Bps.12 0,6 % 1,5 %Known n-octyl-N-imidazole 0.6%> 2 '% n-decyl-N-imidazole 2.0% 2.0% n-dodecyl-N-imidazole> 3%> 3% n-octyl-N- 2-methyl-> 3%> 3% imidazole n-decyl-N-triazole> 3%> 3% according to the invention Bps.12 0.6% 1.5%
Bsp.36 0,6 % 1,5 %Ex. 36 0.6% 1.5%
Bsp.48 0,6 % 0,6-1,0 % Ex. 48 0.6% 0.6-1.0%

Claims

Patentansprüche claims
1. Mikrobizide Mittel enthaltend mindestens eine Verbindung der Formel (I)1. Microbicidal compositions comprising at least one compound of the formula (I)
W=XW = X
R-NR-N
Z=Y (I) in welcherZ = Y (I) in which
R für eine verzweigte, cyclische und/oder durch C|-C19-Alkyl, C2-C10-R for a branched, cyclic and / or by C | -C 19 alkyl, C 2 -C 10 -
Alkenyl und oder OR1 und/oder C(O)OR! substituierte Alkylkette oder Alkenylkette mit 5 bis 20 Kohlenstoffatomen steht, die gegebe¬ nenfalls durch ein oder zwei Schwefel- oder Sauerstoffatome unterbrochen ist,Alkenyl and or OR 1 and / or C (O) OR ! substituted alkyl chain or alkenyl chain with 5 to 20 carbon atoms, which is optionally interrupted by one or two sulfur or oxygen atoms,
W, X, Y, Z unabhängig voneinander für Stickstoff oder die Gruppe CR2 stehen, wobei mindestens zwei für die Gruppe CR stehen, und worinW, X, Y, Z independently of one another represent nitrogen or the group CR 2 , at least two standing for the group CR, and in which
R2 für Wasserstoff oder geradkettiges oder verzweigtes Cj-C^- Alkyl steht,R 2 represents hydrogen or straight-chain or branched C j -C ^ alkyl,
R1 für geradkettiges oder verzweigtes Cj-C^-Alkyl, C2-C10-Alke- nyl oder für einfach bis dreifach durch Methyl, Chlor und/oder Fluor substituiertes Benzyl oder Cinnamyl steht.R 1 represents straight-chain or branched C j ^ -C alkyl, C 2 -C 10 is -Alke- nyl or mono- to trisubstituted by methyl, chlorine and / or fluorine-substituted benzyl or cinnamyl.
2. Mittel gemäß Anspruch 1, enthaltend Verbindungen der Formel (I),2. Composition according to claim 1, containing compounds of formula (I),
in welcherin which
R für eine verzweigte, cyclische oder einfach bis dreifach durch CrC16- Alkyl, C2-C6-Alkenyl, OR1 und/oder C(O)OR1 Gruppen substituierteR for a branched, cyclic or monosubstituted to trisubstituted by C r C 16 alkyl, C 2 -C 6 alkenyl, OR 1 and / or C (O) OR 1 groups
Alkylkette oder Alkenylkette mit 5 bis 14 Kohlenstoffatomen steht, die gegebenenfalls durch ein Sauerstoff atom unterbrochen ist, W für die Gruppen CH oder C-(CrC10)-Alkyl steht,Alkyl chain or alkenyl chain with 5 to 14 carbon atoms, which is optionally interrupted by an oxygen atom, W represents the groups CH or C- (C r C 10 ) -alkyl,
Z, X für Stickstoff oder die Gruppe CH stehen, undZ, X represent nitrogen or the group CH, and
Y für die Gruppe CH steht, undY represents the group CH, and
R1 für CrC6-Alkyl steht.R 1 represents C r C 6 alkyl.
3. Mittel gemäß Anspruch 1, enthaltend Verbindungen der Formel (I),3. Composition according to claim 1, containing compounds of formula (I),
in welcherin which
R für eine verzweigte oder einfach bis zweifach durch C1-C3-Alkyl, OR1 und/oder C(O)OR1 Gruppen in α- oder ß-Position substituierte Alkylkette oder Alkenylkette mit 9 bis 12 Kohlenstoffatomen steht, die gegebenenfalls durch ein Sauer Stoff atom unterbrochen ist, oder für einfach, zweifach oder dreifach durch C4-C15, OR1 und/oder COOR1 substituiertes Cyclopentyl, Cyclohexyl, Cycloheptyl oder Cyclooctyl steht,R represents a branched or mono- to disubstituted or substituted by C 1 -C 3 alkyl, OR 1 and / or C (O) OR 1 groups in the α- or β-position alkyl chain or alkenyl chain with 9 to 12 carbon atoms, which may be by an oxygen atom is interrupted, or stands for cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl which is substituted once, twice or three times by C 4 -C 15 , OR 1 and / or COOR 1 ,
W für CH, C-Me, C-Et oder C-Propyl steht,W represents CH, C-Me, C-Et or C-propyl,
Z, Y für CH stehen,Z, Y stand for CH,
X für Stickstoff steht, undX represents nitrogen, and
R1 für Me, Et, n-, i-Pr, n-, i-, s-, t-Bu oder n-Pentyl steht.R 1 represents Me, Et, n-, i-Pr, n-, i-, s-, t-Bu or n-pentyl.
4. Mittel gemäß Anspruch 1 zum Schutz von Anstrichen bzw. Anstrichmitteln. 4. Means according to claim 1 for the protection of paints or paints.
5. Verbindungen der Formel (II)5. Compounds of formula (II)
R"R "
^ > (II)^> (II)
R -N NR -N N
in welcherin which
R3 für eine in α-Position durch C C9-n- Alkylkette substituierte n-Alkyl- kette mit C7-C14-Kohlenstoffatomen steht, oder für ein in 2-, 3- oderR 3 represents an n-alkyl chain with C 7 -C 14 carbon atoms which is substituted in the α-position by CC 9 -n-alkyl chain, or for an in 2-, 3- or
4-Position substituiertes Cyclohexyl oder Cyclopentyl steht, wobei der Substituent eine C4-C]5- Alkyl- oder Alkenylgruppe darstellt, und4-substituted cyclohexyl or cyclopentyl, where the substituent represents a C 4 -C 5 alkyl or alkenyl group, and
R4 für H oder CrC6-Alkyl steht.R 4 represents H or C r C 6 alkyl.
6. Verbindungen der Formel (II) gemäß Anspruch 5,6. Compounds of formula (II) according to claim 5,
in welcherin which
R3 für eine in α-Position durch Cj- bis C5-n-Alkylkette substituierte n- Alkylkette mit C8-C12-Kohlenstoffatomen steht, oder für ein in 2- oder 4-Position substituiertes Cyclohexyl steht, wobei der Substituent eine C5-C12-Alkyl- oder Alkenylgruppe darstellt, undR 3 represents an n-alkyl chain with C 8 -C 12 carbon atoms substituted in the α-position by C j - to C 5 -n-alkyl chain, or stands for a cyclohexyl substituted in the 2- or 4-position, the substituent represents a C 5 -C 12 alkyl or alkenyl group, and
R4 für H oder C,-C4-Alkyl steht.R 4 represents H or C, -C 4 alkyl.
7. Verbindungen der Formel (II) gemäß Anspruch 5,7. Compounds of formula (II) according to claim 5,
in welcherin which
R3 für eine in α-Position durch Cj- bis C3-n-Alkylkette substituierte n- Alkylkette mit C9-Cπ-Atomen steht, oder eine in 2-Position substi- tuiertes Cyclohexyl steht, wobei der Substituent eine Alkyl- oderR 3 represents an n-alkyl chain with C 9 -C π atoms substituted in the α-position by C j - to C 3 -n-alkyl chain, or a cyclohexyl substituted in the 2-position, the substituent being an alkyl - or
Alkenylgruppe mit C6-C12 darstellt, und R4 für H oder Me, Et, n-, i-Pr, n-, i-, s-, t-Bu oder n-Pentyl steht.Represents alkenyl group with C 6 -C 12 , and R 4 represents H or Me, Et, n-, i-Pr, n-, i-, s-, t-Bu or n-pentyl.
8. Verfahren zum Schützen von technischen Materialien, dadurch gekennzeich¬ net, daß man Verbindungen der Formel (I) nach Anspruch 1, auf die zu schützenden Materialien aufbringt oder mit diesen vermischt.8. A method for protecting industrial materials, characterized in that compounds of the formula (I) according to Claim 1 are applied to the materials to be protected or mixed with them.
9. Verwendung von Verbindungen der Formel (I) und (II) nach den Ansprüchen 1 bis 7 zum Schutz von technischen Materialien.9. Use of compounds of formula (I) and (II) according to claims 1 to 7 for the protection of industrial materials.
10. Verwendung von Verbindungen der Formeln (I) und (II) nach den Ansprüchen 1 bis 7 zur Bekämpfung von Schädlingen.10. Use of compounds of the formulas (I) and (II) according to Claims 1 to 7 for controlling pests.
11. Verfahren zur Bekämpfung von Schädlingen, dadurch gekennzeichnet, daß man Verbindungen der Formeln (I) oder (IT) nach den Ansprüchen 1 und 6 auf Schädlinge und/oder ihren Lebensraum einwirken läßt.11. A method for controlling pests, characterized in that compounds of the formulas (I) or (IT) according to claims 1 and 6 are allowed to act on pests and / or their habitat.
12. Verfahren zur Herstellung von mikrobiziden Mitteln, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) und (II) nach den Ansprüchen 1 bis 7 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt.12. A process for the preparation of microbicidal agents, characterized in that compounds of the formulas (I) and (II) according to Claims 1 to 7 are mixed with extenders and / or surface-active agents.
13. Verfahren zur Herstellung von Verbindungen der Formel (I) nach Anspruch 1, dadurch gekennzeichnet, daß man Imidazol, gegebenenfalls in Gegenwart eines Lösungsmittels, mit Alkalihydriden behandelt und anschließend mit Halogenalkenen versetzt. 13. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that imidazole, optionally in the presence of a solvent, is treated with alkali metal hydrides and then mixed with haloalkenes.
PCT/EP1994/003745 1993-11-24 1994-11-11 Alkyl-n-pyrroles WO1995014383A1 (en)

Priority Applications (1)

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Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4339982 1993-11-24
DEP4339982.7 1993-11-24
DE4416409A DE4416409A1 (en) 1993-11-24 1994-05-10 Alkyl-N-azoles
DEP4416409.2 1994-05-10

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
JP2009013172A (en) * 2007-06-06 2009-01-22 Sk Kaken Co Ltd Disinfectant compound

Citations (5)

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Publication number Priority date Publication date Assignee Title
DE2442703A1 (en) * 1974-09-06 1976-03-18 Agfa Gevaert Ag COLOR PHOTOGRAPHIC MATERIAL WITH NEW 2-AEQUIVALENT YELLOW COUPLERS
FR2283893A1 (en) * 1974-09-06 1976-04-02 Goldschmidt Ag Th 1-Higher-2-lower-alkyl imidazoles suitable as microbicides - prepd. from higher-alkyl halide and substd. imidazole
DE2750030A1 (en) * 1977-11-09 1979-05-10 Basf Ag INSECTICIDES
DE2750031A1 (en) * 1977-11-09 1979-05-10 Basf Ag INSECTICIDES
JPS6335564A (en) * 1986-07-30 1988-02-16 Hodogaya Chem Co Ltd Imidazole derivative and plant growth regulator containing said derivative as active component

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Publication number Priority date Publication date Assignee Title
DE2442703A1 (en) * 1974-09-06 1976-03-18 Agfa Gevaert Ag COLOR PHOTOGRAPHIC MATERIAL WITH NEW 2-AEQUIVALENT YELLOW COUPLERS
FR2283893A1 (en) * 1974-09-06 1976-04-02 Goldschmidt Ag Th 1-Higher-2-lower-alkyl imidazoles suitable as microbicides - prepd. from higher-alkyl halide and substd. imidazole
DE2750030A1 (en) * 1977-11-09 1979-05-10 Basf Ag INSECTICIDES
DE2750031A1 (en) * 1977-11-09 1979-05-10 Basf Ag INSECTICIDES
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JP2009013172A (en) * 2007-06-06 2009-01-22 Sk Kaken Co Ltd Disinfectant compound

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