WO1994029268A1 - Iodopropargyl carbamates and their use as biocides in the protection of plants and materials - Google Patents

Iodopropargyl carbamates and their use as biocides in the protection of plants and materials Download PDF

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Publication number
WO1994029268A1
WO1994029268A1 PCT/EP1994/001691 EP9401691W WO9429268A1 WO 1994029268 A1 WO1994029268 A1 WO 1994029268A1 EP 9401691 W EP9401691 W EP 9401691W WO 9429268 A1 WO9429268 A1 WO 9429268A1
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optionally
formula
compounds
alkyl
carbon atoms
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PCT/EP1994/001691
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German (de)
French (fr)
Inventor
Lutz Heuer
Peter Wachtler
Martin Kugler
Heinrich Schrage
Hans-Ulrich Buschhaus
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Bayer Aktiengesellschaft
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Priority claimed from DE4332508A external-priority patent/DE4332508A1/en
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to EP94916987A priority Critical patent/EP0702670A1/en
Priority to AU68450/94A priority patent/AU6845094A/en
Publication of WO1994029268A1 publication Critical patent/WO1994029268A1/en

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    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/24—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

  • the present invention relates to new propargyl carbamates, processes for their preparation and their use as biocides in plant and material protection. From U.S. 3,923,870 are iodopropargyl carbamates of the general type
  • R 1 , R 2 independently of one another represent hydrogen, alkyl or phenyl or R 1 and R 2 form a 5- to 8-membered ring
  • R 3 , R 4 independently of one another, optionally by 1 to 3 oxygen,
  • Sulfur or nitrogen atoms are interrupted and / or optionally substituted alkyl, or represent optionally substituted aryl, aralkyl, or together with the nitrogen atom to which they are attached form an optionally substituted 5- to 8-membered ring which is optionally interrupted by 1 to 3 oxygen, sulfur and / or nitrogen atoms and / or which is optionally benzo-fused.
  • Ar preferably represents aryl having 6 to 10 carbon atoms, which can be substituted one to five times, in the same way or differently, by halogen, hydroxyl, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy by 1 up to 4 carbon atoms, straight-chain or branched alkylthio with 1 to 4 carbon atoms, straight-chain or branched alkylsulfinyl with 1 to 4 carbon atoms, straight-chain or branched alkylsulfonyl with
  • each of these radicals may be mono- to fivefold substituted by halogen, hydroxy, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, straight-chain or branched alkylsulfinyl having 1 to 4 carbon atoms, straight-chain or branched alkylsulfonyl having 1 to 4 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkoxy having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkoxy having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloal
  • Ethoxycarbonyl methoximinomethyl, methoximinoethyl, ethoxyiminomethyl, ethoximinoethyl, propane-1,3-diyl, butane-1,4-diyl, dioxymethylene, dioxyethylene, dioxypropylene, difiuordioxymethylene, tetrafluorodioxyethylene, cyclopropyl, cyclopentyl, cyclohexyl, 1-pyrrolidinyl, 1-pyrrolidinyl 1-perhydroazepinyl, 4-morpholinyl, phenyl, phenoxy, benzyl,
  • Cyano nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t- butoxy, methylthio, ethylthio, methylsulphinyl, Methylsuifonyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, methoximinoethyl, ethoxyiminomethyl, ethoximinoethyl, propane-1,3-diyl, butane-1,4- diyl, dioxymethylene, dioxyethylene, dioxy prop
  • aralkyl preferably stands for aryl-C 1 C 6 alkyl, where aryl has the meaning given above and alkyl particularly preferably stands for methylene, ethylene, n-, i-propylene or n-, i-, s- or t-butylene
  • Alkyl hereinafter represents optionally substituted straight-chain or branched or cyclic alkyl having preferably 1 to 30, particularly preferably 1 to 18 carbon atoms, which is optionally interrupted by 1 to 3, preferably 1 or 2, oxygen, sulfur or nitrogen atoms.
  • Alkyl radicals R 3 and R 4 are preferably the substituents already shown under aryl.
  • R 1 , R 2 independently of one another represent hydrogen, C 1 -C 6 alkyl or R 1 and R 2 together form a five- to six-membered ring,
  • R 3 , R 4 independently of one another, optionally interrupted and / or interrupted by 1 or 2 oxygen, sulfur and / or nitrogen atoms optionally by halogen, alkyl, alkylthio, alkoxy, haloalkyl, haloalkoxy each having 1 to 6 carbon atoms in the alkyl part or aryl or by the group CO 2 R 1 substituted straight-chain, branched or cyclic C 1 -C 18 alkyl, or for optionally by Halogen, alkyl, alkoxy, alkylthio, haloalkyl each having 1 to 6 carbon atoms in the alkyl part or aryl-substituted aryl, hetaryl or aralkyl having 1 to 6 carbon atoms in the alkyl part, or together with the nitrogen atom to which they are attached a five- to six-membered group Form a ring which is optionally interrupted by 1 or 2 oxygen, sulfur and / or nitrogen atoms and / or is
  • R 1 , R 2 independently of one another represent hydrogen or methyl
  • R 3 , R 4 independently of one another for optionally interrupted by 1 or 2 oxygen, sulfur and / or nitrogen atoms and / or optionally by fluorine, chlorine, methyl, ethyl, n-, i-propyl, n-, i-, s - or t-butyl, methoxy, ethoxy, n-, i-propyloxy, n-, i-, s- or t-butyloxy, methylthio, ethylthio, n-, i-propylthio, n-, i-, s- or t-butylthio,
  • Haloalkyl, haloalkoxy each having 1 to 5 halogen atoms and 1 to 4 carbon atoms, phenyl or the group CO 2 R 1 substituted, straight-chain, branched or cyclic C 1 -C 14 alkyl, or optionally by fluorine, chlorine, methyl, ethyl , n-, i-Propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n-, i-propyloxy, n-, i-, s- or t-butyloxy, methylthio, ethylthio, n -, i-Propylthio, n-, i-, s- or t-butylthio, haloalkyl, haloalkoxy, each with 1 to 5 Halogen atoms and 1 to 4 carbon atoms, phenyl substituted
  • X represents hydrogen or iodine with compounds of the formula (III) optionally in the presence of a diluent, in the presence of a
  • X represents hydrogen or iodine with amines of the formula (V)
  • X represents hydrogen or iodine
  • Y represents a leaving group, such as halogen, O-tosyl or O-mesyl, and is reacted with amines of the formula (V) in the presence of a base and carbon dioxide and optionally in the presence of a diluent
  • the method 4 is also known in principle.
  • the iodination is preferably carried out with elemental iodine, Na I, K I, I Cl in the presence of NaOH, KOH or NaOCl and optionally in the presence of elemental chlorine.
  • Preferred diluents are polar diluents such as methanol, ethanol, propanol, isopropanol, butanol, polyethylene glycols, polypropylene glycols and other alcohols, as well as ketones such as acetone and methyl butyl ketone, dimethyl sulfoxide, dimethylformamide and water or else non-polar diluents such as toluene, ethyl acetate, diethyl ether, diethyl ether, with simultaneous use of phase transfer catalysts and mixtures of different diluents.
  • the reaction is generally carried out at temperatures from -10 ° C to 80 ° C, preferably -5 ° C to 20 ° C
  • Method 3 is new and is also the subject of the application.
  • the leaving group Y is preferably bromine, chlorine, iodine or the groups
  • the amine of the formula (V) is preferably reacted with carbon dioxide in the presence of one or more basic compounds of the elements lithium, sodium, potassium, rubidium and then the propyl derivative is added.
  • a wide variety of basic reacting amines can be used in the process according to the invention, preferably those of the formula (V).
  • amine equivalent 0.01 to 10,000 equivalents of carbon dioxide are used in the process according to the invention. This ratio is preferably 1: 0.5 to 1,000, in particular 1: 1 to 10.
  • alkylating agent for example, from 0.01 to 10.0 equivalents of alkylating agent are used per amine equivalent used in the process according to the invention. This ratio is preferably 1: 0.3 to 10, in particular 1: 0.4 to 3. It is an essential feature of the present invention that one works in the presence of one or more basic compounds of the elements lithium, sodium, potassium, rubidium. Suitable basic compounds are, for example, basic salts, oxides, hydrides and hydroxides.
  • Examples include: lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, lithium oxide, sodium peroxide, potassium oxide, potassium peroxide, lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, rubidium carbonate, rubidium hydrogen carbonate, ammonium carbonate, ammonium carbonate and / or naturally occurring and / or Mixtures as well as DBU or DBN.
  • Alkali carbonates and / or hydrogen carbonates are preferred, very particularly preferably potassium carbonate.
  • the process according to the invention is optionally carried out in the presence of auxiliary bases, i.e. in the presence of further bases, for example in an amount of less than 0.5 mol, based on the amount of base used.
  • auxiliary bases examples include halides of alkali metals, zeolites, potassium acetate, lithium perchlorate, potassium formate, sodium acetate,
  • DBU 7-methyl-1,5,7-triazabicyclo (4.4.0) dec-5-ene
  • MTBD 7-methyl-1,5,7-triazabicyclo (4.4.0) dec-5-ene
  • cyclohexyl-tetraguanidine cyclohexyl-tetramethylguanidine
  • N, N, N, N, N-tetramethyl-1,8 -naphthalenediamine pentamethylpiperdine
  • N N-dimethylpyrridine
  • N-butyl-tetraethylguanidine pentamethylpiperdine, N, N-dimethylpyrridine, N-butyl-tetraethylguanidine
  • Amines such as triethylamine, trimethylamine, N-methylmorpholine, pyridine, N, N-dimethylpyridine and tetramethylethylene diamine, amine used, alcoholates such as potassium t-butoxide, sodium methylate, sodium ethylate, sodium neopentylate and
  • Phenyl- and Neoprylithium, as well as Grignard reagent .. it is advantageous to carry out the process according to the invention in the presence of a diluent. Diluents are advantageously used in an amount such that the reaction mixture remains readily stirrable throughout the process.
  • Possible diluents are, for example: hydrocarbons such as petroleum ether, benzene, toluene, chlorobenzene, dichlorobenzene, hexane, cyclohexane, methacrylate clohexane, pentane, heptane, octane and technical hydrocarbon mixtures, for example so-called white spirits with components with boiling points in the range from 40 to 250 °, for example C, ethers such as dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, methyl t-butyl ether, tetrahydrofuran, 1,4-dioxane and polyethers of ethylene oxide and / or propylene oxide, amines such as trimethyl, triethyl, tripropyl , Tributyl, diethyl and dibutylamine, as well as n-methylmorpholine, pyridine, N, N-dimethyl
  • diluent mixtures can also be used in the process according to the invention.
  • Preferred solvents are dimethylformamide and dimethyl sulfoxide as well
  • the process according to the invention is generally carried out by first bringing the basic reacting amine and the carbon dioxide together in the presence of a basic compound of the elements mentioned and allowing them to react with one another.
  • the alkylating agent is advantageously only added when when the reaction of the amine with the carbon dioxide has largely or completely expired
  • the progress of the reaction of the amine with the carbon dioxide can be recognized, for example, by the heat tone.
  • the process according to the invention is carried out in both stages, for example at temperatures from 50 to 130 ° C. Temperatures in the range from 30 ° C. to + 150 ° C. are preferred, in particular those in the range from -10 ° C. to + 100 ° C.
  • the pressure is not critical in the method according to the invention. In principle, it is possible to work at normal pressure, but also at elevated or reduced pressure. It is preferred to work at normal pressure or at pressures of up to 5 bar. Especially at elevated temperatures, it is advisable to choose a higher pressure.
  • the process according to the invention can be carried out under a carbon dioxide atmosphere, but also in an atmosphere which contains carbon dioxide and other, preferably inert, gases.
  • the substance according to the invention is suitable as a pesticide, in particular as a fungicide in crop protection.
  • Fungicides are used in crop protection to combat plasmadiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Xanthomonas species such as Xanthomonas oryzae
  • Xanthomonas oryzae Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation: Xanthomonas species, such as Xanthomonas oryzae;
  • Pseudomonas species such as Pseudomonas lachrymans
  • Erwinia species such as Erwinia amylovora
  • Pythium species such as Pythium ultimum
  • Phytophthora species such as Phytophthora infestans
  • Pseudoperonospora species such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
  • Plasmopara species such as Plasmopara viticola
  • Peronospora species such as Peronospora pisi or P. brasssicae;
  • Erysiphe species such as Erysiphe graminis
  • Sphaerotheca species such as Sphaerotheca fuliginea
  • Podosphaera species such as Podosphaera leucitricha
  • Venturia species such as Venturia inaequalis
  • Pyrenophora species such as Pyrenophora teres or P. graminea;
  • Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
  • Cochliobolus species such as Cochliobolus sativus
  • Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
  • Uromyces species such as Uromyces appendiculatus
  • Puccinia species such as Puccinia recondita
  • Tilletia species such as Tilletia caries
  • Ustilago species such as Ustilago nuda or Ustilago avenae
  • Pellicularia species such as Pellicularia sasakii
  • Pyricularia species such as Pyricularia oryzae
  • Fusarium species such as Fusarium culmorum
  • Botrytis species such as Botrytis cinerea
  • Septoria species such as Septoria nodorum
  • Leptosphaeria species such as Leptosphaeria nodorum
  • Cercospora species such as Cercospora canescens
  • Alternaria species such as Alternaria brassicae
  • Pseudocercosporella species such as Pseudocercosporella herpotrichoides.
  • the fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds and of the soil.
  • the substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.
  • 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 formulations.
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, 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, pressurized 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 .
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and Waser;
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as butane, propane, nitrogen and carbon dioxide;
  • Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays
  • Adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids 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% by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaridzides and herbicides, and also in mixtures with fertilizers and growth regulators.
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, foaming, brushing, etc.
  • the active ingredients can also be applied.
  • the application rate can be varied over a wide range depending on the type of application.
  • the active substance concentrations in the treatment of parts of plants in the use forms are generally between 1 and 0.001% by weight, preferably between 0.5 and 0.001%.
  • amounts of active ingredient of 0.001 to 50 g per kg 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% are required at the site of action.
  • the active ingredients or agents according to the invention also have a strong
  • microorganisms Action against microorganisms. They are used in material protection to protect technical materials: they are primarily effective against mold, wood-staining and wood-destroying fungi and bacteria, as well as against yeasts, algae and slime organisms.
  • the following types of microorganisms may be mentioned by way of example, but without limitation:
  • Altemaria such as Altemaria tenuis, Aspergillus such as Aspergillus niger and Aspergülus terreus, Aureobasidium such as Aureobasidium pullulans, Chaetomium such as Chaetomium globosum, Cladosporium such as Cladosporium herbarum, Coniophora such as Coniophora souna, Gliocladium such as Gliocinecilluscesin, such as Paiocinium latinus Penicillium brevicaule, Penicillium glaucum and Penicillium pinophilum, Polyporus like Polyporus versicolor, Sclerophoma like Sclerophoma pityophila, Streptoverticillium like Streptoverticillium reticulum, Trichoderma like Trichoderma viride, Trichophyton like Trichytesyut;
  • Escherichia such as Escherichia coli
  • Pseudomonas such as Pseudomonas areuginosa
  • Staphylococcus such as Staphylococcus aureus
  • Candida like Candida albicans The amount of active ingredients used depends on the type and occurrence of the microorganisms, the number of bacteria and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.001 to 20% by weight, preferably 0.05 to 10% by weight, of the active compound mixtures, based on the material to be protected.
  • the new active ingredients can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with solvents or diluents, emulsifiers, dispersants and / or binders or fixatives, optionally siccatives and UV stabilizers and optionally dyes and pigments and other processing aids.
  • Suitable solvents or diluents are organic chemical solvents or solvent mixtures and / or a polar organic solvent or solvent mixtures and / or an oily or oil-like organic chemical solvent or solvent mixture and / or water with preferably an emulsifier and / or wetting agent .
  • the respective mineral oils / mineral oil-containing solvent mixtures or their aromatic fractions are preferably used as customary non-volatile, water-insoluble oily or oily solvents. Examples include white spirit, petroleum or alkylbenzenes, along with spindle oil and monochlomaphthalene.
  • the boiling ranges of these low volatility solvents (mixtures) span the range from approx. 170 ° C to a maximum of 350 ° C.
  • the previously described volatile oily or oily solvents can be partially replaced by more volatile organic chemical solvents.
  • part of the solvent or solvent mixture described above is preferably replaced by a polar organic chemical solvent or solvent mixture.
  • Solvents which contain hydroxyl groups, ester groups, ether groups or mixtures of this functionality are preferably used. Esters or glycol ethers may be mentioned as examples.
  • binders are understood to be water-thinnable or soluble in organic chemical solvents, dispersible or emulsifiable synthetic resins, binding drying oils, for example based on acrylic resins, vinyl resins, polyester resins, polyurethane resins, alkyd resins, phenolic resins, hydrocarbon resins, silicone resins .
  • the binder used can be used as a solution, emulsion or dispersion. Mixtures of alkyd resins and drying vegetable oil are preferably used. Alkyd resins with an oil content of between 45 and 70% are particularly preferred. All or part of the binder mentioned can be replaced by a fixative mixture or a plasticizer mixture. These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
  • the plasticizers come from the chemical classes or phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate and amyl stearate, oleates such as butyl oleate, glycerol glycol ether and higher or glycerol ether p-toluenesulfonic acid ester.
  • phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate
  • phosphoric acid esters such as tributyl phosphate
  • adipic acid esters such as di- (2-ethylhexyl) adipate
  • stearates such as butyl stearate and amy
  • Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylbenzophenone.
  • a solvent or diluent water is preferably used, optionally in a mixture with one or more of the abovementioned solvents or. Diluents, emulsifiers and dispersants.
  • industrial materials are 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, are also mentioned which can be impaired by the multiplication of microorganisms.
  • Preferred technical materials for the purposes of the invention are adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants, aqueous hydraulic fluids and cooling circuits and generally aqueous functional liquids.
  • the effectiveness and the spectrum of activity of the active compounds according to the invention or of the agents, concentrates or very generally formulations which can be prepared therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active compounds are used to enlarge the spectrum of action or to achieve special effects such as e.g. added protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.
  • Sulfenamides such as dichlofluanid (Euparen), tolylfluanid (Methyleuparen), Folpet, Fluorfolpet; Benzimidazoles such as Carbendazim (MBC), Benomyl, Fuberidazole, Thiabendazole or their salts; Thiocyanates such as thiocyanatomethylthiobenzothiazole (TCMTB), methylene bisthiocyanate (MBT); quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
  • Morpholine derivatives such as C 11 -C 14 -4-alkyl-2,6-dimethyl-morpholine homologous (tridemorph), ( ⁇ ) -cis-4- [3-tert-butylphenyl) -2-methylpropyl] -2,6- dimethylmorpholine (fenpropimorph), falimorph; Phenols such as o-phenylphenol, tribromophenol, tetrachlorophenol, pentachlorophenol, 3-methyl-4-chlorophenol, dichlorophen, chlorophen or their salts;
  • Azoles such as triadimefon, triadimenol, bitertanol, tebuconazole, propiconazole, azaconazole, hexaconazole, prochloraz; iodopropargyl derivatives such as iodopropargyl butyl carbamate (IPBC), chlorophenyl formal,
  • phenyl carbamate hexyl carbamate, cyclohexyl carbamate, iodopropargyloxyethylphenyl carbamate;
  • Iodine derivatives such as diiodomethyl-p-arylsulfones e.g. Diiodomethyl p-tolyl sulfone;
  • Bromine derivatives such as bronopol
  • Isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one (octhilinones);
  • Benzisothiazolinones cyclopentene isothiazolines
  • Pyridines such as 1-hydroxy-2-pyridinthione (and their Na, Fe, Ma, Zn salts), tetrachloro-4-methylsulphonylpyridine
  • Metal soaps such as tin, copper, zinc naphthenate, o-toate, -2-ethylhexanoate, oleate, phosphate benzoate, oxides such as TBTO, Cu 2 O, CuO, ZnO;
  • Organic tin compounds such as tributyltin naphthenate and tributyltin oxide; Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethyldiuramidisulfide (TMTD);
  • TMTD tetramethyldiuramidisulfide
  • Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil) etc.
  • Microbicides with activated halogen groups such as Cl-Ac, MCA, tectamer, bronopol, bromidox;
  • Benzothiazoles such as 2-mercaptobenzothiazole; so. Dazomet;
  • Quinolines such as 8-hydroxyquinoline;
  • Formaldehyde-releasing compounds such as benzyl alcohol mono (poly) hemiformal, oxazolidines, hexahydro-s-triazines, N-methylolchloroacetamide;
  • Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, 1- (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxypyrazole (TIA-230), chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrimfos, Fenitrothion, Fention, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxion, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprofos, Triazophos and Trichlorphon.
  • chlorpyrifos Coumaphos, Demeton, Demeton-S-methyl, diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrimfos, Fenitrothion, F
  • Carbamates such as aldicarb, bendiocarb, BPMC (2- (1-methylpropyl) phenylmethylcarbamate), butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur and Thiodicarb.
  • Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin (FMC 54 800), cycloprothrin, cyfluthrin, decamethrione, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- ( chlor-2-trifluoromethylvinyl) cyclopropane carboxylate fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin and resmethrin; Nitroimides such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazol-2-anine (imidacloprid).
  • Organosilicon compounds preferably dimethyl (phenyl) silylmethyl-3-phenoxy-benzyl ether such as e.g. Dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or dimethyl (phenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl (9-ethoxyphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether or (phenyl) [3- (3-phenoxyphenyl) propyl] (dimethyl) silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl) propyl] dimethyl silane.
  • dimethyl (phenyl) silylmethyl-3-phenoxy-benzyl ether such as e.g. Dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or dimethyl (phenyl
  • microbicidal agents or concentrates used to protect the industrial materials contain the active compounds according to the invention in a concentration of 0.01 to 95% by weight, in particular 0.01 to 60% by weight, in addition, if appropriate, 0.001 to 10% by weight suitable further fungicide, insecticide or another active ingredient as mentioned above
  • 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 following examples serve to illustrate the invention without limiting it. Parts and percentages mean parts by weight or percentages by weight. Example A1 (preparation of the preliminary stage)
  • N, N-dibutylpropagyl carbamate 100 g (0.775 mol) of dibuylamine, 189.0 g (1.37 ml) of K 2 CO 3 and 500 ml of DMF are mixed with 440 g of CO 2 in a 3 1 VA autoclave and 30 heated to 100 ° C. for min. After cooling to 50 ° C. (pressure: 75 bar), 60.0 g (95%) (0.765 ml) of propyl chloride are added and the mixture is kept at 50 ° C. for 6 h. After relaxing, the residue is filtered off with suction and washed with 1 1 CH 2 CH 2 and the organic phase is distilled.

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Abstract

The invention concerns propargyl carbamates of formula (I) in which R?1 and R2¿, independently of each other, are hydrogen, alkyl or phenyl, or R?1 and R2¿ together form a 5- to 8-membered ring, and R?3 and R4¿, independently of each other, are alkyl (which may optionally have 1 to 3 oxygen, sulphur or nitrogen atoms in the carbon chain and/or may optionally be susbtituted) or optionally substituted aryl or aralkyl, or R?3 and R4¿, together with the nitrogen atom to which they are bound, form an optionally substituted 5- to 8-membered ring which may optionally include 1 to 3 oxygen, sulphur and/or nitrogen atoms in the ring and/or may optionally be benzoanellated. The invention also concerns a method of preparing them and their use as biocides in the protection of plants and materials.

Description

IODPROPARGYLCARBAMATE UND IHRE VERWENDUNG ALS BIOZIDE IM PFLANZEN- UND MATERIALSCHUTZ IODOPROPARGYLCARBAMATES AND THEIR USE AS BIOCIDES IN PLANT AND MATERIAL PROTECTION
Die vorliegende Erfindung betrifft neue Propargylcarbamate, Verfahren zu ihrer Herstellung und ihre Verwendung als Biozide im Pflanzen- und Materialschutz. Aus US-3 923 870 sind Iodpropargylcarbamate des allgemeinen Typs The present invention relates to new propargyl carbamates, processes for their preparation and their use as biocides in plant and material protection. From U.S. 3,923,870 are iodopropargyl carbamates of the general type
Figure imgf000003_0001
Figure imgf000003_0001
bekannt.  known.
Aus US-4 865 892 sind Verbindungen des Typs From U.S. 4,865,892 are compounds of the type
Figure imgf000003_0002
bekannt und aus DE 3.216.895 des Typs
Figure imgf000003_0002
known and from DE 3,216,895 of the type
Figure imgf000004_0002
Figure imgf000004_0002
Diesen Verbindungen wird eine antimikrobielle, fungizide, bakterizide Verwendung im Material- oder im Pflanzenschutz zugeschrieben. Die Verwendung dieser Stoffe wird jedoch durch eintretende Zersetzung dieser Verbindung im Anwendungsgebiet eingeschränkt. Dadurch werden sowohl höhere Anfangsdosierungen nötig als rein biologisch erforderlich, auch treten Verfärbungen auf, was insbesondere bei der Verwendung im Materialschutz zu Problemen führt. Es wurden nun neue Propagylcarbamate der allgemeinen Formel (I) An antimicrobial, fungicidal, bactericidal use in material or plant protection is attributed to these compounds. However, the use of these substances is restricted by the decomposition of this compound in the area of application. As a result, higher starting doses are required than are purely biologically necessary, and discoloration also occurs, which leads to problems particularly when used in material protection. New propagyl carbamates of the general formula (I)
Figure imgf000004_0001
in welcher R1, R2 unabhängig voneinander für Wasserstoff, Alkyl oder Phenyl stehen oder R1 und R2 einen 5- bis 8-gliedrigen Ring bilden,
Figure imgf000004_0001
in which R 1 , R 2 independently of one another represent hydrogen, alkyl or phenyl or R 1 and R 2 form a 5- to 8-membered ring,
R3, R4 unabhängig voneinander für gegebenenfalls durch 1 bis 3 Sauerstoff-, R 3 , R 4 independently of one another, optionally by 1 to 3 oxygen,
Schwefel-, oder Stickstoffatome unterbrochenes und/oder gegebenenfalls substituiertes Alkyl, oder für gegebenenfalls substituiertes Aryl, Aralkyl stehen, oder zusammen mit dem Stickstoffatom an das sie gebunden sind einen gegebenenfalls substituierten 5- bis 8-gliedrigen Ring bilden, der gegebenenfalls durch 1 bis 3 Sauerstoff-, Schwefel- und/oder Stickstoffatome unterbrochen ist, und/oder der gegebenenfalls benzoanelliert ist, gefunden. Sulfur or nitrogen atoms are interrupted and / or optionally substituted alkyl, or represent optionally substituted aryl, aralkyl, or together with the nitrogen atom to which they are attached form an optionally substituted 5- to 8-membered ring which is optionally interrupted by 1 to 3 oxygen, sulfur and / or nitrogen atoms and / or which is optionally benzo-fused.
Ar steht im folgenden bevorzugt für Aryl mit 6 bis 10 Kohlenstoff atomen, das einfach bis fünffach, gleichartig oder verschieden substituiert sein kann durch Halogen, Hydroxy, Cyano, Nitro, geradkettiges oder verzweigtes Alkyl mit 1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkoxy mit 1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkylthio mit 1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkylsulfinyl mit 1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkylsulfonyl mitIn the following, Ar preferably represents aryl having 6 to 10 carbon atoms, which can be substituted one to five times, in the same way or differently, by halogen, hydroxyl, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy by 1 up to 4 carbon atoms, straight-chain or branched alkylthio with 1 to 4 carbon atoms, straight-chain or branched alkylsulfinyl with 1 to 4 carbon atoms, straight-chain or branched alkylsulfonyl with
1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, geradkettiges oder verzweigtes Halogenalkoxy mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, geradkettiges oder verzweigtes Halogenalkylthio mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, geradkettiges oder verzweigtes Halogenalkylsulfinyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, geradkettiges oder verzweigtes Halogenalkylsulfonyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, Dialkylamino mit 1 bis 4 Kohlenstoffatomen in jedem Alkylteil, Alkoxycarbonyl mit 1 bis 4 Kohlenstoffatomen im Alkoxyteil, Alkoximinoalkyl mit 1 bis 4 Kohlenstoffatomen im Alkoxyteil und 1 bis 4 Kohlenstoffatomen im Alkylteil, gegebenenfalls einfach bis dreifach, gleichartig oder verschieden durch Halogen, Alkyl mit 1 bis 3 Kohlenstoffatomen und/oder Halogenalkyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 gleichen oder verschiedenen Halogenatomen substituiertes, zweifach verknüpftes Alkylen mit 1 bis 3 Kohlenstoffatomen, gegebenen falls einfach bis dreifach, gleichartig oder verschieden durch Halogen, Alkyl mit 1 bis 3 Kohlenstoffatomen und/oder Halogenalkyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 Halogenatomen substituiertes Dioxyalkylen mit 1 bis 4 Kohlenstoffatomen, gegebenenfalls einfach bis dreifach, gleichartig oder verschieden durch Halogen, Alkyl mit 1 bis 3 Kohlenstoffatomen und/oder Halogenalkyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 Halogenatomen substituiertes Cycloalkyl mit 3 mit 6 Kohlenstoffatomen, gegebenenfalls einfach bis dreifach, gleichartig oder verschieden durch Halogen, Alkyl mit 1 bis 3 Kohlenstoffatomen und/oder Halogenalokyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 Halogenatomen substituiertes, gesättigtes Heterocyclyl mit 5 bis 7 Ringgliedern sowie 4 bis 6 Kohlenstoffatomen und 1 oder 2 gleichen oder verschiedenen Heteroatomen, wie Stickstoff, Sauerstoff und/oder Schwefel, und ferner durch Phenyl, Phenoxy, Benzyl, Benzyloxy, Phenylethyl oder Phenylethyloxy, wobei jeder der 6 letztgenannten Substituenten im Phenylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Halogen, Alkyl mit 1 bis 31 to 4 carbon atoms, straight-chain or branched haloalkyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkoxy with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkylthio with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkylsulfinyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, dialkylamino with 1 to 4 Carbon atoms in each alkyl part, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, optionally single to triple, identical or different by halogen, Alkyl with 1 to 3 carbon atoms and / or haloalkyl with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted, double-linked alkylene with 1 to 3 carbon atoms if single to triple, identical or different by halogen, alkyl having 1 to 3 carbon atoms and / or haloalkyl having 1 to 3 carbon atoms and 1 to 7 halogen atoms, dioxyalkylene having 1 to 4 carbon atoms, optionally single to triple, identical or different by halogen, Alkyl having 1 to 3 carbon atoms and / or haloalkyl having 1 to 3 carbon atoms and 1 to 7 halogen atoms, substituted cycloalkyl having 3 with 6 carbon atoms, optionally mono- to triple, identical or different by halogen, alkyl having 1 to 3 carbon atoms and / or haloalkyl 1 to 3 carbon atoms and 1 to 7 halogen atoms, saturated heterocyclyl with 5 to 7 ring members and 4 to 6 carbon atoms and 1 or 2 identical or different heteroatoms, such as nitrogen, oxygen and / or sulfur, and furthermore phenyl, phenoxy, benzyl, Benzyloxy, phenylethyl or phenylethyloxy, each of the 6 let The above-mentioned substituents in the phenyl moiety can be substituted one to three times, in the same way or differently, by halogen, alkyl having 1 to 3
Kohlenstoffatomen, Alkoxy mit 1 bis 3 Kohlenstoffatomen, Halogenalkyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 gleichen oder verschiedenen Halogenatomen und/oder durch Halogenalkoxy mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 gleichen oder verschiedenen Halogenatomen. oder auch bevorzugt für gegebenenfalls benzoannelliertes Heteoaryl mit 2 bis 9 Kohlenstoffatomen und 1 bis 3 gleich oder verschiedenen Heteroatomen, wie Stickstoff, Sauerstoff und/oder Schwefel, wobei jeder dieser Reste einfach bis fünffach substituiert sein kann durch Halogen, Hydroxy, Cyano, Nitro, geradkettiges oder verzweigtes Alkyl mit 1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkoxy mit 1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkylthio mit 1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkylsulfinyl mit 1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkylsulfonyl mit 1 bis 4 Kohlenstoffatomen, geradkettiges oder verzweigtes Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, geradkettiges oder verzweigtes Halogenalkoxy mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, geradkettiges oder verzweigtes Halogenalkylthio mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, geradkettiges oder verzweigtes Halogenalkylsulfinyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, geradkettiges oder verzweigtes Halogenalkylsulfonyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, Dialkylamino mit 1 bis 4 Kohlenstoffatomen in jedem Alkylteil, Alkoxycarbonyl mit 1 bis 4 Kohlenstoffatomen im Alkoxyteil, Alkoximinoalkyl mit 1 bis 4 Kohlenstoffatomen im Alkoxyteil und 1 bis 4 Kohlenstoffatomen im Alkylteil, gegebenenfalls einfach bis dreifach, gleichartig oder verschieden durch Halogen, Alkyl mit 1 bis 3 Kohlenstoffatomen und/oder Halogenalkyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 gleichen oder verschiedenen Halogenatomen substituiertes, zweifach verknüpftes Alkylen mit 1 bis 4 Kohlenstoffatomen, gegebenenfalls einfach bis dreifach, gleichartig oder verschieden durch Halogen, Alkyl mit 1 bis 3 Kohlenstoffatomen und/oder Halogenalkyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 Halogenatomen substituiertes Dioxyalkylen mit 1 bis 4 Kohlenstoffatomen, gegebenenfalls einfach bis dreifach, gleichartig oder verschieden durch Halogen, Alkyl mit 1 bis 3 Kohlenstoffatomen und/oderCarbon atoms, alkoxy with 1 to 3 carbon atoms, haloalkyl with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms and / or by haloalkoxy with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms. or also preferably for optionally benzo-fused heteroaryl having 2 to 9 carbon atoms and 1 to 3 identical or different heteroatoms, such as nitrogen, oxygen and / or sulfur, it being possible for each of these radicals to be mono- to fivefold substituted by halogen, hydroxy, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, straight-chain or branched alkylsulfinyl having 1 to 4 carbon atoms, straight-chain or branched alkylsulfonyl having 1 to 4 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkoxy having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkylthio having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkylsulfinyl 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, dialkylamino with 1 to 4 carbon atoms in each alkyl part, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, Alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, optionally single to triple, identical or different by halogen, alkyl with 1 to 3 carbon atoms and / or haloalkyl with 1 to 3 carbon atoms and 1 to 7 The same or different halogen atoms substituted, double-linked alkylene with 1 to 4 carbon atoms, optionally single to triple, identical or different by halogen, alkyl with 1 to 3 carbon atoms and / or haloalkyl with 1 to 3 carbon atoms and 1 to 7 halogen atoms substituted dioxyalkylene with 1 up to 4 carbon atoms, optionally single to triple, identical or different by halogen, alkyl having 1 to 3 carbon atoms and / or
Halogenalkyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 Halogenatomen substituiertes Cycloalkyl mit 3 mit 6 Kohlenstoffatomen, gegebenenfalls einfach bis dreifach, gleichartig oder verschieden durch Halogen, Alkyl mit 1 bis 3 Kohlenstoffatomen und/oder Halogenalokyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 Halogenatomen substituiertes, gesättigtes Heterocyclyl mit 5 bis 7 Ringgliedern sowie 4 bis 6 Kohlenstoffatomen und 1 oder 2 gleichen oder verschiedenen Heteroatomen, wie Stickstoff, Sauerstoff und/oder Schwefel, und ferner durch Phenyl, Phenoxy, Benzyl, Benzyloxy, Phenylethyl oder Phenylethyloxy, wobei jeder der 6 letztgenannten Substituenten im Phenylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Halogen, Alkyl mit 1 bis 3 Kohlenstoffatomen, Alkoxy mit 1 bis 3 Kohlenstoffatomen, Halogenalkyl mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 gleichen oder verschiedenenHaloalkyl with 1 to 3 carbon atoms and 1 to 7 halogen atoms, substituted cycloalkyl with 3 with 6 carbon atoms, optionally single to triple, identical or different by halogen, alkyl with 1 to 3 carbon atoms and / or halogenoalkyl with 1 to 3 carbon atoms and 1 to 7 halogen atoms substituted, saturated heterocyclyl having 5 to 7 ring members and 4 to 6 carbon atoms and 1 or 2 identical or different heteroatoms, such as nitrogen, oxygen and / or sulfur, and furthermore by phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy, each of which 6 latter substituents in the phenyl part can be monosubstituted to trisubstituted, identical or different, by halogen, alkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, haloalkyl with 1 to 3 carbon atoms and 1 to 7 identical or different
Halogenatomen und/oder durch Halogenalkoxy mit 1 bis 3 Kohlenstoffatomen und 1 bis 7 gleichen oder verschiedenen Halogenatomen. steht besonders bevorzugt für Phenyl oder Naphthyl, wobei jeder dieser Reste einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Hydroxy, Cyano, Nitro, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s-oder t-Butoxy, Methylthio, Ethylthio, Methylsulfinyl, Methylsuifonyl, Trifluormethyl, Trifluormethoxy, Trifluormethylthio, Trifluormethylsulfinyl, Trifluormethylsulfonyl, Dimethylamino, Diethylamino, Methoxycarbonyl,Halogen atoms and / or by haloalkoxy having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms. particularly preferably represents phenyl or naphthyl, where each of these radicals can be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i -, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, methylsulfinyl, methylsuifonyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl , Dimethylamino, diethylamino, methoxycarbonyl,
Ethoxycarbonyl, Methoximinomethyl, Methoximinoethyl, Ethoxyiminomethyl, Ethoximinoethyl, Propan-1,3-diyl, Butan-1,4-diyl, Dioxymethylen, Dioxyethylen, Dioxypropylen, Difiuordioxymethylen, Tetrafluordioxyethylen, Cyclopropyl, Cyclopentyl, Cyclohexyl, 1-Pyrrolidinyl, 1-Piperidinyl, 1-Perhydroazepinyl, 4-Morpholinyl, Phenyl, Phenoxy, Benzyl,Ethoxycarbonyl, methoximinomethyl, methoximinoethyl, ethoxyiminomethyl, ethoximinoethyl, propane-1,3-diyl, butane-1,4-diyl, dioxymethylene, dioxyethylene, dioxypropylene, difiuordioxymethylene, tetrafluorodioxyethylene, cyclopropyl, cyclopentyl, cyclohexyl, 1-pyrrolidinyl, 1-pyrrolidinyl 1-perhydroazepinyl, 4-morpholinyl, phenyl, phenoxy, benzyl,
Benzyloxy, Phenylethyloxy, wobei jeder der 6 letzgenananten Reste im Phenylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Ethoxy, Trifluormethyl und/oder Trifluormethoxy, oder auch bevorzugt für Furanyl, Thienyl, Pyrrolyl, Oxazolyl, Thiazolyl, Isoxyzolyl, Isothiazolyl, Pyrazolyl, Imidazolyl, Oxadiazolyl, Thiadiazolyl, Triazolyl, Pyridyl, Pyridazinyl, Pyrimidinyl, Pyrazinyl oder Triazinyl, wobei jeder dieser Reste benzoannelliert sein kann und einfach bis dreifach gleichartig oder verschiedenn substituiert sein kann durch Fluor, Chlor, Brom, Hydroxy,Benzyloxy, phenylethyloxy, where each of the 6 last-mentioned residues in the phenyl part can be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy, or also preferably for furanyl, thienyl , Pyrrolyl, oxazolyl, thiazolyl, isoxyzolyl, isothiazolyl, pyrazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl, each of which radicals can be benzo-fused and substituted by three or the same same way, or simply substituted by three identical or fluorine radicals , Chlorine, bromine, hydroxy,
Cyano, Nitro, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy, Methylthio, Ethylthio, Methylsulfinyl, Methylsuifonyl, Trifluormethyl, Trifluormethoxy, Trifluormethylthio, Trifluormethylsulfinyl, Trifluormethylsulfonyl, Dimethylamino, Diethylamino, Methoxycarbonyl, Ethoxycarbonyl, Methoximinomethyl, Methoximinoethyl, Ethoxyiminomethyl, Ethoximinoethyl, Propan-1,3-diyl, Butan-1,4-diyl, Dioxymethylen, Dioxyethylen, Dioxy propylen, Difluordioxymethylen, Tetrafluordioxyethylen, Cyclopropyl,Cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t- butoxy, methylthio, ethylthio, methylsulphinyl, Methylsuifonyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, methoximinoethyl, ethoxyiminomethyl, ethoximinoethyl, propane-1,3-diyl, butane-1,4- diyl, dioxymethylene, dioxyethylene, dioxy propylene, difluorodioxymethylene, tetrafluorodioxyethylene, cyclopropyl,
Cyclopentyl, Cyclohexyl, 1-Pyrrolidinyl, 1-Piperidinyl, 1-Perhydroazepinyl, 4-Morpholinyl, Phenyl, Phenoxy, Benzyl, Benzyloxy, Phenylethyloxy, wobei jeder der 6 letzgenananten Reste im Phenylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Ethoxy, Trifluormethyl und/oder Trifluormethoxy. Cyclopentyl, cyclohexyl, 1-pyrrolidinyl, 1-piperidinyl, 1-perhydroazepinyl, 4-morpholinyl, phenyl, phenoxy, benzyl, benzyloxy, phenylethyloxy, where each of the 6 last-mentioned residues in the phenyl part can be mono- to triple, identical or differently substituted by fluorine , Chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy.
Aralkyl steht im folgenden vorzugsweise für Aryl-C1C6alkyl, wobei Aryl die oben angegebene Bedeutung hat und Alkyl besonders bevorzugt für Methylen, Ethylen, n-, i-Propylen oder n-, i-, s- oder t-Butylen steht In the following, aralkyl preferably stands for aryl-C 1 C 6 alkyl, where aryl has the meaning given above and alkyl particularly preferably stands for methylene, ethylene, n-, i-propylene or n-, i-, s- or t-butylene
Alkyl steht im folgenden für gegebenenfalls substituiertes geradkettiges oder verzweigtes oder cyclisches Alkyl mit vorzugsweise 1 bis 30, besonder bevorzugt 1 bis 18 Kohlenstoffatomen, das gegebenenfalls durch 1 bis 3, vorzugsweise 1 oder 2 Sauerstoff-, Schwefel- oder Stickstoffatome unterbrachen ist. Insbesondere seien genannt: Methyl, Ethyl, n-, i-Propyl, n-, i-, s-, t-Butyl, n-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decanyl, n-Undecanyl, n-Dodecanyl, n-Tridecanyl, n-Tetradecanyl, n-Pentadecanyl, n-Hexadecanyl, n-Heptadecanyl sowie deren verzweigte Isomere, Cyclopropyl, Cyclobutyl, Cyclpentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecanyl, Cycloundecanyl und Cyclododecanyl. Als Substituenten derAlkyl hereinafter represents optionally substituted straight-chain or branched or cyclic alkyl having preferably 1 to 30, particularly preferably 1 to 18 carbon atoms, which is optionally interrupted by 1 to 3, preferably 1 or 2, oxygen, sulfur or nitrogen atoms. The following may be mentioned in particular: methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n- Decanyl, n-undecanyl, n-dodecanyl, n-tridecanyl, n-tetradecanyl, n-pentadecanyl, n-hexadecanyl, n-heptadecanyl and their branched isomers, cyclopropyl, cyclobutyl, cyclpentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctyl, cyclooctyl, cyclooctyl, cyclooctyl Cycloundecanyl and cyclododecanyl. As a substituent of
Alkylreste R3 bzw. R4 seien vorzugsweise die schon unter Aryl aufgezeigten Substituenten genannt. Alkyl radicals R 3 and R 4 are preferably the substituents already shown under aryl.
Bevorzugt sind Verbindungen der Formel (I), in welcher Compounds of the formula (I) in which
R1, R2 unabhängig voneinander für Wasserstoff, C1-C6-Alkyl stehen oder R1 und R2 zusammen einen fünf- bis sechsgliedrigen Ring bilden , R 1 , R 2 independently of one another represent hydrogen, C 1 -C 6 alkyl or R 1 and R 2 together form a five- to six-membered ring,
R3, R4 unabhängig voneinander für gegebenenfalls durch 1 oder 2 Sauerstoff-, Schwefel- und/oder Stickstoffatome unterbrochenes und/oder gegebenenfalls durch Halogen, Alkyl, Alkylthio, Alkoxy, Halogenalkyl, Halogenalkoxy mit jeweils 1 bis 6 Kohlenstoffatomen im Alkylteil oder Aryl oder durch die Gruppe CO2R1 substituiertes geradkettiges, verzweigtes oder cyclisches C1-C18-Alkyl stehen, oder für gegebenenfalls durch Halogen, Alkyl, Alkoxy, Alkylthio, Halogenalkyl mit jeweils 1 bis 6 Kohlenstoffatomen im Alkylteil oder Aryl substituiertes Aryl, Hetaryl oder Aralkyl mit 1 bis 6 Kohlenstoffatomen im Alkylteil stehen, oder zusammen mir dem Stickstoffatom, an das sie gebunden sind einen fünf- bis sechsgliederigen Ring bilden der gegebenenfalls durch 1 oder 2 Sauerstoff-, Schwefel- und/oder Stickstoffatome unterbrochen ist und/oder gegebenenfalls benzoanelliert ist und/oder gegebenenfalls durch Halogen, Alkyl, Alkoxy, Alkylthio- oder Aryl substituiert ist. R 3 , R 4 independently of one another, optionally interrupted and / or interrupted by 1 or 2 oxygen, sulfur and / or nitrogen atoms optionally by halogen, alkyl, alkylthio, alkoxy, haloalkyl, haloalkoxy each having 1 to 6 carbon atoms in the alkyl part or aryl or by the group CO 2 R 1 substituted straight-chain, branched or cyclic C 1 -C 18 alkyl, or for optionally by Halogen, alkyl, alkoxy, alkylthio, haloalkyl each having 1 to 6 carbon atoms in the alkyl part or aryl-substituted aryl, hetaryl or aralkyl having 1 to 6 carbon atoms in the alkyl part, or together with the nitrogen atom to which they are attached a five- to six-membered group Form a ring which is optionally interrupted by 1 or 2 oxygen, sulfur and / or nitrogen atoms and / or is optionally benzo-fused and / or is optionally substituted by halogen, alkyl, alkoxy, alkylthio or aryl.
Besonders bevorzugt sind Verbindungen der Formel (I) in welcher Compounds of the formula (I) in which are particularly preferred
R1, R2 unabhängig voneinander für Wasserstoff oder Methyl stehen, R 1 , R 2 independently of one another represent hydrogen or methyl,
R3, R4 unabhängig voneinander für gegebenenfalls durch 1 oder 2 Sauerstoff-, Schwefel- und/oder Stickstoffatome unterbrochenes und/oder gegebenenfalls durch Fluor, Chlor, Methyl, Ethyl, n-, i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n-, i-Propyloxy, n-, i-, s- oder t-Butyloxy, Methylthio, Ethylthio, n-, i-Propylthio, n-, i-, s- oder t-Butylthio, R 3 , R 4 independently of one another for optionally interrupted by 1 or 2 oxygen, sulfur and / or nitrogen atoms and / or optionally by fluorine, chlorine, methyl, ethyl, n-, i-propyl, n-, i-, s - or t-butyl, methoxy, ethoxy, n-, i-propyloxy, n-, i-, s- or t-butyloxy, methylthio, ethylthio, n-, i-propylthio, n-, i-, s- or t-butylthio,
Halogenalkyl, Halogenalkoxy mit jeweils 1 bis 5 Halogenatomen und 1 bis 4 Kohlenstoffatomen, Phenyl oder die Gruppe CO2R1 substituiertes, geradkettiges, verzweigtes oder cyclisches C1-C14-Alkyl stehen, oder für gegebenenfalls durch Fluor, Chlor, Methyl, Ethyl, n-, i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n-, i-Propyloxy, n-, i-, s- oder t-Butyloxy, Methylthio, Ethylthio, n-, i-Propylthio, n-, i-, s- oder t-Butylthio, Halogenalkyl, Halogenalkoxy mit jeweils 1 bis 5 Halogenatomen und 1 bis 4 Kohlenstoffatomen, Phenyl substituiertesHaloalkyl, haloalkoxy each having 1 to 5 halogen atoms and 1 to 4 carbon atoms, phenyl or the group CO 2 R 1 substituted, straight-chain, branched or cyclic C 1 -C 14 alkyl, or optionally by fluorine, chlorine, methyl, ethyl , n-, i-Propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n-, i-propyloxy, n-, i-, s- or t-butyloxy, methylthio, ethylthio, n -, i-Propylthio, n-, i-, s- or t-butylthio, haloalkyl, haloalkoxy, each with 1 to 5 Halogen atoms and 1 to 4 carbon atoms, phenyl substituted
Phenyl, Naphthyl, Biphenyl, Benzyl, Phenylethyl, Pyridyl, Furyl, Thiophenyl Pyrrolyl, Oxazolyl, Thiazolyl, Pyrazolyl, Imidazolyl oder Triazoyl stehen, oder zusammen mit dem Stickstoffatom an das sie gebunden sind einen Pyrrolidin-, Piperidin-, Morpholin-, Tetrahydroisochinolin oder Piperazinring bilden, der gegebenenfalls durchPhenyl, naphthyl, biphenyl, benzyl, phenylethyl, pyridyl, furyl, thiophenyl pyrrolyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl or triazoyl, or together with the nitrogen atom to which they are attached a pyrrolidine, piperidine, morpholine, tetrahydroisoquinoline Form piperazine ring, if necessary, by
Fluor, Chlor, Methyl, Methoxy, Trifluormethyl, Ethyl, Ethoxy substituiert ist Fluorine, chlorine, methyl, methoxy, trifluoromethyl, ethyl, ethoxy is substituted
Ganz besonders bevorzugt sind Verbindungen der Formel (I) in welcher R3 und R4 jeweils für den gleichen Rest stehen, oder R3 für Me und R4 die oben angegebenen Bedeutungen hat. Compounds of the formula (I) in which R 3 and R 4 each represent the same radical, or R 3 for Me and R 4 have the meanings indicated above, are very particularly preferred.
Desweiteren wurde ein Verfahren zur Herstellung der Verbindungen der Formel (I) gefunden, in dem man Furthermore, a process for the preparation of the compounds of formula (I) has been found in which
1. Verbindungen der Formel (II) 1. Compounds of formula (II)
Figure imgf000011_0001
Figure imgf000011_0001
worin  wherein
X für Wasserstoff oder Iod steht mit Verbindungen der Formel (III)
Figure imgf000012_0001
gegebenenfalls in Gegenwart eines Verdünnungsmittels, in Gegenwart einerX represents hydrogen or iodine with compounds of the formula (III)
Figure imgf000012_0001
optionally in the presence of a diluent, in the presence of a
Base umsetzt, oder Base implements, or
2. Verbindungen der Formel (IV) 2. Compounds of the formula (IV)
Figure imgf000012_0002
worin
Figure imgf000012_0002
wherein
X für Wasserstoff oder Iod steht mit Aminen der Formel (V) X represents hydrogen or iodine with amines of the formula (V)
Figure imgf000012_0003
gegebenenfalls in Gegenwart eines Verdünnungsmittels, in Gegenwart einer Base umsetzt, oder
Figure imgf000012_0003
optionally in the presence of a diluent, in the presence of a base, or
3. Verbindungen der Formel (VI)
Figure imgf000013_0001
3. Compounds of the formula (VI)
Figure imgf000013_0001
worin  wherein
X für Wasserstoff oder Iod steht X represents hydrogen or iodine
Y für eine Abgangsgruppe, wie Halogen, O-Tosyl oder O-Mesyl, steht mit Aminen der Formel (V) in Gegenwart einer Base und Kohlendioxid und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt und Y represents a leaving group, such as halogen, O-tosyl or O-mesyl, and is reacted with amines of the formula (V) in the presence of a base and carbon dioxide and optionally in the presence of a diluent
4. für den Fall, daß X in den Formel (II), (IV) oder (VI) für Wasserstoff steht, anschließend in Gegenwart einer Hilfsbase und gegebenenfalls einem Verdünnungsmittel iodiert. 4. in the event that X in the formula (II), (IV) or (VI) is hydrogen, then iodized in the presence of an auxiliary base and optionally a diluent.
Die Verfahren 1 und 2 sind im Prinzip bekannt und werden entsprechend der EP-430 127, US 4 865 892 und GB 2 220 000 durchgeführt The methods 1 and 2 are known in principle and are carried out in accordance with EP-430 127, US 4,865,892 and GB 2,220,000
Das Verfahren 4 ist ebenfalls im Prinzip bekannt. Die Iodierung wird dabei vorzugsweise mit elementarem Iod, Na I, K I, I Cl in Gegenwart von NaOH, KOH oder NaOCl und gegebenenfalls in Gegenwart von elementarem Chlor durchgeführt. The method 4 is also known in principle. The iodination is preferably carried out with elemental iodine, Na I, K I, I Cl in the presence of NaOH, KOH or NaOCl and optionally in the presence of elemental chlorine.
Als Verdünnungsmittel kommen vorzugsweise polare Verdünnungsmittel wie Methanol, Ethanol, Propanol, iso-Propanol, Butanol, Polyethylenglykole, Polypropylenglykole und andere Alkohole sowie Ketone wie Aceton und Methylbutylketon, Dimethylsulfoxid, Dimethylformamid und Wasser oder auch unpolare Verdünnungsmittel wie Toluol, Ethylacetat, Diethylether, Methylenchlorid, bei gleichzeitiger Verwendung von Phasentransferkatalysatoren sowie Mischungen verschiedener Verdünnnungsmittel in Frage. Die Umsetzung wird im allgemeinen bei Temperaturen von -10°C bis 80°C, vorzugsweise -5°C bis 20°C durchgeführt Preferred diluents are polar diluents such as methanol, ethanol, propanol, isopropanol, butanol, polyethylene glycols, polypropylene glycols and other alcohols, as well as ketones such as acetone and methyl butyl ketone, dimethyl sulfoxide, dimethylformamide and water or else non-polar diluents such as toluene, ethyl acetate, diethyl ether, diethyl ether, with simultaneous use of phase transfer catalysts and mixtures of different diluents. The reaction is generally carried out at temperatures from -10 ° C to 80 ° C, preferably -5 ° C to 20 ° C
Das Verfahren 3 ist neu und ebenfalls Gegenstand der Anmeldung. Method 3 is new and is also the subject of the application.
Als Abgangsgruppe Y kommen vorzugsweise Brom, Chlor, Iod oder die Gruppen , ,The leaving group Y is preferably bromine, chlorine, iodine or the groups
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0003
, O-SO2-Me, O-SO2-CF3, O-SO2-nC4H9 und
Figure imgf000014_0004
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0003
, O-SO 2 -Me, O-SO 2 -CF 3 , O-SO 2 -nC 4 H 9 and
Figure imgf000014_0004
O-SO2-CH2CF3 in Frage. O-SO 2 -CH 2 CF 3 in question.
Bevorzugt werden Verbindungen der Formel (VI) eingesetzt in welcher R1 und R2 für Wasserstoff stehen. Compounds of the formula (VI) in which R 1 and R 2 are hydrogen are preferably used.
Vorzugsweise wird in dem Verfahren 3 das Amin der Formel (V) mit Kohlendioxid in Gegenwart von einer oder mehreren basischen Verbindungen der Elemente Lithium, Natrium, Kalium, Rubidium zur Reaktion gebracht und dann das Propylderivat hinzufügt. In process 3, the amine of the formula (V) is preferably reacted with carbon dioxide in the presence of one or more basic compounds of the elements lithium, sodium, potassium, rubidium and then the propyl derivative is added.
In das erfindungsgemäße Verfahren können die verschiedensten basisch reagierenden Amine eingesetzt werden, vorzugsweise solche der Formel (V). A wide variety of basic reacting amines can be used in the process according to the invention, preferably those of the formula (V).
Pro eingesetztes Aminäquivalent werden in das erfindungsgemäße Verfahren 0,01 bis 10.000 Äquivalente Kohlendioxid eingesetzt. Vorzugsweise beträgt dieses Verhältnis 1:0,5 bis 1.000, insbesondere 1:1 bis 10. For the amine equivalent used, 0.01 to 10,000 equivalents of carbon dioxide are used in the process according to the invention. This ratio is preferably 1: 0.5 to 1,000, in particular 1: 1 to 10.
Pro eingesetztes Aminäquivalent werden in das erfindungsgemäße Verfahren beispielsweise 0,01 bis 10.0 Äquivalente Alkylierungsmittel eingesetzt Vorzugsweise beträgt dieses Verhältnis 1:0,3 bis 10, insbesondere 1:0,4 bis 3. Es ist ein wesentliches Merkmal der vorliegenden Erfindung, daß man in Gegenwart einer oder mehrerer basischen Verbindungen der Elemente Lithium, Natrium, Kalium, Rubidium arbeitet. Als basische Verbindungen kommen z.B. basisch reagierende Salze, Oxide, Hydride und Hydroxide in Frage. Beispielsweise seien genannt: Lithiumhydrid, Natriumhydrid, Kaliumhydrid, Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid, Rubidiumhydroxid, Lithiumoxid, Natriumperoxid, Kaliumoxid, Kaliumperoxid, Lithiumcarbonat Lithiumhydrogencarbonat Natriumcarbonat, Natriumhydrogencarbonat, Kaliumcarbonat Kaliumhydrogencarbonat, Rubidiumcarbonat Rubidiumhydrogencarbonat, Ammoniumcarbonat Ammoniumcarbamat, und/oder deren natürlich vorkommende oder synthetisch erhältliche Gemische sowie DBU oder DBN. For example, from 0.01 to 10.0 equivalents of alkylating agent are used per amine equivalent used in the process according to the invention. This ratio is preferably 1: 0.3 to 10, in particular 1: 0.4 to 3. It is an essential feature of the present invention that one works in the presence of one or more basic compounds of the elements lithium, sodium, potassium, rubidium. Suitable basic compounds are, for example, basic salts, oxides, hydrides and hydroxides. Examples include: lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, lithium oxide, sodium peroxide, potassium oxide, potassium peroxide, lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, rubidium carbonate, rubidium hydrogen carbonate, ammonium carbonate, ammonium carbonate and / or naturally occurring and / or Mixtures as well as DBU or DBN.
Bevorzugt sind Alkalicarbonate und/oder Hydrogencarbonate, ganz besonders bevorzugt Kaliumcarbonat. Das erfindungsgemäße Verfahren wird gegebenenfalls in Gegenwart von Hilfsbasen durchgeführt, d.h. in Gegenwart von weiteren Basen, beispielsweise in einer Menge von weniger als 0,5 Mol, bezogen auf die eingesetzte Menge an Base. Alkali carbonates and / or hydrogen carbonates are preferred, very particularly preferably potassium carbonate. The process according to the invention is optionally carried out in the presence of auxiliary bases, i.e. in the presence of further bases, for example in an amount of less than 0.5 mol, based on the amount of base used.
Als solche Hilfsbasen kommen beispielsweise in Frage: Halogenide von Alkalimetallen, Zeolithe, Kaliumacetat Lithiumperchlorat, Kaliumformiat, Natriumacetat,Examples of such auxiliary bases are: halides of alkali metals, zeolites, potassium acetate, lithium perchlorate, potassium formate, sodium acetate,
Titanalkoholaten, Titanalkoholate, Titansäureamide, Amidinbasen, Guanidinbasen wie 1,5-Diazabicyclo(4.3.0)non-5-en (DBN), 1,8-Diazabicyclo(5.4.0)undec-7-enTitanium alcoholates, titanium alcoholates, titanium amides, amidine bases, guanidine bases such as 1,5-diazabicyclo (4.3.0) non-5-ene (DBN), 1,8-diazabicyclo (5.4.0) undec-7-ene
(DBU), 7-Methyl-1,5,7-triazabicyclo(4.4.0)dec-5-en (MTBD), Cyclohexyl-tetraguanidin, Cyclohexyl-tetramethylguanidin, N,N,N,N-Tetramethyl-1,8-naphthalindiamin, Pentamethylpiperdin, N,N-Dimethylpyrridin, N-Butyl-tetraethylguanidin,(DBU), 7-methyl-1,5,7-triazabicyclo (4.4.0) dec-5-ene (MTBD), cyclohexyl-tetraguanidine, cyclohexyl-tetramethylguanidine, N, N, N, N-tetramethyl-1,8 -naphthalenediamine, pentamethylpiperdine, N, N-dimethylpyrridine, N-butyl-tetraethylguanidine,
N-t-Butyl-N',N'-dimethylacetamidin, N-Cyclohexyl-tetraethylguanidin und N-t- Butyl-tetraethylguanidin sowie 1,4-Diazabicyclo(2.2.2)octan (DABCO), tertiäreN-t-Butyl-N ', N'-dimethylacetamidine, N-cyclohexyl-tetraethylguanidine and N-t-butyl-tetraethylguanidine as well as 1,4-diazabicyclo (2.2.2) octane (DABCO), tertiary
Amine wie Triethylamin, Trimethylamin, N-Methylmorpholin, Pyridin, N,N-Dimethylpyridin und Tetramethylethylendiamin, eingesetztes Amin, Alkoholate wie Kalium-t-butylat, Natriummethylat, Natriumethylat, Natriumneopentylat undAmines such as triethylamine, trimethylamine, N-methylmorpholine, pyridine, N, N-dimethylpyridine and tetramethylethylene diamine, amine used, alcoholates such as potassium t-butoxide, sodium methylate, sodium ethylate, sodium neopentylate and
Kaliumneopentylat, Alkyl- und Arylmetallverbindungen wie Butyl, Methyl-,Potassium neopentylate, alkyl and aryl metal compounds such as butyl, methyl,
Phenyl- und Neoprylithium, sowie Grignardreagenzie.. lm allgemeinen ist es vorteilhaft das erfindungsgemäße Verfahren in Gegenwart von Verdünnungsmittel durchzuführen. Verdünnungsmittel werden vorteilhafterweise in einer solchen Menge eingesetzt, daß das Reaktionsgemisch während des ganzen Verfahrens gut rührbar bleibt. Als Verdünnungsmittel kommen beispielsweise in Frage: Kohlenwasserstoffe wie Petrolether, Benzol, Toluol, Chlorbenzol, Dichlorbenzol, Hexan, Cyclohexan, Methancyclohexan, Pentan, Heptan, Octan und technische Kohlenwasserstoffgemische, beispielsweise sogenannte White Spirits mit Komponenten mit Siedepunkten im Bereich von beipielsweise 40 bis 250°C, Ether wie Dimethyl-, Diethyl-, Dipropyl-, Diisopropyl, Dibutyl-, Methyl-t-butylether, Tetrahydrofuran, 1,4-Dioxan und Polyether des Ethylenoxids und/oder Propylenoxids, Amine wie Trimethyl-, Triethyl-, Tripropyl-, Tributyl-, Diethyl- und Dibutylamin, sowie n-Methylmorpholin, Pyridin, N,N-Dimethylpyridin und Tetramethylethylendiamin, Ester wie Methyl-, Ethyl- und Butylacetat sowie Dimethyl-, Dibutyl- und Ethylencarbonat, Nitroverbindungen wie Nitromethan, Nitroethan, Nitropropan und Nitrobenzol, Nitrile wie Acetonitril, Propionitril und Benzonitril sowie Verbindungen wie Tetrahydrothiophendioxid und Dimethylsulfoxid, Ketone wie Aceton, Methylbutylketon und Methylethylketon, verflüssigtes Kohlendioxid des Ethylenoxids und/oder Propylenoxids und Amide wie Hexamethylenphosphortriamid, N-Methylpyrrolidon, N-Methylcaprolactam, 1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidin, Octylpyrrolidon, Octylcaprolacton, 1,3-Dimethyl-2-imidazolindion, Dimethylformamid, Dimethylacetamid und Formamid. Phenyl- and Neoprylithium, as well as Grignard reagent .. In general, it is advantageous to carry out the process according to the invention in the presence of a diluent. Diluents are advantageously used in an amount such that the reaction mixture remains readily stirrable throughout the process. Possible diluents are, for example: hydrocarbons such as petroleum ether, benzene, toluene, chlorobenzene, dichlorobenzene, hexane, cyclohexane, methacrylate clohexane, pentane, heptane, octane and technical hydrocarbon mixtures, for example so-called white spirits with components with boiling points in the range from 40 to 250 °, for example C, ethers such as dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, methyl t-butyl ether, tetrahydrofuran, 1,4-dioxane and polyethers of ethylene oxide and / or propylene oxide, amines such as trimethyl, triethyl, tripropyl , Tributyl, diethyl and dibutylamine, as well as n-methylmorpholine, pyridine, N, N-dimethylpyridine and tetramethylethylenediamine, esters such as methyl, ethyl and butyl acetate as well as dimethyl, dibutyl and ethylene carbonate, nitro compounds such as nitromethane, nitroethane, nitropropane and Nitrobenzene, nitriles such as acetonitrile, propionitrile and benzonitrile as well as compounds such as tetrahydrothiophene dioxide and dimethyl sulfoxide, ketones such as acetone, meth ylbutyl ketone and methyl ethyl ketone, liquefied carbon dioxide of ethylene oxide and / or propylene oxide and amides such as hexamethylene phosphorus triamide, N-methylpyrrolidone, N-methylcaprolactam, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidine, octylpyrrolidone, Octylcaprolactone, 1,3-dimethyl-2-imidazolinedione, dimethylformamide, dimethylacetamide and formamide.
Außerdem kann man in das erfindungsgemäße Verfahren auch VerdünnungsmittelGemische einsetzen. In addition, diluent mixtures can also be used in the process according to the invention.
Bevorzugte Lösungsmittel sind Dimethylformamid und Dimethylsulfoxid sowiePreferred solvents are dimethylformamide and dimethyl sulfoxide as well
Gemische dieser mit anderen oben genannten Lösungsmitteln. Mixtures of these with other solvents mentioned above.
Das erfindungsgemäße Verfahren führt man im allgemeinen so durch, daß man zunächst das basisch reagierende Amin und das Kohlendioxid in Gegenwart einer basischen Verbindung der genannten Elemente zusammenbringt und miteinander reagieren läßt. Das Alkylierungsmittel fügt man vorteilhafterweise erst dann zu, wenn die Umsetzung des Amins mit dem Kohlendioxid weitgehend oder vollständig abgelaufen ist Das Fortschreiten der Reaktion des Amins mit dem Kohlendioxid kann man z.B. an der Wärmetönung erkennen. The process according to the invention is generally carried out by first bringing the basic reacting amine and the carbon dioxide together in the presence of a basic compound of the elements mentioned and allowing them to react with one another. The alkylating agent is advantageously only added when when the reaction of the amine with the carbon dioxide has largely or completely expired The progress of the reaction of the amine with the carbon dioxide can be recognized, for example, by the heat tone.
Das erfindungsgemäße Verfahren wird in beiden Stufen beispielsweise bei Temperaturen von 50 bis 130°C durchgeführt Bevorzugt sind Temperaturen im Bereich 30°C bis +150°C, insbesondere solche im Bereich -10°C bis +100°C. The process according to the invention is carried out in both stages, for example at temperatures from 50 to 130 ° C. Temperatures in the range from 30 ° C. to + 150 ° C. are preferred, in particular those in the range from -10 ° C. to + 100 ° C.
Der Druck ist beim erfindungsgemäßen Verfahren nicht kritisch. Es kann grundsätzlich bei Normaldruck, aber auch bei erhöhtem oder erniedrigtem Druck gearbeitet werden, Vorzugsweise arbeitet man bei Normaldruck oder bei Drucken bis zu 5 bar. Insbesondere bei erhöhter Temperatur empfiehlt es sich, den Druck entsprechend höher zu wählen. The pressure is not critical in the method according to the invention. In principle, it is possible to work at normal pressure, but also at elevated or reduced pressure. It is preferred to work at normal pressure or at pressures of up to 5 bar. Especially at elevated temperatures, it is advisable to choose a higher pressure.
Man kann das erfindungsgemäße Verfahren unter einer Kohlendioxid-Atmosphäre durchführen, aber auch in einer Atmosphäre, die Kohlendioxid und noch andere, vorzugsweise inerte Gase enthält. The process according to the invention can be carried out under a carbon dioxide atmosphere, but also in an atmosphere which contains carbon dioxide and other, preferably inert, gases.
Die Aufarbeitung erfolgte nach üblicher Art und Weise. Bevorzugt ist das folgende Vorgehen: Abtrennen des Feststoffes und Destillation der flüssigen Phase. So werden überschüssige Base, Lösungsmittel und Produkt in reiner oder wiederverwendbarer Form erhalten. Es entstehen damit .... oder sehr geringe Menge nicht wiederwendbaren Abfalls. The workup was carried out in the usual way. The following procedure is preferred: separation of the solid and distillation of the liquid phase. Excess base, solvent and product are obtained in pure or reusable form. This creates .... or a very small amount of non-reusable waste.
Der erfindungsgemäße Stoff eignet sich als Schädlingsbekämpfungsmittel, insbesondere als Fungizide im Pflanzenschutz. The substance according to the invention is suitable as a pesticide, in particular as a fungicide in crop protection.
Fungizide werden im Pflanzenschutz eingesetzt zur Bekämpfung von Plasmadiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes. Fungicides are used in crop protection to combat plasmadiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
Beispielhaft aber nicht begrenzend seien einige Erreger von pilzlichen Erkrankungen, die unter die oben aufgezählten Oberbegriffe fallen, genannt: Xanthomonas-Arten, wie Xanthomonas oryzae; Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation: Xanthomonas species, such as Xanthomonas oryzae;
Pseudomonas-Arten, wie Pseudomonas lachrymans;  Pseudomonas species, such as Pseudomonas lachrymans;
Erwinia- Arten, wie Erwinia amylovora;  Erwinia species, such as Erwinia amylovora;
Pythium- Arten, wie Pythium ultimum;  Pythium species, such as Pythium ultimum;
Phytophthora-Arten, wie Phytophthora infestans; Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora-Arten, wie Pseudoperonospora humuli oder Pseudoperonospora cubensis;  Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara- Arten, wie Plasmopara viticola;  Plasmopara species, such as Plasmopara viticola;
Peronospora- Arten, wie Peronospora pisi oder P. brasssicae;  Peronospora species, such as Peronospora pisi or P. brasssicae;
Erysiphe- Arten, wie Erysiphe graminis; Erysiphe species, such as Erysiphe graminis;
Sphaerotheca-Arten, wie Sphaerotheca fuliginea;  Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera-Arten, wie Podosphaera leucitricha;  Podosphaera species, such as Podosphaera leucitricha;
Venturia-Arten, wie Venturia inaequalis;  Venturia species, such as Venturia inaequalis;
Pyrenophora-Arten, wie Pyrenophora teres oder P. graminea;  Pyrenophora species, such as Pyrenophora teres or P. graminea;
(Konidienform: Drechslera, Syn: Helminthosporium); (Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus-Arten, wie Cochliobolus sativus;  Cochliobolus species, such as Cochliobolus sativus;
(Konidienform: Drechslera, Syn: Helminthosporium);  (Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces-Arten, wie Uromyces appendiculatus;  Uromyces species, such as Uromyces appendiculatus;
Puccinia-Arten, wie Puccinia recondita;  Puccinia species, such as Puccinia recondita;
Tilletia- Arten, wie Tilletia caries; Tilletia species, such as Tilletia caries;
Ustilago- Arten, wie Ustilago nuda oder Ustilago avenae;  Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia-Arten, wie Pellicularia sasakii;  Pellicularia species, such as Pellicularia sasakii;
Pyricularia-Arten, wie Pyricularia oryzae;  Pyricularia species, such as Pyricularia oryzae;
Fusarium-Arten, wie Fusarium culmorum;  Fusarium species, such as Fusarium culmorum;
Botrytis-Arten, wie Botrytis cinerea; Botrytis species, such as Botrytis cinerea;
Septoria-Arten, wie Septoria nodorum;  Septoria species, such as Septoria nodorum;
Leptosphaeria- Arten, wie Leptosphaeria nodorum;  Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora-Arten, wie Cercospora canescens;  Cercospora species, such as Cercospora canescens;
Alternaria- Arten, wie Alternaria brassicae;  Alternaria species, such as Alternaria brassicae;
Pseudocercosporella- Arten, wie Pseudocercosporella herpotrichoides. Die gute Pflanzenverträglichkeit der Wirkstoffe in den zur Bekämpfung von Pflanzenkrankheiten notwendigen Konzentrationen erlaubt eine Behandlung von oberirdischen Pflanzenteilen, von Pflanz- und Saatgut und des Bodens. Pseudocercosporella species, such as Pseudocercosporella herpotrichoides. The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds and of the soil.
Die erfindungsgemäßen Stoffe können in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate, Aerosole, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut sowie ULV-Formulierungen. The substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV 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 oberflächen-aktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösemittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Waser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe kommen in Frage: z.B. natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomerde und synthestische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate kommen in Frage: 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, Kokusnußschalen, Maiskolben und Tabakstengel; als Emulgier und/oder schaumerzeugende Mittel kommen in Frage: z.B. nicht-ionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkylarylpolyglykol-Ether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose. These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, 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: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and Waser; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as 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: for example 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; as an emulsifier and / or foam-generating agents are suitable: 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 Carboxy-methylcellulose, natürliche und synthetische pulverige, kömige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat sowie natürliche Phospholipide, wie Kephaline und Lecithine, und synthetische Phospholipide und Lecithine, und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein. Adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids 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, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyaninfarbstoffe 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 allgemeinen zwische 0,1 und 95 Gew.-% Wirkstoff, vorzugsweise zwischen 0,5 und 90 %. The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können in den Formulierungen in Mischung mit anderen bekannten Wirkstoffen vorliegen wie Fungizide, Insektizide, Akaridzide und Herbizide sowie in Mischungen mit Düngemitteln und Wachstumsregulatoren. Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen wie gebrauchsfertige Lösungen, emulgierbare Konzentrate, Emulsionen, Schäume, Suspensionen, Spritzpulver, Pasten, lösliche Pulver, Stäubemittel und Granulate, angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Verschäumen, Bestreichen usw. Es ist ferner möglich die Wirkstoffe nach dem Ultra-Low- Volume- Verfahren auszubringen oder die Wirkstoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. Es kann auch das Saatgut der Pflanzen behandelt werden. Beim Einsatz der erfindungsgemäßen Stoffe kann die Aufwandmenge je nach Art der Applikation in einem größeren Bereich variiert werden. So liegen die Wirkstoffkonzentrationen bei der Behandlung von Pflanzenteilen in den Anwendungsformen im allgemeinen zwischen 1 und 0,001 Gew.-%, vorzugsweise zwischen 0,5 und 0,001 %. Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 50 g je kg Saatgut, vorzugsweise 0,01 bis 10 g benötigt. Bei der Behandlung des Bodens sind Wirkstoffkonzentrationen von 0,00001 bis 0,1 Gew.-%, vorzugsweise von 0,0001 bis 0,02 %, am Wirkungsort erforderlich. The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaridzides and herbicides, and also in mixtures with fertilizers and growth regulators. The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient itself into the soil. The seeds of the plants can also be treated. When using the substances according to the invention, the application rate can be varied over a wide range depending on the type of application. The active substance concentrations in the treatment of parts of plants in the use forms are generally between 1 and 0.001% by weight, preferably between 0.5 and 0.001%. In the case of seed treatment, amounts of active ingredient of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g, are generally required. When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.
Die erfindungsgemäßen Wirkstoffe bzw. Mittel weisen desweiteren eine starkeThe active ingredients or agents according to the invention also have a strong
Wirkung gegen Mikroorganismen auf. Sie werden im Materialschutz zum Schutz technischer Materialien verwendet: sie sind vor allem wirksam gegen Schimmelpilze, holzverfärbende und holzzerstörende Pilze und Bakterien, sowie gegen Hefen, Algen und Schleimorganismen. Beispielhaft - ohne jedoch zu limitieren - seien die folgenden Gattungen von Mikroorganismen genannt: Action against microorganisms. They are used in material protection to protect technical materials: they are primarily effective against mold, wood-staining and wood-destroying fungi and bacteria, as well as against yeasts, algae and slime organisms. The following types of microorganisms may be mentioned by way of example, but without limitation:
Altemaria wie Altemaria tenuis, Aspergillus wie Aspergillus niger und Aspergülus terreus, Aureobasidium wie Aureobasidium pullulans, Chaetomium wie Chaetomium globosum, Cladosporium wie Cladosporium herbarum, Coniophora wie Coniophora puteana, Gliocladium wie Gliocladium virens, Lentinus wie Lentinus tigrinus, Paecilomyces wie Paecilomyces varioti, Penicillium wie Penicillium brevicaule, Penicillium glaucum und Penicillium pinophilum, Polyporus wie Polyporus versicolor, Sclerophoma wie Sclerophoma pityophila, Streptoverticillium wie Streptoverticillium reticulum, Trichoderma wie Trichoderma viride, Trichophyton wie Trichophyton mentagrophytes; Altemaria such as Altemaria tenuis, Aspergillus such as Aspergillus niger and Aspergülus terreus, Aureobasidium such as Aureobasidium pullulans, Chaetomium such as Chaetomium globosum, Cladosporium such as Cladosporium herbarum, Coniophora such as Coniophora puteana, Gliocladium such as Gliocinecilluscesin, such as Paiocinium latinus Penicillium brevicaule, Penicillium glaucum and Penicillium pinophilum, Polyporus like Polyporus versicolor, Sclerophoma like Sclerophoma pityophila, Streptoverticillium like Streptoverticillium reticulum, Trichoderma like Trichoderma viride, Trichophyton like Trichytesyut;
Escherichia wie Escherichia coli, Pseudomonas wie Pseudomonas areuginosa, Staphylococcus wie Staphylococcus aureus;  Escherichia such as Escherichia coli, Pseudomonas such as Pseudomonas areuginosa, Staphylococcus such as Staphylococcus aureus;
Candida wie Candida albicans. Die Menge der eingesetzten Wirkstoffe ist von der Art und dem Vorkommen der Mikroorganismen der Keimzahl und von dem Medium abhängig. Die optimale Einsatzmenge kann bei der Anwendung jeweils durch Testreihen ermittelt werden. Im allgemeinen ist es jedoch ausreichend 0,001 bis 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, der Wirkstoffgemische, bezogen auf das zu schützende Material, einzusetzen. Candida like Candida albicans. The amount of active ingredients used depends on the type and occurrence of the microorganisms, the number of bacteria and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.001 to 20% by weight, preferably 0.05 to 10% by weight, of the active compound mixtures, based on the material to be protected.
Die neuen Wirkstoffe können als solche, in Form von Konzentraten oder allgemein üblichen Formulierungen wie Pulver, Granulate, Lösungen, Suspensionen, Emulsionen oder Pasten angewendet werden. The new active ingredients can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
Die genannten Formulierungen können in an sich bekannter Weise hergestellt werden, z.B. durch Vermischen der Wirkstoffe mit Lösungs- bzw. Verdünnungsmitteln, Emulgatoren, Dispergatoren und/oder Binde- oder Fixiermitteln, gegebenenfalls Sikkative und UV-Stabilisatoren und gegebenenfalls Farbstoffen und Pigmenten sowie weiteren Verarbeitungshilfsmitteln. The formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with solvents or diluents, emulsifiers, dispersants and / or binders or fixatives, optionally siccatives and UV stabilizers and optionally dyes and pigments and other processing aids.
Als Lösungs- bzw. Verdünnungsmittel kommen organisch-chemische Lösungsmittel oder Lösungsmittelgemische und/oder ein polares organisches Lösungsmittel oder Lösungsmittelgemische und/oder ein öliges bzw. ölartiges organisch-chemisches Lösungsmittel oder Lösungsmittelgemisch und/oder Wasser mit vorzugsweise einem Emulgator und/oder Netzmittel in Frage. Als übliche schwerflüchtige, wasserunlösliche ölige oder ölartige Lösungsmittel werden vorzugsweise die jeweiligen Mineralöle/mineralölhaltige Lösungsmittelgemische oder deren Aromatenfraktionen verwendet. Beispielhaft seien Testbenzin, Petroleum oder Alkylbenzole genannt, daneben Spindelöl und Monochlomaphthalin. Die Siedebereiche dieser schwerflüchtigen Lösemittel(gemische) überstreichen den Bereich von ca. 170°C bis maximal 350°C. Suitable solvents or diluents are organic chemical solvents or solvent mixtures and / or a polar organic solvent or solvent mixtures and / or an oily or oil-like organic chemical solvent or solvent mixture and / or water with preferably an emulsifier and / or wetting agent . The respective mineral oils / mineral oil-containing solvent mixtures or their aromatic fractions are preferably used as customary non-volatile, water-insoluble oily or oily solvents. Examples include white spirit, petroleum or alkylbenzenes, along with spindle oil and monochlomaphthalene. The boiling ranges of these low volatility solvents (mixtures) span the range from approx. 170 ° C to a maximum of 350 ° C.
Die vorbeschriebenen schwerflüchtigen öligen oder ölartigen Lösungsmittel können teilweise durch leichter flüchtige organisch-chemische Lösungsmittel ersetzt werden. Zur Herstellung eines Holzschutzmittels wird vorzugsweise ein Teil des oben beschriebenen Lösungsmittels oder Lösungsmittelgemisches durch ein polares organisch-chemisches Lösungsmittel oder Lösungsmittelgemisches ersetzt Vorzugsweise gelangen dabei Lösungsmittel, die Hydroxygruppen, Estergruppen, Ethergruppen oder Gemische dieser Funktionalität enthalten, zum Einsatz. Beispielhaft seien Ester oder Glykolether genannt Als Bindemittel werden erfindungsgemäß verstanden wasserverdünnbare bzw. in organisch-chemischen Lösungsmitteln löslich, dispergier- oder emulgierbare Kunstharze, bindende trocknende Öle, z.B. auf Basis von Acrylharzen, Vinylharzen, Polyesterharzen, Polyurethanharzen, Alkydharzen, Phenolharzen, Kohlenwasserstoffharzen, Silikonharzen. Das benutzte Bindemittel kann als Lösung, Emulsion oder Dispersion eingesetzt werden. Vorzugsweise werden Gemische aus Alkydharzen und trocknendem pflanzlichen Öl verwendet. Besonders bevorzugt sind Alkydharze mit einem Ölanteil zwischen 45 und 70 %. Das erwähnte Bindemittel kann ganz oder teilweise durch ein Fixierungsmittelgemisch oder ein Weichmachergemisch ersetzt werden. Diese Zusätze sollen einer Verflüchtigung der Wirkstoffe sowie einer Kristallisation bzw. eines Ausfällens vorbeugen. Vorzugsweise ersetzen sie 0,01 bis 30 % des Bindemittels (bezogen auf 100 % des eingesetzten Bindemittels). The previously described volatile oily or oily solvents can be partially replaced by more volatile organic chemical solvents. To produce a wood preservative, part of the solvent or solvent mixture described above is preferably replaced by a polar organic chemical solvent or solvent mixture. Solvents which contain hydroxyl groups, ester groups, ether groups or mixtures of this functionality are preferably used. Esters or glycol ethers may be mentioned as examples. According to the invention, binders are understood to be water-thinnable or soluble in organic chemical solvents, dispersible or emulsifiable synthetic resins, binding drying oils, for example based on acrylic resins, vinyl resins, polyester resins, polyurethane resins, alkyd resins, phenolic resins, hydrocarbon resins, silicone resins . The binder used can be used as a solution, emulsion or dispersion. Mixtures of alkyd resins and drying vegetable oil are preferably used. Alkyd resins with an oil content of between 45 and 70% are particularly preferred. All or part of the binder mentioned can be replaced by a fixative mixture or a plasticizer mixture. These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
Die Weichmacher stammen aus den chemischen Klassen oder Phthalsäureester wie Dibutyl-, Dioctyl- oder Benzylbutylphthalat Phosphorsäureester wie Tributylphosphat, Adipinsäureester wie Di-(2-ethylhexyl)-adipat, Stearate wie Butylstearat und Amylstearat, Oleate wie Butyloleat, Glycerinether oder höhermolekulare Glykolether, Glycerinester sowie p-Toluolsulfonsäureester. The plasticizers come from the chemical classes or phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate and amyl stearate, oleates such as butyl oleate, glycerol glycol ether and higher or glycerol ether p-toluenesulfonic acid ester.
Fixierungsmittel basieren chemisch auf Polyvinylalkylethern wie z.B. Polyvinylmethylether oder Ketonen wie Benzophenon, Ethylbenzophenon. Als Lösungs- bzw. Verdünnungsmittels kommt vorzugsweise Wasser in Frage, gegebenenfalls in Mischung mit einem oder mehreren der obengenannten Lösungsbzw. Verdünnungsmittel, Emulgatoren und Dispergatoren. Technische Materialien sind erfindungsgemäß nicht lebende Materialien, die für die Verwendung in der Technik zubereitet worden sind. Beispielsweise können technische Materialien, die durch erfindungsgemäße Wirkstoffe vor mikrobieller Veränderung oder Zerstörang 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 beeinträchtigt werden können. Bevorzugte technisehe Materialien im Sinne der Erfindung sind Klebstoffe, Leime, Papiere und Kartone, Leder, Holz, Anstrichmittel, Kühlschmiermittel, wäßrige Hydraulikflüssigkeiten und Kühlkreisläufe und allgemein wäßrige funktionelle Flüssigkeiten. Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylbenzophenone. As a solvent or diluent, water is preferably used, optionally in a mixture with one or more of the abovementioned solvents or. Diluents, emulsifiers and dispersants. According to the invention, industrial materials are 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, are also mentioned which can be impaired by the multiplication of microorganisms. Preferred technical materials for the purposes of the invention are adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants, aqueous hydraulic fluids and cooling circuits and generally aqueous functional liquids.
Die Wirksamkeit und das Wirkungsspektrum der erfindungsgemäßen Wirkstoffe bzw. den daraus herstellbaren Mitteln, Konzentraten oder ganz allgemein Formulierungen kann erhöht werden, wenn gegebenenfalls weitere antimikrobiell wirksame Verbindungen, Fungizide, Bakterizide, Herbizide, Insektizide oder andere Wirkstoffe zur Vergrößerung des Wirkungsspektrums oder Erzielung besonderer Effekte wie z.B. dem zusätzlichen Schutz vor Insekten zugesetzt werden. Diese Mischungen können ein breiteres Wirkungsspektrum besitzen als die erfindungsgemäßen Verbindungen. The effectiveness and the spectrum of activity of the active compounds according to the invention or of the agents, concentrates or very generally formulations which can be prepared therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active compounds are used to enlarge the spectrum of action or to achieve special effects such as e.g. added protection against insects. These mixtures can 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 der 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 that of the individual components. Particularly favorable mix partners are e.g. the following connections:
Sulfenamide wie Dichlofluanid (Euparen), Tolylfluanid (Methyleuparen), Folpet, Fluorfolpet; Benzimidazole wie Carbendazim (MBC), Benomyl, Fuberidazole, Thiabendazole oder deren Salze; Thiocyanate wie Thiocyanatomethylthiobenzothiazol (TCMTB), Methylenbisthiocyanat (MBT); quartäre Ammoniumverbindungen wie Benzyldimethyltetradecylammoniumchlorid, Benzyl-dimethyl-dodecyl-ammoniumchlorid, Didecyl-dimethyl-ammoniumchlorid; Sulfenamides such as dichlofluanid (Euparen), tolylfluanid (Methyleuparen), Folpet, Fluorfolpet; Benzimidazoles such as Carbendazim (MBC), Benomyl, Fuberidazole, Thiabendazole or their salts; Thiocyanates such as thiocyanatomethylthiobenzothiazole (TCMTB), methylene bisthiocyanate (MBT); quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
Morpholinderivate wie C11-C14-4-Alkyl-2,6-dimethyl-morpholin-homologe(Tridemorph),(±)-cis-4-[3-tert-Butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholin (Fenpropimorph), Falimorph; Phenole wie o-Phenylphenol, Tribromphenol, Tetrachlorphenol, Pentachlorphenol, 3-Methyl-4-chlorphenol, Dichlorophen, Chlorophen oder deren Salze; Morpholine derivatives such as C 11 -C 14 -4-alkyl-2,6-dimethyl-morpholine homologous (tridemorph), (±) -cis-4- [3-tert-butylphenyl) -2-methylpropyl] -2,6- dimethylmorpholine (fenpropimorph), falimorph; Phenols such as o-phenylphenol, tribromophenol, tetrachlorophenol, pentachlorophenol, 3-methyl-4-chlorophenol, dichlorophen, chlorophen or their salts;
Azole wie Triadimefon, Triadimenol, Bitertanol, Tebuconazole, Propiconazole, Azaconazole, Hexaconazole, Prochloraz; lodpropargylderivate wie lodpropargyl-butylcarbamat (IPBC), -chlorophenylformal,Azoles such as triadimefon, triadimenol, bitertanol, tebuconazole, propiconazole, azaconazole, hexaconazole, prochloraz; iodopropargyl derivatives such as iodopropargyl butyl carbamate (IPBC), chlorophenyl formal,
-phenylcarbamat, -hexylcarbamat, -cyclohexylcarbamat, Iodpropargyloxyethylphenylcarbamat; Iodderivate wie Diiodmethyl-p-arylsulfone z.B. Diiodmethyl-p-tolylsulfon; phenyl carbamate, hexyl carbamate, cyclohexyl carbamate, iodopropargyloxyethylphenyl carbamate; Iodine derivatives such as diiodomethyl-p-arylsulfones e.g. Diiodomethyl p-tolyl sulfone;
Bromderivate wie Bronopol; Bromine derivatives such as bronopol;
Isothiazolinone wie N-Methylisothiazolin-3-on, 5-Chloro-N-methylisothiazolin-3-on, 4,5-Dichloro-N-octylisothiazolin-3-on, N-Octylisothiazolin-3-on (Octhilinone); Isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one (octhilinones);
Benzisothiazolinone, Cyclopentenisothiazoline; Pyridine wie 1-Hydroxy-2-pyridinthion (und ihre Na-, Fe-, Ma, Zn-Salze), Tetrachlor-4-methylsulphonylpyridin; Metallseifen wie Zinn-, Kupfer-, Zink-naphthenat, -oc-toat, -2-ethylhexanoat, -oleat, phosphat -benzoat, Oxide wie TBTO, Cu2O, CuO, ZnO; Benzisothiazolinones, cyclopentene isothiazolines; Pyridines such as 1-hydroxy-2-pyridinthione (and their Na, Fe, Ma, Zn salts), tetrachloro-4-methylsulphonylpyridine; Metal soaps such as tin, copper, zinc naphthenate, o-toate, -2-ethylhexanoate, oleate, phosphate benzoate, oxides such as TBTO, Cu 2 O, CuO, ZnO;
Organische Zinnverbindungen wie Tributylzinnnaphthenat und Tributylzinnoxid; Dialkyldithiocarbamate wie Na- und Zn-Salze von Dialkyldithiocarbamaten, Tetramethyldiuramidisulfid (TMTD); Organic tin compounds such as tributyltin naphthenate and tributyltin oxide; Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethyldiuramidisulfide (TMTD);
Nitrile wie 2,4,5,6-Tetrachlorisophthalonitril (Chlorthalonil) u.a. Mikrobizide mit aktivierten Halogengruppen wie Cl-Ac, MCA, Tectamer, Bronopol, Bromidox; Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil) etc. Microbicides with activated halogen groups such as Cl-Ac, MCA, tectamer, bronopol, bromidox;
Benzthiazole wie 2-Mercaptobenzothiazol; s.o. Dazomet; Benzothiazoles such as 2-mercaptobenzothiazole; so. Dazomet;
Chinoline wie 8-Hydroxychinolin; Formaldehydabspaltende Verbindungen wie Benzylalkohol-mono(poly)hemiformal, Oxazolidine, Hexahydro-s-triazine, N-Methylolchloracetamid; Quinolines such as 8-hydroxyquinoline; Formaldehyde-releasing compounds such as benzyl alcohol mono (poly) hemiformal, oxazolidines, hexahydro-s-triazines, N-methylolchloroacetamide;
Tris-N-(Cyclohexyldiazeniumdioxy)-Aluminium N-(Cyclohexyldiazeniumdioxy)-Tributylzinn bzw. K.Salze, Bis-(N-cyclohexyl)diazinium (-dioxy- Kupfer oder Aluminium); Tris-N- (cyclohexyldiazeniumdioxy) aluminum N- (cyclohexyldiazeniumdioxy) -tributyltin or K. salts, bis- (N-cyclohexyl) diazinium (-dioxy-copper or aluminum);
Als Insektizide werden bevorzugt zugesetzt: The following are preferably added as insecticides:
Phosphorsäureester wie Azinphos-ethyl, Azinphos-methyl, 1-(4-Chlorphenyl)-4-(O-ethyl, S-propyl)phosphoryloxypyrazol (TIA-230), Chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrimfos, Fenitrothion, Fention, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxion, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprofos, Triazophos und Trichlorphon. Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, 1- (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxypyrazole (TIA-230), chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrimfos, Fenitrothion, Fention, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxion, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprofos, Triazophos and Trichlorphon.
Carbamate wie Aldicarb, Bendiocarb, BPMC (2-(1-Methylpropyl)phenylmethylcarbamat), Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur und Thiodicarb. Carbamates such as aldicarb, bendiocarb, BPMC (2- (1-methylpropyl) phenylmethylcarbamate), butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur and Thiodicarb.
Pyrethroide wie Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin (FMC 54 800), Cycloprothrin, Cyfluthrin, Decamethrion, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chlor-2-trifluormethylvinyl)cyclopropancarboxylat Fenpropathrin, Fenfluthrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate, Permethrin und Resmethrin; Nitroimide wie 1-[(6-Chlor-3-pyridinyl)-methyl]-4,5-dihydro-N-nitro-1H-imidazol-2-anin (Imidacloprid). Organosiliciumverbindungen, vorzugsweise Dimethyl(phenyl)silylmethyl-3-phenoxy-benzylether wie z.B. Dimethyl (4-ethoxyphenyl)-silylmethyl-3-phenoxybenzylether oder Dimethyl(phenyl)-silylmethyl-2-phenoxy-6-pyridylmethylether wie z.B. Dimethyl(9-ethoxyphenyl)-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. Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin (FMC 54 800), cycloprothrin, cyfluthrin, decamethrione, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- ( chlor-2-trifluoromethylvinyl) cyclopropane carboxylate fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin and resmethrin; Nitroimides such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazol-2-anine (imidacloprid). Organosilicon compounds, preferably dimethyl (phenyl) silylmethyl-3-phenoxy-benzyl ether such as e.g. Dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or dimethyl (phenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl (9-ethoxyphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether or (phenyl) [3- (3-phenoxyphenyl) propyl] (dimethyl) silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl) propyl] dimethyl silane.
Als andere Wirkstoffe kommen in Betracht Algizide, Molluskizide, Wirkstoffe gegen "sea animals", die sich auf z.B. Schiffsbodenanstrichen ansiedeln. Die zum Schutz der technischen Materialien verwendeten mikrobiziden Mittel oder Konzentrate enthalten die erfindungsgemäßen Wirkstoffe in einer Konzentration von 0,01 bis 95 Gew.-%, insbesondere 0,01 bis 60 Gew.-%, daneben gegebenenfalls 0,001 bis 10 Gew.-% eines geeigneten weiteren Fungizids, Insektizids oder eines weiteren Wirkstoffs wie oben genannt Algicides, molluscicides, active substances against "sea animals", which relate to e.g. Place ship floor paints. The microbicidal agents or concentrates used to protect the industrial materials contain the active compounds according to the invention in a concentration of 0.01 to 95% by weight, in particular 0.01 to 60% by weight, in addition, if appropriate, 0.001 to 10% by weight suitable further fungicide, insecticide or another active ingredient as mentioned above
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. Die nachfolgenden Beispiele dienen zur Erläuterung der Erfindung ohne sie darauf zu limitieren. Teile und Prozentangaben bedeuten Gewichtsteile bzw. Gewichtsprozente. Beispiel A1 (Herstellung der Vorstufe) 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 following examples serve to illustrate the invention without limiting it. Parts and percentages mean parts by weight or percentages by weight. Example A1 (preparation of the preliminary stage)
N,N-nDibutyl-0-propagylcarbamat (A) N, N- n dibutyl-0-propagyl carbamate (A)
In einem 100 ml Kolben werden 50 ml Dimethylformamid, 10,0 g (0,078 mol) Dibutylamin und 18,87 g (0,137 mol) Kaliumcarbonat vorgelegt und 5,78 g Propagylchlorid zugegeben. Dabei wird ständig eine CO2-Atmosphäre aufrechterhalten. Die Reaktion wird bei 25°C so lange gerührt bis nach GC-Analyse kein Dibutylamin mehr vorhanden ist 50 ml of dimethylformamide, 10.0 g (0.078 mol) of dibutylamine and 18.87 g (0.137 mol) of potassium carbonate are placed in a 100 ml flask and 5.78 g of propagyl chloride are added. A CO 2 atmosphere is constantly maintained. The reaction is stirred at 25 ° C. until dibutylamine is no longer present after GC analysis
Nach salzsaurer Extraktion wird das Produkt destilliert (Kp1.3 = 97 - 98°C) After hydrochloric acid extraction the product is distilled (bp 1.3 = 97 - 98 ° C)
Man erhält (1 % der Theorie des Produktes (A)). (C13-NMR: δ = 155,1; 79,3; 74,4; 52,5; 47,6; 46,8; 31,1; 30,6; 20,2; One obtains (1% of the theory of the product (A)). (C 13 -NMR: δ = 155.1; 79.3; 74.4; 52.5; 47.6; 46.8; 31.1; 30.6; 20.2;
14,0 ppm/TMS)  14.0 ppm / TMS)
Beispiel 1 example 1
N,N-nDibutyl-o-(3-Iod)-propagylcarbamat N, N- n dibutyl-o- (3-iodine) propagyl carbamate
10,6 g Verbindung (A) in 20 ml Dipropylenglykol werden bei 0-5°C mit 5 g 40 % NaOH 30 min lang gerührt und dann mit 6,43 g Iod in kleinen Portionen versetzt Nach 30 min bei 0-5°C und der letzten Zugabe von Iod werden 21,5 g (6,2 %ige) NaOCl-Lösung bei 0-5°C bis zur Entfärbung zulaufen gelassen. Das Reaktionsgemisch wird auf Wasser gegeben, mit Ether extrahiert getrocknet, eingeengt, am Kugelrohr vom Edukt befreit und der Sumpf an Kieselgel, Toluol, Ether 10:1 chromatographiert. 10.6 g of compound (A) in 20 ml of dipropylene glycol are stirred at 0-5 ° C with 5 g of 40% NaOH for 30 min and then mixed with 6.43 g of iodine in small portions after 30 min at 0-5 ° C and the last addition of iodine, 21.5 g (6.2%) NaOCl solution are run in at 0-5 ° C. until decolorization. The reaction mixture is poured into water, extracted with ether, dried, concentrated, the educt is removed on a Kugelrohr and the bottom is chromatographed on silica gel, toluene, ether 10: 1.
Ausbeute: 6,35 g (38 %) M(+) (Massenspektrum): 337; v = 2210 m-1 Beispiel A2 Yield: 6.35 g (38%) M (+) (mass spectrum): 337; v = 2210 m -1 Example A2
N,N-Dibutylpropagylcarbamat (A) 100 g (0,775 mol) Dibuylamin, 189,0 g (1,37 ml) K2CO3 und 500 ml DMF werden in einem 3 1 VA- Autoklav mit 440 g CO2 versetzt und 30 min auf 100°C erwärmt Nach Abkühlen auf 50°C (Druck: 75 bar) wird mit 60,0 g (95 %) (0,765 ml) Propagylchlorid versetzt und 6 h bei 50°C gehalten. Nach Entspannen wird abgesaugt der Rückstand mit 1 1 CH2CH2 gewaschen und die organische Phase destilliert. N, N-dibutylpropagyl carbamate (A) 100 g (0.775 mol) of dibuylamine, 189.0 g (1.37 ml) of K 2 CO 3 and 500 ml of DMF are mixed with 440 g of CO 2 in a 3 1 VA autoclave and 30 heated to 100 ° C. for min. After cooling to 50 ° C. (pressure: 75 bar), 60.0 g (95%) (0.765 ml) of propyl chloride are added and the mixture is kept at 50 ° C. for 6 h. After relaxing, the residue is filtered off with suction and washed with 1 1 CH 2 CH 2 and the organic phase is distilled.
Man erhält 118,94 g (69,2 %) des Produktes (A). 118.94 g (69.2%) of product (A) are obtained.
Beispiel A3 Example A3
N,N-Dibutylpropagylcarbamat N, N-dibutylpropagyl carbamate
10,0 g (0,078 mol) Dibutylamin, 18,87 g (0,137mol) K2CO3 und 250 ml DMSO werden 1 h bei 25°C mit CO2 unter (Normaldruck) begast. Man setzt 5,78 g (0,078 mol) Propagylchlorid zu und rührt 4 h. Nach Analyse in GC (Flächenprozent) erhält man 99,4 % des Produktes (A). 10.0 g (0.078 mol) of dibutylamine, 18.87 g (0.137 mol) of K 2 CO 3 and 250 ml of DMSO are gassed with CO 2 under (normal pressure) at 25 ° C. for 1 h. 5.78 g (0.078 mol) of propagyl chloride are added and the mixture is stirred for 4 h. After analysis in GC (area percent), 99.4% of the product (A) is obtained.
Beispiel A4 Example A4
21,2 g Verbindung (A) in 40 g Ethanol werden mit 10 g NaOH (40 % in H2O) bei 0-5°C versetzt und anschließend in sechs Portionen 25,4 g Iod hinzugefügt Nach Zugabe von 10 ml 6,2 %iger NAOCl wird 4 Tage stehen gelassen, mit Wasser, Diethylether extrahiert, getrocknet, und an Kieselgel/Aktivkohle chromatographiert (Toluol/Ethylacetat 10:1). 21.2 g of compound (A) in 40 g of ethanol are mixed with 10 g of NaOH (40% in H 2 O) at 0-5 ° C. and then 25.4 g of iodine are added in six portions. After adding 10 ml of 6, 2% NAOCl is left to stand for 4 days, extracted with water, diethyl ether, dried and chromatographed on silica gel / activated carbon (toluene / ethyl acetate 10: 1).
Man erhält 22,9 g (68 %) der Verbindung des Beispiels 2. Beispiel 45 22.9 g (68%) of the compound of Example 2 are obtained. Example 45
N-Methyl-n-phenyl-propagylcarbamat N-methyl-n-phenyl-propagyl carbamate
8,29 g (0,078 mol) N-Methylanüin, 18,87 g K2CO3 und 50 ml DMSO werden 1 h bei 25°C mit CO2 begast Anschließend werden 5,78 g (0,78 mol) Propagylchlorid zugesetzt und 45 h 25°C werden im GC-MS, bezogen auf den Umsatz (76 %) 74,4 % 83 (M+: 189 U, Basis 106) 8.29 g (0.078 mol) of N-methylanüin, 18.87 g of K 2 CO 3 and 50 ml of DMSO are gassed with CO 2 for 1 h at 25 ° C. Then 5.78 g (0.78 mol) of propagyl chloride are added and 45 h 25 ° C in GC-MS, based on the conversion (76%) 74.4% 83 (M + : 189 U, basis 106)
neben 20,3 % N-methyl-N-phenyi-Na-propagylamin in addition to 20.3% N-methyl-N-phenyi-Na propagylamine
beobachtet. observed.
Nach Aufarbeitung wie im Versuch 1 beschrieben erhält man analog den Beispielen und entsprechend der allgemeinen Beschreibung die in der nachstehenden Tabelle 1 aufgeführten Verbindungen der Formel (I). After working up as described in Experiment 1, the compounds of the formula (I) listed in Table 1 below are obtained analogously to the examples and in accordance with the general description.
Figure imgf000031_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0002
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0002
Stabüitätsüberprüfung Stability check
Figure imgf000044_0001
Figure imgf000044_0001
Je 0,5 g der Verbindung wurden in 1,0 g Ethylenglykol eingetragen. Dabei bildet sich eine Suspension von IPBC und eine Emulsion der Verbindung des Beispiels 1 in Ethylenglykol. Beide Gemische werden 42 Tage bei 50°C im verschlossenen Röhrchen gelagert, anschließend geöffnet, mit Ethylacetat auf 100 ml verdünnt und auf ihren Gehalt an Edukt hin mittels HPLC- Analyse untersucht Man findet  0.5 g of the compound was added to 1.0 g of ethylene glycol. This forms a suspension of IPBC and an emulsion of the compound of Example 1 in ethylene glycol. Both mixtures are stored for 42 days at 50 ° C. in a sealed tube, then opened, diluted to 100 ml with ethyl acetate and their content of starting material is examined by means of HPLC analysis
IPBC : 64 % in deutlich gelber LösungIPBC: 64% in a clear yellow solution
Verbindung des Beispiel 1 : 99,3 % in nahezu farbloser Lösung Compound of Example 1: 99.3% in almost colorless solution
*(HPLC-Analyse) * (HPLC analysis)

Claims

Patentansprüche Patent claims
1. Propagylcarbamate der allgemeinen Formel (I) 1. Propagylcarbamates of the general formula (I)
Figure imgf000045_0001
in welcher
Figure imgf000045_0001
in which
R1, R2 unabhängig voneinander für Wasserstoff, Alkyl oder Phenyl stehen oder R1 und R2 einen 5- bis 8-gliedrigen Ring bilden, R3, R4 unabhängig voneinander für gegebenenfalls durch 1 bis 3 Sauerstoff-,R 1 , R 2 independently of one another represent hydrogen, alkyl or phenyl or R 1 and R 2 form a 5- to 8-membered ring, R 3 , R 4 independently of one another represent optionally 1 to 3 oxygen,
Schwefel-, oder Stickstoffatome unterbrochenes und/oder gegebenenfalls substituiertes Alkyl, oder für gegebenenfalls substituiertes Aryl, Aralkyl stehen, oder zusammen mit dem Stickstoffatom an das sie gebunden sind einen gegebenenfalls substituierten 5- bis 8-gliedrigen Ring bilden, der gegebenenfalls durch 1 bis 3 Sauerstoff-, Schwefel- und/oder Stickstoffatome unterbrochen ist, und/oder gegebenenfalls benzoanelliert ist. Sulfur or nitrogen atoms stand for interrupted and/or optionally substituted alkyl, or for optionally substituted aryl, aralkyl, or together with the nitrogen atom to which they are bonded they form an optionally substituted 5- to 8-membered ring, which may optionally be replaced by 1 to 3 Oxygen, sulfur and/or nitrogen atoms are interrupted and/or optionally benzo-fused.
2. Verbindungen gemäß Anspruch 1 der Formel (I), in welcher R1, R2 unabhängig voneinander für Wasserstoff, C1-C6- Alkyl stehen oder R1 und R2 zusammen einen fünf- bis sechsgliedrigen Ring bilden , R3, R4 unabhängig voneinander für gegebenenfalls durch 1 oder 2 Sauerstoff-, Schwefel- und/oder Stickstoffatome unterbrochenes und/oder gegebenenfalls durch Halogen, Alkyl, Alkylthio, Alkoxy, Halogenalkyl, Halogenalkoxy mit jeweils 1 bis 6 Kohlenstoffatomen im Alkylteil oder Aryl oder durch die Gruppe CO2R1 substituiertes geradkettiges, verzweigtes oder cyclisches C 1-C18-Alkyl stehen, oder für gegebenenfalls durch Halogen, Alkyl, Alkoxy, Alkylthio, Halogenalkyl mit jeweils 1 bis 6 Kohlenstoffatomen im Alkylteil oder Aryl substituiertes Aryl, Hetaryl oder Aralkyl mit 1 bis 6 Kohlenstoffatomen im Alkylteil stehen, oder zusammen mir dem Stickstoffatom, an das sie gebunden sind einen fünf- bis sechsgliederigen Ring bilden der gegebenenfalls durch 1 oder 2 Sauerstoff-, Schwefel- und/oder Stickstoffatome unterbrochen ist und/oder gegebenenfalls durch Halogen, Alkyl, Alkoxy, Alkylthio- oder Aryl substituiert ist, und/oder gegebenenfalls benzoanelliert ist. 2. Compounds according to claim 1 of the formula (I), in which R 1 , R 2 independently represent hydrogen, C 1 -C 6 alkyl or R 1 and R 2 together form a five- to six-membered ring, R 3 , R 4 independently of each other for optionally interrupted by 1 or 2 oxygen, sulfur and / or nitrogen atoms and / or optionally by halogen, alkyl, alkylthio, alkoxy, haloalkyl, haloalkoxy, each with 1 to 6 carbon atoms in the alkyl part or aryl or straight-chain, branched or cyclic C 1 -C 18 alkyl substituted by the group CO 2 R 1 , or aryl, hetaryl or aryl optionally substituted by halogen, alkyl, alkoxy, alkylthio, haloalkyl, each with 1 to 6 carbon atoms in the alkyl part or aryl Aralkyl with 1 to 6 carbon atoms in the alkyl part, or together with the nitrogen atom to which they are bonded form a five- to six-membered ring which is optionally interrupted by 1 or 2 oxygen, sulfur and / or nitrogen atoms and / or optionally by Halogen, alkyl, alkoxy, alkylthio- or aryl is substituted, and/or is optionally benzo-fused.
3. Verbindungen gemäß Anspruch 1 der Formel (I) in welcher R1, R2 unabhängig voneinander für Wasserstoff oder Methyl stehen, 3. Compounds according to claim 1 of the formula (I) in which R 1 , R 2 independently represent hydrogen or methyl,
R3, R4 unabhängig voneinander für gegebenenfalls durch 1 oder 2 Sauerstoff-, Schwefel- und/oder Stickstoffatome unterbrochenes und/oder gegebenenfalls durch Fluor, Chlor, Methyl, Ethyl, n-, i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n-, i-Propyloxy, n-, i-, s- oder t-Butyloxy, Methylthio, Ethylthio, n-, i-Propylthio, n-, i-, s- oder t-Butylthio, R 3 , R 4 independently of one another for optionally interrupted by 1 or 2 oxygen, sulfur and/or nitrogen atoms and/or optionally by fluorine, chlorine, methyl, ethyl, n-, i-propyl, n-, i-, s - or t-butyl, methoxy, ethoxy, n-, i-propyloxy, n-, i-, s- or t-butyloxy, methylthio, ethylthio, n-, i-propylthio, n-, i-, s- or t-butylthio,
Halogenalkyl, Halogenalkoxy mit jeweils 1 bis 5 Halogenatomen und 1 bis 4 Kohlenstoffatomen, Phenyl oder die Gruppe CO2R1 substituiertes, geradkettiges, verzweigtes oder cyclisches C1-C14- Alkyl stehen, oder für gegebenenfalls durch Fluor, Chlor, Methyl, Ethyl, n-, i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n-, i-Propyloxy, n-, i-, s- oder t-Butyloxy, Methylthio, Ethylthio, n-, i-Propylthio, n-, i-, s- oder t-Butylthio, Halogenalkyl, Halogenalkoxy mit jeweils 1 bis 5 Halogenatomen und 1 bis 4 Kohlenstoffatomen, Phenyl substituiertes Phenyl, Naphthyl, Biphenyl, Benzyl, Phenylethyl, Pyridyl, Furyl, Thiophenyl Pyrrolyl, Oxazolyl, Thiazolyl, Pyrazolyl, Imidazolyl oder Triazoyl stehen, oder zusammen mit dem Sückstoffatom an das sie gebunden sind einen Pyrrolidin-, Piperidin-, Morpholin- oder Piperazinring bilden, der gegebenenfalls durch Fluor, Chlor, Methyl, Methoxy, Trifluormethyl, Ethyl, Ethoxy substituiert ist Haloalkyl, haloalkoxy, each with 1 to 5 halogen atoms and 1 to 4 carbon atoms, phenyl or the group CO 2 R 1 substituted, straight-chain, branched or cyclic C 1 -C 14 alkyl, or optionally by fluorine, chlorine, methyl, ethyl , n-, i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n-, i-propyloxy, n-, i-, s- or t-butyloxy, methylthio, ethylthio, n-, i-propylthio, n-, i-, s- or t-butylthio, haloalkyl, haloalkoxy each with 1 to 5 halogen atoms and 1 to 4 carbon atoms, phenyl substituted phenyl, naphthyl, biphenyl, benzyl, phenylethyl, pyridyl, furyl, thiophenyl pyrrolyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl or triazoyl, or together with the sugar atom to which they are bound a pyrrolidine, piperidine, morpholine or piperazine ring form, which is optionally substituted by fluorine, chlorine, methyl, methoxy, trifluoromethyl, ethyl, ethoxy
4. Verbindungen der Formel (I) gemäß Anspruch 1 in welcher R3 und R4 jeweils für den gleichen Rest stehen, oder R3 für Methyl steht und R4 die in den Ansprüchen 1 bis 3 angegebene Bedeutungen hat. 4. Compounds of the formula (I) according to claim 1 in which R 3 and R 4 each represent the same radical, or R 3 represents methyl and R 4 has the meanings given in claims 1 to 3.
5. Schädlingsbekämpfungsmittel, gekennzeichnet durch einen Gehalt an mindestens einer Verbindung der Formel (I) nach Anspruch 1. 5. Pesticides, characterized by a content of at least one compound of the formula (I) according to claim 1.
6. Verfahren zur Bekämpfung von Schädlingen, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) nach Anspruch 1 auf Schädlinge und/oder ihren Lebensraum einwirken läßt 6. A method for combating pests, characterized in that compounds of the formula (I) according to claim 1 are allowed to act on pests and / or their habitat
7. Verfahren zur Herstellung von Verbindungen der Formel (I) 7. Process for the preparation of compounds of formula (I)
Figure imgf000047_0001
in welcher
Figure imgf000047_0001
in which
R1, R2, R3 und R4 die in Anspruch 1 angegebene Bedeutung haben, dadurch gekennzeichnet, daß man R 1, R 2 , R 3 and R 4 have the meaning given in claim 1, characterized in that one
1. Verbindungen der Formel (II) 1. Compounds of the formula (II)
Figure imgf000048_0001
worin
Figure imgf000048_0001
wherein
X für Wasserstoff oder Iod steht mit Verbindungen der Formel (III) X represents hydrogen or iodine with compounds of the formula (III)
Figure imgf000048_0002
gegebenenfalls in Gegenwart eines Verdünnungsmittels, in Gegenwart einer Base umsetzt, oder
Figure imgf000048_0002
optionally reacted in the presence of a diluent, in the presence of a base, or
2. Verbindungen der Formel (IV) 2. Compounds of the formula (IV)
Figure imgf000048_0003
worin
Figure imgf000048_0003
wherein
X für Wasserstoff oder Iod steht mit Aminen der Formel (V) X stands for hydrogen or iodine with amines of the formula (V)
Figure imgf000049_0001
gegebenenfalls in Gegenwart eines Verdünnungsmittels, in Gegenwart einer Base umsetzt, oder
Figure imgf000049_0001
optionally reacted in the presence of a diluent, in the presence of a base, or
3. Verbindungen der Formel (VI) 3. Compounds of the formula (VI)
Figure imgf000049_0002
worin
Figure imgf000049_0002
wherein
X für Wasserstoff oder Iod steht X stands for hydrogen or iodine
Y für eine Abgangsgruppe, wie Halogen, O-Tosyl oder O-Mesyl, steht mit Aminen der Formel (V) in Gegenwart einer Base und Kohlendioxid und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt und Y represents a leaving group, such as halogen, O-tosyl or O-mesyl, is reacted with amines of the formula (V) in the presence of a base and carbon dioxide and optionally in the presence of a diluent and
4. für den Fall, daß X in den Formel (II), (IV) oder (VI) für Wasserstoff steht, anschließend in Gegenwart einer Hilfsbase und gegebenenfalls einem Verdünnungsmittel iodiert. 4. in the event that
8. Verwendung von Verbindungen der Formel (I) nach Anspruch 1 zur Bekämpfung von Schädlingen. 8. Use of compounds of the formula (I) according to claim 1 for combating pests.
9. Verfahren zur Herstellung von Schädlingsbekämpfungsmitteln, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) nach Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt 9. A process for the production of pesticides, characterized in that compounds of the formula (I) according to claim 1 are mixed with extenders and/or surface-active agents
10. Verfahren zum Schutz von technischen Materialien, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) nach Anspruch 1 auf die zu schützenden Materialien aufbringt oder beimischt 10. A process for the protection of technical materials, characterized in that compounds of the formula (I) according to claim 1 are applied or added to the materials to be protected
PCT/EP1994/001691 1993-06-07 1994-05-25 Iodopropargyl carbamates and their use as biocides in the protection of plants and materials WO1994029268A1 (en)

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Cited By (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006721A1 (en) * 1996-08-09 1998-02-19 Bayer Aktiengesellschaft Phenyl-substituted cyclic ketoenol
US6015823A (en) * 1996-11-28 2000-01-18 Bayer Aktiengesellschaft 4-Cyclohexylphenyl-oxazolines and their use for controlling animal pests
US6133296A (en) * 1996-05-10 2000-10-17 Bayer Aktiengesellschaft Substituted pyridyl keto enols
US6251833B1 (en) 1997-03-03 2001-06-26 Christoph Erdelen 2-arylcyclopentan-1,3-diones
US6255342B1 (en) 1996-08-05 2001-07-03 Bayer Aktiengesellschaft 2-and 2,5-substituted phenylketoenols
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US6683028B1 (en) 1999-01-08 2004-01-27 Bayer Aktiengesellschaft Cyclic guanidine derivatives and their use as pesticides
US6710045B2 (en) 2000-07-13 2004-03-23 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides (IV)
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US6743940B2 (en) 2000-12-15 2004-06-01 Ciba Specialty Chemicals Corporation 4-aminobut-2-ynecarboxylic acid derivatives
US6806292B2 (en) * 2000-01-31 2004-10-19 Bayer Aktiengesellschaft Substituted imide derivatives
WO2004111042A1 (en) 2003-06-12 2004-12-23 Bayer Cropscience Aktiengesellschaft N-heterocyclyl phenyl-substituted cyclic ketoenols
US6838462B2 (en) 2001-04-20 2005-01-04 Bayer Cropscience Lp Insecticidal azoles
US6861391B1 (en) 1999-09-29 2005-03-01 Bayer Aktiengesellschaft Trifluoromethyl-substituted spirocyclic ketoenols
US6906007B2 (en) 2000-06-19 2005-06-14 Bayer Cropscience Ag Phenyl-substituted 5,6-dihydropyrone derivatives for use as pesticides and herbicides
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US8129658B2 (en) 2009-08-06 2012-03-06 Applied Materials, Inc. Systems for thin film laser scribing devices
US8333843B2 (en) 2009-04-16 2012-12-18 Applied Materials, Inc. Process to remove metal contamination on a glass substrate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3234037A1 (en) * 1982-09-14 1984-03-29 Bayer Ag, 5090 Leverkusen IODOPROPARGYLSULFAMIDE
EP0257888A2 (en) * 1986-08-26 1988-03-02 Sumitomo Chemical Company, Limited An iodopropargyl carbamate derivative, a method for its production and fungicidal compositions containing it as an active ingredient
EP0258030A2 (en) * 1986-08-26 1988-03-02 Sumitomo Chemical Company, Limited A fungicidal composition containing an iodopropargyl carbamate
EP0490566A1 (en) * 1990-12-10 1992-06-17 Rohm And Haas Company Preparation and use of N-iodopropargyl oxycarbonyl amino acid esters and derivatives as antimicrobial agents

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3234037A1 (en) * 1982-09-14 1984-03-29 Bayer Ag, 5090 Leverkusen IODOPROPARGYLSULFAMIDE
EP0257888A2 (en) * 1986-08-26 1988-03-02 Sumitomo Chemical Company, Limited An iodopropargyl carbamate derivative, a method for its production and fungicidal compositions containing it as an active ingredient
EP0258030A2 (en) * 1986-08-26 1988-03-02 Sumitomo Chemical Company, Limited A fungicidal composition containing an iodopropargyl carbamate
EP0490566A1 (en) * 1990-12-10 1992-06-17 Rohm And Haas Company Preparation and use of N-iodopropargyl oxycarbonyl amino acid esters and derivatives as antimicrobial agents

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6133296A (en) * 1996-05-10 2000-10-17 Bayer Aktiengesellschaft Substituted pyridyl keto enols
US6504036B1 (en) 1996-08-05 2003-01-07 Bayer Aktiengesellschaft 2- and 2.5-substituted phenylketoenols
US6255342B1 (en) 1996-08-05 2001-07-03 Bayer Aktiengesellschaft 2-and 2,5-substituted phenylketoenols
US6596873B1 (en) 1996-08-05 2003-07-22 Bayer Aktiengesellschaft 2-and 2,5-substituted phenylketoenols
WO1998006721A1 (en) * 1996-08-09 1998-02-19 Bayer Aktiengesellschaft Phenyl-substituted cyclic ketoenol
US6770595B2 (en) 1996-11-20 2004-08-03 Bayer Aktiengesellschaft Cyclic imines as pesticides
US6274613B1 (en) 1996-11-20 2001-08-14 Bayer Aktiengesellschaft Cyclic imines as pesticides
US6399771B1 (en) 1996-11-20 2002-06-04 Bayer Aktiengesellschaft Cyclic imines as pesticides
US7122506B2 (en) 1996-11-20 2006-10-17 Bayer Aktiengesellschaft Cyclic imines as pesticides
US6015823A (en) * 1996-11-28 2000-01-18 Bayer Aktiengesellschaft 4-Cyclohexylphenyl-oxazolines and their use for controlling animal pests
US6265430B1 (en) 1996-12-04 2001-07-24 Bayer Aktiengesellschaft 3-thiocarbamoylpyrazole derivatives as pesticides
US6630594B2 (en) 1996-12-12 2003-10-07 Bayer Aktiengesellschaft Methods of making substituted phenylketoenols
US6391912B1 (en) 1996-12-12 2002-05-21 Bayer Aktiengesellschaft Substituted phenylketoenols
US6251833B1 (en) 1997-03-03 2001-06-26 Christoph Erdelen 2-arylcyclopentan-1,3-diones
US6503912B1 (en) 1998-01-08 2003-01-07 Bayer Aktiengesellschaft Substituted guanidine derivatives
US6667310B2 (en) 1998-01-08 2003-12-23 Bayer Aktiengesellschaft Substituted guanidine derivatives
US6441030B1 (en) 1998-10-09 2002-08-27 Bayer Aktiengesellschaft 3-phenyl-pyrones
US6683028B1 (en) 1999-01-08 2004-01-27 Bayer Aktiengesellschaft Cyclic guanidine derivatives and their use as pesticides
US6670385B1 (en) 1999-05-28 2003-12-30 Bayer Aktiengesellschaft α-phenyl-βketosulfone
US6849744B2 (en) 1999-05-28 2005-02-01 Bayer Aktiengesellschaft α-phenyl-β-keto sulfones
US6861391B1 (en) 1999-09-29 2005-03-01 Bayer Aktiengesellschaft Trifluoromethyl-substituted spirocyclic ketoenols
US6806292B2 (en) * 2000-01-31 2004-10-19 Bayer Aktiengesellschaft Substituted imide derivatives
US6911416B2 (en) 2000-05-12 2005-06-28 Bayer Aktiengesellschaft Substituted N-benzoyl-n′(tetrazolylphenyl)-ureas and their use as pest control agents
US6906007B2 (en) 2000-06-19 2005-06-14 Bayer Cropscience Ag Phenyl-substituted 5,6-dihydropyrone derivatives for use as pesticides and herbicides
US6710045B2 (en) 2000-07-13 2004-03-23 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides (IV)
US6927215B2 (en) 2000-07-13 2005-08-09 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides (I)
US6908937B2 (en) 2000-07-13 2005-06-21 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers (II)
US6995185B2 (en) 2000-09-22 2006-02-07 Bayer Cropscience Ag Δ1-pyrrolines used as pesticides
US7419936B2 (en) 2000-09-22 2008-09-02 Bayer Cropscience Ag Optically active 2,5-bisaryl-Δ1-pyrrolines and their use as pest control agents
US7179806B2 (en) 2000-12-05 2007-02-20 Bayer Cropscience Ag Δ1-pyrrolines used as pesticides
US6743940B2 (en) 2000-12-15 2004-06-01 Ciba Specialty Chemicals Corporation 4-aminobut-2-ynecarboxylic acid derivatives
EP1215198A1 (en) * 2000-12-15 2002-06-19 Ciba SC Holding AG 4-Aminobut-2-yne carboxylic acid derivatives and their use as antimicrobial agents
US7186722B2 (en) 2001-02-13 2007-03-06 Bayer Cropscience Ag 2-heteroaryl-3,4-dihydro-2h-pyrrole derivatives and the use thereof as pesticides
US7238697B2 (en) 2001-02-22 2007-07-03 Bayer Cropscience Ag Pyridylpyrimidines for use as pesticides
US7087616B2 (en) 2001-02-22 2006-08-08 Bayer Cropscience Ag Pyrazolyl pyrimidines
US6838462B2 (en) 2001-04-20 2005-01-04 Bayer Cropscience Lp Insecticidal azoles
US7417150B2 (en) 2001-04-20 2008-08-26 Bayer Cropscience Ag Azoles having an insecticidal action
US8101772B2 (en) 2001-08-16 2012-01-24 Bayer Cropscience Ag Fungicidal active substance combinations containing trifloxystrobin
EP2301348A1 (en) 2001-08-16 2011-03-30 Bayer CropScience AG Fungicidal active substance combinations containing trifloxystrobin
US8461349B2 (en) 2001-08-16 2013-06-11 Bayer Cropscience Ag Fungicidal active substance combinations containing trifloxystrobin
US9326514B2 (en) 2001-08-16 2016-05-03 Bayer Intellectual Property Gmbh Fungicidal active substance combinations containing trifloxystrobin
EP2316268A1 (en) 2001-08-16 2011-05-04 Bayer CropScience AG Fungicidal combinations comprising trifloxystrobin
US8063096B2 (en) 2001-09-24 2011-11-22 Bayer Cropscience Ag Spirocyclic 3-phenyl-3substituted-4-ketolactams and-lactones
US7425575B2 (en) 2001-09-24 2008-09-16 Bayer Cropscience Ag Spirocyclic 3-phenyl-3-substituted 4-ketolactams and 4-ketolactones
EP2030969A1 (en) 2001-09-24 2009-03-04 Bayer CropScience AG Spirocyclic 3-phenyl-3-substituted 4-ketolactams and 4-ketolactones
US7332512B2 (en) 2001-11-05 2008-02-19 Bayer Cropscience Ag Halogenated nitrobutadienes for controlling animal pests
US7115603B2 (en) 2001-11-07 2006-10-03 Bayer Cropscience Ag A1-pyrrolines
WO2003048138A1 (en) 2001-12-06 2003-06-12 Bayer Cropscience Aktiengesellschaft [1.2]-oxazin-3,5-diones
US7345080B2 (en) 2002-02-19 2008-03-18 Bayer Cropscience Ag Substituted 4-pyrazolyl pyrazonlines used for pest control
US7365098B2 (en) 2002-05-13 2008-04-29 Bayer Cropscience Ag N'-cyano-N-methyl-imidamide derivatives
EP2233466A1 (en) 2002-08-28 2010-09-29 Bayer CropScience AG 4-Alkoxy-1-amino-1-cyclohexanecarboxylic acid derivatives and their use as intermediates
WO2004024688A1 (en) 2002-08-28 2004-03-25 Bayer Cropscience Aktiengesellschaft Substituted spirocyclic ketoenols
US7297797B2 (en) 2002-09-24 2007-11-20 Bayer Cropscience Ag Pyrrolines
US7227043B2 (en) 2002-10-22 2007-06-05 Bayer Cropscience Ag 2-phenyl-2-substituted-1,3-diketones
US7888285B2 (en) 2003-03-14 2011-02-15 Bayer Cropscience Ag 2,4,6-phenyl substituted cyclic ketoenols
WO2004111042A1 (en) 2003-06-12 2004-12-23 Bayer Cropscience Aktiengesellschaft N-heterocyclyl phenyl-substituted cyclic ketoenols
US7420062B2 (en) 2003-07-14 2008-09-02 Bayer Cropscience, Ag Hetaryl-substituted pyrazolidindione derivatives with pesticidal characteristics
US8119566B2 (en) 2003-08-14 2012-02-21 Bayer Cropscience Ag 4-biphenyl-substituted pyrazolidin-3,5-dione derivatives
US8586783B2 (en) 2003-08-14 2013-11-19 Bayer Cropscience Ag 4-biphenyl-substituted pyrazolidin-3,5-dione derivatives
US8987500B2 (en) 2003-08-14 2015-03-24 Bayer Cropscience Ag 4-biphenyl-substituted pyrazolidin-3,5-dione derivatives
US7569517B2 (en) 2003-08-14 2009-08-04 Bayer Cropscience Ag 4-biphenyl-substituted pyrazolidin-3 5-diones pesticide agent and/or microbicide and/or herbicide
US7727933B2 (en) 2003-11-22 2010-06-01 Bayer Cropscience Ag 2-ethyl-4,6-dimethyl-phenyl-substituted spirocyclic tetramic acid derivatives
EP2218330A1 (en) 2003-11-22 2010-08-18 Bayer CropScience AG Process for the preparation of 2-ethyl-4,6-dimethylphenyl acetic acid by reacting 2-ethyl-4,6-dimethylbromobenzene with tert.-butylacetate
US7947704B2 (en) 2004-03-25 2011-05-24 Bayer Cropscience Ag 2,4,6-phenyl-substituted cyclic ketoenols
WO2005092897A2 (en) 2004-03-25 2005-10-06 Bayer Cropscience Ag 2,4,6-phenylsubstituted cyclic ketoenoles
US8410289B2 (en) 2004-06-25 2013-04-02 Bayer Cropscience Ag Spirocyclic 3'-alkoxytetramic acids and-tetronic acids
EP2246328A1 (en) 2004-06-25 2010-11-03 Bayer CropScience AG 3'-Alkoxy spirocyclic tetronic acid derivatives
WO2006000355A1 (en) 2004-06-25 2006-01-05 Bayer Cropscience Aktiengesellschaft 3'-alkoxy spirocyclic tetramic and tetronic acids
US8629084B2 (en) 2004-09-16 2014-01-14 Bayer Cropscience Ag Iodine-phenyl-substituted cyclic cetoenols
WO2006029799A1 (en) 2004-09-16 2006-03-23 Bayer Cropscience Ag Iodine-phenyl-substituted cyclic cetoenols
EP2253207A1 (en) 2004-11-04 2010-11-24 Bayer CropScience AG Substituted phenyl acetic acid esters
EP2218710A1 (en) 2004-11-04 2010-08-18 Bayer CropScience AG Procedure for the preparation of 2,6-diethyl-4-methylphenylacetic acid
EP2216317A1 (en) 2004-11-04 2010-08-11 Bayer CropScience AG Phenyl acetic acid halogenides
EP2216316A1 (en) 2004-11-04 2010-08-11 Bayer CropScience Aktiengesellschaft Phenyl acetic acid derivatives
US8383853B2 (en) 2004-11-04 2013-02-26 Bayer Cropscience Ag Method for preparing 2,6-diethyl-4-methylphenylacetic acid
WO2007096058A1 (en) 2006-02-21 2007-08-30 Bayer Cropscience Ag Cycloalkylphenyl substituted cyclic ketoenols
EP2186805A1 (en) 2006-02-21 2010-05-19 Bayer CropScience AG Cycloalkyl-phenyl-substituted cyclic ketoenoles
EP2184275A1 (en) 2006-02-21 2010-05-12 Bayer CropScience AG Cycloalkyl-phenyl-substituted cyclic ketoenoles
EP2186791A1 (en) 2006-02-21 2010-05-19 Bayer CropScience AG Cycloalkyl-phenyl-substituted cyclic ketoenoles
US8067458B2 (en) 2006-04-22 2011-11-29 Bayer Cropscience Ag Alkoxyalkyl-substituted cyclic ketoenols
EP2080758A2 (en) 2007-11-29 2009-07-22 Bayer CropScience AG Halogen substituted delta-1-pyrrolines
WO2009115262A1 (en) 2008-03-19 2009-09-24 Bayer Cropscience Ag 4'4'-dioxaspiro-spirocyclically substituted tetramates
EP2103615A1 (en) 2008-03-19 2009-09-23 Bayer CropScience AG 4'4'-Dioxaspiro-spirocyclic substituted tetramates
US8333843B2 (en) 2009-04-16 2012-12-18 Applied Materials, Inc. Process to remove metal contamination on a glass substrate
US8129658B2 (en) 2009-08-06 2012-03-06 Applied Materials, Inc. Systems for thin film laser scribing devices

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