EP0702670A1 - Iodopropargylcarbamates et leur utilisation comme biocides pour la protection des vegetaux et des materiaux - Google Patents

Iodopropargylcarbamates et leur utilisation comme biocides pour la protection des vegetaux et des materiaux

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Publication number
EP0702670A1
EP0702670A1 EP94916987A EP94916987A EP0702670A1 EP 0702670 A1 EP0702670 A1 EP 0702670A1 EP 94916987 A EP94916987 A EP 94916987A EP 94916987 A EP94916987 A EP 94916987A EP 0702670 A1 EP0702670 A1 EP 0702670A1
Authority
EP
European Patent Office
Prior art keywords
optionally
formula
compounds
alkyl
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94916987A
Other languages
German (de)
English (en)
Inventor
Lutz Heuer
Peter Wachtler
Martin Kugler
Heinrich Schrage
Hans-Ulrich Buschhaus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE4332508A external-priority patent/DE4332508A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0702670A1 publication Critical patent/EP0702670A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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

L'invention concerne des propargylcarbamates de formule (I) dans laquelle R1, R2 désignent, indépendamment l'un de l'autre, un hydrogène, un alkyle ou un phényle, ou R1 et R2 forment un noyau de 5 à 8 chaînons, R3, R4 désignent, indépendamment l'un de l'autre, un alkyle interrompu éventuellement par 1 à 3 atomes d'oxygène, de soufre ou d'azote et/ou éventuellement substitué, ou un aryle ou un aralkyle éventuellement substitué, ou bien forment, conjointement avec l'atome d'azote auquel ils sont liés, un noyau de 5 à 8 chaînons, éventuellement substitué, interrompu éventuellement par 1 à 3 atomes d'oxygène, de soufre et/ou d'azote, et/ou éventuellement benzoannellé. L'invention concerne en outre un procédé de fabrication de ces composés et leur utilisation comme biocides pour la protection des végétaux et des matériaux.
EP94916987A 1993-06-07 1994-05-25 Iodopropargylcarbamates et leur utilisation comme biocides pour la protection des vegetaux et des materiaux Withdrawn EP0702670A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4318890 1993-06-07
DE4318890 1993-06-07
DE4332508A DE4332508A1 (de) 1993-06-07 1993-09-24 Propagylcarbamate
DE4332508 1993-09-24
PCT/EP1994/001691 WO1994029268A1 (fr) 1993-06-07 1994-05-25 Iodopropargylcarbamates et leur utilisation comme biocides pour la protection des vegetaux et des materiaux

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