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EP0741713A1 - Derives microbicides d'halogenalcenylazolyle - Google Patents

Derives microbicides d'halogenalcenylazolyle

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Publication number
EP0741713A1
EP0741713A1 EP95906335A EP95906335A EP0741713A1 EP 0741713 A1 EP0741713 A1 EP 0741713A1 EP 95906335 A EP95906335 A EP 95906335A EP 95906335 A EP95906335 A EP 95906335A EP 0741713 A1 EP0741713 A1 EP 0741713A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
formula
alkyl
chlorine
bromine
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Withdrawn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
EP95906335A
Other languages
German (de)
English (en)
Inventor
Manfred Jautelat
Stefan Dutzmann
Heinz-Wilhelm Dehne
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
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0741713A1 publication Critical patent/EP0741713A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to new haloalkenyl azolyl derivatives, a process for their preparation and their use as microbicides in crop protection and in material protection.
  • R 1 stands for optionally substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl, optionally substituted aryl or for optionally substituted heteroaryl,
  • R 2 represents alkyl, haloalkyl, 1-hydroxyhalogenalkyl, 1-hydroxyalkyl, 2-hydroxyalkyl, 1-alkenyl or 2-alkenyl,
  • X 1 represents fluorine, chlorine, bromine or iodine.
  • X 2 represents fluorine, chlorine, bromine or iodine and
  • Y stands for nitrogen or a CH group, and their acid addition salts and metal salt complexes found.
  • the compounds of the formula (I) contain an asymmetrically substituted carbon atom and can therefore be obtained in the two optical isomer forms.
  • the substances of the formula (I) can exist in two geometric isomer forms.
  • the present invention relates to both the isomer mixtures and the individual isomers. It has also been found that haloalkenyl azolyl derivatives of the formula (I) and their acid addition salts and metal salts are obtained when alkynes of the formula
  • R 3 represents alkyl or haloalkyl and Z represents chlorine, bromine, iodine, methyl sulfonyloxy or 4-methylphenylsulfonyloxy,
  • R 4 represents hydrogen, alkyl or haloalkyl
  • R 5 represents hydrogen or alkyl
  • R 6 represents hydrogen or alkyl
  • R 7 represents hydrogen or alkyl
  • R 1 , R 2 and Y have the meanings given above, with halogen or halogen-providing compounds in the presence of a diluent, or d) by using haloalkenyl azolyl derivatives of the formula
  • R 8 represents 1-hydroxyalkyl or 2-hydroxyalkyl, reacted with thionyl chloride in the presence of a diluent and, if appropriate, subsequently treated with an acid binder, and optionally then adding an acid or a metal salt to the compounds of formula (I) thus obtained.
  • the substances according to the invention have a better microbicidal activity both in crop protection and in material protection than the constitutionally most similar, known compounds of the same direction of action.
  • the fungicidal properties of the substances according to the invention exceed 4- (1-chloro-cyclopropyl) -1,1,2-trichloro-4-hydroxy-5- (1,2,4-triazol-1-yl) pent-1-en.
  • R 1 preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, where each of these radicals can be monosubstituted to triple, identical or differently substituted by halogen, cycloalkyl having 3 to 7 carbon atoms, phenyl and / or halophenyl, or alkenyl having 2 up to 6 carbon atoms, where each of these radicals can be substituted once to three times, identically or differently by
  • cycloalkyl having 3 to 7 carbon atoms where each of these cycloalkyl radicals can be substituted once to three times, identically or differently by halogen and / or alkyl having 1 to 4 carbon atoms, or for phenyl which can be substituted once to three times, similarly or differently by Halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkoxy with 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkylthio with 1 or 2 carbon atoms and 1 to 5 identical or different which halogen atoms, cycloalkyl with 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, alk
  • Haloalkoxy and haloalkylthio each with 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine or chlorine atoms, formyl, dialkoxymethyl with 1 or 2 carbon atoms in each alkoxy group, acyl with 2 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy part and 1 to 3 carbon atoms in the alkyl part, nitro and / or cyano.
  • halogen atoms such as fluorine or chlorine atoms, formyl, dialkoxymethyl with 1 or 2 carbon atoms in each alkoxy group, acyl with 2 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy part and 1 to 3 carbon
  • R 2 preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6
  • Carbon atoms and 1 to 5 fluorine and / or chlorine atoms for straight-chain or branched 1-hydroxyalkyl with 1 to 6 carbon atoms, for straight-chain or branched 2-hydroxyalkyl with 2 to 6 carbon atoms, straight-chain or branched 1-hydroxyhaloalkyl with 1 to 6 carbon atoms and 1 to 3 halogen atoms, for straight-chain or branched 1-alkenyl with 2 to 6 carbon atoms or for straight-chain or branched 2-alkenyl with 2 to 6 carbon atoms.
  • X 1 also preferably represents fluorine, chlorine, bromine or iodine.
  • X 2 also preferably represents fluorine, chlorine, bromine or iodine.
  • Y also preferably represents a nitrogen atom or a CH group.
  • R 1 particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, tert-pentyl, 1-ethyl-1-methyl-propyl, 1 , 1-Dimethyl-pentyl, 1,1,2-trimethylpropyl or 1,1-dimethyl-prop-2-enyl, where each of the aforementioned radicals can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, phenyl ,
  • R 2 particularly preferably represents methyl, ethyl, n-propyl, i-butyl, n-butyl, n-pentyl, chloromethyl, fluoromethyl, 2-chloroethyl, 2-fluoroethyl, 3-chloropropyl, 3-fluoropropyl, trichloromethyl, trifluoromethyl, Hydroxymethyl, 1-hydroxyethyl, 1-hydroxy-propyl, 1-hydroxy-butyl, 2-hydroxy-prop-2-yl, 3-hydroxy-but-2-yl, 3-hydroxy-pent-3-yl, 2- Hydroxy-ethyl, 2-hydroxy-1-propyl, 2-hydroxy-2-methyl-propyl, 2-hydroxy-1-butyl, 1-hydroxy-2,2,2- trichloro-ethyl, vinyl, 1-propenyl, 1-butenyl, 2-butenyl, 1-propen-2-yl or 2-buten-2-yl.
  • X 1 also particularly preferably represents fluorine, chlorine, bromine or iodine.
  • X 2 also particularly preferably represents fluorine, chlorine, bromine or iodine.
  • Y also particularly preferably represents a nitrogen atom or a CH group.
  • Preferred compounds according to the invention are also addition products of acids and those haloalkenylazolyl derivatives of the formula (I) in which R 1 , R 2 , X 1 , X 2 and Y have those meanings which have been mentioned as preferred for these substituents.
  • the acids which can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid , Citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids, such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid, furthermore saccharin and thiosaccharin.
  • hydrohalic acids such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fum
  • preferred compounds according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. And IV. To VIII. Subgroup of the periodic table of the elements and those haloalkenylazolyl derivatives of the formula (I) in which R 1 , R 2 , X 1 , X 2 and Y have those meanings which have been mentioned as preferred for these substituents.
  • Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred.
  • Anions of these salts are those which are derived from acids which lead to physiologically tolerable addition products.
  • Particularly preferred acids in this connection are the hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, as well as phosphoric acid, nitric acid and sulfuric acid.
  • Examples of substances according to the invention are the haloalkenyl azolyl derivatives listed in the following table.
  • Formula (II) provides a general definition of the alkynes required as starting materials when carrying out the process according to the invention.
  • R 1 and Y preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these radicals.
  • alkynes of the formula (II) are known or can be prepared in a simple manner by known methods (cf. EP-OS 0 353 558, EP-OS 0 440 949 and EP-OS 0 440 950).
  • Suitable bases for carrying out the first stage of the process according to the invention are all strong alkali metal bases which are customary for such metalation reactions.
  • Butyllithium, lithium diisopropylamide, sodium hydride, sodium amide and potassium tert-butoxide are preferably usable.
  • reaction temperatures can be varied within a certain range when carrying out the metalation in the first stage of the process according to the invention. In general, temperatures between -70 ° C and 0 ° C, preferably at temperatures between -60 ° C and 0 ° C.
  • the procedure is generally under normal pressure.
  • Formula (III) provides a general definition of the compounds required as reaction components in carrying out variant (a) in the first stage of the process according to the invention.
  • R 3 preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 fluorine and / or chlorine atoms.
  • Z also preferably represents chlorine, bromine, iodine, methylsulfonyloxy or 4-methylphenylsulfonyloxy.
  • R 3 particularly preferably represents methyl, ethyl, n-propyl, i-butyl, n-butyl, n-pentyl, chloromethyl, fluoromethyl, 2-chloroethyl, 2-fluoroethyl, 3-chloropropyl, 3-fluoropropyl, trichloromethyl, trifluoromethyl.
  • Z also particularly preferably represents chlorine, bromine, iodine, methylsulfonyloxy or
  • variant (a) When variant (a) is carried out in the first stage of the process according to the invention, all customary diluents for such reactions are used organic solvents in question. Those diluents which have been mentioned as preferred in connection with the metalation reaction can preferably be used.
  • the reaction temperatures can be varied within a certain range. In general, temperatures between -40 ° C and + 50 ° C, preferably between -40 ° C and room temperature.
  • the amounts of the reaction components are chosen so that 1 mol to 1.5 mol, preferably 1 to 1.3 mol, of compound are generally present per mol of metallized alkyne of formula (III) is present.
  • the reaction mixture obtained in the metallization is generally used without prior work-up.
  • the work-up is carried out by customary methods. In general, the procedure is that of dilution with a water-immiscible oran solvent, the organic phase is washed, dried and concentrated and the remaining residue is either recrystallized or chromatographed for further purification. However, it is also possible to concentrate the reaction mixture after the reaction has ended and to remove any remaining impurities from the remaining residue by recrystallization or chromatography.
  • Formula (IV) provides a general definition of the carbonyl compounds required as reaction components when carrying out variant (b) in the first stage of the process according to the invention.
  • R 4 preferably represents hydrogen, straight-chain or branched alkyl having 1 to 5 carbon atoms or straight-chain or branched haloalkyl having 1 to 5 carbon atoms and 1 to 3 halogen atoms.
  • R 5 preferably represents hydrogen or straight-chain or branched alkyl having 1 to 5 carbon atoms.
  • R 4 particularly preferably represents hydrogen, methyl, ethyl, propyl or trichloromethyl.
  • R 5 particularly preferably represents hydrogen, methyl, ethyl or propyl.
  • the carbonyl compounds of formula (IV) are known.
  • all organic solvents customary for such reactions are suitable as diluents. Those diluents which have been mentioned as preferred in connection with the metalation reaction can preferably be used.
  • reaction temperatures and the other reaction conditions correspond to those which are also used when variant (a) is carried out.
  • Formula (V) provides a general definition of the oxiranes which are required as reaction components in carrying out variant (c) in the first stage of the process according to the invention.
  • R 6 preferably represents hydrogen or alkyl having 1 to 4 carbon atoms.
  • R 7 preferably represents hydrogen or alkyl having 1 to 4 carbon atoms.
  • R 6 particularly preferably represents hydrogen, methyl, ethyl or propyl.
  • R 7 particularly preferably represents hydrogen, methyl, ethyl or propyl.
  • the oxiranes of the formula (V) are known.
  • all organic solvents customary for such reactions are suitable as diluents. Those diluents which have been mentioned as preferred in connection with the metalation reaction can preferably be used.
  • the reaction temperatures and the other reaction conditions correspond to those which are also used when variant (a) is carried out.
  • Suitable halogens for carrying out the second stage of the process according to the invention are fluorine, chlorine, bromine and iodine as reaction components, furthermore mixed halogens such as chlorine (I) fluoride, bromine (I) fluoride, iodine (I) fluoride , Bromine (I) chloride, iodine (I) chloride or iodine (I) bromide (see Methodicium Chimicium, F. Körte, Vol. 7, p. 842 (1976)).
  • Halogen-providing compounds which can be used are, for example, sulfuryl chloride, N-bromosuccinimide with hydrochloric acid, N-chlorosuccinimide with hydrobromic acid or N-chlorosuccinimide with hydrogen fluoride / pyridine (see Synthesis 1973, 780).
  • halogens to the alkynes of the formula (VI) can be effected by the action of light, by heat, by radical-forming substances, such as organic peroxides, by surface-active substances, such as activated carbon, or metal salts, such as copper (II) chloride or iron (III ) chloride, are favored.
  • the isomer ratio (E / Z) can be influenced (see Houben-Weyl, Methods of Org. Chemistry, Vol. V / 3, p. 551 (1962)).
  • Halogenated organic solvents customary for such reactions can be used as diluents when carrying out the second stage of the process according to the invention.
  • Halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride can preferably be used.
  • the temperatures can be varied within a certain range when carrying out the second stage of the process according to the invention. In general, temperatures between -10 ° C and + 120 ° C, preferably between -5 ° C and + 80 ° C.
  • an equivalent amount or an excess of halogen or halogen-providing compound is generally employed per mole of alkyne of the formula (VI). The Refurbishment is carried out using customary methods.
  • the general procedure is to dilute with an organic solvent which is sparingly soluble in water, to wash with water and to concentrate the organic phase after drying.
  • the resulting products can optionally be further purified using customary methods.
  • haloalkenyl azolyl derivatives of the formula (Ia) serve as starting materials which can be prepared according to variants (b) or (c) of the process according to the invention.
  • Halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride can preferably be used.
  • Suitable acid binders for carrying out the process according to variant (d) according to the invention are all inorganic or organic bases which can usually be used for the elimination of hydrogen chloride.
  • Those preferably utilizable are alkaline earth or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or ammonium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali metal or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine , N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
  • the temperatures can be varied within a substantial range when carrying out the method according to variant (d).
  • the reaction with thionyl chloride is carried out at temperatures between 0 ° C. and 80 ° C., preferably between 20 ° C. and 60 ° C.
  • hydrogen chloride is optionally required in the presence of an acid binder
  • the reaction is generally carried out at temperatures between 0 ° C. and 100 ° C., preferably between 20 ° C. and 80 ° C.
  • an equivalent amount or also an excess of thionyl chloride is employed per mole of haloalkenyl azolyl derivative of the formula (Ia). If a separate splitting off of hydrogen chloride is necessary, 1 to 2 moles of acid binder are used for 1 mole of chlorinated product. The processing takes place according to usual methods.
  • haloalkenyl azolyl derivatives of the formula (I) obtainable by the process according to the invention can be converted into acid addition salts or metal salt complexes.
  • the acid addition salts of the compounds of formula (I) can be easily prepared by conventional salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. Hydrochloric acid can be obtained and in a known manner, e.g. by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent.
  • a suitable inert solvent e.g. Hydrochloric acid
  • metal salt complexes of the compounds of formula (I) preference is given to those salts of metals which have already been mentioned as preferred metal salts in connection with the description of the metal salt complexes according to the invention.
  • the metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol and adding it to compounds of the formula (I).
  • Metal salt complexes can be isolated in a known manner, for example by filtering off, and optionally purified by recrystallization.
  • the active compounds according to the invention have a strong microbicidal action and can be used to protect against undesirable microorganisms, such as fungi and bacteria, in crop protection and in the material.
  • Fungicides are used in crop protection to combat Plasmodio-phoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Some pathogens of fungal and bacterial 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. brassicae;
  • Erysiphe species such as Erysiphe graminis
  • Sphaerotheca species such as Sphaerotheca fuliginea
  • Podosphaera species such as Podosphaera leucotricha
  • 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 active compounds according to the invention are particularly suitable for combating cereal and rice diseases, such as pseudocercosporella, erysiphe, fusarium, pyrenophora, cochliobolus, pyricularia and pellicularia, and for combating botrytis in fruit, wine and vegetable production. They also have a good and broad in vitro effect.
  • the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
  • technical materials are to be understood as non-living materials that have been prepared for use in technology.
  • technical materials which are to be protected against microbial change or destruction by active substances according to the invention 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.
  • technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.
  • Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials.
  • the active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
  • microorganisms of the following genera may be mentioned:
  • Alternaria such as Alternaria tenuis, Aspergillus, such as Aspergillus niger,
  • Chaetomium like Chaetomium globosum
  • Coniophora such as Coniophora puetana
  • Lentinus such as Lentinus tigrinus
  • Penicillium such as Penicillium glaucum
  • Polyporus such as Polyporus versicolor
  • Aureobasidium such as Aureobasidium pullulans
  • Sclerophoma such as Sclerophoma pityophila
  • Trichoderma like Trichoderma viride
  • Escherichia such as Escherichia coli
  • Pseudomonas such as Pseudomonas aeruginosa
  • Staphylococcus such as Staphylococcus aureus.
  • the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm fog 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 Cold and warm fog formulations.
  • 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, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents such as alcohols, for example, can also be used as auxiliaries.
  • 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 water
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example.
  • Aerosol propellants such as halogenated hydrocarbons such as butane, propane, nitrogen and carbon dioxide
  • Solid carrier materials are suitable: for example natural stone powder, such as kaolins, Clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates;
  • Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks;
  • suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations In crop protection, the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can be used in the formulations in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of activity or to prevent the development of resistance.
  • Difenoconazole dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine
  • Fenarimol Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam,
  • copper preparations such as: copper hydroxide, copper naphthenate,
  • Mancopper Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157
  • Chlormephos Chlorpyrifos, ChlorpyrifosM, Cis-Resmethrin, Clocythrin, Clofentezin,
  • Cyanophos cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,
  • Fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
  • Fenoxycarb fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil,
  • Methami dophos methidathione, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,
  • Tebufenozid Tebufenpyrad
  • Tebupirimphos Teflubenzuron
  • Tefluthrin Temephos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenethriazonium, Triomenethriazonium, Tri
  • 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, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
  • the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
  • amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
  • active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.
  • the agents used to protect industrial materials generally contain the active ingredients in an amount of 1 to 95%, preferably 10 to 75%.
  • the application concentrations of the active compounds according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.
  • the effectiveness and the spectrum of activity of the active ingredients to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be produced therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients are used to enlarge the spectrum of activity or Achieving special effects such as added protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.
  • Sulfenamides such as dichlorfluanid (Euparen), tolyfluanid (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, dodecyldimethylammonium chloride;
  • Morpholine derivatives such as C 11 -C 14 -4-alkyl-2,6-dimethyl-morpholine homologue (tridemorph), (+) - cis-4- [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, cyproconazole or 1- (2-chlorophenyl) -2- (1,2,4-triazol-1-yl-methyl) -3,3- dimethyl-butan-2-ol.
  • Iodopropargyl derivatives such as iodopropargyl butyl carbamate (EPBC), chlorophenyl formal, phenyl carbamate, hexyl carbamate, cyclohexyl carbamate, iodopropargyloxyethylphenyl carbamate;
  • EPBC iodopropargyl butyl carbamate
  • chlorophenyl formal phenyl carbamate
  • hexyl carbamate hexyl carbamate
  • cyclohexyl carbamate iodopropargyloxyethylphenyl carbamate
  • Iodine derivatives such as diiodomethyl-p-arylsulfones e.g. Diiodomethyl p-tolyl sulfone;
  • Bromine derivatives such as bromopol
  • Isothiazolines such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one (octilinone);
  • Pyridines such as 1-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine;
  • Metal soaps such as tin, copper, zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate, oxides such as TBTO, Cu 2 O, CuO, ZnO;
  • Organic tin compounds such as tributyltin naphtenate and tributyltin oxide;
  • Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethyltiuram disulfide (TMTD);
  • Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil) etc.
  • Halogenated microbicides such as Cl-Ac, MCA, tectamer, bromopol, bromidox;
  • Benzothiazoles such as 2-mercaptobenzothiazoles; so. Dazomet;
  • Quinolines such as 8-hydroxyquinoline; Formaldehyde releasing compounds such as benzyl alcohol mono (poly) hemiformal,
  • 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, dichlorfos, dimethoate, ethoprophos, etrimfos, fenitrothion, fention, heptenophos, parathion, parathion-methyl, phosalone, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulprofos, triazophon and triazophon.
  • phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, 1- (4-chlorophenyl) -4- (O-
  • Carbamates such as aldicarb, bendiocarb, BPMC (2- (1-methylpropyl) phenylmethylcarbamate), butocarboxime, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarbox.
  • Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin (FMC 54800), cycloprothrin, cyfluthrin, decamethrione, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- ( -2-trifluoromethylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin and resmethrin; Nitroimino and nitromethylene compounds like - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazol2-amine (imidachloprid).
  • Organosilicon compounds preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or dimethyl (phenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl (9-ethoxyphenyl ) -silylmethyl-2-phenoxy-6-pyridylmethyl ether or (phenyl) [3- (3-phenoxyphenyl) propyl] (dimethyl) -silanes such as (4-ethoxyphenyl) - [3 (4-fluoro-3-phenoxyphenyl) - propyl] dimethylsilane.
  • ⁇ 0.4-1.2 (m, 4H); 1.8 (t, 3H); 2.65 (m. 2H); 4.2 (OH); 4.65 (AB system, 2H);
  • ⁇ 0.4 (m, 2H); 0.8 (m, 1H); 1.05 (m, 1H); 2.5 (s, 3H); 3.1 (d. 1H); 3.7 (d. 1H);
  • the mixture is subsequently stirred at -30 ° C. to -40 ° C. for 1 hour and then a solution of 17.2 g (0.11 mol) of ethyl iodide in 20 ml of absolute tetrahydrofuran is added dropwise.
  • the reaction mixture is then stirred under ammonia reflux.
  • the ammonia is allowed to evaporate, the residue is mixed with ethyl acetate and water, the organic phase is separated off, dried over sodium sulfate and concentrated under reduced pressure.
  • ⁇ 0.5-1.2 (m, 4H); 2.8 (m, 2H); 4.25 (m. 2H); 4.5 (OH); 4.65 (AB, 2H); 8.0 (s. 1H); 8.3 (s, 1H) ppm.
  • a mixture of 1.77 g (5 mmol) of 6- (1-chlorocyclopropyl) -3,4-dichloro-2,6-dihydroxy-2-methyl-7- (1,2,4-triazol-1-yl) -hept-3-ene and 20 ml of methylene chloride are mixed at room temperature with stirring with 0.71 g (6 mmol) of thionyl chloride and then heated under reflux for 5 hours. Then the reaction mixture is mixed with aqueous sodium carbonate solution and extracted several times with methylene chloride. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The remaining product is chromatographed on silica gel using ethyl acetate.
  • Botrytis test (bean) / protective
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Emulsifier 0.6 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are placed in a greenhouse at a temperature of approx. 15 ° C and a relative humidity of approx. 80%.
  • Evaluation is carried out 10 days after the inoculation.
  • Emulsifier 0.6 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.
  • Evaluation is carried out 7 days after the inoculation.
  • Active ingredients according to the invention are added to an agar which is produced using malt extract in concentrations of 0.1 mg / 1 to 800 mg / l. After the agar solidifies, it is contaminated with pure cultures of the respective microorganisms. After two weeks of storage at 28 ° C and 60 to 70% relative humidity, the minimum inhibitory concentration (MIC value) is determined. The MIC value indicates the lowest concentration of active ingredient at which no growth occurs due to the microbe species used.
  • the compound (1-8) to be tested for its fungicidal activity was incorporated into a polyvinyl acetate emulsion paint in various concentrations. The paint was then spread on both sides on a suitable surface. A part of the test specimens was leached with running water (24 h; 20 ° C) before the test for mold resistance.
  • test specimens prepared in this way were placed on an agar culture medium.
  • the test specimens and culture medium were contaminated with fungal spores from the paint destroyers Alternaria tenuis, Aspergillus flavus, Aspergillus ustus, Aspergillus niger, Cladosporium herbarum, Paecilomyces variotii, Penicillium citrinum, Aureobasidium puUulans and Stachybotrys atra Corda.
  • the evaluation was carried out.
  • Paint films with the compound (1-8) according to the invention have good mold resistance without washout load from 0.3% active substance content, and good effectiveness was found with washout load at 0.6% active substance content.
  • Wood test Mycelium pieces were cut out from colonies of wood-destroying Basidiomycetes and incubated on an agar culture medium at 26 ° C. The inhibition of hyphal growth on nutrient-containing nutrient media was compared with the hyphal growth on nutrient media without the addition of an active ingredient and rated as a percentage inhibition.

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

Abstract

Nouveaux dérivés d'halogénalcénylazolyle de formule (I) dans laquelle R1 désigne un alcyle éventuellement substitué, un alcényle éventuellement substitué, un cycloalkyle éventuellement substitué, un aryle éventuellement substitué ou un hétéroaryle éventuellement substitué, R2 désigne un alkyle, un halogénalkyle, un 1-hydroxyalkyle, un 2-hydroxyalkyle, un 1-hydroxyhalogénalkyle, un 1-alcényle ou un 2-alcényle, X1 désigne fluor, chlore, brome ou iode, X2 désigne fluor, chlore, brome ou iode et Y désigne l'azote ou un group CH. L'invention concerne également les sels d'addition d'acide et les complexes de sels métalliques de ces dérivés, un procédé pour la préparation des nouvelles substances, et leur utilisation comme microbicides dans la protection des plantes et des matériaux.
EP95906335A 1994-01-25 1995-01-12 Derives microbicides d'halogenalcenylazolyle Withdrawn EP0741713A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4402034A DE4402034A1 (de) 1994-01-25 1994-01-25 Halogenalkenyl-azolyl-Derivate
DE4402034 1994-01-25
PCT/EP1995/000115 WO1995019971A1 (fr) 1994-01-25 1995-01-12 Derives microbicides d'halogenalcenylazolyle

Publications (1)

Publication Number Publication Date
EP0741713A1 true EP0741713A1 (fr) 1996-11-13

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Country Status (6)

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US (1) US5760067A (fr)
EP (1) EP0741713A1 (fr)
JP (1) JPH09507671A (fr)
AU (1) AU1456595A (fr)
DE (1) DE4402034A1 (fr)
WO (1) WO1995019971A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999004634A1 (fr) * 1997-07-23 1999-02-04 Basf Aktiengesellschaft Agent de protection phytosanitaire sous forme de granule a liberation controlee du principe actif
EP1150567A4 (fr) 1999-02-08 2003-01-15 Cognis Corp Revetements pigmentes presentant un affaiblissement des couleurs reduit
WO2018081221A1 (fr) 2016-10-31 2018-05-03 Eastman Chemical Company Préparation enzymatique de propamocarb

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Publication number Priority date Publication date Assignee Title
EP0097425B1 (fr) * 1982-06-14 1987-04-08 Imperial Chemical Industries Plc Triazolyléthanols possédant une activité fongicide ou régulatrice de croissance des plantes
GB8620501D0 (en) * 1986-08-22 1986-10-01 Ici Plc Heterocyclic compounds
ES2064392T3 (es) * 1988-08-03 1995-02-01 Bayer Ag Derivados de vinilazol halogenado.
DE4003180A1 (de) * 1990-02-03 1991-08-08 Bayer Ag Halogenallyl-azolyl-derivate
DE4003181A1 (de) * 1990-02-03 1991-08-08 Bayer Ag Halogenallyl-azolyl-derivate
EP0470466A3 (en) * 1990-08-09 1992-07-29 Bayer Ag Halogenalkyl-azolyl derivatives
ES2098285T3 (es) * 1990-08-09 1997-05-01 Bayer Ag Derivados de halogenoalquil-azolilo.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9519971A1 *

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AU1456595A (en) 1995-08-08
DE4402034A1 (de) 1995-07-27
WO1995019971A1 (fr) 1995-07-27
JPH09507671A (ja) 1997-08-05
US5760067A (en) 1998-06-02

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