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EP0000017A1 - 1-(2-Phenylethyl)-triazolium salts, their preparation and their use as fungicides - Google Patents

1-(2-Phenylethyl)-triazolium salts, their preparation and their use as fungicides Download PDF

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Publication number
EP0000017A1
EP0000017A1 EP78100029A EP78100029A EP0000017A1 EP 0000017 A1 EP0000017 A1 EP 0000017A1 EP 78100029 A EP78100029 A EP 78100029A EP 78100029 A EP78100029 A EP 78100029A EP 0000017 A1 EP0000017 A1 EP 0000017A1
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EP
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Prior art keywords
optionally substituted
phenylethyl
formula
triazolium
alkyl
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Granted
Application number
EP78100029A
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German (de)
French (fr)
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EP0000017B1 (en
Inventor
Helmut Dr. Timmler
Wolfgang Dr. Krämer
Karl Heinz Prof.Dr. Büchel
Wilhelm Dr. Brandes
Paul-Ernst Dr. Frohberger
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Bayer AG
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Bayer AG
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    • 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
    • A01N43/64—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 1- (2-phenylethyl) triazolium salts, a process for their preparation and their use as fungicides.
  • the 1- (2-phenylethyl) triazolium salts according to the invention show a considerably higher fungicidal activity, in particular against rust and mildew types, than the 1- [ ⁇ -aryl- ⁇ - (R- oxy) ethyl] - imidazoles and -triazoles, for example 1- [ ⁇ -butoxy- ⁇ - (4'-chlorophenyl) ethyl 7-imidazole, which are chemically and functionally obvious substances, and as the zinc-ethylene-1,2-bis-dithiocarbamidate , which is a known substance with the same direction of action.
  • the active compounds according to the invention thus represent an enrichment of the technology.
  • the alkyl part preferably occurs at the nitrogen atom 4 of the 1,2,4-triazol-1-yl radical, as can be seen from the nuclear magnetic resonance data; depending on the reactivity of the alkyl halide and the starting product of formula II, however, alkylation on nitrogen atom 1 of the 1,2,4-triazol-1-yl radical can also be carried out. Both types of compounds and the mixtures obtained in this alkylation are claimed according to the invention.
  • Formula (II) provides a general definition of the 1-phenyl-2-triazolyl-ethyl derivatives to be used as starting materials.
  • R preferably represents halogen, in particular fluorine, chlorine and bromine; for nitro and cyano; further preferably for alkyl and alkylsulfonyl with 1 to 4 carbon atoms, for alkoxy and alkylthio with 1 to 2 carbon atoms and for haloalkyl with up to 4 and up to 5 halogen atoms, in particular with up to 2 carbon atoms and up to 3 identical or different halogen atoms, where as halogen atom preferably fluorine and chlorine come into consideration and trifluoromethyl may be mentioned as an example of haloalkyl.
  • R also preferably represents phenyl or phenoxy which may be mono- or polysubstituted in the same way or differently, the preferred substituents being: halogen, in particular fluorine, chlorine and bromine; Cyano, nitro, and haloalkyl with up to 2 carbon atoms and up to 3 identical or different halogen atoms, fluorine and chlorine preferably being considered as halogen atoms, and trifluoromethyl is particularly mentioned as an example of haloalkyl.
  • the index n preferably stands for integers from 0 to 3.
  • R 1 preferably has the meaning given in the definition of the invention.
  • R 2 preferably represents alkyl, alkenyl and alkynyl each having up to 4 carbon atoms, cycloalkyl, and preferably aryl, arylalkyl or arylalkenyl optionally substituted in the aryl part having 6 to 10 carbon atoms in the aryl part and up to 4 carbon atoms in the alkyl or alkenyl part, such as, for example, phenyl, naphthyl, benzyl, naphthylmethyl and styryl, the preferred substituents being: halogen; especially fluorine, chlorine, bromine; Cyano, nitro, amino, alkyl having 1 to 4 carbon atoms, haloalkyl having up to 2 carbon atoms and up to 3 identical or different halogen atoms, the halogen being in particular fluorine and chlorine, for example trifluoromethyl, and optionally halogen, in particular flu
  • R z preferably represents the radicals which have already been mentioned as preferred for R 2 , and also hydrogen.
  • the index n preferably has the meaning given in the definition of the invention.
  • R 4 preferably represents the radicals which are already present in R 2 are preferably mentioned, as well as for haloalkyl with 1 to 2 carbon and 1 to 5 halogen atoms, fluorine and chlorine being mentioned in particular as halogens, such as trifluoromethyl, dichloromethyl and chloromethyl, and for phenoxyalkyl with 1 or 2 carbon atoms optionally substituted in the phenyl part Alkyl part, the preferred substituents being: halogen, in particular fluorine or chlorine, amino, cyano, nitro or alkyl having 1 to 2 carbon atoms.
  • R 4 also preferably represents amino, alkylamino, dialkylamino and alkyl-alkylcarbonylamino, each having 1 to 4, in particular 1 to 2, carbon atoms in each alkyl part and also phenylamino optionally substituted by halogen, in particular fluorine or chlorine, nitro and cyano.
  • the procedure is expediently started from an 1-hydroxy-1-phenyl-2-triazolylethane derivative, the latter in a suitable inert solvent using alkali metal hydride or alkali metal amide in the alkali metal alcoholate of the formula ( IV) transferred, and the latter is reacted immediately without isolation with a halide of the formula (V), the compounds of the formula (II) being obtained in one operation with the emergence of alkali halide.
  • the preparation of the alkanolates of the formula (IV) and the reaction with the halide of the formula (V) are advantageously carried out in a two-phase system, such as, for example, aqueous sodium hydroxide solution or potassium hydroxide solution / toluene or methylene chloride, with the addition of a phase transfer Catalyst, such as ammonium or Fhosphoniumharmen performed.
  • R and n have the meaning given above and X represents halogen
  • R 3 has the meaning given above, in a known manner in the presence of an inert organic solvent, for example acetone, and in the presence of an acid binder, for example potassium carbonate, at temperatures between 60 and 100 ° C, and optionally the thioethers obtained in a manner known per se at temperatures between -30 and 80 ° C oxidized with inorganic or organic oxidizing agents, such as m-chloroperbenzoic acid or potassium permanganate.
  • inert organic solvent for example acetone
  • an acid binder for example potassium carbonate
  • the 1-halogen-1-phenyl-2-triazolyl-ethane derivatives of the formula (VI) are also known (compare DT-OS 25 47 954 [Le A 16 750]).
  • R 5 preferably represents optionally substituted straight-chain or branched alkyl having 1 to 6 carbon atoms, the preferred substituents being: alkylcarbonyl having 1 to 4 carbon atoms in the alkyl part and optionally substituted phenyl or benzoyl, where as.
  • Substituents are preferably the radicals which have already been mentioned for R in the starting materials of the formula (II).
  • X preferably represents fluorine, chlorine, bromine or iodine.
  • Z preferably represents the anion of an inorganic or organic acid.
  • halide anions fluoride, chloride, bromide and iodide; also nitrate, sulfate and phosphate anions; as well as acetate, propionate, glycolate, lactate, malonate, succinate, maleate, fumarate, tartrate, citrate, benzoate, methyl sulfonate, ethyl sulfonate, p-toluenesulfonate, benzenesulfonate or salicylate anions .
  • Polar organic solvents are preferably used as diluents for the reaction according to the invention. These preferably include nitriles, such as acetonitrile; Sulfoxides such as dimethyl sulfoxide; Formamides such as dimethylformamide; Ketones such as acetone; Ethers such as diethyl ether and tetrahydrofuran and chlorinated hydrocarbons such as methylene chloride and chloroform.
  • nitriles such as acetonitrile
  • Sulfoxides such as dimethyl sulfoxide
  • Formamides such as dimethylformamide
  • Ketones such as acetone
  • Ethers such as diethyl ether and tetrahydrofuran and chlorinated hydrocarbons such as methylene chloride and chloroform.
  • reaction temperatures can be varied within a wide range in the process according to the invention. In general, between about 0 to 120 ° C, preferably at 20 to 90 ° C, or at the boiling point of the solvent.
  • the process according to the invention is preferably carried out in molar amounts.
  • the compounds of the formula (I) are isolated in a customary manner.
  • the anion exchange which may be carried out in accordance with the method according to the invention, is carried out in a generally known manner (cf. German Offenlegungsschrift 2,504,114) by using the 1- (2-phenylethyl) triazolium halides of the formula (I) e.g. converted into the corresponding triazolium hydroxides by means of a base or an anion exchange resin and then reacted with an appropriate acid.
  • the active substances according to the invention have a strong fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents to control felts. Fungitoxic agents in crop protection are used to combat Plasmodiophoromycetes, 'Oomycetes, Chytridiomyce_es, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • the active compounds according to the invention have a broad spectrum of activity and can be used against parasitic fungi which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens. They are particularly effective against parasitic fungi on above-ground parts of plants.
  • the active compounds according to the invention can be used with particularly good success for combating Venturia species, such as against the pathogen causing apple scab (Fusicladium dendriticum), for powdery mildew fungi, for example for combating powdery mildew (Podosphaera leucotricha) and powdery mildew, and for other cereal diseases.
  • Venturia species such as against the pathogen causing apple scab (Fusicladium dendriticum)
  • powdery mildew fungi for example for combating powdery mildew (Podosphaera leucotricha) and powdery mildew, and for other cereal diseases.
  • the active compounds according to the invention can be used as crop protection agents for treating seeds or soil and for treating above-ground parts of plants.
  • the active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are manufactured in a known manner, e.g. B. 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.
  • 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.
  • organic solvents can also be used as auxiliary solvents.
  • aromatics such as xylene, toluene, benzene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B.
  • Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and pressure, e.g. B.
  • aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
  • 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, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents for improving the bed structure.
  • active compounds such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents for improving the bed structure.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, dusting, scattering, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.
  • the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 0.1 and 0.00001 percent by weight. Preferably between 0.05 and 0.0001%.
  • active compound 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
  • Active ingredients of 1 to 100 g per cbm of soil, in particular 10 to 200 g, are required for soil treatment.
  • Podosphaera test (apple) / protective The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.
  • the spray liquid is used to spray young apple seedlings that are in the 4- to 6-leaf stage until they drip wet.
  • the plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. They are then inoculated by dusting with conidia of the powdery mildew pathogen (Podosphaera leucotricha) and placed in a greenhouse at a temperature of 21 to 23 ° C and a relative humidity of approx. 70%.
  • the infestation of the seedlings is determined 10 days after the inoculation.
  • the rating values obtained are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.
  • the amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.
  • the spray liquid is used to spray young apple seedlings that are in the 4- to 6-leaf stage until they drip wet.
  • the plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. They are then inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum) and incubated for 18 hours in a humid chamber at 18 to 20 ° C and 100% relative humidity.
  • the infestation of the seedlings is determined 15 days after the inoculation.
  • the rating values received are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.
  • active compound 0.25 part by weight of active compound is taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether, and 975 parts by weight of water are added.
  • the concentrate is diluted with water to the desired final concentration of the spray mixture.
  • the single-leafed barley young plants of the Amsel variety are sprayed with the preparation of active compound as dewy. After drying, the barley plants are dusted with spores from Erysiphe graminis var.hordei.
  • the stocking of the plants with mildew pustules is evaluated.
  • the degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infection and 100% the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.
  • Active substances Active substances, active substance concentrations in the spray mixture and degrees of infestation are shown in the table below.
  • the active ingredients are used as powdered seed treatment agents. They are produced by stripping the respective active ingredient with a mixture of the same. Parts by weight of talc and diatomaceous earth to a fine powdery mixture with the desired concentration of active ingredient.
  • the degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infection and 100% the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.
  • Active substances, active substance concentrations in the seed treatment agent as well as its application rate and the percentage of mildew infestation are shown in the table below.
  • the amount of active ingredient required for the desired active ingredient concentration in the nutrient medium is mixed with the stated amount of the solvent mixture.
  • the concentrate is thoroughly mixed with the liquid nutrient medium cooled to 42 ° C in the stated ratio and poured into Petri dishes with a diameter of 9 cm. Control plates are also set up without admixture.
  • the plates are inoculated with the fungus species listed in the table and incubated at about 21 ° C.

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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)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

1. 1-(2-Phenylethyl)-triazolium salts of the general formula see diagramm : EP0000017,P19,F1 in which R represents halogen, alkyl with 1 to 4 carbon atoms and phenyl or phenoxy optionally substituted by halogen, n represents integers from 0 to 3, R**1 represents the group -O-R**2 , alkylmercapto or alkylcarbonyloxy with in each case 1 to 4 carbon atoms in the alkyl part, R**2 represents alkenyl with 2 to 4 carbon atoms and benzyl optionally substituted by halogen, R**3 represents alkyl with 1 to 6 carbon atoms, pinacolyl and benzyl or benzoylmethyl optionally substituted by halogen and Z represents halogen.

Description

Die vorliegende Erfindung betrifft neue 1-(2-Phenyläthyl)-triazolium-Salze,ein Verfahren zu ihrer Herstellung sowie ihre Verwendung als Fungizide.The present invention relates to new 1- (2-phenylethyl) triazolium salts, a process for their preparation and their use as fungicides.

Es ist bereits bekannt geworden, daß 1-[ß-Aryl-ß-(R-oxy)-äthyl]-imidazole, wie z.B. 1-[ß-Butoxy-ß-(4'-chlorphenyl)-äthyl]-imidazol und 1-[ß-Aryl-ß-(R-oxy)-äthyl]-triazole, wie z.B. l-[ß-Allyloxy-ß-(4'-chlorphenyl)-äthyl]-1,2,4-triazol, eine gute fungizide Wirksamkeit aufweisen (vgl. Deutsche Offenlegungsschriften 2 063 857 und 2 640 823). Deren Wirkung ist jedoch in bestimmten Indikationsbereichen, insbesondere bei niedrigen Aufwandmengen und -konzentrationen, nicht immer voll befriedigend. Weiterhin ist allgemein seit längerer Zeit bekannt, daß Zink-äthylen-1,2-bisdithiocarbamidat ein gutes Mittel zur Bekämpfung von pilzlichen Pflanzenkrankheiten ist (vgl. Phytopathology 33, 1113 (1963)). Jedoch ist dessen Einsatz als Saatgutbeizmittel nur beschränkt möglich, da es bei niedrigen Aufwandmengen und -konzentrationen wenig wirksam ist.It has already been known that 1- [ß-aryl-ß- (R-oxy) ethyl] imidazoles, such as e.g. 1- [ß-butoxy-ß- (4'-chlorophenyl) ethyl] imidazole and 1- [ß-aryl-ß- (R-oxy) ethyl] triazoles, e.g. l- [ß-allyloxy-ß- (4'-chlorophenyl) ethyl] -1,2,4-triazole, have a good fungicidal activity (cf. German Offenlegungsschriften 2,063,857 and 2,640,823). However, their effect is not always completely satisfactory in certain indication areas, particularly when low amounts and concentrations are applied. Furthermore, it has generally been known for a long time that zinc ethylene 1,2-bisdithiocarbamidate is a good means of combating fungal plant diseases (cf. Phytopathology 33, 1113 (1963)). However, its use as a seed dressing is only possible to a limited extent, since it is not very effective at low application rates and concentrations.

Es wurden nun als neue Verbindungen die 1-(2-Phenyläthyl)-triazolium-Salze der Formel

Figure imgb0001
in welcher

  • R für Halogen, Alkyl, Alkoxy, Alkylthio, Alkylsulfonyl, Halogenalkyl, Nitro, Cyano, gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes Phenoxy steht,
  • R1 für die Gruppierungen -0-R2, -S(O)m-R3 oder -O-CO-R4 steht,
  • R2 für Alkyl, Alkenyl., Alkinyl, Cycloalkyl, gegebenenfalls substituiertes Aryl, gegebenenfalls substituiertes Arylalkyl oder gegebenenfalls substituiertes Arylalkenyl steht,
  • R3 für Wasserstoff oder R2 steht,
  • R4 Für R2 und Halogenalkyl, gegebenenfalls substituiertes Phenoxyalkyl, Amino, Alkylamino, Di- . alkylamino, Alkyl-alkylcarbonylamino oder gegebenenfalls substituiertes Phenylamino steht,
  • R 5 für gegebenenfalls substituiertes Alkyl steht,
  • n für ganze Zahlen von 0 bis 5 steht,
  • m für ganze Zahlen von 0 bis 2 steht und
  • Z für das Anion einer anorganischen oder organischen Säure sowie deren Hydrate steht, gefunden. Sie weisen starke fungizide Eigenschaften auf.
There were now as new compounds the 1- (2-phenylethyl) triazolium salts of the formula
Figure imgb0001
 in which
  • R represents halogen, alkyl, alkoxy, alkylthio, alkylsulfonyl, haloalkyl, nitro, cyano, optionally substituted phenyl or optionally substituted phenoxy,
  • R 1 represents the groupings -0-R 2 , -S (O) m -R 3 or -O-CO-R 4 ,
  • R 2 represents alkyl, alkenyl, alkynyl, cycloalkyl, optionally substituted aryl, optionally substituted arylalkyl or optionally substituted arylalkenyl,
  • R 3 represents hydrogen or R 2 ,
  • R 4 For R 2 and haloalkyl, optionally substituted phenoxyalkyl, amino, alkylamino, di-. alkylamino, alkyl-alkylcarbonylamino or optionally substituted phenylamino,
  • R 5 represents optionally substituted alkyl,
  • n stands for integers from 0 to 5,
  • m stands for integers from 0 to 2 and
  • Z stands for the anion of an inorganic or organic acid and its hydrates. They have strong fungicidal properties.

Weiterhin wurde gefunden, daß man die 1-(2-Phenyläthyl)-triazolium-Salze der Formel (I) erhält, wenn man 1-Phenyl-2-triazolyl-äthyl-Derivate der Formel

Figure imgb0002
in welcher

  • R, R1 und n die oben angegebene Bedeutung haben, mit Halogeniden der Formel
    Figure imgb0003
  • in welcher
  • R die oben angegebene Bedeutung hat und
  • X für Halogen steht,
  • in Gegenwart eines Verdünnungsmittels umsetzt und gegebenenfalls das Halogenid in den erhaltenen Triazolium-Halogeniden in an sich bekannter Weise gegen ein anderes Anion austauscht.
It has also been found that the 1- (2-phenylethyl) triazolium salts of the formula (I) are obtained if 1-phenyl-2-triazole y l-ethyl derivatives of the formula
Figure imgb0002
 in which
  • R, R 1 and n have the meaning given above, with halides of the formula
    Figure imgb0003
  • in which
  • R has the meaning given above and
  • X represents halogen,
  • in the presence of a diluent and, if appropriate, the halide in the triazolium halides obtained is exchanged for another anion in a manner known per se.

In manchen Fällen erweist es sich als vorteilhaft, anstelle der Halogenide der Formel (III) entsprechende reaktive Ester einzusetzen, die durch Umsetzung der entsprechenden Alkohole mit den entsprechenden Säuren erhalten werden.In some cases it proves advantageous to use appropriate reactive esters instead of the halides of the formula (III), which are obtained by reacting the corresponding alcohols with the corresponding acids.

Ueberraschenderweise zeigen die erfindungsgemäßen 1-(2-Phenyl- äthyl)-triazolium-Salze eine erheblich höhere fungizide Wirksamkeit, insbesondere gegen Rost- und Mehltauarten, als die aus dem Stand der Technik bekannten 1-[β-Aryl-β-(R-oxy)-äthyl]-imidazole und -triazole, beispielsweise 1-[β-Butoxy-β-(4'-chlor-phenyl)-äthyl7-imidazol, welche chemisch und wirkungsmäßig naheliegende Stoffe darstellen, und als das Zink-äthylen-1,2-bis-dithiocarbamidat, welches ein bekannter Stoff gleicher Wirkungsrichtung ist. Die erfindungsgemäßen Wirkstoffe stellen somit eine Bereicherung der Technik dar.Surprisingly, the 1- (2-phenylethyl) triazolium salts according to the invention show a considerably higher fungicidal activity, in particular against rust and mildew types, than the 1- [β-aryl-β- (R- oxy) ethyl] - imidazoles and -triazoles, for example 1- [β-butoxy-β- (4'-chlorophenyl) ethyl 7-imidazole, which are chemically and functionally obvious substances, and as the zinc-ethylene-1,2-bis-dithiocarbamidate , which is a known substance with the same direction of action. The active compounds according to the invention thus represent an enrichment of the technology.

Verwendet man [1-(2,4-Dichlorphenyl)-2-(1,2,4-triazol-1-yl)-äthyl]-(2,4-dichlorbenzyl)-äther und Monochlorpinakolin als Ausgangsstoffe, so kann der Reaktionsablauf durch das folgende Formelschema wiedergegeben werden:

Figure imgb0004
If [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] - (2,4-dichlorobenzyl) ether and monochloropinacoline are used as starting materials, the reaction can proceed can be represented by the following formula:
Figure imgb0004

Dabei tritt der Alkylteil bevorzugt an das Stickstoffatom 4 des 1,2,4-Triazol-1-yl-Restes, wie aus den Kernresonanzdaten hervorgeht; in Abhängigkeit von der Reaktivität des Alkylhalogenids und des Ausgangsprodukts der Formel II kann jedoch auch eine Alkylierung am Stickstoffatom 1 des 1,2,4-Triazol-1-yl-Restes erfolgen. Beide Verbindungstypen, sowie die bei dieser Alkylierung erhaltenen Gemische werden erfindungsgemäß beansprucht.The alkyl part preferably occurs at the nitrogen atom 4 of the 1,2,4-triazol-1-yl radical, as can be seen from the nuclear magnetic resonance data; depending on the reactivity of the alkyl halide and the starting product of formula II, however, alkylation on nitrogen atom 1 of the 1,2,4-triazol-1-yl radical can also be carried out. Both types of compounds and the mixtures obtained in this alkylation are claimed according to the invention.

Die als Ausgangsstoffe zu verwendenden 1-Phenyl-2-triazolyl- äthyl-Derivate sind durch die Formel (II) allgemein definiert. In dieser Forrel steht R vorzugsweise für Halogen, insbesondere Fluor, Chlor und Brom; für Nitro und Cyano; ferner vorzugsweise für Alkyl und Alkylsulfonyl mit 1 bis 4 Kohlenstoffatomen, für Alkoxy und Alkylthio mit 1 bis 2 Kohlenstoffatomen sowie für Halogenalkyl mit bis zu 4 und bis zu 5 Halogenatomen, insbesondere mit bis zu 2 Kohlenstoffatomen und bis zu 3 gleichen oder verschiedenen Halogenatomen, wobei als Halogenatomo vorzugsweise Fluor und Chlor in Betracht kommen und als Beispiel für Halogenalkyl speziell Trifluormethyl genannt sei. R steht außerdem vorzugsweise für gegebenenfalls ein- oder mehrfach, gleichartig oder verschieden substituiertes Phenyl oder Phenoxy, wobei als Substituenten vorzugsweise infrage kommen: Halogen, insbesondere Fluor, Chlor und Brom; Cyano, Nitro, sowie Halogenalkyl mit bis zu 2 Kohlenstoffatomen und bis zu 3 gleichen oder verschiedenen Halogenatomen, wobei als Halogenatome vorzugsweise Fluor und Chlor in Betracht kommen und als Beispiel für Halogenalkyl speziell Trifluormethyl genannt sei. Der Index n steht vorzugsweise für ganze Zahlen von 0 bis 3.Formula (II) provides a general definition of the 1-phenyl-2-triazolyl-ethyl derivatives to be used as starting materials. In this Forrel, R preferably represents halogen, in particular fluorine, chlorine and bromine; for nitro and cyano; further preferably for alkyl and alkylsulfonyl with 1 to 4 carbon atoms, for alkoxy and alkylthio with 1 to 2 carbon atoms and for haloalkyl with up to 4 and up to 5 halogen atoms, in particular with up to 2 carbon atoms and up to 3 identical or different halogen atoms, where as halogen atom preferably fluorine and chlorine come into consideration and trifluoromethyl may be mentioned as an example of haloalkyl. R also preferably represents phenyl or phenoxy which may be mono- or polysubstituted in the same way or differently, the preferred substituents being: halogen, in particular fluorine, chlorine and bromine; Cyano, nitro, and haloalkyl with up to 2 carbon atoms and up to 3 identical or different halogen atoms, fluorine and chlorine preferably being considered as halogen atoms, and trifluoromethyl is particularly mentioned as an example of haloalkyl. The index n preferably stands for integers from 0 to 3.

R1 hat vorzugsweise die in der Erfindungsdefinition angegebene Bedeutung. R2 steht vorzugsweise für Alkyl, Alkenyl und Alkinyl mit jeweils bis zu 4 Kohlenstoffatomen, Cycloalkyl, sowie vorzugsweise für gegebenenfalls im Arylteil substituiertes Aryl, Arylalkyl oder Arylalkenyl mit 6 bis 10 Kohlenstoffatomen im Arylteil und bis zu 4 Kohlenstoffatomen im Alkyl- bzw. Alkenylteil, wie beispielsweise Phenyl, Naphthyl, Benzyl, Naphthylmethyl und Styryl, wobei als Substituenten vorzugsweise infrage kommen: Halogen; insbesondere Fluor, Chlor, Brom; Cyano, Nitro, Amino, Alkyl mit 1 bis 4 Kohlenstoffatomen, Halogenalkyl mit bis zu 2 Kohlenstoff- und bis zu 3 gleichen oder verschiedenen Halogenatomen, wobei als Halogene insbesondere Fluor und Chlor stehen, wie beispielsweise Trifluormethyl, sowie gegebenenfalls durch Halogen, insbesondere Fluor oder Chlor, substituiertes Phenoxy. Rz steht vorzugsweise für die Reste, die bei R2 bereits vorzugsweise genannt wurden, sowie für Wasserstoff. Der Index n hat vorzugsweise die in der Erfindungsdefinition angegebene Bedeutung. R4 steht vorzugsweise für die Reste, die bei R2 bereits vorzugsweise genannt werden, sowie für Halogenalkyl mit 1 bis 2 Kohlenstoff- und 1 bis 5 Halogenatomen, wobei als Halogene insbesondere Fluor und Chlor genannt sind, wie beispielsweise Trifluormethyl, Dichlormethyl und Chlormethyl, sowie für gegebenenfalls im Phenylteil substituiertes Phenoxyalkyl mit 1 oder 2 Kohlenstoffatomen im Alkylteil, wobei als Substituenten vorzugsweise infrage kommen: Halogen, insbesondere Fluor oder Chlor, Amino, Cyano, Nitro oder Alkyl mit 1 bis 2 Kohlenstoffatomen.R 1 preferably has the meaning given in the definition of the invention. R 2 preferably represents alkyl, alkenyl and alkynyl each having up to 4 carbon atoms, cycloalkyl, and preferably aryl, arylalkyl or arylalkenyl optionally substituted in the aryl part having 6 to 10 carbon atoms in the aryl part and up to 4 carbon atoms in the alkyl or alkenyl part, such as, for example, phenyl, naphthyl, benzyl, naphthylmethyl and styryl, the preferred substituents being: halogen; especially fluorine, chlorine, bromine; Cyano, nitro, amino, alkyl having 1 to 4 carbon atoms, haloalkyl having up to 2 carbon atoms and up to 3 identical or different halogen atoms, the halogen being in particular fluorine and chlorine, for example trifluoromethyl, and optionally halogen, in particular fluorine or Chlorine, substituted phenoxy. R z preferably represents the radicals which have already been mentioned as preferred for R 2 , and also hydrogen. The index n preferably has the meaning given in the definition of the invention. R 4 preferably represents the radicals which are already present in R 2 are preferably mentioned, as well as for haloalkyl with 1 to 2 carbon and 1 to 5 halogen atoms, fluorine and chlorine being mentioned in particular as halogens, such as trifluoromethyl, dichloromethyl and chloromethyl, and for phenoxyalkyl with 1 or 2 carbon atoms optionally substituted in the phenyl part Alkyl part, the preferred substituents being: halogen, in particular fluorine or chlorine, amino, cyano, nitro or alkyl having 1 to 2 carbon atoms.

R4 steht außerdem vorzugsweise für Amino, Alkylamino, Dialkylamino und Alkyl-alkylcarbonyl-amino mit jeweils 1 bis 4, insbesondere 1 bis 2 Kohlenstoffatomen in jedem Alkylteil sowie für gegebenenfalls durch Halogen, insbesondere Fluor oder Chlor, Nitro und Cyano substituiertes Phenylamino.R 4 also preferably represents amino, alkylamino, dialkylamino and alkyl-alkylcarbonylamino, each having 1 to 4, in particular 1 to 2, carbon atoms in each alkyl part and also phenylamino optionally substituted by halogen, in particular fluorine or chlorine, nitro and cyano.

Die Ausgangsstoffe der Formel (II) sind teilweise bekannt (vergleiche DT-OS 25 47 953 und DT-OS 26 40 823), teilweise sind sie Gegenstand eigener, älterer Anmeldungen, die noch nicht zum Stand der Technik gehören (vergleiche die Deutschen Patentanmeldungen P 26 28 419.5 [Le A 17 198] vom 24.6.1976 und P 26 45 496.6[Le A 17 456J vom 8.10.1976). Noch nicht bekannte Ausgangsstoffe der Formel (II) können nach den dort beschriebenen Verfahren erhalten werden, indem man z.B.Some of the starting materials of the formula (II) are known (compare DT-OS 25 47 953 and DT-OS 26 40 823), and in some cases they are the subject of our own, earlier applications which do not yet belong to the prior art (compare the German patent applications P 26 28 419.5 [Le A 17 198] from June 24, 1976 and P 26 45 496.6 [Le A 17 456J from October 8, 1976). Starting substances of formula (II) which are not yet known can be obtained by the processes described therein, for example by

a) Alkanolate von 1-Hydroxy-1-phenyl-2-triazolyl-äthan-Derivaten der Formela) Alkanolates of 1-hydroxy-1-phenyl-2-triazolyl-ethane derivatives of the formula

Figure imgb0005

  • in welcher
  • R und n die oben angegebene Bedeutung haben . und
  • M für ein Alkalimetall, vorzugsweise Lithium, Natrium und Kalium, eine quarternäre Ammonium- oder Phosphoniumgruppe steht,
  • mit einem Halogenid der Formel
    Figure imgb0006
    in welcher
  • R' die oben angegebene Bedeutung hat und
  • Hal für Chlor oder Brom steht,

in Gegenwart eines organischen Lösungsmittels, wie beispielsweise Dioxan oder Chloroform, bei Temperaturen zwischen 20 und 120°C umsetzt. Zur Isolierung der Endprodukte wird das Reaktionsgemisch vom Lösungsmittel befreit und der Rückstand mit Wasser und einem organischen Lösungsmittel versetzt. Die organische Phase wird abgetrennt, in üblicher Weise aufgearbeitet und gereinigt.
Figure imgb0005
  • in which
  • R and n have the meaning given above. and
  • M represents an alkali metal, preferably lithium, sodium and potassium, a quaternary ammonium or phosphonium group,
  • with a halide of the formula
    Figure imgb0006
     in which
  • R 'has the meaning given above and
  • Hal represents chlorine or bromine,

in the presence of an organic solvent, such as dioxane or chloroform, at temperatures between 20 and 120 ° C. To isolate the end products, the reaction mixture is freed from the solvent and the residue is mixed with water and an organic solvent. The organic phase is separated off, worked up and purified in a conventional manner.

In einer bevorzugten Ausführungsform wird zweckmäßigerweise so verfahren, daß man von einem l-Hydroxy-l-phenyl-2-triazolyl- äthan-Derivat ausgeht, letzteres in einem geeigneten inerten Lösungsmittel mittels Alkalimetall-hydrid oder Alkalimetallamid in das Alkalimetall-alkoholat der Formel (IV) überführt, und letzteres ohne Isolierung sofort mit einem Halogenid der Formel (V) umsetzt, wobei unter Austritt von Alkalihalogenid die Verbindungen der Formel (II) in einem Arbeitsgang erhalten werden.In a preferred embodiment, the procedure is expediently started from an 1-hydroxy-1-phenyl-2-triazolylethane derivative, the latter in a suitable inert solvent using alkali metal hydride or alkali metal amide in the alkali metal alcoholate of the formula ( IV) transferred, and the latter is reacted immediately without isolation with a halide of the formula (V), the compounds of the formula (II) being obtained in one operation with the emergence of alkali halide.

Nach einer weiteren bevorzugten Ausführungsform werden zweckmäßigerweise die Herstellung der Alkanolate der Formel (IV) sowie die Umsetzung mit dem Halogenid der Formel (V) in einem Zweiphasensystem, wie beispielsweise wässrige Natron- oder Kalilauge/Toluol oder Methylenchlorid, unter Zusatz eines Phasen-Transfer-Katalysators, wie beispielsweise Ammonium- oder Fhosphoniumverbindungen, durchgeführt.According to a further preferred embodiment, the preparation of the alkanolates of the formula (IV) and the reaction with the halide of the formula (V) are advantageously carried out in a two-phase system, such as, for example, aqueous sodium hydroxide solution or potassium hydroxide solution / toluene or methylene chloride, with the addition of a phase transfer Catalyst, such as ammonium or Fhosphoniumverbindungen performed.

Die Ausgangsstoffe der Formel (II) können auch erhalten werden, wenn manThe starting materials of formula (II) can also be obtained if one

b) die den Alkanolaten der Formel (IV) zugrunde liegenden 1-Hydroxy-1-phenyl-2-triazolyl-äthaneb) the 1-hydroxy-1-phenyl-2-triazolylethane on which the alkanolates of the formula (IV) are based

  • -mit entsprechenden Säureanhydriden nach bekannten Methoden, z.B. in molaren Mengen in Gegenwart eines inerten organischen Lösungsmittels, beispielsweise Aceton, oder mit einem Ueberschuß an Säureanhydrid und in Gegenwart eines sauren oder basischen Katalysators, beispielsweise Natriumacetat, bei Temperaturen zwischen 0 und 150°C umsetzt und die Verbindungen der Formel (II) in üblicher Weise isoliert, oderwith appropriate acid anhydrides by known methods, e.g. in molar amounts in the presence of an inert organic solvent, for example acetone, or with an excess of acid anhydride and in the presence of an acidic or basic catalyst, for example sodium acetate, at temperatures between 0 and 150 ° C and the compounds of formula (II) in the usual way Way isolated, or
  • -mit entsprechenden Isocyanaten nach bekannten Methoden, z.B. in molaren Mengen in Gegenwart eines inerten organischen Lösungsmittels, beispielsweise Benzol, und in Gegenwart eines Katalysators, beispielsweise Dibutylzinndilaurat, bei Temperaturen zwischen 0 und 100°C umsetzt und die Verbindungen der Formel (II) .in üblicher Weise isoliert, oderwith corresponding isocyanates by known methods, e.g. in molar amounts in the presence of an inert organic solvent, for example benzene, and in the presence of a catalyst, for example dibutyltin dilaurate, at temperatures between 0 and 100 ° C. and the compounds of the formula (II) are isolated in a conventional manner, or
c) 1-Halogen-1-phenyl-2-triazolyl-äthane der Formelc) 1-Halogen-1-phenyl-2-triazolyl-ethane of the formula

Figure imgb0007
Figure imgb0007

in welcherin which

R und n die oben angegebene Bedeutung haben und X für Halogen steht,R and n have the meaning given above and X represents halogen,

mit Mercaptanan der Formel

Figure imgb0008
in welcherwith mercaptanane of the formula
Figure imgb0008
 in which

R3 die oben angegebene Bedeutung hat, in bekannter Weise in Gegenwart eines inerten organischen Lösungsmittels, beispielswiese Aceton, und in Gegenwart eines Säurebindeaittels, beispielsweise Kaliumcarbonat, bei Temperaturen zwischen 60 und 100°C umsetzt, und gegebenenfalls die dabei erhaltenen Thioäther in an sich bekannter Weise bei Temperaturen zwischen -30 und 80°C mit anorganischen oder organischen Oxidationsmitteln, wie beispielsweise m-Chlorperbenzoesäure oder Kaliumpermanganat, oxidiert. Die Isolierung der Verbindungen der Formel (II) erfolgt in üblicher Weise.R 3 has the meaning given above, in a known manner in the presence of an inert organic solvent, for example acetone, and in the presence of an acid binder, for example potassium carbonate, at temperatures between 60 and 100 ° C, and optionally the thioethers obtained in a manner known per se at temperatures between -30 and 80 ° C oxidized with inorganic or organic oxidizing agents, such as m-chloroperbenzoic acid or potassium permanganate. The compounds of the formula (II) are isolated in a customary manner.

Die den Alkanolaten der Formel (IV) zugrunde liegenden 1-Hydroxy-1-phenyl-2-triazolyl-äthan-Derivate sind bekannt (vergleiche DT-OS 24 31 407 [Le A 15 735] und DT-OS 25 47 953 [Le A 16 749]).The 1-hydroxy-1-phenyl-2-triazolyl-ethane derivatives on which the alkanolates of the formula (IV) are based are known (compare DT-OS 24 31 407 [Le A 15 735] and DT-OS 25 47 953 [Le A 16 749]).

Die 1-Halogen-1-phenyl-2-triazolyl-äthan-Derivate der Formel (VI) sind ebenfalls bekannt (vergleiche DT-OS 25 47 954 [Le A 16 750]).The 1-halogen-1-phenyl-2-triazolyl-ethane derivatives of the formula (VI) are also known (compare DT-OS 25 47 954 [Le A 16 750]).

Als Beispiele für die erfindungsgemäß als Ausgangsstoffe zu verwendenden l-Phenyl-2-triazolyl-äthyl-Derivate der Formel (II) seien im einzelnen folgende Verbindungen der Tabellen 1, 2 und 3 genannt:The following compounds of Tables 1, 2 and 3 may be mentioned individually as examples of the l-phenyl-2-triazolyl-ethyl derivatives of the formula (II) to be used according to the invention:

Figure imgb0009
Figure imgb0009
Figure imgb0010
Figure imgb0010
Figure imgb0011
Figure imgb0011
Figure imgb0012
Figure imgb0012
Figure imgb0013
Figure imgb0013
Figure imgb0014
Figure imgb0014
Figure imgb0015
Figure imgb0015

Die außerdem als Ausgangsstoffe zu verwendenden Halogenide sind durch die Formel (III) allgemein definiert. In dieser Formel steht R5 vorzugsweise für gegebenenfalls substituiertes geradkettiges oder verzweigtes Alkyl mit 1 bis 6 Kohlenstoffatomen, wobei als Substituenten vorzugsweise infrage kommen: Alkylcarbonyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil sowie gegebenenfalls substituiertes Phenyl oder Benzoyl, wobei als. Substituenten vorzugsweise die Reste infrage kommen, die für R bei den Ausgangsstoffen der Formel (II) bereits vorzugsweise genannt wurden. X steht vorzugsweise für Fluor, Chlor, Brom oder Jod.The halides also to be used as starting materials are generally defined by the formula (III). In this formula, R 5 preferably represents optionally substituted straight-chain or branched alkyl having 1 to 6 carbon atoms, the preferred substituents being: alkylcarbonyl having 1 to 4 carbon atoms in the alkyl part and optionally substituted phenyl or benzoyl, where as. Substituents are preferably the radicals which have already been mentioned for R in the starting materials of the formula (II). X preferably represents fluorine, chlorine, bromine or iodine.

Die Ausgangsstoffe der Formel (III) sind allgemein bekannte Verbindungen der organischen Chemie, bzw. können sie auf allgemein bekannte und übliche Weise erhalten werden. Als Beispiele seien genannt:

  • Methylfluorid, Methylchlorid, Methylbromid, Methyljodid, Aethylbromid, Aethyljodid, Chloraceton, Bromaceton, Fluoraceton, Aethyl-chlormethyl-keton, Fluorpinakolin, Chlorpinakolin, Brompinakolin, Benzylchlorid, a-(4-Biphenylyl)-benzylchlorid, w-Bromacetophenon, ω-Chlor-acetophenon, ω-Chlor-(4-chloraceto= phenon), ω-Brom-(4-chloracetophenon), ω-Chlor-(2,4-dichlor- acetophenon), ω-Brom-(2,4-dichloracetophenon), 4-Chlorbenzylmethylbromid, 2,4-Dichlorbenzylchlorid, 2-(4-Chlorphenylcarbonyl)-äthylchlorid, 2-(4-Chlorphenylcarbonyl)-äthylbromid.
The starting materials of the formula (III) are generally known compounds of organic chemistry, or they can be obtained in a generally known and customary manner. Examples include:
  • Methyl fluoride, methyl chloride, methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, chloroacetone, bromoacetone, fluorine acetone, ethyl-chloromethyl ketone, Fluorpinakolin, C h lorpinakolin, Brompinakolin, benzyl, a- (4-biphenylyl) benzyl chloride, w-bromoacetophenone, ω- Chloroacetophenone, ω-chloro (4-chloroaceto = phenone), ω-bromo (4-chloroacetophenone), ω-chloro (2,4-dichloroacetophenone), ω-bromo (2,4-dichloroacetophenone) ), 4-chlorobenzylmethyl bromide, 2,4-dichlorobenzyl chloride, 2- (4-chlorophenylcarbonyl) ethyl chloride, 2- (4-chlorophenylcarbonyl) ethyl bromide.

In der Formel (I) steht Z vorzugsweise für das Anion einer anorganischen oder organischen Säure. Dazu gehören vorzugsweise die Halogenid-Anionen Fluorid, Chlorid, Bromid und Jodid; ferner Nitrat-, Sulfat- und Phosphat-Anionen; sowie Acetat-, Propionat-, Glykolat-, Lactat-, Malonat-, Succinat-, Maleat-, Fumarat-, Tartrat-, Citrat-, Benzoat, Methylsulfonat-, Aethylsulfonat-, p-Toluolsulfonat-, Benzolsulfonat- oder Salicylat-Anionen.In formula (I), Z preferably represents the anion of an inorganic or organic acid. These preferably include the halide anions fluoride, chloride, bromide and iodide; also nitrate, sulfate and phosphate anions; as well as acetate, propionate, glycolate, lactate, malonate, succinate, maleate, fumarate, tartrate, citrate, benzoate, methyl sulfonate, ethyl sulfonate, p-toluenesulfonate, benzenesulfonate or salicylate anions .

Für die erfindungsgemäße Umsetzung kommen als Verdünnungsmittel vorzugsweise polare organische Lösungsmittel infrage. Hierzu gehören vorzugsweise Nitrile, wie Acetonitril; Sulfoxide, wie Dimethylsulfoxid; Formamide, wie Dimethylformamid; Ketone, wie Aceton; Aether, wie Diäthyläther und Tetrahydrofuran sowie Chlorkohlenwasserstoffe, wie Methylenchlorid und Chloroform.Polar organic solvents are preferably used as diluents for the reaction according to the invention. These preferably include nitriles, such as acetonitrile; Sulfoxides such as dimethyl sulfoxide; Formamides such as dimethylformamide; Ketones such as acetone; Ethers such as diethyl ether and tetrahydrofuran and chlorinated hydrocarbons such as methylene chloride and chloroform.

Die Reaktionstemperaturen können beim erfindungsgemäßen Verfahren in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man zwischen etwa 0 bis 120°C, vorzugsweise bei 20 bis 90°C, bzw. bei der Siedetemperatur des jeweiligen Lösungsmittels.The reaction temperatures can be varied within a wide range in the process according to the invention. In general, between about 0 to 120 ° C, preferably at 20 to 90 ° C, or at the boiling point of the solvent.

Bei der Durchführung des erfindungsgemäßen Verfahrens arbeitet man vorzugsweise in molaren Mengen, Die Isolierung der Verbindungen der Formel (I) erfolgt in üblicher Weise.The process according to the invention is preferably carried out in molar amounts. The compounds of the formula (I) are isolated in a customary manner.

Der, entsprechend dem erfindungagemäßen Verfahren, gegebenanfalls durchzuführende Anionenaustausch erfolgt in allgemein bekannter Weise (vgl.Deutsche Offenlegungsschrift 2 504 114), indem man die 1-(2-Phenyläthyl)-triazolium-halogenide der Formel (I) z.B. mittels einer Base oder einem Anionenaustauschharz in die entsprechenden Triazoliumhydroxide überführt und diese anschließend mit einer entsprechenden Säure umsetzt.The anion exchange, which may be carried out in accordance with the method according to the invention, is carried out in a generally known manner (cf. German Offenlegungsschrift 2,504,114) by using the 1- (2-phenylethyl) triazolium halides of the formula (I) e.g. converted into the corresponding triazolium hydroxides by means of a base or an anion exchange resin and then reacted with an appropriate acid.

Die erfindungsgemäßen Wirkstoffe weisen eine starke fungitoxische Wirkung auf. Sie schädigen Kulturpflanzen in den zur Bekämpfung von Pilzen notwendigen Konzentrationen nicht. Aus diesen Gründen sind sie für den Gebrauch als Pflanzenschutzmittel zur Bekämpfung von Filzen geeignet. Fungitoxische Mittel im Pflanzenschutz werden eingesetzt zur Bekämpfung von Plasmodiophoromycetes,' Oomycetes, Chytridiomyce_es, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.The active substances according to the invention have a strong fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents to control felts. Fungitoxic agents in crop protection are used to combat Plasmodiophoromycetes, 'Oomycetes, Chytridiomyce_es, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Die erfindungsgemäßen Wirkstoffe haben ein breites Wirkungsspektrum und können angewandt werden gegen parasitäre Pilze, die oberirdische Pflanzenteile befallen oder die Pflanzen vom Boden her angreifen, sowie gegen samenübertragbare Krankheitserreger. Eine besonders gute Wirksamkeit entfalten sie gegen parasitäre Pilze auf oberirdischen Pflanzenteilen.The active compounds according to the invention have a broad spectrum of activity and can be used against parasitic fungi which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens. They are particularly effective against parasitic fungi on above-ground parts of plants.

Als Pflanzenschutzmittel können die erfindungsgemäßen Wirkstoffe mit besonders gutem Erfolg zur Bekämpfung von Venturia-Arten, wie gegen den Erreger des Apfelschorfs (Fusicladium dendriticum), von echten Mehltaupilzen, beispielsweise zur Bekämpfung von Apfelmehltau (Podosphaera leucotricha) und Getreidemehltau sowie gegen andere Getreidekrankheiten verwendet werden.As crop protection agents, the active compounds according to the invention can be used with particularly good success for combating Venturia species, such as against the pathogen causing apple scab (Fusicladium dendriticum), for powdery mildew fungi, for example for combating powdery mildew (Podosphaera leucotricha) and powdery mildew, and for other cereal diseases.

Besonders hervorzuheben ist die teilweise systemische Wirkung der Stoffe. So gelingt es, Pflanzen gegen Pilzbefall zu schützen, wenn man den Wirkstoff über den Boden und die Wurzel den oberirdischen Teilen der Pflanze zuführt.Of particular note is the partially systemic effect of the substances. This is how plants can be protected against fungal attack if the active ingredient is supplied to the aerial parts of the plant via the soil and the roots.

Als Pflanzenschutzmittel können die erfindungsgemäßen Wirkstoffe zur Saatgut- oder Bodenbehandlung und zur Behandlung oberirdischer Pflanzenteile benutzt werden.The active compounds according to the invention can be used as crop protection agents for treating seeds or soil and for treating above-ground parts of plants.

Die erfindungspemäßen Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate. Diese werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z. B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, Benzol oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z. B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z. B. Aerosol-Treibgase, wie Dichlordifluormethan oder Trichlorfluormethan; als feste Trägerstoffe: natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als Emulgiermittel; nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fettsäure-Ester,Polyoxy- äthylen-Fettalkohol-Äther, z.B. Alkylaryl-polyglycol-Äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z. B. Lignin, Sulfitablaugen und Methylcellulose.The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are manufactured in a known manner, e.g. B. 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. In the case of the use of water as an extender, e.g. B. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and pressure, e.g. B. aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. B. lignin, sulfite and methyl cellulose.

Die erfindungsgemäßen Wirkstoffe können in den Formulierungen in Mischung mit anderen bekannten Wirkstoffen vorliegen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Herbiziden, Schutzstoffen gegen Vogelfraß, Wuchsstoffen, Pflanzennährstoffen und Bedenstrukturverbesserungsmitteln.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, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents for improving the bed structure.

Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder der daraus durch weiteres Verdünnen bereiteten Anwendungsformen, wie gebrauchsfertigen Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Spritzen, Sprühen, Stäuben, Streuen, Trockenbeizen, Feuchtbeizen, Naßbeizen, Schlämmbeizen oder Inkrustieren.The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, dusting, scattering, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.

Bei der Verwendung als Blattfungizide können die Wirkstoffkonzentrationen in den Anwendungsformen in einem größeren Bereich variiert werden. Sie liegen im allgemeinen zwischen 0,1 und 0,00001 Gewichtsprozent. Vorzugsweise zwischen 0,05 und 0,0001 %.When used as leaf fungicides, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 0.1 and 0.00001 percent by weight. Preferably between 0.05 and 0.0001%.

Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 50 g je Kilogramm Saatgut, vorzugsweise 0,01 bis 10 g benötigt.In the case of seed treatment, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

Zur Bodenbehandlung sind Wirkstoffmengen von 1 bis 100 g je cbm Boden, wie insbesondere 10 bis 200 g, erforderlich.Active ingredients of 1 to 100 g per cbm of soil, in particular 10 to 200 g, are required for soil treatment.

Die vielseitigen Verwendungsmöglichkeiten gehen aus den nachfolgenden Beispielen hervor.The versatile examples are shown in the following examples.

Beispiel AExample A

Podosphaera-Test (Apfel) / Protektiv

Figure imgb0016
Man vermischt die für die gewünschte Wirkstoffkonzentration in der Spritzflüssigkeit nötige Wirkstoffmenge mit der angegebenen Menge des Lösungsmittels und verdünnt das Konzentrat mit der angegebenen Menge Wasser, welches die genannten Zusätze enthält.Podosphaera test (apple) / protective
Figure imgb0016
 The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

Mit der Spritzflüssigkeit bespritzt man junge Apfelsämlinge, die sich im 4- bis 6-Blattstadium befinden, bis zur Tropfnässe. Die Pflanzen verbleiben 24 Stunden bei 20°C und einer relativen Luftfeuchtigkeit von 70 % im Gewächshaus. Anschließend werden sie durch Bestäuben mit Konidien des Apfelmehltauerregers (Podosphaera leucotricha) inokuliert und in ein Gewächshaus mit einer Temperatur von 21 bis 23 °C und einer relativen Luftfeuchtigkeit von ca. 70 % gebracht.The spray liquid is used to spray young apple seedlings that are in the 4- to 6-leaf stage until they drip wet. The plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. They are then inoculated by dusting with conidia of the powdery mildew pathogen (Podosphaera leucotricha) and placed in a greenhouse at a temperature of 21 to 23 ° C and a relative humidity of approx. 70%.

10 Tage nach der Inokulation wird der Befall der Sämlinge bestimmt. Die erhaltenen Boniturwerte werden in Prozent Befall umgerechnst. 0 % bedeutet keinen Befall, 100 % bedeutet, daß die Pflanzen vollständig befallen sind.The infestation of the seedlings is determined 10 days after the inoculation. The rating values obtained are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.

Wirkstoffe, Wirkstoffkonzentrationen und Ergebnisse gehen aus der nachfolgenden Tabelle hervor:

Figure imgb0017
Figure imgb0018
 Active substances, active substance concentrations and results are shown in the table below:
Figure imgb0017
Figure imgb0018

Beispiel BExample B

Fusicladium-Test (Apfel) / Protektiv

Figure imgb0019
Fusicladium test (apple) / protective
Figure imgb0019

Man vermischt die für die gewünschte Wirkstoffkonzentration in der Spritzflüssigkeit nötigen Wirkstoffmenge mit der angegebenen Menge des Lösungsmittels und verdünnt das Konzentrat mit der angegebenen Menge Wasser, welches die genannten Zusätze enthält.The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

Mit der Spritzflüssigkeit bespritzt man junge Apfelsämlinge, die sich im 4- bis 6-Blattstadium befinden, bis zur Tropfnässe. Die Pflanzen verbleiben 24 Stunden bei 20 °C und einer relativen Luftfeuchtigkeit von 70 % im Gewächshaus. Anschließend werden sie mit einer wässrigen Konidiensuspension des Apfelschorferregers (Fusicladium dendriticum) inokuliert und 18 Stunden lang in einer Feuchtkammer bei 18 bis 20 °C und 100 % relativer Luftfeuchtigkeit inkubiert.The spray liquid is used to spray young apple seedlings that are in the 4- to 6-leaf stage until they drip wet. The plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. They are then inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum) and incubated for 18 hours in a humid chamber at 18 to 20 ° C and 100% relative humidity.

Die Pflanzen kommen dann erneut für 14 Tage ins Gewächshaus.The plants then come back into the greenhouse for 14 days.

15 Tage nach der Inokulation wird der Befall der Sämlinge bestimmt. Die erhaltenen Boniturwerte werden in Prozent Befall umgerechnet. 0 % bedeutet keinen Befall, 100% bedeutet, daß die Pflanzen vollständig befallen sind.The infestation of the seedlings is determined 15 days after the inoculation. The rating values received are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.

Wirkstoffe, Wirkstoffkonzentrationen und Ergebnisse gehen aus der nachfolgenden Tabelle hervor:

Figure imgb0020
Active substances, active substance concentrations and results are shown in the table below:
Figure imgb0020

Beispiel 3Example 3 Sproßbehardlungs-Test / Getreidemehltau / protektivShoot maintenance test / powdery mildew / protective (blattzerstörende Mykose)(leaf-destroying mycosis)

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung nimmt man 0,25 Gewichtsteile Wirkstoff in 25 Gewichtsteilen Dimethylformamid und 0,06 Gewichtsteilen Alkylaryl-polyglykol- äther auf und gibt 975 Gewichtsteile Wasser hinzu. Das Konzentrat verdünnt man mit Wasser auf die gewünschte Endkonzentration der Spritzbrühe.To prepare a suitable preparation of active compound, 0.25 part by weight of active compound is taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether, and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray mixture.

Zur Prüfung auf protektive Wirksamkeit besprüht man die einblättrigen Gerstenjungpflanzen der Sorte Amsel mit der Wirkstoffzubereitung taufeucht. Nach Antrocknen bestäubt man die Gerstenpflanzen mit Sporen von Erysiphe graminis var.hordei.To test for protective activity, the single-leafed barley young plants of the Amsel variety are sprayed with the preparation of active compound as dewy. After drying, the barley plants are dusted with spores from Erysiphe graminis var.hordei.

Nach 6 Tagen Verweilzeit der Pflanzen bei einer Temperatur von 21 bis 22°C und einer Luftfeuchtigkeit von 80 bis 90 % wertet man den Besatz der Pflanzen mit Mehltaupusteln aus. Der Befallsgrad wird in Prozenten des Befalls der unbehandelten Kontrollpflanzen ausgedrückt. Dabei bedeutet 0 % keinen Befall und 100 % den gleichen Befallsgrad wie bei der unbehandelten Kontrolle. Der Wirkstoff ist umso wirksamer, je geringer der Mehltaubefall ist.After 6 days of dwell time of the plants at a temperature of 21 to 22 ° C and a humidity of 80 to 90%, the stocking of the plants with mildew pustules is evaluated. The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infection and 100% the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.

Wirkstoffe, Wirkstoffkonzentrationen in der Spritzbrühe und Befallsgrade gehen aus der nachfolgenden Tabelle hervor.

Figure imgb0021
Figure imgb0022
 Active substances, active substance concentrations in the spray mixture and degrees of infestation are shown in the table below.
Figure imgb0021
Figure imgb0022

Beispiel DExample D

Gerstenmehltau-Test (Erysiphe graminis var. hordei) / systemischBarley powdery mildew test (Erysiphe graminis var. Hordei) / systemic

(pilzliche Getreidesproßkrankheit)(fungal cereal sprout disease)

Die Anwendung der Wirkstoffe erfolgt als pulverförmige Saatgutbehandlungsmittel. Sie werden hergestellt durch Abstrecken des jeweiligen Wirkstoffes mit einem Gemisch aus gleichen. Gewichtsteilen Talkum und Kieselgur zu einer feinpulverigen Mischung mit der gewünschten Wirkstoffkonzentration.The active ingredients are used as powdered seed treatment agents. They are produced by stripping the respective active ingredient with a mixture of the same. Parts by weight of talc and diatomaceous earth to a fine powdery mixture with the desired concentration of active ingredient.

Zur Saatgutbehandlung schüttelt man Gerstensaatgut mit dem abgestreckten Wirkstoff in einer verschlossenen Glasflasche. Das Saatgut sät man mit 3x12 Korn in Blumentöpfe 2 cm tief in ein Gemisch aus einem Volumteil Fruhstorfer Einheitserde und einem Volumteil Quarzsand ein. Die Keimung und der Auflauf erfolgen unter günstigen Bedingungen im Gewächshaus.For seed treatment, shake barley seed with the stripped active ingredient in a sealed glass bottle. The seeds are sown with 3x12 seeds in flower pots 2 cm deep in a mixture of a volume of Fruhstorfer uniform earth and a volume of quartz sand. Germination and casserole take place under favorable conditions in the greenhouse.

7 Tage nach der Aussaat, wenn die Gerstenpflanzen ihr erstes .Blatt entfaltet haben, werden sie mit frischen Sporen von Erysiphe graminis var. hordei bestäubt und bei 21 bis 22°C und 80 bis 90 % rel. Luftfeuchte und 16-stündiger Belichtung weiter kultiviert. Innerhalb von 6 Tagen bilden sich an den Blättern die typischen Mehltaupusteln aus.7 days after sowing, when the barley plants have unfolded their first leaf, they are dusted with fresh spores of Erysiphe graminis var. Hordei and at 21 to 22 ° C and 80 to 90% rel. Humidity and 16-hour exposure further cultivated. The typical mildew pustules form on the leaves within 6 days.

Der Befallsgrad wird in Prozenten des Befalls der unbehandelten Kontrollpflanzen ausgedrückt. So bedeutet 0 % keinen Befall und 100 % den gleichen Befallsgrad wie bei der unbehandelten Kontrolle. Der Wirkstoff ist um so wirksamer je geringer der Mehltaubefall ist.The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infection and 100% the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.

Wirkstoffe, Wirkstoffkonzentrationen im Saatgutbehandlungsmittel sowie dessen Aufwandmenge und der prozentuale Mehltaubefall gehen hervor aus der nachfolgenden Tabelle.

Figure imgb0023
Active substances, active substance concentrations in the seed treatment agent as well as its application rate and the percentage of mildew infestation are shown in the table below.
Figure imgb0023

Beispiel EExample E Myzelwachstums-TestMycelium growth test

Verwendeter Nährboden:

Figure imgb0024
Culture medium used:
Figure imgb0024

Verhältnis von Lösungsmittelgemisch zum Nährboden:

Figure imgb0025
Ratio of solvent mixture to culture medium:
Figure imgb0025

Man vermischt die für die gewünschte Wirkstoffkonzentration im Nährboden nötige Wirkstoffmenge mit der angegebenen Menge des Lösungsmittelgemisches. Das Konzentrat wird im genannten Mengenverhältnis mit dem flüssigen, auf 42°C abgekühlten Nährboden gründlich vermischt und in Petrischalen mit einem Durchmesser von 9 cm gegossen. Ferner werden Kontrollplatten ohne Präparatbeimischung aufgestellt.The amount of active ingredient required for the desired active ingredient concentration in the nutrient medium is mixed with the stated amount of the solvent mixture. The concentrate is thoroughly mixed with the liquid nutrient medium cooled to 42 ° C in the stated ratio and poured into Petri dishes with a diameter of 9 cm. Control plates are also set up without admixture.

Ist der Nährboden erkaltet und fest, werden die Platten mit den in der Tabelle angegebenen Pilzarten beimpft und bei etwa 21°C inkubiert.When the culture medium has cooled down and is solid, the plates are inoculated with the fungus species listed in the table and incubated at about 21 ° C.

Die Auswertung erfolgt je nach der Wachstumsgeschwindigkeit der Pilze nach 4 - 10 Tagen. Bei der Auswertung wird das radiale Myzelwachstum auf den behandelten Nährböden mit dem Wachstum auf dem Kontrollnährboden verglichen. Die Bonitierung des Pilzwachstums geschieht mit folgenden Kennzahlen:

  • 1 kein Pilzwachstum
  • bis 3 sehr starke Hemmung des Wachstums
  • bis 5 mittelstarke Hemmung des Wachstums
  • bis 7 schwäche Hemmung des Wachstums
  • 9 Wachstum gleich der unbehandelten Kontrolle
The evaluation takes place after 4 - 10 days depending on the growth rate of the mushrooms. In the evaluation, the radial mycelial growth on the treated culture media is compared with the growth on the control culture media. Mushroom growth is rated using the following indicators:
  • 1 no fungal growth
  • up to 3 very strong inhibition of growth
  • up to 5 moderate growth inhibition
  • to 7 weak inhibition of growth
  • 9 Growth equal to the untreated control

Wirkstoffe, Wirkstoffkonzentrationen und Resultate gehen aus der nachfolgenden Tabelle hervor:

Figure imgb0026
HerstellungsbeispieleActive substances, active substance concentrations and results are shown in the table below:
Figure imgb0026
 Manufacturing examples

Beispiel 1example 1

Figure imgb0027
Figure imgb0027

20,7 g (0,05 Mol) [1-(2,4-Dichlorphenyl)-2-(1,2,4-triazol-1-yl)-äthyl]-(2,4-dichlorbenzyl)-äther und 6,7 g (0,05 Mol) Monochlor- pinakolin werden in 50 ml Acetonitril 12 Stunden unter Rückfluß erhitzt. Danach läßt man abkühlen, saugt den ausgefallenen Feststoff ab, wäscht mit Aceton nach und trocknet. Man erhält 10,9 g (40 % der Theorie) 1-[2-(2,4-Dichlorbenzyloxy)-2-(2,4-dichlorphenyl)-äthyl]-tert.-butylcarbonylmethyl-1,2,4-triazolium-chlorid vom Schmelzpunkt 216-218°C.20.7 g (0.05 mol) of [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] - (2,4-dichlorobenzyl) ether and 6.7 g (0.05 mol) of monochloro p inakolin are heated for 12 hours under reflux in 50 ml of acetonitrile. Then allowed to cool, the precipitated solid is filtered off, washed with acetone and dried. 10.9 g (40% of theory) of 1- [2- (2,4-dichlorobenzyloxy) -2- (2,4-dichlorophenyl) ethyl] tert-butylcarbonylmethyl-1,2,4-triazolium are obtained -chloride with a melting point of 216-218 ° C.

Herstellung der VorprodukteManufacture of intermediate products

Figure imgb0028
Figure imgb0028

25,8 g (0,1 Mol) 1-Hydroxy-1-(2,4-dichlorphenyl)-2-(1,2,4-triazol-1-yl)-äthan werden in 125 ml Dioxan gelöst und unter Rühren zu einem Gemisch aus 4 g 80%igem Natriumhydrid und 100 ml Dioxan getropft. Danach wird eine Stunde unter Rückfluß erhitzt. Nach dem-Abkühlen werden bei Raumtemperatur zu dem so erhaltenen Natriumsalz 20 g (0,1 Mol) 2,4-Dichlorbenzylchlorid zugetropft. Anschließend erhitzt man mehrere Stunden unter Rückfluß, läßt abkühlen und engt durch Abdestillieren des Lösungsmittels ein. Der Rückstand wird mit Wasser und Methylenchlorid versetzt, die organische Phase abgetrennt, über Natriumsulfat getrocknet und eingeengt. Der feste Rückstand wird aus Ligroin umkristallisiert. Man erhält 29 g (70 % der Theorie) [1-(2,4-Dichlorphenyl)-2-(1,2,4-triazol-1-yl)-äthyl]-(2,4-dichlorbenzyl)-äther vom Schmelzpunkt 84°C.

Figure imgb0029
25,6 g (0,1 Mol) w-(1,2,4-Triazol-1-yl)-2,4-dichloracetophenon werden in 300 ml Methanol gelöst und bei 5 bis 10°C unter Rühren potionsweise mit 4 g (0,1 Mol) Natriumborhydrid versetzt. Anschließend wird eine Stunde bei Raumtemperatur nachgerührt und eine Stunde zum Sieden erhitzt. Nach Abdestillieren des Lösungsmittels wird der Rückstand mit 200 ml Wasser und 40 ml konzentrierter Salzsäure kurzzeitig erhitzt. Nachdem das Reaktionsgemisch mit Natronlauge alkalisch gemacht wurde, kann das feste Reaktionsprodukt abfiltriert werden. Nach dem Umkristallisieren aus Ligroin/ Isopropanol erhält man 21,3 g (82 % der Theorie) l-Hydroxy-l-(2,4-dichlorphenyl)-2-(1,2,4-triazol-1-yl)-äthan vom Schmelzpunkt 90°C.
Figure imgb0030
269 g (1 Mol) ω-Brom-2,4-dichloracetophenon werden in 250 ml Acetonitril gelöst. Lösung tropft man zu einer unter Rückfluß siedenden Suspension von 69 g (1 Mol) 1,2,4-Triazol und 150 g Kaliumcarbonat in 2 1 Acetonitil. Nach 20-stündigem Erhitzen unter Rückfluß wird die erkaltete Suspension filtriert, das Filtrat vom Lösungsmittel befreit und der Rückstand mit Essigester aufgenommen, mit Wasser gewaschen, über Natriumsulfat getrocknet und vom Lösungsmittel befreit. Der Essigester-Rückstand kristallisiert beim Versetzen mit Isopropanol aus. Nach dem Umkristallisieren aus Ligroin/Isopropanol erhält man 154 g (60 % der Theorie) w-(1,2,4-Triazol-1-yl)-2,4-dichloracetophenon vom Schmelzpunkt 117°C.25.8 g (0.1 mol) of 1-hydroxy-1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -ethane are dissolved in 125 ml of dioxane and with stirring added dropwise to a mixture of 4 g of 80% sodium hydride and 100 ml of dioxane. The mixture is then heated under reflux for one hour. After cooling, become at room temperature 20 g (0.1 mol) of 2,4-dichlorobenzyl chloride were added dropwise to the sodium salt thus obtained. The mixture is then heated under reflux for several hours, allowed to cool and concentrated by distilling off the solvent. The residue is mixed with water and methylene chloride, the organic phase is separated off, dried over sodium sulfate and concentrated. The solid residue is recrystallized from ligroin. 29 g (70% of theory) of [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] - (2,4-dichlorobenzyl) ether of Melting point 84 ° C.
Figure imgb0029
 25.6 g (0.1 mol) of w- (1,2,4-triazol-1-yl) -2,4-dichloroacetophenone are dissolved in 300 ml of methanol and at 5 to 10 ° C. with stirring in a pot with 4 g (0.1 mol) sodium borohydride added. The mixture is then stirred for an hour at room temperature and heated to boiling for one hour. After the solvent has been distilled off, the residue is briefly heated with 200 ml of water and 40 ml of concentrated hydrochloric acid. After the reaction mixture has been made alkaline with sodium hydroxide solution, the solid reaction product can be filtered off. After recrystallization from ligroin / isopropanol, 21.3 g (82% of theory) of l-hydroxy-l- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -ethane are obtained from the melting point 90 ° C.
Figure imgb0030
 269 g (1 mol) of ω-bromo-2,4-dichloroacetophenone are dissolved in 250 ml of acetonitrile. Solution is dropped into a bottom river boiling suspension of 69 g (1 mol) of 1,2,4-triazole and 150 g of potassium carbonate in 2 1 of acetonitrile. After refluxing for 20 hours, the cooled suspension is filtered, the filtrate is freed from the solvent and the residue is taken up in ethyl acetate, washed with water, dried over sodium sulfate and freed from the solvent. The ethyl acetate residue crystallized out when added with isopropanol. After recrystallization from ligroin / isopropanol, 154 g (60% of theory) of w- (1,2,4-triazol-1-yl) -2,4-dichloroacetophenone with a melting point of 117 ° C. are obtained.

Beispiel 2Example 2

Figure imgb0031
Figure imgb0031

20,7 g (0,05 Mol) [1-(2,4-Dichlorphenyl)-2-(1,2,4-triazol-1-yl)-äthyl]-(2,6-dichlorbenzyl)-äther und 13,4 g (0,05 Mol) 2,4-Dichlorbenzoylmethylbromid werden in 250 ml Chloroform 15 Stunden unter Rückfluß erhitzt. Man läßt abkühlen und engt durch Abdestillieren des Lösungsmittels im Vakuum ein. Der Rückstand wird mit Aceton kurz aufgekocht. Nach dem Abkühlen wird der kristalline Rückstand abgesaugt, mit Aceton gewaschen und getrocknet. Man erhält 5,6 g (16,5 % der Theorie) 1-[2-(2,6-Di- chlorbenzyloxy)-2-(2,4-dichlorphenyl)-äthyl]-2,4-dichlorbenzoyl- methyl-1,2,4-triazolium-bromid vom Schmelzpunkt 202°C.20.7 g (0.05 mol) of [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] - (2,6-dichlorobenzyl) ether and 13.4 g (0.05 mol) of 2,4-dichlorobenzoylmethyl bromide are refluxed in 250 ml of chloroform for 15 hours. The mixture is allowed to cool and concentrated by distilling off the solvent in vacuo. The residue is briefly boiled with acetone. After cooling, the crystalline residue is filtered off, washed with acetone and dried. 5.6 g (16.5% of theory) of 1- [2- (2,6-dichlorobenzyloxy) -2- (2,4-dichlorophenyl) ethyl] -2,4-dichlorobenzoyl-methyl are obtained. 1,2,4-triazolium bromide with a melting point of 202 ° C.

Beispiel 3Example 3

Figure imgb0032
Figure imgb0032

20,7 g (0,05 Mol) [1-(2,4-Dichlorphenyl)-2-(1,2,4-triazol-1-yl)-äthyl]-(2,6-dichlorbenzyl)-äther und 7,1 g (0,05 Mol) Methyljodid werden in 100 ml Acetonitril 12 Stunden unter Rückfluß er- hitzt. Danach läßt man abkühlen, saugt den ausgefallenen Feststoff ab, wäscht mit Aceton nach und trocknet. Man erhält 26,7 g (96,7 % der Theorie) 1-[2-(2,6-Dichlorbenzyloxy)-2-(2,4-dichlorphenyl)-ächyl]-methyl-1,2,4-triazolium-jodid vom Schmelzpunkt 228 - 230°C (Zers.).20.7 g (0.05 mol) of [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] - (2,6-dichlorobenzyl) ether and 7.1 g (0.05 mol) of methyl iodide in 100 ml of acetonitrile are heated under reflux for 12 hours . Then allowed to cool, the precipitated solid is filtered off, washed with acetone and dried. 26.7 g (96.7% of theory) of 1- [2- (2,6-dichlorobenzyloxy) -2- (2,4-dichlorophenyl) achyl] methyl-1,2,4-triazolium are obtained. iodide with melting point 228 - 230 ° C (dec.).

In analoger Weise werden die folgenden Beispiele der Tabelle 4 erhalten.

Figure imgb0033
Figure imgb0034
In entsprechender Weise können die folgenden Verbindungen der allgemeinen Formel (I) hergestellt werden:
Figure imgb0035
 The following examples in Table 4 are obtained in an analogous manner.
Figure imgb0033
Figure imgb0034
 The following compounds of the general formula (I) can be prepared in a corresponding manner:
Figure imgb0035

Claims (6)

1. 1-(2-Phenyläthyl)-triazolium-Salze der Formel
Figure imgb0036
in welcher R für Halogen, Alkyl, Alkoxy, Alkylthio, Alkylsulfonyl, Halogenalkyl, Nitro, Cyano, gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes Phenoxy steht, R für die Gruppierungen -O-R2, -S(O)m-R3 oder -O-CO-R4 steht, R2 für Alkyl, Alkenyl, Alkinyl, Cycloalkyl, gegebenenfalls substituiertes Aryl, gegebenenfalls substituiertes Arylalkyl oder gegebenenfalls substituiertes Arylalkenyl steht, R 3 für Wasserstoff oder R2 steht, R4 für R 2 und Halogenalkyl, gegebenenfalls substituiertes Phenoxyalkyl, Amino, Alkylamino, Dialkylamino, Alkyl-alkylcarbonylamino oder gegebenenfalls substituiertes Phenylamino steht, R5 für gegebenfalls Alkyl steht, n für ganze Zahlen von 0 bis 5 steht, m für ganze Zahlen von 0 bis 2 steht und Z für das Anion einer anorganischen oder organischen Säure sowie deren Hydrate steht. 1. 1- (2-phenylethyl) triazolium salts of the formula
Figure imgb0036
 in which R represents halogen, alkyl, alkoxy, alkylthio, alkylsulfonyl, haloalkyl, nitro, cyano, optionally substituted phenyl or optionally substituted phenoxy, R represents the groupings -OR 2 , -S (O) m -R 3 or -O-CO-R 4 , R 2 represents alkyl, alkenyl, alkynyl, cycloalkyl, optionally substituted aryl, optionally substituted arylalkyl or optionally substituted arylalkenyl, R 3 represents hydrogen or R 2 , R 4 represents R 2 and haloalkyl, optionally substituted phenoxyalkyl, amino, alkylamino, dialkylamino, alkylalkylcarbonylamino or optionally substituted phenylamino, R 5 represents alkyl, if appropriate, n stands for integers from 0 to 5, m stands for integers from 0 to 2 and Z stands for the anion of an inorganic or organic acid and its hydrates. 2. Verfahren zur Herstellung von 1-(2-Phenyläthyl)-triazolium-Salzen, dadurch gekennzeichnet, daß man 1-Phenyl-2-trizolyl- äthyl-Derivate der Formel
Figure imgb0037
in welcher R, R und n die in Anspruch 1 angegebene Bedeutung haben, mit Halogeniden der Formel
Figure imgb0038
in welcher R 5 die oben angegebene Bedeutung hat und X für Halogen steht, in Gegenwart eines Verdünnungsmittels umsetzt und gegebenenfalls das Halogenid in den erhaltenen Triazolium-Halogeniden in an sich bekannter Weise gegen ein anderes Anion austauscht. 2. Process for the preparation of 1- (2-phenylethyl) triazolium salts, characterized in that 1-phenyl-2-trizolyl Ethyl derivatives of the formula
Figure imgb0037
 in which R, R and n have the meaning given in claim 1, with halides of the formula
Figure imgb0038
 in which R 5 has the meaning given above and X represents halogen, in the presence of a diluent and, if appropriate, the halide in the triazolium halides obtained is exchanged for another anion in a manner known per se. 3. Fungizide Mittel, gekennzeichnet durch einen Gehalt an mindestens einem 1-(2-Phenyläthyl)-triazolium-Salz gemäß Anspruch 13. Fungicidal compositions, characterized by a content of at least one 1- (2-phenylethyl) triazolium salt according to claim 1 4. Verfahren zur Bekämpfung von Pilzen, dadurch gekennzeichnet, daß man 1-(2-Phenyläthyl)-trizolium-Salze gemäß Anspruch 1 auf Pilze oder ihren Lebensraum einwirken läßt.4. A method of combating fungi, characterized in that 1- (2-phenylethyl) trizolium salts according to claim 1 are allowed to act on fungi or their habitat. 5. Verwendung von 1-(2-Phenyläthyl)-triazolium-Salzen gemäß Anspruch 1 zur Bekämpfung von Pilzen.5. Use of 1- (2-phenylethyl) triazolium salts according to claim 1 for combating fungi. 6. Verfahren zur Herstellung von fungiziden Mitteln, dadurch gekennzeichnet, daß man 1-(2-Phenyläthyl)-triazolium-Salze gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt.6. A process for the preparation of fungicidal agents, characterized in that 1- (2-phenylethyl) triazolium salts according to claim 1 are mixed with extenders and / or surface-active agents.
EP78100029A 1977-06-04 1978-06-01 1-(2-phenylethyl)-triazolium salts, their preparation and their use as fungicides Expired EP0000017B1 (en)

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EP0025581B1 (en) * 1979-09-17 1984-02-15 Olympus Optical Co., Ltd. Light source device
EP0027177B1 (en) * 1979-09-18 1984-05-02 Bayer Ag 1-azolyl-1-halogen-alkan-2-ones and process for the preparation of 1-azolyl-1-phenoxy-alkan-2-ones
EP0061789B1 (en) * 1981-03-27 1985-10-23 Janssen Pharmaceutica N.V. Novel antimicrobial triazole derivatives
EP0130366A3 (en) * 1983-06-01 1986-11-26 Basf Aktiengesellschaft Arylalkylimidazolium and triazolium salts, process for their preparation and their use as microbicides
EP0195116A3 (en) * 1985-03-19 1987-06-03 Ripari Gero Ist Farm Biolog Compound having antibacterial and antimycotic activities, preparation thereof and pharmaceutical compositions containing it
EP0275955A1 (en) * 1987-01-21 1988-07-27 Ciba-Geigy Ag Microbicidal composition
WO1994008978A1 (en) * 1992-10-09 1994-04-28 Uniroyal Chemical Company, Inc. Fungicidal substituted azole derivatives
WO2013024076A1 (en) 2011-08-15 2013-02-21 Basf Se Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-ethoxy-ethyl}-1h- [1,2,4]triazole compounds
US9137996B2 (en) 2011-07-15 2015-09-22 Basf Se Fungicidal alkyl- and aryl-substituted 2[-2-chloro-4-(dihalo-phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
US9173402B2 (en) 2011-07-15 2015-11-03 Basf Se Fungicidal alkyl-substituted 2[2-chloro-4-(4-chioro-phenoxy)-phenyl]-1[1,2,4]triazol-1-yl-ethanol compounds
US9247746B2 (en) 2011-08-15 2016-02-02 Basf Se Fungicidal substituted 1-{2-cyclyloxy-2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-ethyl}-1H-[1,2,4]triazole compounds
US9247747B2 (en) 2011-08-15 2016-02-02 Basf Se Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-2-alkynyl/alkenyl-ethyl}-1H-[1,2,4]triazole compounds
US9295259B2 (en) 2011-08-15 2016-03-29 Basf Se Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-3-methyl-butyl}-1H [1,2,4]triazole compounds
US10212934B2 (en) 2014-06-25 2019-02-26 BASF Agro B.V. Pesticidal compositions
US10358426B2 (en) 2011-07-13 2019-07-23 BASF Agro B.V. Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
US10512267B2 (en) 2013-07-08 2019-12-24 BASF Agro, B.V. Compositions comprising a triazole compound and a biopesticide
US10759767B2 (en) 2012-12-20 2020-09-01 BASF Agro B.V. Compositions comprising a triazole compound
US10918107B2 (en) 2015-05-20 2021-02-16 Conopco, Inc. Encapsulated lactams

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GB2143815B (en) * 1983-05-19 1988-01-20 Ciba Geigy Ag Process for the preparation of micro biocidal 1-triazolylethyl ether derivatives
BR122019013926B1 (en) 2013-01-09 2019-10-29 Basf Agro Bv process for preparing a triazole compound of formula i
AU2015342067B2 (en) 2014-11-07 2019-10-31 Basf Se Pesticidal mixtures
JP6903074B2 (en) 2016-03-16 2021-07-14 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ Use of tetrazolinone to control resistant phytopathogens on grains
WO2017157916A1 (en) 2016-03-16 2017-09-21 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on soybean
US11425909B2 (en) 2016-03-16 2022-08-30 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on fruits

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FR2323689A1 (en) * 1975-09-10 1977-04-08 Ici Ltd NEW 1,2,4-TRIAZOLIC FUNGICIDES AND THEIR APPLICATIONS

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0025581B1 (en) * 1979-09-17 1984-02-15 Olympus Optical Co., Ltd. Light source device
EP0027177B1 (en) * 1979-09-18 1984-05-02 Bayer Ag 1-azolyl-1-halogen-alkan-2-ones and process for the preparation of 1-azolyl-1-phenoxy-alkan-2-ones
EP0061789B1 (en) * 1981-03-27 1985-10-23 Janssen Pharmaceutica N.V. Novel antimicrobial triazole derivatives
EP0130366A3 (en) * 1983-06-01 1986-11-26 Basf Aktiengesellschaft Arylalkylimidazolium and triazolium salts, process for their preparation and their use as microbicides
EP0195116A3 (en) * 1985-03-19 1987-06-03 Ripari Gero Ist Farm Biolog Compound having antibacterial and antimycotic activities, preparation thereof and pharmaceutical compositions containing it
EP0275955A1 (en) * 1987-01-21 1988-07-27 Ciba-Geigy Ag Microbicidal composition
US4992458A (en) * 1987-01-21 1991-02-12 Ciba-Geigy Corporation 1-phenoxyphenyl-1-triazolylmethyl-carbinol compound as microbicides
WO1994008978A1 (en) * 1992-10-09 1994-04-28 Uniroyal Chemical Company, Inc. Fungicidal substituted azole derivatives
AU672059B2 (en) * 1992-10-09 1996-09-19 Uniroyal Chemical Co./Uniroyal Chemical Cie Fungicidal substituted azole derivatives
US10358426B2 (en) 2011-07-13 2019-07-23 BASF Agro B.V. Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
US9137996B2 (en) 2011-07-15 2015-09-22 Basf Se Fungicidal alkyl- and aryl-substituted 2[-2-chloro-4-(dihalo-phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
US9173402B2 (en) 2011-07-15 2015-11-03 Basf Se Fungicidal alkyl-substituted 2[2-chloro-4-(4-chioro-phenoxy)-phenyl]-1[1,2,4]triazol-1-yl-ethanol compounds
US9247746B2 (en) 2011-08-15 2016-02-02 Basf Se Fungicidal substituted 1-{2-cyclyloxy-2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-ethyl}-1H-[1,2,4]triazole compounds
US9247747B2 (en) 2011-08-15 2016-02-02 Basf Se Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-2-alkynyl/alkenyl-ethyl}-1H-[1,2,4]triazole compounds
US9295259B2 (en) 2011-08-15 2016-03-29 Basf Se Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-3-methyl-butyl}-1H [1,2,4]triazole compounds
WO2013024076A1 (en) 2011-08-15 2013-02-21 Basf Se Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-ethoxy-ethyl}-1h- [1,2,4]triazole compounds
US10759767B2 (en) 2012-12-20 2020-09-01 BASF Agro B.V. Compositions comprising a triazole compound
US10512267B2 (en) 2013-07-08 2019-12-24 BASF Agro, B.V. Compositions comprising a triazole compound and a biopesticide
US10212934B2 (en) 2014-06-25 2019-02-26 BASF Agro B.V. Pesticidal compositions
US10918107B2 (en) 2015-05-20 2021-02-16 Conopco, Inc. Encapsulated lactams

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ES470458A1 (en) 1979-01-01

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