EP0000112B1 - Triazol-substituted sulphur derivatives, their preparation and their utilisation as fungicides - Google Patents

Triazol-substituted sulphur derivatives, their preparation and their utilisation as fungicides Download PDF

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Publication number
EP0000112B1
EP0000112B1 EP78100044A EP78100044A EP0000112B1 EP 0000112 B1 EP0000112 B1 EP 0000112B1 EP 78100044 A EP78100044 A EP 78100044A EP 78100044 A EP78100044 A EP 78100044A EP 0000112 B1 EP0000112 B1 EP 0000112B1
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Prior art keywords
triazole
ethyl
parts
dichlorophenyl
carbon atoms
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French (fr)
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EP0000112A1 (en
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Ernst-Heinrich Dr. Pommer
Friedrich Dr. Linhart
Ernst Dr. Buschmann
Bernd Dr. Zeeh
York Dr. Hartleben
Klaus Dr. Gutsche
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BASF SE
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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 invention relates to valuable triazole-substituted sulfur compounds, their salts and metal complex salts with good fungicidal activity, to processes for their preparation and to fungicides which contain these compounds as active compounds.
  • imidazole-substituted sulfur compounds as fungicides for controlling phytopathogenic fungi (DE-OS 25 41 833).
  • they often only act against a specific fungus or against a specific class of fungus, or cause damage to the crop plants or, when used as a mordant, cause germination delays and damage caused by emergence, so that their general and broad application are subject to strict limits.
  • the salts have the general formula II in which R ', R 2 , n and k have the meanings given above and HS denotes any organic or inorganic acid which, however, must not be phytotoxic at the application rates used and must be able to react with the compounds of the general formula 1 To form salts.
  • Particularly suitable acids are sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, trichloroacetic acid, dichloropropionic acid, oxalic acid, toluenesulfonic acid and dodecylbenzenesulfonic acid.
  • the compounds of the general formula II can be prepared by simply adding the acids HS to the compounds of the general formula I, if appropriate in a solvent.
  • the metal complex salts have the general formula Ila in which R 1 , R 2 , n and k have the meanings given above, p and q are the numbers 1 to 4, Y ⁇ is an equivalent of an anion of an inorganic or organic acid and Me is a metal from the 1st, 11th and IV. To VIII. Subgroup and from de II. And IV. Main group of the periodic system.
  • Such metals are: copper, iron, zinc and tin.
  • the metal complex salts can be prepared by reacting a metal salt with a compound of the general formula I in a solvent.
  • the compounds of the general formula can be reacted with 2-haloethyl-1,2,4-triazoles of the general formula III in which R 1 and n have the meaning given above and X is chlorine, bromine or iodine, with a mercaptide of the general formula IV in which R 2 has the meaning given above, in a solvent.
  • the mercaptide is prepared from the associated mercaptan by reaction with a base before or during the reaction.
  • the compounds of general formula I in which k represents the numbers 1 or 2, are converted from compounds of general formula I, in which k represents the number 0, by oxidation with an oxygen-donating reagent according to the customary, generally known methods of oxidizing sulfides Sulfoxides and sulfones manufactured.
  • the fungicidal compounds according to the invention are obtained either in the form of the free bases or their salts.
  • the salts can be converted to the free bases in the usual manner, e.g. by reaction with alkali such as sodium or potassium hydroxide, sodium or potassium carbonate, ammonia or similar alkalis.
  • alkali such as sodium or potassium hydroxide, sodium or potassium carbonate, ammonia or similar alkalis.
  • suitable acids e.g.
  • inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, organic acids such as trichloroacetic acid, dichloropropionic acid, oxalic acid, toluenesulfonic acid or higher alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid can be converted into the salts which are valuable in terms of application technology.
  • Hydrogen chloride is gassed into the extract, 25.9 parts of 1 - [2-butylmercapto-2 - (2,4-dichlorophenyl) - ethyl - (1)] 1,2,4-triazole hydrochloride precipitate out, which after recrystallization from ethyl acetate melt at 143 ° C.
  • the triazole-substituted sulfur compounds according to the invention and their salts and metal complex salts are notable for excellent activity against a broad spectrum of phytopathogenic fungi. Some of them are systemically effective and can be used as foliar and soil fungicides, but also as mordants and as technical fungicides.
  • the fungicidal compounds are particularly interesting for controlling a large number of fungi on different crop plants.
  • crops to mean, in particular, wheat, rye, barley, oats, rice, corn, cotton, soybeans, coffee, sugar cane, fruit and ornamental plants in horticulture, and also vegetables such as cucumbers, beans and pumpkin plants.
  • the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • formulations or the ready-to-use preparations produced therefrom, such as solutions, emulsions, suspensions, powders, dusts, pickles, pastes or granules, are used in a known manner.
  • the application rates are between 0.01 and 3, but preferably between 0.01 and 1 kg of active ingredient per hectare.
  • the agents according to the invention can also be present together with other active ingredients, such as e.g. Herbicides, insecticides, growth regulators and fungicides or also mixed with fertilizers and applied.
  • active ingredients such as e.g. Herbicides, insecticides, growth regulators and fungicides or also mixed with fertilizers and applied.
  • the fungicidal spectrum of activity is enlarged; a number of these fungicide mixtures also have synergistic effects, i.e. the fungicidal activity of the combination product is greater than that of the added activity of the individual components.
  • Leaves of barley seedlings grown in pots are sprayed with aqueous emulsions of 80% (% by weight) active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with oidia (spores) of the barley powdery mildew (Erysiphe graminis var. Hordei).
  • the test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the extent of mildew development is determined.
  • Leaves of potted wheat seedlings of the "Jubilar” variety are sprayed with aqueous emulsions of 80% (weight percent) active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with oidia (spores) of the powdery mildew (Erysiphe graminis var. Tritici).
  • the test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. The extent of mildew development is determined after 10 days.
  • leaves of pots of oat seed of the "Flämings Krone" variety are dusted with spores of the oat crown rust (Puccinia coronata) and placed in a chamber with high atmospheric humidity.
  • the infected plants are then sprayed to runoff point with 0.05% (by weight) aqueous spray liquors which contain 80% active ingredient and 20% lignin sulfonate in the dry matter.
  • the test plants are grown in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70% rel. Humidity set up. After 8 days, the extent of the rust fungus development on the leaves is determined.
  • active ingredient 2 20 parts by weight of active ingredient 2 are mixed well with 3 parts by weight of the sodium acid of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill.
  • a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
  • active ingredient 1 40 parts by weight of active ingredient 1 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of active ingredient.
  • active ingredient 2 20 parts are intimately mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

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

Description

Die Erfindung betrifft wertvolle triazolsubstituierte Schwefelverbindungen, ihre Salze und Metallkomplexsalze mit guter fungizider Wirkung sowie Verfahren zu ihrer Herstellung und Fungizide, die diese Verbindungen als Wirkstoffe enthalten.The invention relates to valuable triazole-substituted sulfur compounds, their salts and metal complex salts with good fungicidal activity, to processes for their preparation and to fungicides which contain these compounds as active compounds.

Es ist bekannt, imidazolsubstituierte Schwefelverbindungen als Fungizide zur Bekämpfung pflanzenpathogener Pilze zu verwenden (DE-OS 25 41 833). Sie wirken jedoch häufig nur gegen einen bestimmten Pilz oder nur gegen eine bestimmte Pilzklasse, oder verursachen Schäden an den Kulturpflanzen oder bewirken bei der Verwendung als Beizmittel Keimverzögerungen und Auflaufschäden, so daß ihrer allgemeinen und breiten Anwendung enge Grenzen gesetzt sind.It is known to use imidazole-substituted sulfur compounds as fungicides for controlling phytopathogenic fungi (DE-OS 25 41 833). However, they often only act against a specific fungus or against a specific class of fungus, or cause damage to the crop plants or, when used as a mordant, cause germination delays and damage caused by emergence, so that their general and broad application are subject to strict limits.

Es wurde gefunden, daß triazolsubstituierte Schwefelverbindungen der allgemeinen Formel I

Figure imgb0001
in weicner

  • R' Wasserstoff, Fluor, Chlor, Brom, einen Alkylrest mit 1 bis 5 Kohlenstoffatomen, eine Trifluormethyl-, Phenyl- oder Alkoxygruppe mit 1 bis 3 Kohlenstoffatomen,
  • n die Zahlen 1 bis 3 bedeutet, wobei für n gleich 2 oder 3 die Reste R' gleich oder verschieden sein können,
  • R2 einen geradkettigen oder verzweigten Alkylrest mit 1 bis 14 Kohlenstoffatomen, der für den Fall des verzweigten Alkylrestes mehr als 2 Kohlenstoffatome enthält, einen Phenylrest der Formel
    Figure imgb0002
    oder einen Benzylrest der Formel
    Figure imgb0003
    bedeutet,
  • R4 Wasserstoff, Fluor, Chlor, Brom, einen Alkylrest mit 1 bis 5 Kohlenstoffatomen, eine Trifluormethyl-, Phenyl- oder Alkoxygruppe mit 1 bis 3 Kohlenstoffatomen,
  • R5 Wasserstoff, Fluor, Chlor, Brom, einen Alkylrest mit 1 bis 5 Kohlenstoffatomen, eine Trifluormethyl-, Phenyl- oder Alkoxygruppe mit 1 bis 3 Kohlenstoffatomen,
  • m die Zahlen 1 bis 3 bedeutet, wobei für m gleich 2 oder 3 die Reste R4 gleich oder verschieden sein können,
  • I die Zahlen 1 bis 3 bedeutet, wobei für 1 gleich 2 oder 3 die Reste R5 gleich oder verschieden sein können und
  • k die Zahlen 0, 1 oder 2 bedeutet,
  • und ihre Salze und Metallkomplexsalze eine sehr gute fungizide Wirkung besitzen, keine mit den bekannten Wirkstoffen vergleichbaren Schädigungen an Kulturpflanzen hervorrufen und in ihrer ausgezeichneten Wirksamkeit gegen ein breites Spektrum von Pilzen den bekannten Wirkstoffen überlegen sind, wobei ihre gleichzeitige Wirksamkeit sowohl gegen Pilze aus der Klasse der Ascomyceten als auch gegen solche aus der Klasse der Basidiomyceten hervorzuheben ist.
It has been found that triazole-substituted sulfur compounds of the general formula I
Figure imgb0001
 in weicner
  • R 'is hydrogen, fluorine, chlorine, bromine, an alkyl radical with 1 to 5 carbon atoms, a trifluoromethyl, phenyl or alkoxy group with 1 to 3 carbon atoms,
  • n denotes the numbers 1 to 3, where the radicals R 'can be identical or different for n equal to 2 or 3,
  • R 2 is a straight-chain or branched alkyl radical having 1 to 14 carbon atoms and, in the case of the branched alkyl radical, contains more than 2 carbon atoms, a phenyl radical of the formula
    Figure imgb0002
     or a benzyl radical of the formula
    Figure imgb0003
     means
  • R 4 is hydrogen, fluorine, chlorine, bromine, an alkyl radical with 1 to 5 carbon atoms, a trifluoromethyl, phenyl or alkoxy group with 1 to 3 carbon atoms,
  • R 5 is hydrogen, fluorine, chlorine, bromine, an alkyl radical with 1 to 5 carbon atoms, a trifluoromethyl, phenyl or alkoxy group with 1 to 3 carbon atoms,
  • m denotes the numbers 1 to 3, where, for m equal to 2 or 3, the radicals R 4 can be identical or different,
  • I denotes the numbers 1 to 3, where 1 is 2 or 3 and the radicals R 5 may be the same or different and
  • k means the numbers 0, 1 or 2,
  • and their salts and metal complex salts have a very good fungicidal activity, do not cause damage to crop plants comparable to the known active compounds and are superior in their effectiveness against a broad spectrum of fungi to the known active compounds, their simultaneous activity against both fungi from the class of Ascomycetes as well as against those from the class of Basidiomycetes is to be emphasized.

Die Salze haben die allgemeine Formel II

Figure imgb0004
in der R', R2, n und k die oben angegebenen Bedeutungen haben und HS eine beliebige organische oder anorganische Säure bedeutet, die jedoch bei den verwendeten Aufwandmengen nicht phytotoxisch sein darf und in der Lage sein muß, mit den Verbindungen der allgemeinen Formel 1 Salze zu bilden. Als Säuren eignen sich besonders Schwefelsäure, Salpetersäure, Salzsäure, Bromwasserstoffsäure, Jodwasserstoffsäure, Phosphorsäure, Trichloressigsäure, Dichlorpropionsäure, Oxalsäure, Toluolsulfonsäure und Dodecylbenzolsulfonsäure.The salts have the general formula II
Figure imgb0004
 in which R ', R 2 , n and k have the meanings given above and HS denotes any organic or inorganic acid which, however, must not be phytotoxic at the application rates used and must be able to react with the compounds of the general formula 1 To form salts. Particularly suitable acids are sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, trichloroacetic acid, dichloropropionic acid, oxalic acid, toluenesulfonic acid and dodecylbenzenesulfonic acid.

Die Verbindungen der allgemeinen Formel II können durch einfache Addition der Säuren HS an die Verbindungen der allgemeinen Formel I, gegebenenfalls in einem Lösungsmittel, hergestellt werden.The compounds of the general formula II can be prepared by simply adding the acids HS to the compounds of the general formula I, if appropriate in a solvent.

Die Metallkomplexsalze haben die allgemeine Formel Ila

Figure imgb0005
in der R1, R2, n und k die oben angegebenen Bedeutungen haben, p und q die Zahlen 1 bis 4 bedeuten, YΘ ein Äquivalent eines Anions einer anorganischen oder organischen Säure bedeutet und Me ein Metall aus der 1., 11. und IV. bis VIII. Nebengruppe und aus de II. und IV. Hauptgruppe des periodischen Systems darstellen kann.The metal complex salts have the general formula Ila
Figure imgb0005
 in which R 1 , R 2 , n and k have the meanings given above, p and q are the numbers 1 to 4, YΘ is an equivalent of an anion of an inorganic or organic acid and Me is a metal from the 1st, 11th and IV. To VIII. Subgroup and from de II. And IV. Main group of the periodic system.

Solche Metalle sind beispielsweise: Kupfer, Eisen, Zink und Zinn.Examples of such metals are: copper, iron, zinc and tin.

Die Metallkomplexsalze können durch Umsetzung eines Metallsalzes mit einer Verbindung der allgemeinen Formel I in einem Lösungsmittel hergestellt werden.The metal complex salts can be prepared by reacting a metal salt with a compound of the general formula I in a solvent.

Die Verbindungen der allgemeinen Formel lassen sich für den Fall k = 0 durch Umsetzung von 2-Halogenäthyl-1,2,4-triazolen der allgemeinen Formel III

Figure imgb0006
in welcher R1 und n die oben angegebene Bedeutung besitzen und X Chlor, Brom oder Jod bedeutet, mit einem Mercaptid der allgemeinen Formel IV
Figure imgb0007
in welcher R2 die oben angegebene Bedeutung besitzt, in einem Lösungsmittel herstellen. Das Mercaptid wird vor oder während der Umsetzung aus dem zugehörigen Mercaptan durch Reaktion mit einer Base hergestellt.In the case of k = 0, the compounds of the general formula can be reacted with 2-haloethyl-1,2,4-triazoles of the general formula III
Figure imgb0006
 in which R 1 and n have the meaning given above and X is chlorine, bromine or iodine, with a mercaptide of the general formula IV
Figure imgb0007
 in which R 2 has the meaning given above, in a solvent. The mercaptide is prepared from the associated mercaptan by reaction with a base before or during the reaction.

Die Verbindungen der allgemeinen Formel III sind bekannt aus der DE-OS 25 47 954.The compounds of general formula III are known from DE-OS 25 47 954.

Die Verbindungen der allgemeinen Formel I, in denen k die Zahlen 1 oder 2 darstellt, werden aus Verbindungen der allgemeinen Formel I, in denen k die Zahl 0 bedeutet, durch Oxidation mit einem sauerstoffabgebenden Reagens nach den üblichen allgemein bekannten Verfahren der Oxidation von Sulfiden zu Sulfoxiden und Sulfonen hergestellt. Die Verbindungen der allgemeinen Formel I, bei denen k = 2 bedeutet, lassen isch auch durch Oxidation der Verbindungen der allgemeinen Formel 1, bei denen k = 1 bedeutet, nach den üblichen Methoden herstellen.The compounds of general formula I, in which k represents the numbers 1 or 2, are converted from compounds of general formula I, in which k represents the number 0, by oxidation with an oxygen-donating reagent according to the customary, generally known methods of oxidizing sulfides Sulfoxides and sulfones manufactured. The compounds of the general formula I in which k = 2 can also be prepared by oxidation of the compounds of the general formula 1 in which k = 1 by the customary methods.

In Abhängigkeit von den Bedingungen, unter denen die Reaktionen durchgeführt werden, fallen die erfindungsgemäßen fungiziden Verbindungen entweder in Form der freien Basen oder ihrer Salze an. Die Salze können in der üblichen Weise in die freien Basen umgewandelt werden, z.B. durch Umsetzung mit Alkali wie Natrium- oder Kaliumhydroxid, Natrium- oder Kaliumcarbonat, Ammoniak oder ähnlichen Alkalien. Die Verbindungen in Basenform können durch Umsetzung mit geeigneten Säuren, z.B. anorganischen Säuren, wie Salzsäure, Bromwasserstoffsäure, Jodwasserstoffsäure, Schwefelsäure, Salpetersäure, Phosphorsäure, organischen Säuren, wie Trichloressigsäure, Dichlorpropionsäure, Oxalsäure, Toluolsulfonsäure oder höhere Alkylbenzolsulfonsäuren wie Dodecylbenzolsulfonsäure in die anwendungstechnisch wertvollen Salze umgewandelt werden.Depending on the conditions under which the reactions are carried out, the fungicidal compounds according to the invention are obtained either in the form of the free bases or their salts. The salts can be converted to the free bases in the usual manner, e.g. by reaction with alkali such as sodium or potassium hydroxide, sodium or potassium carbonate, ammonia or similar alkalis. The compounds in base form can be reacted with suitable acids, e.g. inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, organic acids such as trichloroacetic acid, dichloropropionic acid, oxalic acid, toluenesulfonic acid or higher alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid can be converted into the salts which are valuable in terms of application technology.

Einige charakteristische Beispiele sollen das Herstellungsverfahren erläutern.Some characteristic examples are intended to explain the manufacturing process.

Im folgenden verstehen sich alle Teile als Gewichtsteile und alle Prozente als Gewichtsprozente.In the following, all parts are parts by weight and all percentages are percentages by weight.

Beispiel 1example 1

21 Teile 4-Chlorthiophenol, 400 Teile Aceton, 20,2 Teile 1 - [2 - (3 - Bromphenyl) - 2 - chloräthyl - (1)] - 1,2,4 - triazol und 22 Teile Kaliumcarbonat werden unter gutem Rühren 8 Stunden zum Sieden erhitzt. Man engt ein und verrührt den Rückstand mit 200 Teilen Wasser, extrahiert 2 mal mit 150 Teilen Methylenchlorid, wäscht den Extrakt 2 mal mit 50 Teilen Wasser, trocknet mit Magnesiumsulfat, filtriert und dampft ein. Das zurückbleibende ÖI wird in Äthylacetat gelöst und in die Lösung Chlorwasserstoff bis zur Sättigung eingeleitet. Beim Absaugen erhält man 30 teile 1 - [2 - (3 - Bromphenyl) - 2 - (4 - chlorphenylmercapto) - äthyl - (1)J - 1,2,4 - triazolhydrochlorid, das nach dem Umkristallisieren aus Isopropanol bei 172 bis 173°C schmilzt.21 parts of 4-chlorothiophenol, 400 parts of acetone, 20.2 parts of 1 - [2 - (3-bromophenyl) - 2-chloroethyl - (1)] - 1,2,4-triazole and 22 parts of potassium carbonate are 8 with good stirring Heated to boiling for hours. The mixture is concentrated and the residue is stirred with 200 parts of water, extracted twice with 150 parts of methylene chloride, the extract is washed twice with 50 parts of water, dried with magnesium sulfate, filtered and evaporated. The remaining oil is dissolved in ethyl acetate and hydrogen chloride is introduced into the solution until saturation. Aspiration gives 30 parts of 1 - [2 - (3 - bromophenyl) - 2 - (4 - chlorophenylmercapto) - ethyl - (1) J - 1,2,4 - triazole hydrochloride, which after recrystallization from isopropanol at 172 to 173 ° C melts.

Beispiel 2Example 2

Eine Mischung von 24 Teilen 4-Chlorthiophenol, 22 Teilen 1 - [2 - Chlor - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] - 1,2,4 - triazol, 25 Teilen Kaliumcarbonat und 400 Teilen Aceton wird 12 Stunden unter Luftausschluß zum Sieden erhitzt. Anschließend wird filtriert und das Filtrat eingeengt. Nach dem Umkristallisieren aus Cyclohexan verbleiben 22 Teile 1 - [2 - (4 - Chlorphenylmercapto) - 2 - (2,4 - dichlorphenyl) - äthyl - (1)J - 1,2,4 - triazol vom Schmelzpunkt 72°C.A mixture of 24 parts of 4-chlorothiophenol, 22 parts of 1 - [2 - chloro-2 - (2,4-dichlorophenyl) - ethyl - (1)] - 1,2,4-triazole, 25 parts of potassium carbonate and 400 parts of acetone is heated to boiling for 12 hours in the absence of air. It is then filtered and the filtrate is concentrated. After recrystallization from cyclohexane, 22 parts of 1 - [2 - (4 - chlorophenylmercapto) - 2 - (2,4-dichlorophenyl) - ethyl - (1) J - 1,2,4-triazole with a melting point of 72 ° C. remain.

Deisper 5Deisper 5

Zu einer gut gerührten Suspension von 3,33 Teilen Natriumhydrid in 150 Teilen Tetrahydrofuran gibt man 22,4 Teile 4-Chlorbenzylmercaptan und rührt 1/2 Stunde. Anschließend tropft man 27,5 Teile 1 - [2 - Chlor - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] - 1,2,4 - triazol, gelöst in 40 Teilen Tetrahydrofuran, zu und läßt 2 Tage rühren. Danach werden 10 Teile Wasser zugetropft und die Reaktionsmischung wird eingedampft. Man verrührt den Rückstand mit 200 Teilen Wasser und ebensoviel Essigester, trennt den letzteren ab, wächst ihn mit Wasser, trocknet mit Natriumsulfat, filtriert und leitet Chlorwasserstoff bis zur Sättigung ein. Es fallen 30,6 Teile 1 - [2 - (4 - Chlorbenzylmercapto) - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] - 1,2,4 - triazolhydrochlorid aus, die nach dem Umkristallisieren bei 178°C schmelzen.22.4 parts of 4-chlorobenzyl mercaptan are added to a well-stirred suspension of 3.33 parts of sodium hydride in 150 parts of tetrahydrofuran and the mixture is stirred for 1/2 hour. 27.5 parts of 1 - [2-chloro-2 - (2,4-dichlorophenyl) - ethyl - (1)] - 1,2,4-triazole, dissolved in 40 parts of tetrahydrofuran, are then added dropwise and the mixture is left for 2 days stir. Then 10 parts of water are added dropwise and the reaction mixture is evaporated. The residue is stirred with 200 parts of water and as much ethyl acetate, the latter is separated off, it is grown with water, dried with sodium sulfate, filtered and hydrogen chloride is passed in until it is saturated. There are 30.6 parts of 1 - [2 - (4 - chlorobenzylmercapto) - 2 - (2,4 - dichlorophenyl) - ethyl - (1)] - 1,2,4 - triazole hydrochloride, which after recrystallization at 178 ° C melt.

Beispiel 4Example 4

3,33 Teile Natriumhydrid werden in 150 Teilen Tetrahydrofuran suspendiert und mit 12,6 Teilen Butylmercaptan zur Reaktion gebracht. Dann gibt man bei Raumtemperatur 27,5 Teile 1 - [2 - Chlor - 2 - (2,4 - dichlorophenyl) - äthyl - (1)] - 1,2,4 - triazol, die man zuvor in 50 Teilen Tetrahydrofuran gelöst hat, zu und läßt 3 Tage rühren. Anschließend tropft man 10 Teile Wasser zu, dampft ein, schlämmt mit Wasser auf und extrahiert mit Äthylacetat. In den Extrakt gast man Chlorwasserstoff ein, wobei 25,9 Teile 1 - [2 - Butylmercapto - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] 1,2,4 triazolhydrochlorid ausfallen, die nach dem Umkristallisieren aus Äthylacetat bei 143°C schmelzen.3.33 parts of sodium hydride are suspended in 150 parts of tetrahydrofuran and reacted with 12.6 parts of butyl mercaptan. Then, at room temperature, 27.5 parts of 1 - [2-chloro-2 - (2,4-dichlorophenyl) - ethyl - (1)] - 1,2,4-triazole, which had previously been dissolved in 50 parts of tetrahydrofuran, are added , and allows to stir for 3 days. Then 10 parts of water are added dropwise, the mixture is evaporated, suspended in water and extracted with ethyl acetate. Hydrogen chloride is gassed into the extract, 25.9 parts of 1 - [2-butylmercapto-2 - (2,4-dichlorophenyl) - ethyl - (1)] 1,2,4-triazole hydrochloride precipitate out, which after recrystallization from ethyl acetate melt at 143 ° C.

Beispiel 5Example 5

10 Teile 1 - [2 - (4 - Chlorphenylmercapto) - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] - 1,2,4 - triazol werden in 100 Teilen Diäthyläther gelöst und mit einer gesättigten Lösung von Oxalsäure in Diäthyläther versetzt. Es fallen 9,5 Teile 1 -[2 - (4 - Chlorphenylmercapto) - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] - 1,2,4 - triazoloxalat mit dem Schmelzpunkt 155°C aus.10 parts of 1 - [2 - (4 - chlorophenylmercapto) - 2 - (2,4 - dichlorophenyl) - ethyl - (1)] - 1,2,4 - triazole are dissolved in 100 parts of diethyl ether and with a saturated solution of oxalic acid added to diethyl ether. 9.5 parts of 1 - [2 - (4 - chlorophenylmercapto) - 2 - (2,4-dichlorophenyl) - ethyl - (1)] - 1,2,4-triazole oxalate with a melting point of 155 ° C. precipitate out.

Beispiel 6Example 6

10 Teile 1 - [2 - (4 - Chlorphenylmercapto) - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] - 1,2.4 - triazol werden in 50 Teilen Eisessig gelöst und bei 10°C mit 2,95 Teilen 30 prozentigem Wasserstoffperoxid versetzt. Nach mehrtägigem Stehen bei Raumtemperatur gießt man auf 500 Teile Wasser, extrahiert die Mischung mit Methylenchlorid, wäscht letzteres mit Wasser, trocknet es mit Magnesiumsulfat und dampft ein. Man erhält 8 Teile 1 - [2 - (2 - Chlorphenylmercapto) - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] - 1,2,4 - triazoloxid, die nach dem Umkristallisieren aus Tetrachlormethan bei 127°C schmelzen.10 parts of 1 - [2 - (4 - chlorophenylmercapto) - 2 - (2,4 - dichlorophenyl) - ethyl - (1)] - 1,2,4 - triazole are dissolved in 50 parts of glacial acetic acid and at 10 ° C with 2.95 Share 30 percent hydrogen peroxide. After standing at room temperature for several days, the mixture is poured onto 500 parts of water, the mixture is extracted with methylene chloride, the latter is washed with water, dried with magnesium sulfate and evaporated. 8 parts of 1 - [2 - (2 - chlorophenylmercapto) - 2 - (2,4-dichlorophenyl) - ethyl - (1)] - 1,2,4-triazole oxide are obtained, which after recrystallization from carbon tetrachloride at 127 ° C. melt.

Beispiel 7Example 7

10 Teile 1 - [2 - (4 - Chlorphenylmercapto) - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] - 1,2,4 - triazol werden in einer Mischung aus 50 Teilen Eisessig und 50 Teilen Acetanhydrid gelöst und mit 9 Teilen 30%igem Wasserstoffperoxid versetzt. Man erwärmt 1 Tag auf 80°C, gießt dann auf 300 Teile Wasser und saugt die ausfallenden Kristalle ab. Man erhält 8,4 Teile 1 - [2 - (4 - Chlorphenylmercapto) - 2 - (2,4 - dichlorphenyl) - äthyl - (1)J - 1,2,4 - triazoldioxid, die nach dem Reinigen bei 145°C schmelzen.10 parts of 1 - [2 - (4 - chlorophenylmercapto) - 2 - (2,4 - dichlorophenyl) - ethyl - (1)] - 1,2,4 - triazole are dissolved in a mixture of 50 parts of glacial acetic acid and 50 parts of acetic anhydride and mixed with 9 parts of 30% hydrogen peroxide. The mixture is heated to 80 ° C. for 1 day, then poured onto 300 parts of water and the crystals which precipitate are filtered off with suction. 8.4 parts of 1 - [2 - (4 - chlorophenylmercapto) - 2 - (2,4 - dichlorophenyl) - ethyl - (1) J - 1,2,4 - triazole dioxide are obtained, which after cleaning at 145 ° C. melt.

Die folgende Tabelle zeigt ein Auswahl der erfindungsgemäßen biologisch aktiven Schwefelverbindungen der allgemeinen Formel I bz. II, welche auf die in den Beispielen angegebene Art hergestellt wurden:

Figure imgb0008
The following table shows a selection of the biologically active sulfur compounds according to the invention of the general formula I or II, which were prepared in the manner given in the examples:
Figure imgb0008

Allgemeine Formel IIa

Figure imgb0009
General formula IIa
Figure imgb0009

Die erfindungsgemäßen triazolsubstituierten Schwefelverbindungen und ihre Salze und Metallkomplexsalze zeichen sich durch eine hervorragende Wirksamkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen aus. Sie sind zum Teil systemisch wirksam und können als Blatt- und Bodenfungizide, aber auch als Beizmittel sowie als technische Fungizide eingesetzt werden.The triazole-substituted sulfur compounds according to the invention and their salts and metal complex salts are notable for excellent activity against a broad spectrum of phytopathogenic fungi. Some of them are systemically effective and can be used as foliar and soil fungicides, but also as mordants and as technical fungicides.

Besonders interessant sind die fungiziden Verbindungen für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen. Unter-Kulturpflanzen verstehen wir in diesem Zusammenhang insbesondere Weizen, Roggen, Gerste, Hafer, Reis, Mais, Baumwolle, Soja, Kaffee, Zuckerrohr, Obst und Zierpflanzen im Gartenbau, sowie Gemüse wie Gurken, Bohnen und Kürbisgewächse.The fungicidal compounds are particularly interesting for controlling a large number of fungi on different crop plants. In this context, we understand crops to mean, in particular, wheat, rye, barley, oats, rice, corn, cotton, soybeans, coffee, sugar cane, fruit and ornamental plants in horticulture, and also vegetables such as cucumbers, beans and pumpkin plants.

Die Verbindungen sind insbesondere geeignet zur Bekämpfung folgender Pflanzenkrankheiten:

  • Erysiphe graminis (echter Mehltau) an Getreide,
  • Erysiphe cichoriacearum (echter Mehltau) an Kürbisgewächsen,
  • Podosphaera leucotricha an Äpfeln,
  • Uncinula necator an Reben,
  • Erysiphe polygoni an Bohnen,
  • Sphaerotheca pannosa an Rosen,
  • Puccinia-Arten an Getreide,
  • Uromvces-Arten an Bohnen.
The compounds are particularly suitable for controlling the following plant diseases:
  • Erysiphe graminis (powdery mildew) on cereals,
  • Erysiphe cichoriacearum (powdery mildew) on pumpkin plants,
  • Podosphaera leucotricha on apples,
  • Uncinula necator on vines,
  • Erysiphe polygoni on beans,
  • Sphaerotheca pannosa on roses,
  • Puccinia species on cereals,
  • Uromvces species on beans.

Die erfindungsgemäßen Substanzen können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollen in jedem Fall eine feine und gleichmäßige Verteilung der wirksamen Substanz gewährleisten. Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gegebenenfalls under Verwendung von Emulgiermitteln und Dispergiermitteln, wobei im Falle der Benutzung von Wasser als Verdünnungsmittel auch andere organische Lösungsmittel als Hilfslösungsmittel verwendet werden können. Als Hilfsstoffe kommen dafür im wesentlichen in Frage:

  • Lösungsmittel wie Aromaten (z.B. Xylol, Benzol), chlorierte Aromaten (z.B. Chlorbenzole), Paraffine (z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Butanol), Amine (z.B. Äthanolamin, Dimethylformamid) und Wasser; Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, Silikate); Emulgiermittel wie nichtionogene und anionische Emulgatoren (z.B. Polyoxyäthylen - Fettalkohol - Äther, Alkylsulfonate und Arylsulfonate) und Dispergiermittel, wie Lignin, Sulfitablaugen und Methylcellulose.
The substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes; in any case, they should ensure a fine and uniform distribution of the active substance. The formulations are prepared in a known manner, for example by extending the active ingredient with solvents and / or carriers, if appropriate using emulsifiers and dispersants, and if water is used as the diluent, other organic solvents can also be used as auxiliary solvents. The following are essentially suitable as auxiliaries:
  • Solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene - fatty alcohol - ether, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite liquors and methyl cellulose.

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

Die Formulierungen, bzw. die daraus hergestellten gebrauchsfertigen Zubereitungen, wie Lösungen, Emulsionen, Suspensionen, Pulver, Stäube, Beizen, Pasten oder Granulate werden in bekannter Weise angewendet.The formulations, or the ready-to-use preparations produced therefrom, such as solutions, emulsions, suspensions, powders, dusts, pickles, pastes or granules, are used in a known manner.

Die Aufwandmengen liegen nach Art des gewünschten Effektes zwischen 0,01 und 3, vorzugsweise jedoch zwischen 0,01 und 1 kg Wirkstoff pro Hektar.Depending on the type of effect desired, the application rates are between 0.01 and 3, but preferably between 0.01 and 1 kg of active ingredient per hectare.

Die erfindungsgemäßen Mittel können in diesen Anwendungsformen auch zusammen mit anderen Wirkstoffen vorliegen, wie z.B. Herbiziden, Insektiziden, Wachstumsregulatoren und Fungiziden oder auch mit Düngemitteln vermischt und ausgebracht werden. Beim Vermischen mit Fungiziden. erhält man dabei in vielen Fällen eine Vergrößerung des fungiziden Wirkungsspektrums; bei einer Anzahl dieser Fungizidmischungen treten auch synergistische Effekte auf, d.h. die fungizide Wirksamkeit des Kombinationsproduktes ist größer als die der addierten Wirksamkeiten der Einzelkomponenten.In these use forms, the agents according to the invention can also be present together with other active ingredients, such as e.g. Herbicides, insecticides, growth regulators and fungicides or also mixed with fertilizers and applied. When mixed with fungicides. in many cases, the fungicidal spectrum of activity is enlarged; a number of these fungicide mixtures also have synergistic effects, i.e. the fungicidal activity of the combination product is greater than that of the added activity of the individual components.

Die folgende Liste von Fungiziden, mit denen die erfingungsgemäßen Verbindungen kombiniert werden können, soll die Kombinationsmöglichkeiten erläutern, nicht aber einschränken.The following list of fungicides with which the compounds according to the invention can be combined is intended to explain the possible combinations, but not to limit it.

Fungizide, die mit den erfindungsgemäßen Verbindungen kombiniert werden können, sind beispielsweise:

  • Dithiocarbamate und deren Derivate, wie
  • Ferridimethyldithiocarbamat,
  • Zinkdimethyldithiocarbamat,
  • Manganäthylenbisdithiocarbamat,
  • Mangan-Zink-äthylendiamin-bis-dithiocarbamat,
  • Zinkäthylenbisdithiocarbamat,
  • Tetramethylthiuramdisulfide,
  • Ammoniak-Komplex von Zink-(N,N-äthylen-bis-dithiocarbamat)
  • und N,N'-Polyäthylen-bis-(thiocarbamoyi)-disulfid,
  • Zink-(N,N'-propylen-bis-dithiocarbamat),
  • Ammoniak-Komplex von Zink-(N,N'-propylen-bis-dithiocarbamat)
  • und N,N'-Polypropylen-bis-(thiocarbamoyl)-disulfid
  • Nitroderivate, wie
  • Dinitro-( 1-methylheptyl)-phenylcrotonat,
  • 2-sec-Butyl-4,6-dinitrophenyl-3,3-dimethylacrylat,
  • 2-sec-Butyl-4,6-dinitrophenyl-isopropylcarbonat;
  • heterocyclische Strukturen, wie
  • N-Trichlormethylthio-tetrahydrophthalimid,
  • N-Trichlormethylthio-phthalimid,
  • 2-Heptadecyl-2-imidazolin-acetat,
  • 2,4-Dichloro-6-(o-chloranilino)-s-triazin,
  • 0,0-Diäthyl-phthalimidophosphonothioat,
  • 5-Amino-1-(bis-(dimethylaminol-phosphinyl)-3-phenyl-1,2,4-triazol,
  • 5-Äthoxy-3-trichlormethyl-1,2,4-thiadiazol,
  • 2,3-Dicyano-1,4-dithiaanthrachinon,
  • 2-Thio-1,3-dithio-(4,5-b)-chinoxylin,
  • 1-(Butylcarbamoyl)-2-benzimidazol-carbaminsäuremethylester,
  • 2-Methoxycarbonylamino-benzimidazol,
  • 2-Rhodanmethylthio-benzthiazol,
  • 4-(2-Chlorphenylhydrazono)-3-methyl-5-isoxazolon, Pyridin-2-thio-1-oxid,
  • 8-Hydroxychinolin bzw. dessen Kupfersalz,
  • 2,3-Dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxid,
  • 2,3-Dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,
  • 2-(Furyl-(2)-benzimidazol,
  • 5-Methyl-5-vinyl-3-(3,5-dichlorphenyl)-2,4-dioxo-1,3-oxazolidin,
  • N-Cyclohexyl-2,5-dimethylfuran-3-hydroxamsäuremethylester,
  • Piperazin-1,4-diyl-bis-(1-(2,2,2-trichlor-äthyl)-formamid),
  • 2-(Thiazolyl-(4)-benzimidazol,
  • 5-Butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidin,
  • Bis-(p-Chlorphenyl)-3-pyridinmethanol,
  • 1,2-Bis-(3-äthoxycarbonyl-2-thioureido)-benzol,
  • 1,2-Bis-(3-methoxycarbonyl-2-thioureido)-benzol
  • und verschiedene Fungizide, wie
  • Dodecylguanidinacetat,
  • 3-(2-(3,5-Dimethyl-2-oxycyclohexyl)-2-hydroxyäthyl)-glutarimid, Hexachlorbenzol,
  • N-Dichlorfluormethylthio-N',N'-dimethyl-N-phenyl-schwefel- säurediamid,
  • 2,5-Dimethyl-furan-3-carbonsäureanilid,
  • 2,5-Dimethyl-furan-3-carbonsäure-cyclohexylamid,
  • 2-Methyl-benzoesäure-anilid,
  • 2-Jod-benzoesäure-anilid,
  • 1-(3,4-Dichloranilino)-1-formylamino-2,2,2-trichloräthan,
  • 2,6-Dimethyl-N-tridecyl-morpholin bzw. dessen Salze,
  • 2,6-Dimethyl-N-cyclododecyl-morpholin bzw. dessen Salze.
Fungicides that can be combined with the compounds according to the invention are, for example:
  • Dithiocarbamates and their derivatives, such as
  • Ferridimethyldithiocarbamate,
  • Zinc dimethyldithiocarbamate,
  • Manganese ethylene bisdithiocarbamate,
  • Manganese-zinc-ethylenediamine-bis-dithiocarbamate,
  • Zinc ethylene bisdithiocarbamate,
  • Tetramethylthiuram disulfide,
  • Ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate)
  • and N, N'-polyethylene-bis- (thiocarbamoyi) disulfide,
  • Zinc (N, N'-propylene-bis-dithiocarbamate),
  • Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate)
  • and N, N'-polypropylene bis (thiocarbamoyl) disulfide
  • Nitroderivatives, such as
  • Dinitro- (1-methylheptyl) phenylcrotonate,
  • 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate,
  • 2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate;
  • heterocyclic structures, such as
  • N-trichloromethylthio-tetrahydrophthalimide,
  • N-trichloromethylthio-phthalimide,
  • 2-heptadecyl-2-imidazoline acetate,
  • 2,4-dichloro-6- (o-chloroanilino) -s-triazine,
  • 0,0-diethyl phthalimidophosphonothioate,
  • 5-amino-1- (bis- (dimethylaminol-phosphinyl) -3-phenyl-1,2,4-triazole,
  • 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole,
  • 2,3-dic y ano-1,4-dithiaanthraquinone,
  • 2-thio-1,3-dithio- (4,5-b) -quinoxylin,
  • 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester,
  • 2-methoxycarbonylamino-benzimidazole,
  • 2-rhodanmethylthio-benzothiazole,
  • 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide,
  • 8-hydroxyquinoline or its copper salt,
  • 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,
  • 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,
  • 2- (furyl- (2) -benzimidazole,
  • 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine,
  • N-cyclohexyl-2,5-dimethylfuran-3-hydroxamic acid methyl ester,
  • Piperazin-1,4-diyl-bis- (1- (2,2,2-trichloroethyl) formamide),
  • 2- (thiazolyl- (4) -benzimidazole,
  • 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine,
  • Bis- (p-chlorophenyl) -3-pyridinemethanol,
  • 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene,
  • 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene
  • and various fungicides, such as
  • Dodecylguanidine acetate,
  • 3- (2- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) glutarimide, hexachlorobenzene,
  • N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyl-sulfuric acid diamide,
  • 2,5-dimethyl-furan-3-carboxylic acid anilide,
  • 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide,
  • 2-methylbenzoic acid anilide,
  • 2-iodo-benzoic acid anilide,
  • 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane,
  • 2,6-dimethyl-N-tridecyl-morpholine or its salts,
  • 2,6-dimethyl-N-cyclododecyl-morpholine or its salts.

Für die folgenden Versuche wurden zu Vergleichszwecken die beiden folgenden bekannten Wirkstoffe verwendet

Figure imgb0010
bekannt aus DT-OS 25 41 833
Figure imgb0011
bekannt aus DT-OS 25 41 833For the following experiments, the following two known active ingredients were used for comparison purposes
Figure imgb0010
 known from DT-OS 25 41 833
Figure imgb0011
 known from DT-OS 25 41 833

Beispiel 8Example 8 Wirkung gegen GerstenmehltauEffect against barley mildew

Blätter von in Töpfen gewachsenen Gerstenkeimlingen werden mit wäßrigen Emulsionen aus 80% (Gew.%) Wirkstoff und 20% Emulgiermittel besprüht und nach dem Antrocknen des Spritzbelages mit Oidien (Sporen) des Gerstenmehltaus (Erysiphe graminis var. hordei) bestäubt. Die Versuchspflanzen werden anschließend im Gewächshaus bei Temperaturen zwischen 20 und 22°C und 75 bis 80% relativer Luftfeuchtigkeit aufgestellt. Nach 10 Tagen wird das Ausmaß der Mehltaupilzentwicklung ermittelt.

Figure imgb0012
Leaves of barley seedlings grown in pots are sprayed with aqueous emulsions of 80% (% by weight) active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with oidia (spores) of the barley powdery mildew (Erysiphe graminis var. Hordei). The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the extent of mildew development is determined.
Figure imgb0012

Beispiel 9Example 9 Wirkung gegen WeizenmehltauAction against powdery mildew

Blätter von in Töpfen gewachsenen Weizenkeimlingen der Sorte "Jubilar" werden mit wäßrigen Emulsionen aus 80% (Gewichtsprozent) Wirkstoff und 20% Emulgiermittel besprüht und nach dem Antrocknen des Spritzbelages mit Oidien (Sporen) des Weizenmehltaus (Erysiphe graminis var. tritici) bestäubt. Die Versuchspflanzen werden anschließend im Gewächshaus bei Temperaturen zwischen 20 und 22°C und 75 bis 80% relativer Luftfeuchtigkeit aufgestellt. Nach 10 Tagen wird das Ausmaß der Mehltauentwicklung ermittelt.

Figure imgb0013
Leaves of potted wheat seedlings of the "Jubilar" variety are sprayed with aqueous emulsions of 80% (weight percent) active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with oidia (spores) of the powdery mildew (Erysiphe graminis var. Tritici). The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. The extent of mildew development is determined after 10 days.
Figure imgb0013

Beispiel 10Example 10 Wirkung gegen WeizenbraunrostEffect against wheat brown rust

Blätter von in Töpfen gewachsenen Weizensämlingen der Sorte "Caribo" werden mit Sporen des Braunrostes (Puccinia recondita) bestäubt. Danach werden die Töpfe für 24 Stunden bei 20 bis 22°C in eine Kammer mit hoher Luftfeuchtigkeit (90 bis 95%) gestellt. Während dieser Zeit keimen die Sporen aus und die Keimschläuche dringen in das Blattgewebe ein. Die infizierten Pflanzen werden anschließend mit 0,05%, 0,025 und 0,012%igen (Gew.%) wäßrigen Spritzbrühen, die 80% Wirkstoff und 20% Ligninsulfonat in der Trockensubstanz enthalten, tropfnass gespritzt. Nach dem Antrocknen des Spritzbelages werden die Versuchspflanzen im Gewächshaus bei Temperaturen zwischen 20 und 22°C und 65 bis 70% relativer Luftfeuchte aufgestellt. Nach 8 Tagen wird das Ausmaß der Rostpilzentwicklung auf den Blättern ermittelt.

Figure imgb0014
Leaves of "Caribo" wheat seedlings grown in pots are dusted with spores of the brown rust (Puccinia recondita). The pots are then placed in a chamber with high humidity (90 to 95%) at 20 to 22 ° C for 24 hours. During this time, the spores germinate and the germ tubes penetrate the leaf tissue. The infected plants are then sprayed to runoff point with 0.05%, 0.025 and 0.012% (by weight) aqueous spray liquors which contain 80% active ingredient and 20% lignin sulfonate in the dry matter. After the spray coating has dried on, the test plants are placed in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70% relative atmospheric humidity. After 8 days, the extent of the rust fungus development on the leaves is determined.
Figure imgb0014

Beispiel 11 1Example 11 1 Wirkung gegen HaferkronenrostEffect against oat crown rust

In gleicher Weise wie in Beispiel 10 angeführt, werden Blätter von in Töpfen gewachsenen Hafersämlengen der Sorte "Flämings Krone" mit Sporen des Haferkronenrostes (Puccinia coronata) bestäubt und in eine Kammer mit hoher Luftfeuchtigkeit gestellt. Die infizierten Pflanzen werden anschliesend mit 0,05%igen (Gew.%) wäßrigen Spritzbrühen, die 80% Wirkstoff und 20% Ligninsulfonat in der Trockensubstanz enthalten, tropfnaß gespritzt. Nach dem Antrocknen des Spritzbelages werden die Versuchspflanzen im Gewächshaus bei Temperaturen zwischen 20 und 22°C und 65 bis 70% rel. Luftfeuchte aufgestellt. Nach 8 Tagen wird das Ausmaß der Rostpilzentwicklung auf den Blättern ermittelt.

Figure imgb0015
In the same way as given in Example 10, leaves of pots of oat seed of the "Flämings Krone" variety are dusted with spores of the oat crown rust (Puccinia coronata) and placed in a chamber with high atmospheric humidity. The infected plants are then sprayed to runoff point with 0.05% (by weight) aqueous spray liquors which contain 80% active ingredient and 20% lignin sulfonate in the dry matter. After the spray coating has dried on, the test plants are grown in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70% rel. Humidity set up. After 8 days, the extent of the rust fungus development on the leaves is determined.
Figure imgb0015

Wirkung gegen GerstenmehltauEffect against barley mildew BeizmittelanwendungMordant application

100 g-Proben Gerstensaatgut der Sorte "Asse" werden in Glasflaschen etwa 5 Minuten lang mit jeweils 300 mg (= 0,3 Gew.%) der in der Tabelle angeführten Beizmittel sorgfältig gebeizt. Danach werden jeweils 8 Körner in Töpfe eingelegt und mit Erde bedeckt. Zehn Tage nach dem Auflauf des Getreides werden die Blätter mit Oidium (Konidien) des Gerstenmehltaus (Erysiphe graminis var. hordei) bestäubt. Die Versuchspflanzen werden anschließend im Gewächshaus bei Temperaturen zwischen 20 und 22°C rel. Luftfeuchte aufgestellt. Nach weiteren 10 Tagen wird das Ausmaß der Mehltaupilzentwicklung auf den Blättern ermittelt.

Figure imgb0016
100 g samples of barley seeds of the "Asse" variety are carefully dressed in glass bottles for about 5 minutes, each with 300 mg (= 0.3% by weight) of the dressing agents listed in the table. Then 8 grains are placed in pots and covered with earth. Ten days after the emergence of the grain, the leaves are dusted with oidium (conidia) of the barley mildew (Erysiphe graminis var. Hordei). The test plants are then in the greenhouse at temperatures between 20 and 22 ° C rel. Humidity set up. After a further 10 days, the extent of the development of mildew on the leaves is determined.
Figure imgb0016

Beispiel 13Example 13

Man vermischt 90 Gewichtsteile der Verbindung 1 mit 10 Gewichtsteilen N-Methyl-α-pyrrolidon und erhält eine Lösung, die zur Anwendung in Form kleinster Tropfen geeignet ist.90 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone, and a solution is obtained which is suitable for use in the form of tiny drops.

Beispiel 14Example 14

20 Gewichtsteile der Verbindung 2 werden in einer Mischung gelöst, die aus 80 Gewichtsteilen Xylol, 10 Gewichtsteilen des Anlagerungsproduktes von 8 bis 10 Mol Äthylenoxid an 1 Mol Olsäure-N-monoäthanolamid, 5 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Äthylenoxid an 1 Mol Ricinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of compound 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide of 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Beispiel 15Example 15

20 Gewichtsteile der Verbindung 3 werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyclohexanon, 30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 7 Mol Äthylenoxid an 1 Mol Isooctylphenol und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Äthylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of compound 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

Beispiel 16Example 16

20 Gewichtsteile der Verbindung 1 werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyclohexanol, 65 Gewichtsteilen einer Mineralölfraktion vom Siedepunkt 210 bis 280°C und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Athylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of compound 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

Beispiel 17Example 17

20 Gewichtsteile des Wirkstoffs 2 werden mit 3 Gewichtsteilen des Natriumsaizes der Diisobutylnaphthalin-a-sulfonsäure, 17 Gewichtsteilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfit-Ablauge und 60 Gewichtsteilen pulverförmigen Kieselsäuregel gut vermischt und in einer Hammermühle vermahlen. Durch feines Verteilen der Mischung in 20 000 Gewichtsteilen Wasser erhält man eine Spritzbrühe, die 0,1 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of active ingredient 2 are mixed well with 3 parts by weight of the sodium acid of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.

Beispiel 18Example 18

3 Gewichtsteile der Verbindung 3 werden mit 97 Gewichtsteilen feinteiligem Kaolin innig vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gewichtsprozent des Wirkstoffs enthält.3 parts by weight of compound 3 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3 percent by weight of the active ingredient.

Beispiel 19Example 19

30 Gewichtsteile der Verbindung 4 werden mit einer Mischung aus 92 Gewichtsteilen pulverförmigem Kieselsäuregel und 8 Gewichtsteilen Paraffinöl, das auf die Oberfläche dieses Kieselsäuregels gesprüht wurde, innig vermischt. Man erhält auf diese Weise eine Aufbereitung des Wirkstoffs mit guter Haftfähigkeit.30 parts by weight of compound 4 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way a preparation of the active ingredient with good adhesiveness is obtained.

Beispiel 20Example 20

40 Gewichtstelle des Wirkstoffs 1 werden mit 10 Teilen Natriumsalz eines Phenolsulfonsäureharnstoff-formaldehyd-Kondensats, 2 Teilen Kieselgel und 48 Teilen Wasser innig vermischt. Man erhält eine stabile wäßrige Dispersion. Durch Verdünnen mit 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,04 Gewichtsprozent Wirkstoff enthält.40 parts by weight of active ingredient 1 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of active ingredient.

Beispiel 21Example 21

20 Teile des Wirkstoffs 2 werden mit 2 Teilen Calciumsalz der Dodecylbenzolsulfonsäure, 8 Teilen Fettalkohol-polyglykoläther, 2 Teilen Natriumsalz eines Phenolsulfonsäure-harnstoff-formaldehyd-Kondensats und 68 Teilen eines paraffinischen Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.20 parts of active ingredient 2 are intimately mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

Beispiel 22Example 22

9,58 Teile 1 - [2 - (4 - Chlorphenylmercapto) - 2 - (2,4 - dichlorphenyl) - äthyl - (1)] - 1,2,4 - triazol werden in 300 Teilen Äthanol gelöst und tropfenweise mit einer Lösung von 2,2 Teilen hydratwasserhaltigem Kupfer (11) - chlorid in 3 Teilen Wasser versetzt. Nach 20-minutigem führen wird abgesaugt. Man erhält 10 Teile Bis - [1 - (2 - (4 - chlorphenylmercapto - 2 - (2,4 - dichlorphenyl) - äthyl - (1)) - 1,2,4 - triazol] - Kupfer (II) - chlorid vom Schmelzpunkt 196°C.9.58 parts of 1 - [2 - (4 - chlorophenylmercapto) - 2 - (2,4 - dichlorophenyl) - ethyl - (1)] - 1,2,4 - triazole are dissolved in 300 parts of ethanol and added dropwise with a solution 2.2 parts of hydrate-containing copper (11) chloride in 3 parts of water. After 20 minutes of guiding, suction is carried out. 10 parts of bis - [1 - (2 - (4 - chlorophenylmercapto - 2 - (2,4 - dichlorophenyl) - ethyl - (1)) - 1,2,4 - triazole] - copper (II) chloride from Melting point 196 ° C.

Claims (17)

1. A triazole-substituted sulfur compound of the general formula I
Figure imgb0023
where R' denotes hydrogen, fluorine, chlorine, bromine, alkyl of 1 to 5 carbon atoms, trifluoromethyl, phenyl or alkoxy of 1 to 3 carbon atoms,
n denotes one of the integers 1, 2 and 3 (R1 being identical or different when n is 2 or 3),
R2 denotes a linear or branched alkyl of 1 to 14 carbon atoms, which, if it is a branched one, contains more than 2 carbon atoms, phenyl of the formula
Figure imgb0024
or benzyl of the formula
Figure imgb0025
R4 denotes hydrogen, fluoro, chloro, bromo, alkyl of 1 to 5 carbon atoms, trifluoromethyl, phenyl, or alkoxy of 1 to 3 carbon atoms,
R5 denotes hydrogen, fluoro, chloro, bromo, alkyl of 1 to 5 carbon atoms, trifluoromethyl, phenyl, or alkoxy of 1 to 3 carbon atoms,
m denotes one of the integers 1, 2 and 3 (R4 being identical or different when m is 2 or 3),
I denotes one of the integers 1, 2 and 3 (R5 being identical or different when 1 is 2 or 3), and
k denotes one of the integers 0, 1 and 2, and its salts and metal complex salts.
2. A fungicide containing a triazole-substituted sulfur compound of the general formula I as claimed in claim 1.
3. A process for combating fungi, characterized in that the objects to be protected against fungus attack are treated with a triazole-substituted sulfur compound of the general formula I as claimed in claim 1.
4. 1-[2-(4-Bromophenyl)-2-(4-chlorophenylmercapto)-ethyl-(1)]-1,2,4-triazole.
5. i-[2-(4-Bromophenyl)-2-(4-chlorobenzylmercapto)-ethyl-(1)]-1,2,4-triazole.
6. 1-[2-(3-Bromophenyl)-2-(4-chlorophenylmercapto)-ethyl-(1)]-1,2,4-triazole.
7. 1-[2-(3-Bromophenyl)-2-(4-chlorobenzylmercapto)-ethyl-( 1)]-1,2,4-triazole.
8. 1-[2-(4-Chlorophenyl)-2-(4-chlorophenylmercapto)-ethyl-(1)]-1,2,4-triazole.
9. 1-[2-(4-Chlorobenzylmercapto)-2-(4-chlorophenyl)-ethyl-(1)]-1,2,4-triazole.
10. 1-[2-(4-Chlorophenylmercaptol-2-(2,4-dichlorophenyl)-ethyl-(1)]-1,2,4-triazole.
11. 1-[2-(4-Chlorophenylmercapto)-2-(2,4-dichlorophenyl)-ethyl-(1)]-1,2,4-triazole oxide.
12. 1-[2-(4-Chlorophenylmercapto)-2-(2,4-dichlorophenyl)-ethyl-(1)]-1,2,4-triazole dioxide.
13. 1-[2-(4-Chlorobenzylmercapto)-2,4-dichlorophenyl)-ethyl-(1)]-1,2,4-triazofe.
14. 1-[2-(2,4-Dichlorobenzylmercapto)-2-(2,4-dichlorophenyl)-ethyl-(1)]-1,2,4-triazole.
15. 1-[2-(4-tert-Butylphenyl)-2-(2,4-dichlorobenzylmercapto)-ethyl-( 1)]-1,2,4-triazole.
16. 1-[2-Butylmercapto-2-(2,4-dichlorophenyl)-ethyl-(1)]-1,2,4-triazole.
17. 1-[2-(2,4-Dichlorophenyl)-2-dodecylmercaptoethyl-(1)]-1,2,4-triazole.
EP78100044A 1977-06-01 1978-06-01 Triazol-substituted sulphur derivatives, their preparation and their utilisation as fungicides Expired EP0000112B1 (en)

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DE2724684 1977-06-01
DE19772724684 DE2724684A1 (en) 1977-06-01 1977-06-01 TRIAZOLE-SUBSTITUTED SULFUR COMPOUNDS

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EP0000112A1 EP0000112A1 (en) 1978-12-20
EP0000112B1 true EP0000112B1 (en) 1981-09-09

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DE2928768A1 (en) * 1979-07-17 1981-02-12 Bayer Ag 1- (2,4-DICHLORPHENYL) -1- (2,6- DIHALOGENBENZYLMERCAPTO) -2- (1,2,4- TRIAZOL-1-YL) -ETHANE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES
DE3108770A1 (en) * 1981-03-07 1982-09-16 Bayer Ag, 5090 Leverkusen TRIAZOLYLALKYL THIOETHER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS PLANT GROWTH REGULATORS AND FUNGICIDES
CA1179678A (en) * 1981-03-27 1984-12-18 Elmar Sturm Antimicrobial triazole derivatives
DE3342310A1 (en) * 1983-11-23 1985-05-30 Bayer Ag, 5090 Leverkusen USE OF 1- (2,4-DICHLORPHENYL) -1- (4-CHLORBENZYLMERCAPTO) -2- (1,2,4-TRIAZOL-1-YL) -ETHANE TO REGULATE PLANT GROWTH
GB9125791D0 (en) * 1991-12-04 1992-02-05 Schering Agrochemicals Ltd Herbicides
AU672059B2 (en) * 1992-10-09 1996-09-19 Uniroyal Chemical Co./Uniroyal Chemical Cie Fungicidal substituted azole derivatives
KR100927304B1 (en) * 2001-12-27 2009-11-18 다이이찌 세이야꾸 가부시기가이샤 β-amyloid protein production/secretion inhibitors
PL379466A1 (en) 2003-06-30 2006-09-18 Daiichi Sankyo Company , Limited Heterocyclic methyl sulfone derivative

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DE2645496A1 (en) * 1976-10-08 1978-04-13 Bayer Ag (1-PHENYL-2-TRIAZOLYL-AETHYL) -THIOAETHER DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES AND GROWTH REGULATORS

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