+

WO1996039395A1 - Microbicidal (mercapto-triazolylmethyl)-butanols - Google Patents

Microbicidal (mercapto-triazolylmethyl)-butanols Download PDF

Info

Publication number
WO1996039395A1
WO1996039395A1 PCT/EP1996/002404 EP9602404W WO9639395A1 WO 1996039395 A1 WO1996039395 A1 WO 1996039395A1 EP 9602404 W EP9602404 W EP 9602404W WO 9639395 A1 WO9639395 A1 WO 9639395A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
carbon atoms
mercapto
triazolyl
butanols
Prior art date
Application number
PCT/EP1996/002404
Other languages
German (de)
French (fr)
Inventor
Manfred Jautelat
Ralf Tiemann
Stefan Dutzmann
Klaus Stenzel
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU60046/96A priority Critical patent/AU6004696A/en
Publication of WO1996039395A1 publication Critical patent/WO1996039395A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • 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
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • the present invention relates to new mercapto-triazolyl-butanols, a process for their preparation and their use as microbicides.
  • R 1 represents hydrogen, alkyl or optionally substituted cycloalkyl
  • R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms
  • X represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkyl thio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms or phenoxy optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms,
  • n represents the numbers 0, 1, 2 or 3 and Y represents an oxygen atom, a CH 2 group or a direct bond,
  • the substances according to the invention contain at least two asymmetrically substituted carbon atoms. They can therefore be obtained in the form of diastereomers or enantiomers.
  • the present invention relates both to the individual isomers and to their mixtures.
  • R 1 , X, Y and m have the meanings given above,
  • R 1 , X, Y and m have the meanings given above,
  • R 3 represents alkyl having 1 to 4 carbon atoms
  • the substances according to the invention have a better microbicidal activity than the structurally most similar, known compounds of the same action.
  • the substances according to the invention thus exceed the 2,2-
  • the mercapto-triazolyl-butanols according to the invention are generally defined by the formula (I).
  • R 1 preferably stands for hydrogen, straight-chain or branched alkyl having 1 to 12 carbon atoms or for optionally cycloalkyl having 3 to 7 carbon atoms which is monosubstituted to triple, identical or different, substituted by halogen and / or alkyl having 1 to 4 carbon atoms.
  • R 2 preferably represents hydrogen, methyl or ethyl.
  • X preferably represents fluorine, chlorine, bromine, methyl, ethyl, methoxy,
  • n also preferably represents the numbers 0, 1, 2 or 3, where X represents the same or different radicals if m represents 2 or 3.
  • Y also preferably represents an oxygen atom, a CH 2 group or a direct bond.
  • R 1 particularly preferably represents hydrogen, straight-chain or branched
  • R 2 also particularly preferably represents hydrogen, methyl or ethyl.
  • X particularly preferably represents fluorine, chlorine, bromine, methyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl or phenoxy.
  • n also particularly preferably represents the numbers 0, 1, 2 or 3, where X represents the same or different radicals if m represents 2 or 3.
  • Y also particularly preferably represents an oxygen atom, a CH 2 group or a direct bond.
  • Preferred substances according to the invention are also addition products of acids and those mercapto-triazolylbutanols of the formula (I) in which R 1 , R 2 , X, Y and m have those meanings which have been mentioned as preferred for these substituents and this index.
  • the acids which can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, Maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids, such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid, or camphorsulfonic acid, saccharin and thiosaccharine.
  • hydrohalic acids such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, Maleic acid, succinic acid, fumaric
  • preferred compounds according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. And IV. To VIII. Subgroup of the periodic table of the elements and those mercapto-triazolyl-butanols of the formula (I), in to which R 1 , R 2 , X, Y and m have the meanings which have been mentioned as preferred for these substituents and this index.
  • Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred.
  • Anions of these salts are those which are derived from acids which lead to physiologically tolerable addition products.
  • Particularly preferred such acids in this connection are the hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.
  • Formula (II) provides a general definition of the triazolylbutanols required as starting materials when carrying out the process according to the invention.
  • R 1 , X, Y and m preferably have those meanings which have already been mentioned as preferred for these radicals and this index in connection with the description of the substances of the formula (I) according to the invention.
  • the triazolylbutanols of the formula (II) are known or can be prepared by known processes (cf. EP-A 0 055 833 and EP-A 0 301 393).
  • Suitable bases for carrying out the first stage of the process according to the invention are all strong alkali metal bases which are customary for such reactions.
  • inert organic solvents customary for such reactions can be considered as diluents.
  • Ethers such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane, preferably liquid ammonia or strongly polar solvents such as dimethyl sulfoxide are preferably usable.
  • Sulfur is preferably used in the form of powder.
  • water is used when carrying out the first stage of the process according to the invention, if appropriate in the presence of an acid. All inorganic or organic acids customary for such reactions can be considered. Acetic acid, dilute sulfuric acid and dilute hydrochloric acid are preferably usable. However, it is also possible to carry out the hydrolysis with an aqueous ammonium chloride solution.
  • reaction temperatures can be varied within a certain range when carrying out the first stage of the process according to the invention. In general, temperatures between -70 ° C and + 20 ° C, preferably between -70 ° C and 0 ° C.
  • the procedure is generally carried out under normal pressure.
  • 2 to 3 equivalents, preferably 2.0 to 2.5 equivalents, of strong base and then an equivalent amount are generally employed per mole of triazolylbutanol of the formula (II) or an excess of sulfur.
  • the reaction can be carried out under a protective gas atmosphere, for example under nitrogen or argon.
  • the processing takes place according to usual methods.
  • the procedure is that the reaction mixture is extracted with an organic solvent which is sparingly soluble in water, the combined organic phases are dried and concentrated, and the remaining residue is optionally purified by recrystallization and / or chromatography.
  • the compounds of the formula (Ia) required as starting substances when carrying out the second stage of the process according to the invention are substances according to the invention.
  • halogen compounds required as reaction components in carrying out the process according to the invention in the second stage are generally defined by the formula (III).
  • R ⁇ is preferably methyl or ethyl.
  • Shark also preferably represents chlorine, bromine or iodine.
  • Suitable acid binders for carrying out the second stage of the process according to the invention are all customary inorganic or organic bases.
  • Alkaline earth metal or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali metal or alkaline earth metal acetates such as
  • Sodium acetate, potassium acetate, calcium acetate and tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
  • Suitable diluents for carrying out the second stage of the process according to the invention are all inert organic solvents which are customary for such reactions.
  • Ethers such as diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane, furthermore nitriles such as acetonitrile and also strongly polar are preferably usable
  • Solvents such as dimethyl sulfoxide or dimethylformamide.
  • reaction temperatures can be varied within a substantial range when carrying out the second stage of the process according to the invention. In general, temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 100 ° C.
  • halogen compound of the formula (III) and an equivalent amount or also an excess of acid binder are generally employed per mol of mercapto-triazolylbutanol of the formula (Ia) on.
  • the processing takes place according to usual methods.
  • the general procedure is to add aqueous base and a water-immiscible organic solvent to the reaction mixture, and to separate, dry and concentrate the organic phase.
  • the product obtained can optionally be processed by conventional methods, e.g. by recrystallization, from any impurities still present.
  • the mercapto-triazolylbutanols of the formula (I) obtainable by the process according to the invention can be converted into acid addition salts or metal salt complexes.
  • the acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and in a known manner, for example by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent.
  • a suitable inert solvent for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and in a known manner, for example by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent.
  • Metal salt complexes can be prepared in a known manner, e.g. by filtering, isolating and, if necessary, cleaning by recrystallization.
  • the active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.
  • Fungicides are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Xanthomonas species such as Xanthomonas oryzae
  • Pseudomonas species such as Pseudomonas lachrymans
  • Erwinia species such as Erwinia amylovora
  • Pythium species such as Pythium ultimum
  • Phytophthora species such as Phytophthora infestans
  • Pseudoperonospora species such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
  • Plasmopara species such as Plasmopara viticola
  • Peronospora species such as Peronospora pisi or P. brassicae;
  • Erysiphe species such as Erysiphe graminis
  • Sphaerotheca species such as Sphaerotheca fuliginea
  • Podosphaera species such as Podosphaera leucotricha
  • Venturia species such as Venturia inaequalis
  • Pyrenophora species such as Pyrenophora teres or P. graminea; (Coni form: Drechslera, Syn: Helminthosporium);
  • Cochliobolus species such as Cochliobolus sativus
  • Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
  • Uromyces species such as Uromyces appendiculatus
  • Puccinia species such as Puccinia recondita
  • Tilletia species such as Tilletia caries
  • Ustilago species such as Ustilago nuda or Ustilago avenae
  • Pellicularia species such as Pellicularia sasakii
  • Pyricularia species such as Pyricularia oryzae
  • Fusarium species such as Fusarium culmorum
  • Botrytis species such as Botrytis cinerea
  • Septoria species such as Septoria nodorum
  • Leptosphaeria species such as Leptosphaeria nodorum
  • Cercospora species such as Cercospora canescens; Alternaria species, such as Alternaria brassicae;
  • Pseudocercosporella species such as Pseudocercosporella herpotrichoides.
  • the active compounds according to the invention are particularly suitable for combating
  • the substances according to the invention can be used very well against Venturia and Sphae rotheca. They also have a very good in vitro effect.
  • the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
  • technical materials are to be understood as non-living materials that have been prepared for use in technology.
  • technical materials which are to be protected against microbial change or destruction by active substances according to the invention adhesives, glues, paper and cardboard, textiles, leather, wood, Paints and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms.
  • parts of production plants for example cooling water circuits, which may be impaired by the multiplication of microorganisms, may also be mentioned.
  • technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.
  • Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials.
  • the active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
  • microorganisms of the following genera may be mentioned:
  • Alternaria such as Alternaria tenuis
  • Aspergillus such as Aspergillus niger
  • Chaetomium like Chaetomium globosum
  • Coniophora such as Coniophora puetana
  • Lentinus such as Lentinus tigrinus
  • Penicillium such as Penicillium glaucum
  • Polyporus such as Polyporus versicolor
  • Aureobasidium such as Aureobasidium pullulans
  • Sclerophoma such as Sclerophoma pityophila
  • Trichoderma such as Trichoderma viride
  • Escherichia such as Escherichia coli
  • Pseudomonas such as Pseudomonas aeruginosa
  • Staphylococcus such as Staphylococcus aureus.
  • the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules,
  • Aerosols very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm mist formulations.
  • These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means.
  • 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 Means.
  • organic solvents such as alcohols can also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol 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 liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide;
  • solid carriers for example natural rock powder, such as
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal lphthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 0.1
  • active ingredient 95 percent by weight of active ingredient, preferably between 0.5 and 90%.
  • the active compounds according to the invention can be used in the formulations in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of effects or to prevent the development of resistance. In some cases, synergistic effects also occur.
  • Fenpropimorph Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, folpet, fosetyl aluminum, fthalides, fuberidazole, furalaxyl,
  • copper preparations such as: copper hydroxide, copper naphthenate,
  • Mancopper Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
  • Probenazole prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone,
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 4 19, CGA 1 84699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos,
  • Chlorfluazuron Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
  • Tebufenozid Tebufenpyrad
  • Tebupirimiphos Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb,
  • active ingredients as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions,
  • Spray powder, pastes, soluble powders, dusts and granules can be used. They are used in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
  • the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
  • amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
  • active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the place of action.
  • the agents used to protect industrial materials generally contain the active ingredients in an amount of 1 to 95%, preferably 10 to 75%.
  • the application concentrations of the active compounds according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount of use can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.
  • the effectiveness and the spectrum of activity of the active substances to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be produced therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or others are used Active substances to enlarge the spectrum of activity or to achieve special effects such as additional protection against insects are added. These mixtures can have a broader spectrum of activity than the compounds according to the invention.
  • Solvent 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.
  • the plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.
  • Emulsifier 0.6 part by weight of alkylaryl polyglycol ether
  • the plants are placed in a greenhouse at a temperature of approx. 10 ° C and a relative humidity of approx. 80%.

Landscapes

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

Abstract

Disclosed are novel (mercapto-triazolylmethyl)-butanols of formula (I) in which R1, R2 X, Y and m have the meanings indicated in the description, as well as their acid-addition salts and metal salt complexes, a method of producing these substances and their use as microbicides for protecting plants and materials.

Description

M1 krob1z1de (Mercapto-triazolylmethyl )-butanole M1 krob1z1de (mercapto-triazolylmethyl) butanols
Die vorliegende Erfindung betrifft neue Mercapto-triazolyl-butanole, ein Nerfahren zu deren Herstellung und deren Verwendung als Mikrobizide.The present invention relates to new mercapto-triazolyl-butanols, a process for their preparation and their use as microbicides.
Es ist bereits bekannt geworden, daß zahlreiche Azolyl-butanole fungizide Eigen¬ schaften besitzen (vgl. EP-A 0 055 833 und EP-A 0 301 393). So läßt sich zum Beispiel 2,2-Dimethyl-3-hydroxy-4-( 1 ,2,4-triazol- 1 -yl)- 1 -(4-trifluormethoxy-phe- nyl)-pentan zur Bekämpfung von Pilzen verwenden. Die Wirksamkeit dieses Stoffes ist gut, läßt aber bei niedrigen Aufwandmengen in manchen Fällen zu wünschen übrig.It has already become known that numerous azolylbutanols have fungicidal properties (cf. EP-A 0 055 833 and EP-A 0 301 393). For example, 2,2-dimethyl-3-hydroxy-4- (1, 2,4-triazol-1-yl) -1 - (4-trifluoromethoxyphenyl) pentane can be used to combat fungi. The effectiveness of this substance is good, but leaves something to be desired in some cases at low application rates.
Es wurden nun neue Mercapto-triazolyl-butanole der FormelThere were now new mercapto-triazolyl-butanols of the formula
Figure imgf000003_0001
Figure imgf000003_0001
in welcherin which
R1 für Wasserstoff, Alkyl oder gegebenenfalls substituiertes Cycloalkyl steht,R 1 represents hydrogen, alkyl or optionally substituted cycloalkyl,
R2 für Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen steht,R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms,
X für Halogen, Alkyl mit 1 bis 4 Kohlenstoffatomen, Alkoxy mit 1 bis 4 Kohlenstoffatomen, Alkylthio mit 1 bis 4 Kohlenstoffatomen, Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 5 Halogenatomen, Halogenalkoxy mit 1 bis 4 Kohlenstoffatomen und 1 bis 5 Halogenatomen, Halogenalkyl- thio mit 1 bis 4 Kohlenstoffatomen und 1 bis 5 Halogenatomen, gegebe¬ nenfalls durch Halogen und/oder Alkyl mit 1 bis 4 Kohlenstoffatomen substituiertes Phenyl oder für gegebenenfalls durch Halogen und/oder Alkyl mit 1 bis 4 Kohlenstoffatomen substituiertes Phenoxy steht,X represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkyl thio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms or phenoxy optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms,
m für die Zahlen 0, 1, 2 oder 3 steht und Y für ein Sauerstoffatom, eine CH2-Gruppe oder eine direkte Bindung steht,m represents the numbers 0, 1, 2 or 3 and Y represents an oxygen atom, a CH 2 group or a direct bond,
sowie deren Säureadditions-Salze und Metallsalz-Komplexe gefunden.as well as their acid addition salts and metal salt complexes.
Die erfindungsgemäßen Stoffe enthalten mindestens zwei asymmetrisch substitu¬ ierte Kohlenstoffatome. Sie können daher in Form von Diastereomeren oder Enan- tiomeren anfallen. Die vorliegende Erfindung betrifft sowohl die einzelnen Iso¬ meren als auch deren Gemische.The substances according to the invention contain at least two asymmetrically substituted carbon atoms. They can therefore be obtained in the form of diastereomers or enantiomers. The present invention relates both to the individual isomers and to their mixtures.
Weiterhin wurde gefunden, daß man Mercapto-triazolyl-butanole der Formel (I) sowie deren Säureadditions-Salze und Metallsalz-Komplexe erhält, wenn man Triazolyl-butanole der FormelFurthermore, it was found that mercapto-triazolyl-butanols of the formula (I) and their acid addition salts and metal salt complexes are obtained if triazolyl-butanols of the formula
Figure imgf000004_0001
Figure imgf000004_0001
in welcherin which
R1, X, Y und m die oben angegebenen Bedeutungen haben,R 1 , X, Y and m have the meanings given above,
nacheinander mit starken Basen und Schwefel in Gegenwart eines Verdünnungs¬ mittels umsetzt und dann mit Wasser, gegebenenfalls in Gegenwart einer Säure hydrolysiert und gegebenenfalls die dabei entstehenden Verbindungen der Formelreacted successively with strong bases and sulfur in the presence of a diluent and then hydrolyzed with water, optionally in the presence of an acid, and, if appropriate, the compounds of the formula formed in the process
Figure imgf000004_0002
in welcher
Figure imgf000004_0002
in which
R1, X, Y und m die oben angegebenen Bedeutungen haben,R 1 , X, Y and m have the meanings given above,
mit Halogen-Verbindungen der Formel R3 - Hai (III)with halogen compounds of the formula R 3 - shark (III)
in welcherin which
R3 für Alkyl mit 1 bis 4 Kohlenstoffatomen steht undR 3 represents alkyl having 1 to 4 carbon atoms and
Hai für Chlor, Brom oder Iod steht,Shark represents chlorine, bromine or iodine,
in Gegenwart eines Säurebindemittels und in Gegenwart eines Verdünnungsmittels umsetzt,in the presence of an acid binder and in the presence of a diluent,
und gegebenenfalls anschließend an die so erhaltenen Verbindungen der Formel (I) eine Säure oder ein Metallsalz addiert.and optionally then adding an acid or a metal salt to the compounds of formula (I) thus obtained.
Schließlich wurde gefunden, daß die neuen Mercapto-triazolyl-butanole der Formel (I) sowie deren Säureadditions-Salze und Metallsalz-Komplexe sehr gute mikro- bizide Eigenschaften aufweisen und sowohl im Pflanzenschutz als auch im Mate¬ rialschutz eingesetzt werden können.Finally, it was found that the new mercapto-triazolylbutanols of the formula (I) and their acid addition salts and metal salt complexes have very good microbicidal properties and can be used both in crop protection and in material protection.
Überraschenderweise besitzen die erfindungsgemäßen Stoffe eine bessere mikro- bizide Wirksamkeit als die konstitutionell ähnlichsten, vorbekannten Verbindungen gleicher Wirkungsrichtung. So übertreffen die erfindungsgemäßen Stoffe das 2,2-Surprisingly, the substances according to the invention have a better microbicidal activity than the structurally most similar, known compounds of the same action. The substances according to the invention thus exceed the 2,2-
Dimethyl-3-hydroxy-4-( 1 ,2,4-triazol- 1 -yl)- 1 -(4-trifluormethoxy-phenyl)-pentan be¬ züglich der fungiziden Eigenschaften.Dimethyl-3-hydroxy-4- (1, 2,4-triazol-1-yl) -1 - (4-trifluoromethoxy-phenyl) -pentane with regard to the fungicidal properties.
Die erfindungsgemäßen Mercapto-triazolyl-butanole sind durch die Formel (I) allgemein definiert.The mercapto-triazolyl-butanols according to the invention are generally defined by the formula (I).
R1 steht vorzugsweise für Wasserstoff, geradkettiges oder verzweigtes Alkyl mit 1 bis 12 Kohlenstoffatomen oder für gegebenenfalls einfach bis dreifach, gleichartig oder verschieden durch Halogen und/oder Alkyl mit 1 bis 4 Kohlenstoffatomen substituiertes Cycloalkyl mit 3 bis 7 Kohlenstoff¬ atomen.R 1 preferably stands for hydrogen, straight-chain or branched alkyl having 1 to 12 carbon atoms or for optionally cycloalkyl having 3 to 7 carbon atoms which is monosubstituted to triple, identical or different, substituted by halogen and / or alkyl having 1 to 4 carbon atoms.
R2 steht vorzugsweise für Wasserstoff, Methyl oder Ethyl. X steht vorzugsweise für Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy,R 2 preferably represents hydrogen, methyl or ethyl. X preferably represents fluorine, chlorine, bromine, methyl, ethyl, methoxy,
Methylthio, Trichlormethyl, Trifluormethyl, Trifluormethoxy, Difluormeth- oxy, Trifluormethylthio, Phenyl oder Phenoxy.Methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl or phenoxy.
m steht auch vorzugsweise für die Zahlen 0, 1, 2 oder 3, wobei X für gleiche oder verschiedene Reste steht, wenn m für 2 oder 3 steht.m also preferably represents the numbers 0, 1, 2 or 3, where X represents the same or different radicals if m represents 2 or 3.
Y steht auch vorzugsweise für ein Sauerstoffatom, eine CH2-Gruppe oder eine direkte Bindung.Y also preferably represents an oxygen atom, a CH 2 group or a direct bond.
R1 steht besonders bevorzugt für Wasserstoff, geradkettiges oder verzweigtesR 1 particularly preferably represents hydrogen, straight-chain or branched
Alkyl mit 1 bis 6 Kohlenstoffatomen oder für jeweils gegebenenfalls ein- fach bis dreifach, gleichartig oder verschieden durch Fluor, Chlor, Brom,Alkyl having 1 to 6 carbon atoms or for each optionally single to triple, identical or different by fluorine, chlorine, bromine,
Methyl und/oder Ethyl substituiertes Cyclopropyl, Cyclopentyl oderMethyl and / or ethyl substituted cyclopropyl, cyclopentyl or
Cyclohexyl.Cyclohexyl.
R2 steht auch besonders bevorzugt für Wasserstoff, Methyl oder Ethyl.R 2 also particularly preferably represents hydrogen, methyl or ethyl.
X steht besonders bevorzugt für Fluor, Chlor, Brom, Methyl, Methoxy, Methylthio, Trichlormethyl, Trifluormethyl, Trifluormethoxy, Difluormeth- oxy, Trifluormethylthio, Phenyl oder Phenoxy.X particularly preferably represents fluorine, chlorine, bromine, methyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl or phenoxy.
m steht auch besonders bevorzugt für die Zahlen 0, 1, 2 oder 3, wobei X für gleiche oder verschiedene Reste steht, wenn m für 2 oder 3 steht.m also particularly preferably represents the numbers 0, 1, 2 or 3, where X represents the same or different radicals if m represents 2 or 3.
Y steht auch besonders bevorzugt für ein Sauerstoffatom, eine CH2-Gruppe oder eine direkte Bindung.Y also particularly preferably represents an oxygen atom, a CH 2 group or a direct bond.
Bevorzugte erfindungsgemäße Stoffe sind auch Additionsprodukte aus Säuren und denjenigen Mercapto-triazolyl-butanolen der Formel (I), in denen R1, R2, X, Y und m diejenigen Bedeutungen haben, die für diese Substituenten und diesen Index als bevorzugt genannt wurden.Preferred substances according to the invention are also addition products of acids and those mercapto-triazolylbutanols of the formula (I) in which R 1 , R 2 , X, Y and m have those meanings which have been mentioned as preferred for these substituents and this index.
Zu den Säuren, die addiert werden können, gehören vorzugsweise Halogenwasser¬ stoffsäuren, wie z.B. die Chlorwasserstoff säure und die Bromwasserstoffsäure, ins¬ besondere die Chlorwasserstoffsäure, ferner Phosphorsäure, Salpetersäure, mono- und bifunktionelle Carbonsäuren und Hydroxycarbonsäuren, wie z.B. Essigsäure, Maleinsäure, Bernsteinsäure, Fumarsäure, Weinsäure, Zitronensäure, Salicylsäure, Sorbinsäure und Milchsäure, sowie Sulfonsäuren, wie z.B. p-Toluolsulfonsäure und 1,5-Naphthalindisulfonsäure, oder Camphersulfonsäure, Saccharin und Thiosac- charin.The acids which can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, Maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids, such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid, or camphorsulfonic acid, saccharin and thiosaccharine.
Außerdem bevorzugte erfindungsgemäße Verbindungen sind Additionsprodukte aus Salzen von Metallen der II. bis IV. Haupt- und der I. und II. sowie IV. bis VIII. Nebengruppe des Periodensystems der Elemente und denjenigen Mercapto- triazolyl-butanolen der Formel (I), in denen R1, R2, X, Y und m diejenigen Be¬ deutungen haben, die für diese Substituenten und diesen Index als bevorzugt genannt wurden.In addition, preferred compounds according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. And IV. To VIII. Subgroup of the periodic table of the elements and those mercapto-triazolyl-butanols of the formula (I), in to which R 1 , R 2 , X, Y and m have the meanings which have been mentioned as preferred for these substituents and this index.
Hierbei sind Salze des Kupfers, Zinks, Mangans, Magnesiums, Zinns, Eisens und des Nickels besonders bevorzugt. Als Anionen dieser Salze kommen solche in Betracht, die sich von solchen Säuren ableiten, die zu physiologisch verträglichen Additionsprodukten fuhren. Besonders bevorzugte derartige Säuren sind in diesem Zusammenhang die Halogenwasserstoffsäuren, wie z.B. die Chlorwasserstoffsäure und die Bromwasserstoffsäure, ferner Phosphorsäure, Salpetersäure und Schwefel¬ säure.Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to physiologically tolerable addition products. Particularly preferred such acids in this connection are the hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.
Die erfindungsgemäßen Mercapto-triazolyl-butanole der Formel (I), in denen R2 für Wasserstoff steht, können in der "Mercapto"-Form der FormelThe mercapto-triazolylbutanols of the formula (I) in which R 2 is hydrogen can be in the "mercapto" form of the formula
Figure imgf000007_0001
oder in der tautomeren "Thiono"-Form der Formel
Figure imgf000007_0001
or in the tautomeric "thiono" form of the formula
Figure imgf000007_0002
vorliegen. Der Einfachheit halber wird jeweils nur die "Mercapto"-Form aufge¬ führt.
Figure imgf000007_0002
available. For the sake of simplicity, only the "mercapto" form is listed in each case.
Als Beispiele für erfindungsgemäße Stoffe seien die in der folgenden Tabelle aufgeführten Mercapto-triazolyl-butanole genannt. The mercapto-triazolylbutanols listed in the following table may be mentioned as examples of substances according to the invention.
Tabelle 1Table 1
Figure imgf000009_0001
Figure imgf000009_0001
-^m Y R1 R2 - ^ m YR 1 R 2
4-C1 CH2 H H4-C1 CH 2 HH
4-CF3 CH2 H H4-CF 3 CH 2 HH
4-OCF3 CH2 H H4-OCF 3 CH 2 HH
2,4-Cl2 CH2 H H2,4-Cl 2 CH 2 HH
4-CH3 CH2 H H4-CH 3 CH 2 HH
2-C1 CH2 H H2-C1 CH 2 HH
2-F CH2 H H2-F CH 2 HH
4-F CH2 H H4-F CH 2 HH
2-OCHF2 CH2 H H2-OCHF 2 CH 2 HH
4-C1 O H H4-C1 O H H
4-CF3 O H H4-CF 3 OHH
4-OCF3 O H H4-OCF 3 OHH
2,4-Cl2 O H H2,4-Cl 2 OHH
4-CH3 O H H4-CH 3 OHH
2-C1 O H H2-C1 O H H
2-F O H H2-F O H H
4-F O H H4-F O H H
2-OCHF, O H H : Tabelle 1 (Fortsetzung)2-OCHF, OHH: Table 1 (continued)
Xm Y R1 R2 Xm YR 1 R 2
4-C1 - H H4-C1 - H H
4-CF3 - H H4-CF 3 - HH
4-OCF3 - H H4-OCF 3 - HH
2,4-Cl2 - H H2,4-Cl 2 - HH
4-CH3 - H H4-CH 3 - HH
2-C1 - H H2-C1 - H H
2-F - H H2-F - H H
4-F - H H4-F - H H
2-OCHF2 - H H2-OCHF 2 - HH
4-C1 CH2 -CH3 H4-C1 CH 2 -CH 3 H
4-CF3 CH2 -CH3 H4-CF 3 CH 2 -CH 3 H
4-OCF3 CH2 -CH3 H4-OCF 3 CH 2 -CH 3 H
2,4-Cl2 CH2 -CH3 H2,4-Cl 2 CH 2 -CH 3 H
4-CH3 CH2 -CH3 H4-CH 3 CH 2 -CH 3 H
2-C1 CH2 -CH3 H2-C1 CH 2 -CH 3 H
2-F CH2 -CH3 H2-F CH 2 -CH 3 H
4-F CH2 -CH3 H4-F CH 2 -CH 3 H
2-OCHF2 CH2 -CH3 H2-OCHF 2 CH 2 -CH 3 H
4-C1 0 -CH3 H4-C1 0 -CH 3 H
4-CF3 O -CH3 H4-CF 3 O -CH 3 H
2,4-Cl2 O -CH3 H2,4-Cl 2 O -CH 3 H
4-OCF3 O -CH3 H Tabelle 1 (Fortsetzung)4-OCF 3 O -CH 3 H Table 1 (continued)
Xm Y R1 R2 X m YR 1 R 2
2-F O -CH3 H2-FO -CH 3 H
2-OCHF2 O -CH3 H2-OCHF 2 O -CH 3 H
4-C1 - -CH3 H4-C1 - -CH 3 H
4-CF3 - -CH3 H4-CF 3 - -CH 3 H
2,4-Cl2 - -CH3 H2,4-Cl 2 - -CH 3 H
4-OCF3 - -CH3 H4-OCF 3 - -CH 3 H
2-F - -CH3 H2-F - -CH 3 H
2-OCHF2 - -CH3 H2-OCHF 2 - -CH 3 H
4-C1 CH2 C4H9-n H4-C1 CH 2 C 4 H 9 -n H
2,4-Cl2 CH2 -CH(CH3)2 H2,4-Cl 2 CH 2 -CH (CH 3 ) 2 H
4-OCF3 CH2 -C(CH3)3 H4-OCF 3 CH 2 -C (CH 3 ) 3 H
4-C1 CH2 H4-C1 CH 2 H
-<- <
4-C1 CH2 vCi H4-C1 CH 2 v Ci H
0101
4-C1 CH2 H4-C1 CH 2 H
4-C1 CH2 H4-C1 CH 2 H
^ >^>
2,4,6-Cl3 CH2 -CH3 H2,4,6-Cl 3 CH 2 -CH 3 H
~o CH2 -CH3 H Tabelle 1 (Fortsetzung)~ o CH 2 -CH 3 H Table 1 (continued)
χm Y R1 R2 χ m YR 1 R 2
CH2 -CH3 HCH 2 -CH 3 H
4_o-^ 4 _o- ^
4-Cl CH2 H "CH3 4-Cl CH 2 H "CH 3
4-CF3 CH2 H -CH3 4-CF 3 CH 2 H -CH 3
4-OCF3 CH2 H -CH3 4-OCF 3 CH 2 H -CH 3
2,4-Cl2 CH2 H -CH3 2,4-Cl 2 CH 2 H -CH 3
4-CH3 CH2 H -CH3 4-CH 3 CH 2 H -CH 3
2-C1 CH2 H -CH3 2-C1 CH 2 H -CH 3
2-F CH2 H -CH3 2-F CH 2 H -CH 3
4-F CH2 H -CH3 4-F CH 2 H -CH 3
2-OCHF2 CH2 H -CH3 2-OCHF 2 CH 2 H -CH 3
4-Cl O H -CH3 4-Cl OH -CH 3
4-CF3 O H -CH3 4-CF 3 OH -CH 3
4-OCF3 O H -CH3 4-OCF 3 OH -CH 3
2,4-Cl2 O H -CH3 2,4-Cl 2 OH -CH 3
4-CH3 O H -CH3 4-CH 3 OH -CH 3
2-C1 O H -CH3 2-C1 OH -CH 3
2-F O H -CH3 2-FOH -CH 3
4-F O H -CH3 4-FOH -CH 3
2-OCHF2 O H -CH3 2-OCHF 2 OH -CH 3
4-Cl - H -CH3 4-Cl - H -CH 3
4-CF3 - H -CH3 4-CF 3 - H -CH 3
4-OCF3 - H -CH3 Tabelle 1 (Fortsetzung)4-OCF 3 - H -CH 3 Table 1 (continued)
χm Y R1 R2 χ m YR 1 R 2
2,4-Cl2 - H -CH3 2,4-Cl 2 - H -CH 3
4-CH3 - H -CH3 4-CH 3 - H -CH 3
2-C1 - H -CH3 2-C1 - H -CH 3
2-F - H -CH3 2-F - H -CH 3
4-F - H -CH3 4-F - H -CH 3
2-OCHF2 - H -CH3 2-OCHF 2 - H -CH 3
4-Cl CH2 -CH3 -CH3 4-Cl CH 2 -CH 3 -CH 3
4-CF3 CH2 -CH3 -CH3 4-CF 3 CH 2 -CH 3 -CH 3
4-OCF3 CH2 -CH3 -CH3 4-OCF 3 CH 2 -CH 3 -CH 3
2,4-Cl2 CH2 -CH3 -CH3 2,4-Cl 2 CH 2 -CH 3 -CH 3
4-CH3 CH2 -CH3 -CH3 4-CH 3 CH 2 -CH 3 -CH 3
2-C1 CH2 τCH3 -CH3 2-C1 CH 2 τCH 3 -CH 3
2-F CH2 -CH3 -CH3 2-F CH 2 -CH 3 -CH 3
4-F CH2 -CH3 -CH3 4-F CH 2 -CH 3 -CH 3
2-OCHF2 CH2 -CH3 -CH3 2-OCHF 2 CH 2 -CH 3 -CH 3
4-Cl O -CH3 -CH3 4-Cl O -CH 3 -CH 3
4-CF3 O -CH3 -CH3 4-CF 3 O -CH 3 -CH 3
2,4-Cl2 O -CH3 -CH3 2,4-Cl 2 O -CH 3 -CH 3
4-OCF3 O -CH3 -CH3 4-OCF 3 O -CH 3 -CH 3
2-F O -CH3 -CH3 2-FO -CH 3 -CH 3
2-OCHF2 O -CH3 -CH3 2-OCHF 2 O -CH 3 -CH 3
4-Cl - -CH3 -CH3 4-Cl - -CH 3 -CH 3
4-CF3 - -CH3 -CH3 Tabelle 1 (Fortsetzung)4-CF 3 - -CH 3 -CH 3 Table 1 (continued)
Figure imgf000014_0001
Verwendet man 2,2-Dimethyl-3-hydroxy-4-( 1 ,2,4-triazol- 1 -yl)- 1 -(4-trifluormethoxy- phenyl)-pentan als Ausgangsstoff, n-Butyl-lithium als starke Base und Schwefel- Pulver als Reaktionskomponente, so kann der Verlauf der ersten Stufe des erfindungsgemäßen Verfahrens durch das folgende Formelschema veranschaulicht werden:
Figure imgf000014_0001
If 2,2-dimethyl-3-hydroxy-4- (1, 2,4-triazol-1-yl) -1 - (4-trifluoromethoxy-phenyl) -pentane is used as the starting material, n-butyl lithium as the strong base and sulfur powder as a reaction component, the course of the first stage of the process according to the invention can be illustrated by the following formula:
1.Butyl-Iithium 2.Schwefel
Figure imgf000015_0001
1. Butyl Iithium 2. Sulfur
Figure imgf000015_0001
F3C — O— fl -CH—F 3 C - O— fl -CH—
Figure imgf000015_0002
Figure imgf000015_0002
Verwendet man 2,2-Dimethyl-3-hydroxy-4-(5-mercapto- 1 ,2,4-triazol- 1 -yl)- 1 -(4-tri- fluormethoxy-phenyl)-pentan als Ausgangsstoff und Methyliodid als Reaktions¬ komponente, so kann der Verlauf der zweiten Stufe des erfindungsgemäßen Ver- fahrens durch das folgende Formelschema veranschaulicht werden:If one uses 2,2-dimethyl-3-hydroxy-4- (5-mercapto-1, 2,4-triazol-1-yl) - 1 - (4-trifluoromethoxy-phenyl) -pentane as starting material and methyl iodide as Reaction component, the course of the second stage of the process according to the invention can be illustrated by the following formula:
Figure imgf000015_0003
Figure imgf000015_0003
Figure imgf000015_0004
Die bei der Durchführung des erfindungsgemäßen Verfahrens als Ausgangsstoffe benötigten Triazolyl-butanole sind durch die Formel (II) allgemein definiert. In dieser Formel haben R1, X, Y und m vorzugsweise diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Stoffe der Formel (I) für diese Reste und diesen Index als bevorzugt genannt wurden.
Figure imgf000015_0004
Formula (II) provides a general definition of the triazolylbutanols required as starting materials when carrying out the process according to the invention. In this formula, R 1 , X, Y and m preferably have those meanings which have already been mentioned as preferred for these radicals and this index in connection with the description of the substances of the formula (I) according to the invention.
Die Triazolyl-butanole der Formel (II) sind bekannt oder lassen sich nach bekann¬ ten Verfahren herstellen (vgl. EP-A 0 055 833 und EP-A 0 301 393).The triazolylbutanols of the formula (II) are known or can be prepared by known processes (cf. EP-A 0 055 833 and EP-A 0 301 393).
Als Basen kommen bei der Durchführung der ersten Stufe des erfindungsgemäßen Verfahrens alle für derartige Reaktionen üblichen, starken Alkalimetall-Basen in Betracht. Vorzugsweise verwendbar sind n-Butyl-lithium, Lithium-diisopropyl- amid, Natriumhydrid, Natriumamid und auch Kalium-tert.-butylat im Gemisch mit Tetramethylethylen-diamin (= TMEDA).Suitable bases for carrying out the first stage of the process according to the invention are all strong alkali metal bases which are customary for such reactions. Preferably used are n-butyl lithium, lithium diisopropyl amide, sodium hydride, sodium amide and also potassium tert-butoxide in a mixture with tetramethyl ethylene diamine (= TMEDA).
Bei der Durchführung der ersten Stufe des erfindungsgemäßen Verfahrens kom¬ men alle für derartige Umsetzungen üblichen inerten organischen Solventien als Verdünnungsmittel in Betracht. Vorzugsweise verwendbar sind Ether, wie Tetrahy- drofuran, Dioxan, Diethylether und 1,2-Dimethoxyethan, ferner flüssiger Ammo¬ niak oder auch stark polare Solventien, wie Dimethylsulfoxid.When carrying out the first stage of the process according to the invention, all inert organic solvents customary for such reactions can be considered as diluents. Ethers such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane, preferably liquid ammonia or strongly polar solvents such as dimethyl sulfoxide are preferably usable.
Schwefel wird vorzugsweise in Form von Pulver eingesetzt. Zur Hydrolyse verwendet man bei der Durchführung der ersten Stufe des erfindungsgemäßen Verfahrens Wasser, gegebenenfalls in Gegenwart einer Säure. In Frage kommen hierbei alle für derartige Umsetzungen üblichen anorganischen oder organischen Säuren. Vorzugsweise verwendbar sind Essigsäure, verdünnte Schwefelsäure und verdünnte Salzsäure. Es ist jedoch auch möglich, die Hydrolyse mit wäßriger Ammoniumchlorid-Lösung durchzuführen.Sulfur is preferably used in the form of powder. For the hydrolysis, water is used when carrying out the first stage of the process according to the invention, if appropriate in the presence of an acid. All inorganic or organic acids customary for such reactions can be considered. Acetic acid, dilute sulfuric acid and dilute hydrochloric acid are preferably usable. However, it is also possible to carry out the hydrolysis with an aqueous ammonium chloride solution.
Die Reaktionstemperaturen können bei der Durchführung der ersten Stufe des erfindungsgemäßen Verfahrens innerhalb eines bestimmten Bereiches variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -70°C und +20°C, vorzugsweise zwischen -70°C und 0°C.The reaction temperatures can be varied within a certain range when carrying out the first stage of the process according to the invention. In general, temperatures between -70 ° C and + 20 ° C, preferably between -70 ° C and 0 ° C.
Bei der Durchführung aller Schritte des erfindungsgemäßen Verfahrens arbeitet man im allgemeinen unter Normaldruck. Bei der Durchführung der ersten Stufe des erfindungsgemäßen Verfahrens setzt man auf 1 Mol an Triazolyl-butanol der Formel (II) im allgemeinen 2 bis 3 Äqui¬ valente, vorzugsweise 2,0 bis 2,5 Äquivalente, an starker Base und anschließend eine äquivalente Menge oder auch einen Überschuß an Schwefel ein. Die Um- setzung kann unter Schutzgas-atmosphäre, z.B. unter Stickstoff oder Argon, vorge¬ nommen werden. Die Aufarbeitung erfolgt nach üblichen Methoden. Im allge¬ meinen geht man so vor, daß man das Reaktionsgemisch mit einem in Wasser wenig löslichen organischen Solvens extrahiert, die vereinigten organischen Phasen trocknet und einengt und den verbleibenden Rückstand gegebenenfalls durch Umkristallisation und/oder Chromatographie reinigt.When carrying out all steps of the method according to the invention, the procedure is generally carried out under normal pressure. When carrying out the first stage of the process according to the invention, 2 to 3 equivalents, preferably 2.0 to 2.5 equivalents, of strong base and then an equivalent amount are generally employed per mole of triazolylbutanol of the formula (II) or an excess of sulfur. The reaction can be carried out under a protective gas atmosphere, for example under nitrogen or argon. The processing takes place according to usual methods. In general, the procedure is that the reaction mixture is extracted with an organic solvent which is sparingly soluble in water, the combined organic phases are dried and concentrated, and the remaining residue is optionally purified by recrystallization and / or chromatography.
Die bei der Durchführung der zweiten Stufe des erfindungsgemäßen Verfahrens als Ausgangssubstanzen benötigten Verbindungen der Formel (Ia) sind erfindungs¬ gemäße Stoffe.The compounds of the formula (Ia) required as starting substances when carrying out the second stage of the process according to the invention are substances according to the invention.
Die bei der Durchführung des erfindungsgemäßen Verfahrens in der zweiten Stufe als Reaktionskomponenten benötigten Halogen- Verbindungen sind durch die For¬ mel (III) allgemein definiert.The halogen compounds required as reaction components in carrying out the process according to the invention in the second stage are generally defined by the formula (III).
RΛ steht vorzugsweise für Methyl oder Ethyl.R Λ is preferably methyl or ethyl.
Hai steht auch vorzugsweise für Chlor, Brom oder Iod.Shark also preferably represents chlorine, bromine or iodine.
Die Halogen- Verbindungen der Formel (III) sind bekannt.The halogen compounds of the formula (III) are known.
Als Säurebindemittel kommen bei der Durchführung der zweiten Stufe des erfin¬ dungsgemäßen Verfahrens alle üblichen anorganischen oder organischen Basen in Frage. Vorzugsweise verwendbar sind Erdalkali- oder Alkalimetallhydroxide wie Natriumhydroxid, Calciumhydroxid, Kaliumhydroxid, oder auch Ammoniumhy¬ droxid, Alkalimetallcarbonate, wie Natriumcarbonat, Kaliumcarbonat, Kaliumhy- drogencarbonat, Natriumhydrogencarbonat, Alkali- oder Erdalkalimetallacetate wieSuitable acid binders for carrying out the second stage of the process according to the invention are all customary inorganic or organic bases. Alkaline earth metal or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali metal or alkaline earth metal acetates such as
Natriumacetat, Kaliumacetat, Calciumacetat, sowie tertiäre Amine, wie Trimethyl- amin, Triethylamin, Tributylamin, N,N-Dimethylanilin, Pyridin, N-Methylpipe- ridin, N,N-Dimethylaminopyridin, Diazabicyclooctan (DABCO), Diazabicyc- lononen (DBN) oder Diazabicycloundecen (DBU). Als Verdünnungsmittel kommen bei der Durchführung der zweiten Stufe des erfindungsgemäßen Verfahrens alle für derartige Umsetzungen üblichen, inerten organischen Solventien in Betracht. Vorzugsweise verwendbar sind Ether, wie Diethylether, Methyl-tert.-butyl-ether, Ethylenglykol-dimethylether, Tetrahydro- furan und Dioxan, ferner Nitrile, wie Acetonitril, und außerdem stark polareSodium acetate, potassium acetate, calcium acetate and tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). Suitable diluents for carrying out the second stage of the process according to the invention are all inert organic solvents which are customary for such reactions. Ethers such as diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane, furthermore nitriles such as acetonitrile and also strongly polar are preferably usable
Solventien, wie Dimethylsulfoxid oder Dimethylformamid.Solvents such as dimethyl sulfoxide or dimethylformamide.
Die Reaktionstemperaturen können bei der Durchführung der zweiten Stufe des erfindungsgemäßen Verfahrens innerhalb eines größeren Bereiches variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0°C und 120°C, vorzugs- weise zwischen 20°C und 100°C.The reaction temperatures can be varied within a substantial range when carrying out the second stage of the process according to the invention. In general, temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 100 ° C.
Bei der Durchführung der zweiten Stufe des erfindungsgemäßen Verfahrens setzt man auf 1 Mol an Mercapto-triazolyl-butanol der Formel (Ia) im allgemeinen 1 bis 2 Mol an Halogen- Verbindung der Formel (III) sowie eine äquivalente Menge oder auch einen Überschuß an Säurebindemittel ein. Die Aufarbeitung erfolgt nach üblichen Methoden. Im allgemeinen geht man so vor, daß man das Reaktionsge¬ misch mit wäßriger Base und einem mit Wasser wenig mischbaren organischen Lösungsmittel versetzt, die organische Phase abtrennt, trocknet und einengt. Das erhaltene Produkt kann gegebenenfalls nach üblichen Methoden, z.B. durch Um- kristallisation, von noch vorhandenen Verunreinigungen befreit werden.When carrying out the second stage of the process according to the invention, 1 to 2 mol of halogen compound of the formula (III) and an equivalent amount or also an excess of acid binder are generally employed per mol of mercapto-triazolylbutanol of the formula (Ia) on. The processing takes place according to usual methods. The general procedure is to add aqueous base and a water-immiscible organic solvent to the reaction mixture, and to separate, dry and concentrate the organic phase. The product obtained can optionally be processed by conventional methods, e.g. by recrystallization, from any impurities still present.
Die nach dem erfindungsgemäßen Verfahren erhältlichen Mercapto-triazolyl-buta¬ nole der Formel (I) können in Säureadditions-Salze oder Metallsalz-Komplexe überführt werden.The mercapto-triazolylbutanols of the formula (I) obtainable by the process according to the invention can be converted into acid addition salts or metal salt complexes.
Zur Herstellung von Säureadditions-Salzen der Verbindungen der Formel (I) kommen vorzugsweise diejenigen Säuren in Frage, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Säureadditions-Salze als bevorzugteFor the preparation of acid addition salts of the compounds of the formula (I), preference is given to those acids which are already preferred in connection with the description of the acid addition salts according to the invention
Säuren c ge-nannt wurden.Acids c were named.
Die Säureadditions-Salze der Verbindungen der Formel (I) können in einfacher Weise nach üblichen Salzbildungsmethoden, z.B. durch Lösen einer Verbindung der Formel (I) in einem geeigneten inerten Lösungsmittel und Hinzufügen der Säure, z.B. Chlorwasserstoffsäure, erhalten werden und in bekannter Weise, z.B. durch Abfiltrieren, isoliert und gegebenenfalls durch Waschen mit einem inerten organischen Lösungsmittel gereinigt werden. Zur Herstellung von Metall salz-Komplexen der Verbindungen der Formel (I) kommen vorzugsweise diejenigen Salze von Metallen in Frage, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Metall salz-Kom- plexe als bevorzugte Metallsalze genannt wurden.The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and in a known manner, for example by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent. For the preparation of metal salt complexes of the compounds of the formula (I), preference is given to those salts of metals which have already been mentioned as preferred metal salts in connection with the description of the metal salt complexes according to the invention.
Die Metallsalz-Komplexe der Verbindungen der Formel (I) können in einfacherThe metal salt complexes of the compounds of formula (I) can in simpler
Weise nach üblichen Verfahren erhalten werden, so z.B. durch Lösen des Metallsalzes in Alkohol, z.B. Ethanol und Hinzufügen zu Verbindungen der Formel (I). Man kann Metallsalz-Komplexe in bekannter Weise, z.B. durch Abfiltrieren, isolieren und gegebenenfalls durch Umkristallisation reinigen.Can be obtained by conventional methods, e.g. by dissolving the metal salt in alcohol, e.g. Ethanol and adding to compounds of formula (I). Metal salt complexes can be prepared in a known manner, e.g. by filtering, isolating and, if necessary, cleaning by recrystallization.
Die erfindungsgemäßen Wirkstoffe weisen eine starke mikrobizide Wirkung auf und können zur Bekämpfung unerwünschter Mikroorganismen, wie Fungi und Bakterien, im Pflanzenschutz und im Materialschutz eingesetzt werden.The active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.
Fungizide werden im Pflanzenschutz eingesetzt zur Bekämpfung von Plasmodio- phoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.Fungicides are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
Beispielhaft aber nicht begrenzend seien einige Erreger von pilzlichen und bakteriellen Erkrankungen, die unter die oben aufgezählten Oberbegriffe fallen, genannt:Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas-Arten, wie Xanthomonas oryzae; Pseudomonas- Arten, wie Pseudomonas lachrymans;Xanthomonas species, such as Xanthomonas oryzae; Pseudomonas species, such as Pseudomonas lachrymans;
Erwinia-Arten, wie Erwinia amylovora;Erwinia species, such as Erwinia amylovora;
Pythium-Arten, wie Pythium ultimum;Pythium species, such as Pythium ultimum;
Phytophthora- Arten, wie Phytophthora infestans;Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora-Arten, wie Pseudoperonospora humuli oder Pseudoperonospora cubensis;Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara- Arten, wie Plasmopara viticola;Plasmopara species, such as Plasmopara viticola;
Peronospora-Arten, wie Peronospora pisi oder P. brassicae;Peronospora species, such as Peronospora pisi or P. brassicae;
Erysiphe-Arten, wie Erysiphe graminis;Erysiphe species, such as Erysiphe graminis;
Sphaerotheca-Arten, wie Sphaerotheca fuliginea; Podosphaera-Arten, wie Podosphaera leucotricha;Sphaerotheca species, such as Sphaerotheca fuliginea; Podosphaera species, such as Podosphaera leucotricha;
Venturia-Arten, wie Venturia inaequalis;Venturia species, such as Venturia inaequalis;
Pyrenophora- Arten, wie Pyrenophora teres oder P. graminea; (Koni dienform: Drechslera, Syn: Helminthosporium);Pyrenophora species, such as Pyrenophora teres or P. graminea; (Coni form: Drechslera, Syn: Helminthosporium);
Cochliobolus-Arten, wie Cochliobolus sativus;Cochliobolus species, such as Cochliobolus sativus;
(Konidienform: Drechslera, Syn: Helminthosporium);(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces-Arten, wie Uromyces appendiculatus; Puccinia-Arten, wie Puccinia recondita;Uromyces species, such as Uromyces appendiculatus; Puccinia species, such as Puccinia recondita;
Tilletia-Arten, wie Tilletia caries;Tilletia species, such as Tilletia caries;
Ustilago-Arten, wie Ustilago nuda oder Ustilago avenae;Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia-Arten, wie Pellicularia sasakii;Pellicularia species, such as Pellicularia sasakii;
Pyricularia-Arten, wie Pyricularia oryzae; Fusarium- Arten, wie Fusarium culmorum;Pyricularia species, such as Pyricularia oryzae; Fusarium species, such as Fusarium culmorum;
Botrytis-Arten, wie Botrytis cinerea;Botrytis species, such as Botrytis cinerea;
Septoria-Arten, wie Septoria nodorum;Septoria species, such as Septoria nodorum;
Leptosphaeria- Arten, wie Leptosphaeria nodorum;Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora- Arten, wie Cercospora canescens; Alternaria- Arten, wie Alternaria brassicae;Cercospora species, such as Cercospora canescens; Alternaria species, such as Alternaria brassicae;
Pseudocercosporella-Arten, wie Pseudocercosporella herpotrichoides.Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.
Die gute Pflanzenverträglichkeit der Wirkstoffe in den zur Bekämpfung von Pflan¬ zenkrankheiten notwendigen Konzentrationen erlaubt eine Behandlung von ober¬ irdischen Pflanzenteilen, von Pflanz- und Saatgut und des Bodens.The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds and of the soil.
Die erfindungsgemäßen Wirkstoffe eignen sich insbesondere zur Bekämpfung vonThe active compounds according to the invention are particularly suitable for combating
Pyricularia oryzae und Pellicularia sasakii an Reis sowie zur Bekämpfung von Ge¬ treidekrankheiten, wie Pseudocercosporella, Erysiphe- und Fusarium-Arten. Außer¬ dem lassen sich die erfindungsgemäßen Stoffe sehr gut gegen Venturia und Sphae- rotheca einsetzen. Sie besitzen darüber hinaus auch eine sehr gute in-vitro Wir- kung.Pyricularia oryzae and Pellicularia sasakii on rice and for combating cereal diseases, such as Pseudocercosporella, Erysiphe and Fusarium species. In addition, the substances according to the invention can be used very well against Venturia and Sphae rotheca. They also have a very good in vitro effect.
Im Materialschutz lassen sich die erfindungsgemäßen Stoffe zum Schutz von technischen Materialien gegen Befall und Zerstörung durch unerwünschte Mikro¬ organismen einsetzen.In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
Unter technischen Materialien sind im vorliegenden Zusammenhang nichtlebende Materialien zu verstehen, die für die Verwendung in der Technik zubereitet worden sind. Beispielsweise können technische Materialien, die durch erfindungs¬ gemäße Wirkstoffe vor mikrobieller Veränderung oder Zerstörung geschützt werden sollen, Klebstoffe, Leime, Papier und Karton, Textilien, Leder, Holz, Anstrichmittel und Kunststoffartikel, Kühlschmierstoffe und andere Materialien sein, die von Mikroorganismen befallen oder zersetzt werden können. Im Rahmen der zu schützenden Materialien seien auch Teile von Produktionsanlagen, bei¬ spielsweise Kühlwasserkreisläufe, genannt, die durch Vermehrung von Mikro- Organismen beeinträchtigt werden können. Im Rahmen der vorliegenden Erfindung seien als technische Materialien vorzugsweise Klebstoffe, Leime, Papiere und Kartone, Leder, Holz, Anstrichmittel, Kühl Schmiermittel und Wärmeübertragungs¬ flüssigkeiten genannt, besonders bevorzugt Holz.In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention, adhesives, glues, paper and cardboard, textiles, leather, wood, Paints and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, which may be impaired by the multiplication of microorganisms, may also be mentioned. Within the scope of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.
Als Mikroorganismen, die einen Abbau oder eine Veränderung der technischen Materialien bewirken können, seien beispielsweise Bakterien, Pilze, Hefen, Algen und Schleimorganismen genannt. Vorzugsweise wirken die erfindungsgemäßen Wirkstoffe gegen Pilze, insbesondere Schimmelpilze, holzverfärbende und holz¬ zerstörende Pilze (Basidiomyceten) sowie gegen Schleimorganismen und Algen.Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
Es seien beispielsweise Mikroorganismen der folgenden Gattungen genannt:For example, microorganisms of the following genera may be mentioned:
Alternaria, wie Alternaria tenuis,Alternaria, such as Alternaria tenuis,
Aspergillus, wie Aspergillus niger,Aspergillus, such as Aspergillus niger,
Chaetomium, wie Chaetomium globosum,Chaetomium, like Chaetomium globosum,
Coniophora, wie Coniophora puetana,Coniophora, such as Coniophora puetana,
Lentinus, wie Lentinus tigrinus, Penicillium, wie Penicillium glaucum,Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum,
Polyporus, wie Polyporus versicolor,Polyporus, such as Polyporus versicolor,
Aureobasidium, wie Aureobasidium pullulans,Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, wie Sclerophoma pityophila,Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, wie Trichoderma viride, Escherichia, wie Escherichia coli,Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli,
Pseudomonas, wie Pseudomonas aeruginosa,Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, wie Staphylococcus aureus.Staphylococcus, such as Staphylococcus aureus.
Die Wirkstoffe können in Abhängigkeit von ihren jeweiligen physikalischen und/oder chemischen Eigenschaften in übliche Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate,Depending on their respective physical and / or chemical properties, the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules,
Aerosole, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saat¬ gut, sowie ULV-Kalt- und Warmnebel-Formulierungen. Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermi¬ schen 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 wie Alkohole als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkyl- naphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlen¬ wasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssig¬ keiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe kommen in Frage: z.B. natür¬ liche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hoch¬ disperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen- Fettalkohol-Ether, z.B. Alkyl arylpolyglykol-Ether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.Aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm mist formulations. These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. If water is used as an extender, organic solvents such as alcohols can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol 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 liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; The following are suitable as solid carriers: for example natural rock powder, such as kaolins, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natür¬ liche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine, und synthetische Phospholipide. Wei- tere Additive können mineralische und vegetabile Öle sein. Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metal lphthalo- cyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils. Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal lphthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
Die Formulierungen enthalten im Pflanzenschutz im allgemeinen zwischen 0,1 undIn crop protection, the formulations generally contain between 0.1 and
95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.95 percent by weight of active ingredient, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können bei Verwendung im Pflanzenschutz in den Formulierungen in Mischung mit bekannten Fungiziden, Bakteriziden, Akariziden, Nematiziden oder Insektiziden eingesetzt werden, um so z.B. das Wir- kungsspektrum zu verbreitern oder Resistenzentwicklungen vorzubeugen. In manchen Fällen treten auch synergistische Effekte auf.When used in crop protection, the active compounds according to the invention can be used in the formulations in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of effects or to prevent the development of resistance. In some cases, synergistic effects also occur.
Für die Mischungen kommen beispielsweise folgende Stoffe in Frage.The following substances are suitable for the mixtures, for example.
Fungizide:Fungicides:
2-Aminobutan; 2-Anilino-4-methyl-6-cyclopropyl-pyrimidin; 2',6'-Dibromo-2-me- thyl^'-trifluoromethoxy^'-trifluoro-methyl-l^-thiazol-S-carboxanilid; 2,6-Dichlo- ro-N-(4-trifluoromethylbenzyl)-benzamid; (E)-2-Methoximino-N-methyl-2-(2-phen- oxyphenyl)-acetamid; 8-Hydroxychinolinsulfat; Methyl-(E)-2-{2-[6-(2-cyanophen- oxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylat; Methyl-(E)-methoximino- [alpha-(o-tolyloxy)-o-tolyl]-acetat; 2-Phenylphenol (OPP), Aldimorph, Ampro- pylfos, Anilazin, Azaconazol,2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl ^' - trifluoromethoxy ^ '- trifluoro-methyl-l ^ -thiazole-S-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calciumpolysulfid, Captafol, Captan, Carbendazim, Carboxin, Chinomethionat (Quinomethionat), Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinat, Cufraneb, Cymoxanil, Cyproconazole, Cyprofuram,Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, Diclobutrazol, Diclofluanid, Diclomezin, Dicloran, Diethofencarb, Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Dinocap, Diphenyl- amin, Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon, Edifenphos, Epoxyconazole, Ethirimol, Etridiazol, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin,Dichlorophen, diclobutrazol, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, Ditalimfos, dithianon, dodine, Drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, Fenbuconazole, fenfuram, Fenitropan, fenpiclonil, fenpropidin,
Fenpropimorph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl-Aluminium, Fthalide, Fuberidazol, Furalaxyl,Fenpropimorph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, folpet, fosetyl aluminum, fthalides, fuberidazole, furalaxyl,
Furmecyclox,Furmecyclox,
Guazatine,Guazatine,
Hexachlorobenzol, Hexaconazol, Hymexazol, Imazalil, Imibenconazol, Iminoctadin, Iprobenfos (IBP), Iprodion, Isoprothiolan,Hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, Iprobefos (IBP), iprodione, isoprothiolan,
Kasugamycin, Kupfer-Zubereitungen, wie: Kupferhydroxid, Kupfernaphthenat,Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate,
Kupferoxychlorid, Kupfersulfat, Kupferoxid, Oxin-Kupfer und Bordeaux- Mischung,Copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel-dimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol,Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,
Probenazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone,
Quintozen (PCNB),Quintozen (PCNB),
Schwefel und Schwefel-Zubereitungen,Sulfur and sulfur preparations,
Tebuconazol, Tecloftalam, Tecnazen, Tetraconazol, Thiabendazol, Thicyofen,Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,
Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin,Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin,
Triticonazol,Triticonazole,
Validamycin A, Vinclozolin,Validamycin A, vinclozolin,
Zineb, Ziram.Zineb, ziram.
Bakterizide:Bactericides:
Bronopol, Dichlorophen, Nitrapyrin, Nickel-Dimethyldithiocarbamat, Kasugamy¬ cin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy¬ cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insektizide / Akarizide / Nematizide:Insecticides / acaricides / nematicides:
Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha- methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M,Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alpha-methrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,
Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Buto- carboxim, Butylpyridaben,Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 4 19, CGA 1 84699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos,Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 4 19, CGA 1 84699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos,
Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion,Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion,
Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,Diflubenzuron, dimethoate, dimethylvinphos, dioxathione, disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb,Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb,
Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximat, fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinat, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathlocophoside, ixfaphosacidos, hafaftenociazurid, hafafloxazurid, iq Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyd, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, NitenpyramMalathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram
Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos, RH 5992,Quinalphos, RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb,Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb,
Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, XMC, Xylylcarb, Zetamethrin.Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb, Vamidothione, XMC, xylylcarb, zetamethrin.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Herbiziden oder mit Düngemitteln und Wachstumsregulatoren ist möglich.A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Suspensionen,The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions,
Spritzpulver, Pasten, lösliche Pulver, Stäubemittel und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Ver¬ spritzen, Versprühen, Verstreuen, Verstäuben, Verschäumen, Bestreichen usw. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low-Volume-Verfahren aus- zubringen oder die Wirkstoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. Es kann auch das Saatgut der Pflanzen behandelt werden.Spray powder, pastes, soluble powders, dusts and granules can be used. They are used in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
Bei der Behandlung von Pflanzenteilen können die Wirkstoffkonzentrationen in den Anwendungsformen in einem größeren Bereich variiert werden: Sie liegen im allgemeinen zwischen 1 und 0,0001 Gew.-%, vorzugsweise zwischen 0,5 und 0,001 Gew.-%.In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
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 seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
Bei der Behandlung des Bodens sind Wirkstoffkonzentrationen von 0,00001 bis 0,1 Gew.-%, vorzugsweise von 0,0001 bis 0,02 Gew.-% am Wirkungsort erforder- lieh.When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the place of action.
Die zum Schutz technischer Materialien verwendeten Mittel enthalten die Wirkstoffe im allgemeinen in einer Menge von 1 bis 95%, bevorzugt von 10 bis 75 %.The agents used to protect industrial materials generally contain the active ingredients in an amount of 1 to 95%, preferably 10 to 75%.
Die Anwendungskonzentrationen der erfindungsgemäßen Wirkstoffe richten sich nach der Art und dem Vorkommen der zu bekämpfenden Mikroorganismen sowie nach der Zusammensetzung des zu schützenden Materials. Die optimale Einsatz¬ menge kann durch Testreihen ermittelt werden. Im allgemeinen liegen die Anwen¬ dungskonzentrationen im Bereich von 0,001 bis 5 Gewichts-%, vorzugsweise von 0,05 bis 1,0 Gewichts-% bezogen auf das zu schützende Material. Die Wirksamkeit und das Wirkungsspektrum der erfindungsgemäß im Material¬ schutz zu verwendenden Wirkstoffe bzw. der daraus herstellbaren Mittel, Kon¬ zentrate oder ganz allgemein Formulierungen kann erhöht werden, wenn gegebe¬ nenfalls weitere antimikrobiell wirksame Verbindungen, Fungizide, Bakterizide, Herbizide, Insektizide oder andere Wirkstoffe zur Vergrößerung des Wirkungs¬ spektrums oder Erzielung besonderer Effekte wie z.B. dem zusätzlichen Schutz vor Insekten zugesetzt werden. Diese Mischungen können ein breiteres Wirkungs¬ spektrum besitzen als die erfindungsgemäßen Verbindungen.The application concentrations of the active compounds according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount of use can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected. The effectiveness and the spectrum of activity of the active substances to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be produced therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or others are used Active substances to enlarge the spectrum of activity or to achieve special effects such as additional protection against insects are added. These mixtures can have a broader spectrum of activity than the compounds according to the invention.
Die Herstellung und die Verwendung der erfindungsgemäßen Stoffe gehen aus den folgenden Beispielen hervor. The preparation and use of the substances according to the invention can be seen from the following examples.
HerstellungsbeispieleManufacturing examples
Beispiel 1example 1
Figure imgf000028_0001
Figure imgf000028_0001
Ein Gemisch aus 1,72 g (5 mmol) 2,2-Dimethyl-3-hydroxy-4-(l,2,4-triazol-l-yl)-l- (4-trifluormethoxy-phenyl)-pentan und 30 ml absolutem Tetrahydrofuran wird beiA mixture of 1.72 g (5 mmol) of 2,2-dimethyl-3-hydroxy-4- (l, 2,4-triazol-l-yl) -l- (4-trifluoromethoxyphenyl) pentane and 30 ml of absolute tetrahydrofuran is added to
-20°C mit 4,4 ml (11 mmol) n-Butyl-lithium in Hexan versetzt und 30 Minuten bei 0°C nachgerührt. Anschließend wird das Reaktionsgemisch auf -70°C abge¬ kühlt, unter Rühren mit 0,19 g (6 mmol) Schwefel -Pulver versetzt, dann 1 Stunde bei -70°C und danach 2 Stunden bei 0°C gerührt. Man verdünnt das entstehende Gemisch mit Ethylacetat und schüttelt mehrfach mit gesättigter, wäßriger Ammo¬ niumchlorid-Lösung aus. Die organische Phase wird über Natriumsulfat getrocknet und dann unter vermindertem Druck eingeengt. Das anfallende Rohprodukt (2,2 g) wird durch Chromatographie an Kieselgel mit einem Gemisch aus Petrolether und Ethylacetat = 1 :1 als Laufmittel gereinigt. Man erhält auf diese Weise 1,4 g (75 % der Theorie) an 2,2-Dimethyl-3-hydroxy-4-(5-mercapto-l,2,4-triazol-l-yl)-l-(4-tri- fluormethoxy-phenyl)-pentan in Form einer Festsubstanz vom Schmelzpunkt 125 bis 126°C.-20 ° C with 4.4 ml (11 mmol) of n-butyl lithium in hexane and stirred at 0 ° C for 30 minutes. The reaction mixture is then cooled to -70 ° C., 0.19 g (6 mmol) of sulfur powder is added with stirring, then the mixture is stirred at -70 ° C. for 1 hour and then at 0 ° C. for 2 hours. The resulting mixture is diluted with ethyl acetate and shaken out several times with saturated, aqueous ammonium chloride solution. The organic phase is dried over sodium sulfate and then concentrated under reduced pressure. The resulting crude product (2.2 g) is purified by chromatography on silica gel using a mixture of petroleum ether and ethyl acetate = 1: 1 as the eluent. In this way, 1.4 g (75% of theory) of 2,2-dimethyl-3-hydroxy-4- (5-mercapto-l, 2,4-triazol-l-yl) -l- (4th -trifluoromethoxy-phenyl) pentane in the form of a solid with a melting point of 125 to 126 ° C.
GC/MS(ci): 376 (M + H+) GC / MS (ci): 376 (M + H + )
VerwendungsbeispieleExamples of use
Beispiel AExample A
Pyrenophora teres-Test (Gerste) / protektivPyrenophora teres test (barley) / protective
Lösungsmittel: 10 Gewichtsteile N-Methyl-pyrrolidon Emulgator: 0,6 Gewichtsteile AlkylarylpolyglykoletherSolvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
Zur Prüfung auf protektive Wirksamkeit besprüht man junge Pflanzen mit der Wirkstoffzubereitung in der angegebenen Aufwandmenge. Nach Antrocknen des Spritzbelages werden die Pflanzen mit einer Konidiensuspension von Pyrenophora teres besprüht.To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Pyrenophora teres.
Die Pflanzen verbleiben 48 Stunden bei 20°C und 100 % relativer Luftfeuchtigkeit in einer Inkubationskabine.The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.
Die Pflanzen werden in einem Gewächshaus bei einer Temperatur von ca. 20°C und einer relativen Luftfeuchtigkeit von ca. 80 % aufgestellt.The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.
7 Tage nach der Inokulation erfolgt die Auswertung. Dabei bedeutet 0 % einen Wirkungsgrad, der demjenigen der Kontrolle entspricht, während ein Wirkungs- grad von 100 % bedeutet, daß kein Befall beobachtet wird.Evaluation is carried out 7 days after the inoculation. 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
Wirkstoffe, Wirkstoffkonzentrationen und Versuchsergebnisse gehen aus der folgenden Tabelle hervor. Tabelle AActive substances, active substance concentrations and test results are shown in the following table. Table A
Pyrenophora teres-Test (Gerste) / protektivPyrenophora teres test (barley) / protective
Figure imgf000030_0001
Figure imgf000030_0001
Beispiel BExample B
Pseudocercosporella herpotrichoides-Test (Weizen) / protektivPseudocercosporella herpotrichoides test (wheat) / protective
Lösungsmittel: 10 Gewichtsteile N-Methyl-pyrrolidonSolvent: 10 parts by weight of N-methyl-pyrrolidone
Emulgator: 0,6 Gewichtsteile AlkylarylpolyglykoletherEmulsifier: 0.6 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1To produce a suitable preparation of active compound, mix 1
Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.
Zur Prüfung auf protektive Wirksamkeit besprüht man junge Pflanzen mit der Wirkstoffzubereitung in der angegebenen Aufwandmenge. Nach Antrocknen des Spritzbelages werden die Pflanzen an der Halmbasis mit Sporen von Pseudocercosporella herpotrichoides inokuliert.To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants at the stem base are inoculated with spores of Pseudocercosporella herpotrichoides.
Die Pflanzen werden in einem Gewächshaus bei einer Temperatur von ca. 10°C und einer relativen Luftfeuchtigkeit von ca. 80 % aufgestellt.The plants are placed in a greenhouse at a temperature of approx. 10 ° C and a relative humidity of approx. 80%.
21 Tage nach der Inokulation erfolgt die Auswertung. Dabei bedeutet 0 % einenEvaluation is carried out 21 days after the inoculation. 0% means one
Wirkungsgrad, der demjenigen der Kontrolle entspricht, während ein Wirkungs¬ grad von 100 % bedeutet, daß kein Befall beobachtet wird.Efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
Wirkstoffe, Wirkstoffkonzentrationen und Versuchsergebnisse gehen aus der folgenden Tabelle hervor. Active substances, active substance concentrations and test results are shown in the following table.
Tabelle BTable B
Pseudocercosporella herpotrichoides-Test (Weizen) / protektivPseudocercosporella herpotrichoides test (wheat) / protective
Figure imgf000032_0001
Figure imgf000032_0001

Claims

Patentansprüche claims
1. Mercapto-triazolyl-butanole der Formel1. Mercapto-triazolyl-butanols of the formula
Figure imgf000033_0001
Figure imgf000033_0001
in welcherin which
R1 für Wasserstoff, Alkyl oder gegebenenfalls substituiertes Cycloalkyl steht,R 1 represents hydrogen, alkyl or optionally substituted cycloalkyl,
R2 für Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen steht,R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms,
X für Halogen, Alkyl mit 1 bis 4 Kohlenstoffatomen, Alkoxy mit 1 bis 4 Kohlenstoffatomen, Alkylthio mit 1 bis 4 Kohlenstoffatomen, Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 5 Halogen¬ atomen, Halogenalkoxy mit 1 bis 4 Kohlenstoffatomen und 1 bis 5 Halogenatomen, Halogenalkylthio mit 1 bis 4 Kohlenstoffatomen und 1 bis 5 Halogenatomen, gegebenenfalls durch Halogen und/oder Alkyl mit 1 bis 4 Kohlenstoffatomen substituiertes Phenyl oder für gegebenenfalls durch Halogen und/oder Alkyl mit 1 bis 4 Kohlen¬ stoffatomen substituiertes Phenoxy steht,X for halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms Haloalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms or phenoxy optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms,
m für die Zahlen 0, 1, 2 oder 3 steht undm represents the numbers 0, 1, 2 or 3 and
Y für ein Sauerstoffatom, eine CH2-Gruppe oder eine direkte Bindung steht,Y represents an oxygen atom, a CH 2 group or a direct bond,
sowie deren Säureadditions-Salze und Metallsalz-Komplexe.as well as their acid addition salts and metal salt complexes.
2. Mercapto-triazolyl-butanole der Formel (I) gemäß Anspruch 1, in denen R1 für Wasserstoff, geradkettiges oder verzweigtes Alkyl mit 1 bis 122. mercapto-triazolyl-butanols of the formula (I) according to claim 1, in which R 1 represents hydrogen, straight-chain or branched alkyl having 1 to 12
Kohlenstoffatomen oder für gegebenenfalls einfach bis dreifach, gleichartig oder verschieden durch Halogen und/oder Alkyl mit 1 bis 4 Kohlenstoffatomen substituiertes Cycloalkyl mit 3 bis 7 Koh- lenstoffatomen steht,Carbon atoms or represents cycloalkyl having 3 to 7 carbon atoms which is optionally monosubstituted to trisubstituted, identical or different, by halogen and / or alkyl having 1 to 4 carbon atoms,
R2 für Wasserstoff, Methyl oder Ethyl steht,R 2 represents hydrogen, methyl or ethyl,
X für Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Methylthio, Trichlormethyl, Trifluormethyl, Trifluormethoxy, Difluormethoxy, Trifluormethylthio, Phenyl oder Phenoxy steht,X represents fluorine, chlorine, bromine, methyl, ethyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl or phenoxy,
m für die Zahlen 0, 1, 2 oder 3 steht, wobei X für gleiche oder verschiedene Reste steht, wenn m für 2 oder 3 steht undm stands for the numbers 0, 1, 2 or 3, where X stands for the same or different radicals if m stands for 2 or 3 and
Y für ein Sauerstoffatom, eine CH2-Gruppe oder eine direkte Bindung steht.Y represents an oxygen atom, a CH 2 group or a direct bond.
3. Verfahren zur Herstellung von Mercapto-triazolyl-butanolen der Formel (I) gemäß Anspruch 1 sowie von deren Säureadditions-Salzen und Metallsalz-3. A process for the preparation of mercapto-triazolyl-butanols of the formula (I) according to Claim 1 and of their acid addition salts and metal salt
Komplexen, dadurch gekennzeichnet, daß man Triazolyl-butanole der FormelComplexes, characterized in that triazolyl-butanols of the formula
Figure imgf000034_0001
Figure imgf000034_0001
in welcherin which
R1, X, Y und m die oben angegebenen Bedeutungen haben,R 1 , X, Y and m have the meanings given above,
nacheinander mit starken Basen und Schwefel in Gegenwart eines Verdün¬ nungsmittels umsetzt und dann mit Wasser, gegebenenfalls in Gegenwart einer Säure hydrolysiert und gegebenenfalls die dabei entstehenden Verbin¬ dungen der Formel
Figure imgf000035_0001
reacted successively with strong bases and sulfur in the presence of a diluent and then hydrolyzed with water, if appropriate in the presence of an acid, and, if appropriate, the compounds of the formula formed in the process
Figure imgf000035_0001
in welcherin which
R1, X, Y und m die oben angegebenen Bedeutungen haben,R 1 , X, Y and m have the meanings given above,
mit Halogen- Verbindungen der Formelwith halogen compounds of the formula
R3 - Hai (III)R 3 - shark (III)
in welcherin which
R3 für Alkyl mit 1 bis 4 Kohlenstoffatomen steht undR 3 represents alkyl having 1 to 4 carbon atoms and
Hai für Chlor, Brom oder Iod steht,Shark represents chlorine, bromine or iodine,
in Gegenwart eines Säurebindemittels und in Gegenwart eines Verdün- nungsmittels umsetzt,in the presence of an acid binder and in the presence of a diluent,
und gegebenenfalls anschließend an die so erhaltenen Verbindungen der Formel (I) eine Säure oder ein Metallsalz addiert.and optionally then adding an acid or a metal salt to the compounds of formula (I) thus obtained.
4. Mikrobizide Mittel, gekennzeichnet durch einen Gehalt an mindestens einem Mercapto-triazolyl-butanol der Formel (I) gemäß Anspruch 1 bzw. an einem Säureadditions-Salz oder Metallsalz-Komplex eines Mercapto- triazolyl-butanoles der Formel (I).4. Microbicidal agents, characterized by a content of at least one mercapto-triazolyl-butanol of the formula (I) according to claim 1 or of an acid addition salt or metal salt complex of a mercapto-triazolyl-butanol of the formula (I).
5. Verwendung von Mercapto-triazolyl-butanolen der Formel (I) gemäß Anspruch 1 bzw. von deren Säureadditions-Salzen oder Metallsalz-Kom¬ plexen als Mikrobizide im Pflanzenschutz und im Materialschutz.5. Use of mercapto-triazolyl-butanols of the formula (I) according to Claim 1 or of their acid addition salts or metal salt complexes as microbicides in crop protection and in material protection.
6. Verfahren zur Bekämpfung von unerwünschten Mikroorganismen im Pflan¬ zenschutz und im Material schütz, dadurch gekennzeichnet, daß man Mercapto-triazolyl-butanole der Formel (I) gemäß Anspruch 1 bzw. deren Säureadditions-Salze oder Metallsalz-Komplexe auf die Mikroorganismen und/oder deren Lebensraum ausbringt.6. A method for combating undesirable microorganisms in plant protection and in the protective material, characterized in that Mercapto-triazolyl-butanols of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes on the microorganisms and / or their habitat.
7. Verfahren zur Herstellung von mikrobiziden Mitteln, dadurch gekenn- zeichnet, daß man Mercapto-triazolyl-butanole der Formel (I) gemäß7. Process for the preparation of microbicidal agents, characterized in that mercapto-triazolyl-butanols of the formula (I) according to
Anspruch 1 bzw. deren Säureadditions-Salze oder Metallsalz-Komplexe mit Streckmitteln und/oder oberflächenaktiven Stoffen vermischt. Claim 1 or their acid addition salts or metal salt complexes mixed with extenders and / or surface-active substances.
PCT/EP1996/002404 1995-06-06 1996-06-03 Microbicidal (mercapto-triazolylmethyl)-butanols WO1996039395A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU60046/96A AU6004696A (en) 1995-06-06 1996-06-03 Microbicidal (mercapto-triazolylmethyl)-butanols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19520593.6 1995-06-06
DE19520593A DE19520593A1 (en) 1995-06-06 1995-06-06 Mercapto-triazolyl-butanols

Publications (1)

Publication Number Publication Date
WO1996039395A1 true WO1996039395A1 (en) 1996-12-12

Family

ID=7763718

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/002404 WO1996039395A1 (en) 1995-06-06 1996-06-03 Microbicidal (mercapto-triazolylmethyl)-butanols

Country Status (4)

Country Link
AU (1) AU6004696A (en)
DE (1) DE19520593A1 (en)
WO (1) WO1996039395A1 (en)
ZA (1) ZA964651B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997041107A1 (en) * 1996-04-30 1997-11-06 Bayer Aktiengesellschaft Triazolyl mercaptides and their use as microbicides
WO1997042178A1 (en) * 1996-05-02 1997-11-13 Bayer Aktiengesellschaft Acyl mercapto-triazolyl derivatives and the use thereof as microbicides
WO1997044331A1 (en) * 1996-05-21 1997-11-27 Bayer Aktiengesellschaft Thiocyano-triazolyl derivatives and their use as microbicides
WO2010040718A1 (en) * 2008-10-07 2010-04-15 Basf Se Triazole and imidazole compounds, use thereof and agents containing them
WO2010040717A1 (en) * 2008-10-07 2010-04-15 Basf Se Triazole and imidazole compounds, use thereof and agents containing them

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19732033A1 (en) 1997-07-25 1999-01-28 Bayer Ag Triazolinethione-phosphoric acid derivatives

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0251086A2 (en) * 1986-06-23 1988-01-07 The Du Pont Merck Pharmaceutical Company Antifungal carbinols
EP0301393A1 (en) * 1987-07-31 1989-02-01 Bayer Ag 1,4-Disubstituted 1-azolyl-3,3-dymethylbutane derivatives
DE19528046A1 (en) * 1994-11-21 1996-05-23 Bayer Ag New sulphur substd tri:azole derivs

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0251086A2 (en) * 1986-06-23 1988-01-07 The Du Pont Merck Pharmaceutical Company Antifungal carbinols
EP0301393A1 (en) * 1987-07-31 1989-02-01 Bayer Ag 1,4-Disubstituted 1-azolyl-3,3-dymethylbutane derivatives
DE19528046A1 (en) * 1994-11-21 1996-05-23 Bayer Ag New sulphur substd tri:azole derivs

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997041107A1 (en) * 1996-04-30 1997-11-06 Bayer Aktiengesellschaft Triazolyl mercaptides and their use as microbicides
US6057353A (en) * 1996-04-30 2000-05-02 Bayer Aktiengesellschaft Triazolyl-mercaptides and their use as microbicides
WO1997042178A1 (en) * 1996-05-02 1997-11-13 Bayer Aktiengesellschaft Acyl mercapto-triazolyl derivatives and the use thereof as microbicides
US6051592A (en) * 1996-05-02 2000-04-18 Bayer Aktiengesellschaft Acyl-mercapto-triazolyl derivatives and the use thereof as microbicides
US6274610B1 (en) 1996-05-02 2001-08-14 Bayer Aktiengesellschaft Acyl mercapto-triazolyl derivatives and the use thereof as microbicides
WO1997044331A1 (en) * 1996-05-21 1997-11-27 Bayer Aktiengesellschaft Thiocyano-triazolyl derivatives and their use as microbicides
US6166059A (en) * 1996-05-21 2000-12-26 Bayer Aktiengesellschaft Thiocyano- triazolyl derivatives and their use as microbicides
WO2010040718A1 (en) * 2008-10-07 2010-04-15 Basf Se Triazole and imidazole compounds, use thereof and agents containing them
WO2010040717A1 (en) * 2008-10-07 2010-04-15 Basf Se Triazole and imidazole compounds, use thereof and agents containing them

Also Published As

Publication number Publication date
DE19520593A1 (en) 1996-12-12
ZA964651B (en) 1997-01-07
AU6004696A (en) 1996-12-24

Similar Documents

Publication Publication Date Title
EP0832083B1 (en) Microbicidal (mercapto-triazolyl methyl)-dioxacycloalkanes
EP0793657B1 (en) Microbicidal triazolyl derivatives
EP0906292B1 (en) Triazolyl mercaptides and their use as microbicides
EP0828719B1 (en) (mercapto-triazolylmethyl) cyclopentanol microbicides
EP0828734B1 (en) Triazolyl methyl oxiranes
EP0901478A1 (en) Thiocyano-triazolyl derivatives and their use as microbicides
EP0842158A1 (en) Microbicidal 2-phenylethyl-mercapto-triazoles
EP0843668A1 (en) Microbicidal mercapto-triazolyl-ketones
WO1996038424A1 (en) Cycloalkane benzylidines as microbicides
EP0843669A1 (en) Microbicidal mercapto-triazolyl-nitriles
EP0901472B1 (en) Mercapto-imidazolyl derivatives and their use as microbicides
WO1996039395A1 (en) Microbicidal (mercapto-triazolylmethyl)-butanols
DE19520095A1 (en) New 1-((tri- substd.)silyl)methyl-1,2,4-triazole-5-thiol derivs.
WO1996041798A1 (en) Microbicidal (mercapto-triazolylmethyl)-ethanols
WO1996039394A1 (en) Mercapto-bis-triazoles
WO1996036634A1 (en) Oxiranyl-hydroxyethyl triazoles
DE19517719A1 (en) New 1-phenyl-2-triazolyl-ethanol derivs.
DE4412358A1 (en) Cyclopropyl ethyl azoles
DE19622354A1 (en) Halogen thiophene derivatives
WO1996036635A1 (en) Oxiranyl-triazoles
DE19517720A1 (en) New 1-benzyl-2-triazolyl-ethanol derivs.
DE4412332A1 (en) Silyloxy-cyclopropyl-azolyl derivatives

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR BY CA CN CZ HU IL JP KR KZ LK MX NO NZ PL RO RU SK TR UA US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载