WO1996036634A1

WO1996036634A1 - Oxiranyl-hydroxyethyl triazoles

Info

Publication number: WO1996036634A1
Application number: PCT/EP1996/001820
Authority: WO
Inventors: Michael Lindemann; Stefan Dutzmann; Gerd Hänssler; Klaus Stenzel
Original assignee: Bayer Aktiengesellschaft
Priority date: 1995-05-15
Filing date: 1996-05-02
Publication date: 1996-11-21
Also published as: DE19517722A1; AU5812396A

Abstract

Disclosed are novel oxiranyl-hydroxyethyl triazoles of formula (I) in which: X stands for hydrogen, halogen, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms; Z stands for halogen, alkyl with 1-4 carbon atoms, halogen alkyl with 1-4 carbon atoms and 1-5 halogen atoms, alkoxy with 1-4 carbon atoms, halogen alkoxy with 1-4 carbon atoms and 1-5 halogen atoms, nitro, or phenyl which has optionally been substituted once to three times identically or differently with halogen; and m is 0, 1, 2 or 3. Also disclosed are the acid addition salts and metal salt complexes of the claimed triazoles, a process for producing them and their use as microbicides for the protection of plants and materials.

Description

Oxiranyl-hydroxyethyl-triazoles

The present invention relates to new oxiranyl-hydroxyethyl-triazoles, a process for their preparation and their use as microbicides.

It has already become known that numerous azolyl-methyl-oxiranes and hydroxyethyl-azolyl derivatives have fungicidal properties (cf. EP-A 0 327 913 and DE-A 4 419 812). For example, 3,3-dimethyl-2- (2-chlorophenyl) -2- (1, 2,4-triazole-1-yl-methyl) -oxirane and 2- (2-chlorophenyl) -3 - (1 - chloro-cyclopropyl) -3-hydroxy-4- (l, 2,4-triazol-l-yl) -but-l-ene to combat

Use mushrooms. The action of these substances is good, but leaves something to be desired in some cases at low application rates.

There have now been new oxiranyl-hydroxyethyl-triazoles of the formula

in which

X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms,

Z represents halogen, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to

4 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, nitro or optionally single to triple, identical or different phenyl substituted by halogen and

m represents the numbers 0, 1, 2 or 3,

as well as their acid addition salts and metal salt complexes. The substances according to the invention contain two asymmetrically substituted carbon atoms. They can therefore be obtained in the form of diastereomers or optical isomers. The present invention relates both to the individual isomers and to their mixtures.

It has also been found that oxiranyl-hydroxyethyl-triazoles of the formula (I) and their acid addition salts and metal salt complexes are obtained if triazolyl-butenols of the formula

in which

X, Z and m have the meanings given above,

reacted with peracids in the presence of a diluent and optionally then adding an acid or a metal salt to the compounds of formula (I) thus obtained.

Finally, it was found that the new oxiranyl-hydroxyethyl-triazoles of the formula (I) and their acid addition salts and metal salt complexes have very good microbicidal properties and can be used in a protective manner both in crop protection and in the material.

Surprisingly, the substances according to the invention have a better microbicidal activity than the constitutionally most similar, known compounds of the same direction of action. The substances according to the invention thus exceed the 3.3-

Dimethyl-2- (2-chlorophenyl) -2- (1,2,4-triazol-l-yl-methyl) -oxirane and 2- (2-chlorophenyl) -3- (1-chloro-cyclopro-opyl ) -3-hy droxy-4- (1, 2,4-triazol-1-yl) -but-1-ene with regard to their fungicidal properties. Formula (I) provides a general definition of the oxiranyl-hydroxyethyl-triazoles according to the invention.

X preferably represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl,

Isopropyl, methoxy and ethoxy.

Z preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, methoxy, Ethoxy, trifluoromethoxy, difluoromethoxy, nitro or for phenyl which is optionally mono- or disubstituted, identical or different, by fluorine and / or chlorine.

m preferably represents the numbers 0, 1, 2 or 3. If m represents 2 or 3, Z can represent the same or different radicals.

Preferred substances according to the invention are also addition products of acids and those oxiranyl-hydroxyethyl-triazoles of the formula (I) in which X, Z and m have the meanings given as preferred.

The acids that can be added preferably include hydrohalic acids, e.g. the hydrochloric acid and the hydrobromic acid, in particular the hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid as well as sulfonic acids, e.g. p-

Toluenesulfonic acid, 1,5-naphthalenedisulfonic acid, camphorsulfonic acid, saccharin and thiosaccharin.

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 oxiranyl-hydroxyethyl-triazoles of the formula (I), in which X, Z and m have the meanings given as preferred.

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 are too physiologically compatible Lead addition products. Particularly preferred acids in this context are the hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulfuric acid.

Examples of oxiranyl-hydroxyethyl-triazoles of the formula (I) are the substances listed in the table below.

Table 1

If 2- (2-chlorophenyl) -3- (l-fluoro-cyclopropyl) -3-hydroxy-4- (l, 2,4-triazol-l-yl) -but-l-ene is used as Starting material and 3-chloroperbenzoic acid as a reaction component, the course of the process according to the invention can be illustrated by the following formula:

Formula (II) provides a general definition of the triazolyl-butenols required as starting materials when carrying out the process according to the invention. In this formula, X, Z and m preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these radicals or this index.

The triazolyl-butenols of the formula (II) are known or can be prepared by methods known in principle (cf. DE-A 4 419 812).

Suitable reaction components when carrying out the process according to the invention are all peracids customary for such reactions. Perbenzoic acid, 3-chloro-perbenzoic acid and

Peracetic acid.

Suitable diluents for carrying out the process according to the invention are all inert organic solvents which are customary for such reactions. Halogenated aliphatic hydrocarbons, such as methylene chloride, chloroform or carbon tetrachloride, and also aliphatic carboxylic acids, such as acetic acid or glacial acetic acid, are preferably usable.

The reaction temperatures can be varied within a certain range when carrying out the process according to the invention. In general, temperatures between -20 ° C and + 60 ° C, preferably between 0 ° C and 40 ° C. When carrying out the process according to the invention, work is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

When carrying out the process according to the invention, 1 to 5 moles, preferably 1.2 to 2 moles, of peracid are generally employed per mole of triazolyl-butenol of the formula (II). The processing takes place according to usual methods. In general, the reaction mixture is mixed with water, extracted several times with a water-immiscible organic solvent, the combined organic phases are washed successively with an aqueous alkaline solution and aqueous sodium thiosulfate solution, then dried and concentrated. The remaining residue can, if appropriate, be freed of any impurities which may be present by customary methods, for example by chromatography or recrystallization.

The oxiranyl-hydroxyethyl-triazoles of the formula (I) according to the invention can be converted into acid addition salts or metal salt complexes.

For the preparation of acid addition salts of the compounds of formula (I), preference is given to those acids which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention.

The acid addition salts of the compounds of formula (I) can in simpler

Manner according to usual salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. Hydrogen chloride acid can be obtained and in a known manner, e.g. by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent.

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.

The metal salt complexes of the compounds of formula (I) can in simpler

Be obtained by conventional methods, such as by dissolving the Metal salt in alcohol, for example ethanol and adding to compounds of formula (I). Metal salt complexes can be isolated in a known manner, for example by filtering off, and optionally purified by recrystallization.

The active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms, such as fungi and

Bacteria can be used in crop protection and material protection.

Fungicides are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens of fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation:

Xanthomonas species, such as Xanthomonas oryzae; Pseudomonas species, such as Pseudomonas lachrymans; Erwinia species, such as Erwinia amylovora;

Pythium species, such as Pythium ultimum; Phytophthora species, such as Phytophthora infestans;

Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis; Plasmopara species, such as Plasmopara viticola;

Peronospora species, such as Peronospora pisi or P. brassicae; Erysiphe species, such as Erysiphe graminis;

Sphaerotheca species, such as Sphaerotheca fuliginea; Podosphaera species, such as Podosphaera leucotricha; Venturia species, such as Venturia inaequalis;

Pyrenophora species, such as Pyrenophora teres or P. graminea;

(Conidial form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus;

(Conidial form: Drechslera, Syn: Helminthosporium); Uromyces species, such as Uromyces appendiculatus;

Puccinia species, such as Puccinia recondita;

Tilletia species, such as Tilletia caries;

Ustilago species, such as Ustilago nuda or Ustilago avenae; Pellicularia species, such as Pellicularia sasakii; Pyricularia species, such as Pyricularia oryzae; Fusarium species, such as Fusarium culmorum; Botrytis species, such as Botrytis cinerea; Septoria species, such as Septoria nodorum;

Leptosphaeria species, such as Leptosphaeria nodorum; Cercospora species, such as Cercospora canescens; Alternaria species, such as Alternaria brassicae; Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds and of the soil.

The active compounds according to the invention are particularly suitable for combating Pyricularia oryzae and Pellicularia sasakii on rice and for combating cereal diseases, such as Leptosphaeria nodorum, Cochliobolus sativus, Pyrenophora teres, Pseudocercosporella herpotrichoides, Erysiphe and Fusarium species. In addition, the substances according to the invention have a very good and broad in vitro effect.

In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired ones

Use microorganisms.

In the present context, technical materials are understood to mean 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 can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked by microorganisms or can be decomposed. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, are also mentioned, which are produced by increasing

Microorganisms can be affected. Within the scope of the present invention, preference is given to adhesives, glues and papers as technical materials and cartons, leather, wood, paints, cooling lubricants and heat transfer fluids, 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 ones according to the invention preferably act

Active substances against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes), as well as against slime organisms and algae.

For example, 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 puteana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, like Trichoderma viride,

Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeroginosa,

Staphylococcus, such as Staphylococcus aureus.

The substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents come in essential in question: 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, e.g. Aerosol propellants such as butane, propane, nitrogen and carbon dioxide; as fixed

Carriers are possible: e.g. natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite,

Dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifiers and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%. When used in crop protection as such or in their formulations, the active compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In some cases, synergistic effects also occur, which means that the mixture has a higher activity than the sum of the effects of the individual components.

The following substances can be considered as mixing partners:

Fungicides: 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1, 3-thiazole-5-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, calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorozhalonolinolonolinolonolinolinolinothalonolinol, chlorothalonolinophenol

Cymoxanil, cyproconazole, cyprofuram,

Dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolon, epimolazone, edifenazolone, edifenazolone, edifenazolone, edifenazolone, edifenazole

Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fen-propimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, fuberriafilil, fuberri Furalaxyl, furmecyclox,

Guazatine,

Hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, Iprobefos (IBP), iprodione, isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,

Nickel dimethyldithiocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,

Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,

Quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,

Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin,

Triticonazole,

Validamycin A, vinclozolin,

Zineb, ziram

Bactericides: bronopol, dichlorophene, nitrapyrin, nickel-dimethyldithiocarbamate, kasugamycin,

Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofta¬ lam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

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, Butocarboxin, Butylpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan

157419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrinomyrin, Cyatin Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Ethifenin, Ethifenin, Ethifenin, Methamino, Emamofen, Emfom, Oxametheno Ethoprophos, Etrimphos,

Fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, Flufen- prox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,

Lambda cyhalothrin, lufenuron,

Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin,

Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxi, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos,

Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, RH 5992, Salithion, Sebufos, Silafiuofen, Sulfotep, Sulprof

Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhriazurium, Tralomenhroniazonium Zetamethrin.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules become. They are used in the customary manner, for example 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 prepare the active ingredient or the like Inject active ingredient into the soil yourself. The seeds of the plants can also be treated.

When treating 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.

In the case of seed treatment, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

The agents used to protect industrial materials generally contain the active ingredients in an amount of 1 to 95%, preferably 10 to

75%.

The application concentrations of the active compounds according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount can be determined by test series. In general, the

Application concentrations 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 necessary, if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients to increase the spectrum of action or to achieve special effects such as additional protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention. In many cases synergistic effects, ie the effectiveness of the mixture is greater than the effectiveness of the individual components.

The preparation and use of the substances according to the invention are illustrated by the following examples.

Manufacturing examples

example 1

A solution of 5 g (17 mmol) of 2- (2-chlorophenyl) -3- (l-fluoro-cyclopropyl) -3-hydroxy-4- (l, 2,4-triazol-l-yl) -but-l -en in 100 ml dichloromethane with 8 g

(23 mmol) 3-chloro-perbenzoic acid were added and the mixture was stirred at room temperature for 15 hours. Then the reaction mixture is mixed with water and extracted several times with dichloromethane. The combined organic phases are washed first with aqueous sodium carbonate solution and then with 5% by weight aqueous sodium thiosulfate solution. After drying over sodium sulfate, the organic phase is concentrated under reduced pressure. The remaining residue is chromatographed on silica gel using ethyl acetate: cyclohexane = 2: 1 as eluent. By concentrating the eluate, 3.6 g (65% of theory) of 2- (2-chlorophenyl) -3 - (1-fluoro-cyclopropyl) -1, 2-epoxy-4- (1, 2,4- triazol-1 -yl) -butan-3 -ol. ¹ H-NMR spectrum (200 MHz, CDC1 ₃ , TMS)

δ = 0.1-0.5 (m, 2H); 0.7-1.0 (m, 2H); 2.9-3.1 (m, 1H); 3.59 (d, J = 4Hz); 3.67

(d, J = 4Hz, together 1H); 4.08 (s, 1H); 4.21 (d, J = 13Hz); 4.6 (d, J =

13Hz, together 1H); 4.88 (d, J = 13Hz); 5.0 (d, J = 13Hz, together

1H); 7.2-7.7 (m, 4H); 7.98 (s); 8.0 (s, together 1H); 8.11 (s); 8.13 (s, together 1H) ppm. Production of starting substances:

A solution of 6.2 g (22 mmol) l-chloro-2- (l-fluorocyclopropyl) -3- (2-chlorophenyl) but-3-en-2-ol, 5.2 g (75 mmol) 1 , 2,4-triazole and 3.4 g (30 mmol) of potassium tert-butoxide in 50 ml of dimethylformamide are stirred at 80 ° C. for 8 hours.

The reaction mixture is then concentrated by removing the solvent under reduced pressure. The remaining residue is taken up in ethyl acetate, washed with water, the organic phase is dried over sodium sulfate and concentrated by stripping off the solvent under reduced pressure. The remaining residue is mixed with ethyl acetate: cyclohexane = 2: 1

Eluent chromatographed on silica gel. Concentration of the eluate gives 0.7 g (10% of theory) of (2-chlorophenyl) -3- (l-fluorocyclopropyl) -3-hydroxy-4- (1, 2,4-triazol-1-yl) -but- 1 -en. 1H NMR spectrum (200 MHz, CDC1 ₃ , TMS)

δ = 0.2-0.5 (m, 2H); 0.75-0.95 (m, 2H), 4.43 (d, J = 14 Hz, 1H); 4.9 (d, J = 14

Hz, 1H); 5.36 (d, J = 2Hz, 1H); 5.65 (dJ = 2 Hz, 1H), 7.3-7.8 (m, 4H), 8.0 (s, 1H), 8.22 (s, 1H) ppm.

A solution of 5 g (25 mmol) of α-bromo-2-chlorostyrene in 10 ml of absolute diethyl ether is added dropwise under an argon atmosphere and with stirring at room temperature into a mixture of 0.85 g (35 mmol) of magnesium shavings and 10 ml of diethyl ether. When the addition is complete, the reaction mixture is kept under for 1 hour

Reflux heated. The Grignard solution thus obtained is added dropwise at room temperature with stirring to a solution of 3.8 g (28 mmol) of 1-fluorocyclopropylchloromethyl ketone in 10 ml of diethyl ether. After the addition has ended, the mixture is heated under reflux for a further 4 hours. Then the reaction mixture is mixed with saturated, aqueous ammonium chloride solution, the resulting mixture is poured onto water and extracted several times with diethyl ether. The combined organic phases are washed with saturated, aqueous sodium chloride solution and, after drying over sodium sulfate, concentrated by stripping off the solvent under reduced pressure. 6.2 g (90% of theory) of l-chloro-2- (l-fluorocyclopropyl) -3- (2-chlorophenyl) but-3-en-2-ol are obtained.

The substances of the formula (I) listed in Table 2 below are also prepared by the method given in Example 1.

Table 2

*) The compounds were characterized by the signals listed below in the ¹ H-NMR spectrum (200 MHz, CDC1 ₃ , TMS).

Example 2

δ = 0.2-1.0 (m, 4H); 2.94 (d, J = 5Hz); 3.06 (d, J = 4Hz, together IH); 3.39 (d, J = 4Hz); 3.61 (d, J = 5Hz, together IH); 4.27 (d, J = MHz); 4.52 (d, J = 15Hz _; together IH); 4.86 (d, J = 15Hz); 5.08 (d, J = MHz, together IH); 5.3 (s, IH); 7.0-7.65 (m, 4H); 8.0 (s); 8.01 (s, together IH); 8.34 (8s, IH) ppm. Example 3

δ = 0.1-1.0 (m, 4H); 2.5 (d, J = 4Hz); 2.65 (d, J = 4Hz); 2.78 (d, J = 5Hz); 3.35 (d, J = 5Hz, together 2H); 4.3-4.75 (m, 2H); 7.2-7.7 (m, 4H); 7.98 (s); 8.0 (s, together IH); 8.08 (s); 8.21 (s, together IH) ppm.

Example 4

δ = 0.1-0.8 (m, 4H); 2.83 (d, J = 5Hz); 3.0 (d, J = 4Hz, together IH); 3.12

(d, J = 4Hz); 3.4 (d, J = 5Hz, together IH); 4.13 (d, J = 15Hz); 4.56 (d,

J = MHz, together IH); 4.2 (s, IH); 4.76 (d, J = MHz); 4.98 (d, J =

15Hz, together IH); 7.2-7.8 (m, 5H); 7.92 (s); 8.02 (s, together IH); 8.27 (s); 8.42 (s, together IH) ppm.

Example 5

δ = 0.1-1.0 (m, 4H); 2.73 (d, J = 5Hz); 2.97 (d, J = 4Hz, together IH); 3.11

(d, J = 4Hz); 3.3 (d, J = 5Hz, together IH); 4.12 (dd, J = 15 and 5Hz);

4.51 (d, J = MHz, together IH); 4.72 (d, J = MHz); 4.97 (dd, J = 15 and 11Hz, together IH); 7.2-7.6 (m, 4H); 8.0 (s); 8.01 (s, together

IH); 8.26 (s); 8.27 (s, together IH) ppm.

Example 6

δ = 0.1-1.0 (m, 4H); 2.8-3.5 (m, 2H); 4.1-5.0 (m, 2H); 7.0-7.8 (m, 4H); 8.08 (s); 8.12 (s, together IH); 8.15 (s); 8.19 (s, together IH) ppm.

Example 7

δ = 0.1-1.0 (m, 4H); 2.64 (d, J ^■ = 5 Hz); 2.79 (d, J = 5Hz); 2.8 (d, J = 6Hz);

3.39 (d, J = 6Hz, together 2H); 4.35 (dd, J = MHz and 1Hz); 4.54 (d,

J = MHz, together IH); 4.7 (d, J = MHz); 4.7 (dd, J = MHz and 1Hz, together IH); 7.3-7.8 (m, 5H); 7.99 (s); 8.01 (s, together IH); 8.1 (s); 8.22 (s, together IH) ppm. Example 8

δ = 0.1-1.0 (m, 4H); 3.76 (d, J = 5 Hz); 3.0 (d, J = 5Hz, together IH); 3.11 (d, J = 5Hz); 3.3 (d, J = 5Hz, together IH); 4.12 (d, J = 15Hz); 4.52 (d, J = 15Hz, together IH); 4.72 (d, J = 15Hz); 5.0 (d, J = 15Hz, together IH); 7.2-7.7 (m, 4H); 8.01 (s, IH); 8.27 (s, IH) ppm.

Example 9

δ = 0.1-1.0 (m, 4H); 2.9-3.9 (m, 2H); 4.4-5.2 (m, 2H); 7.2-7.8 (m, 4H); 7.58 (s); 8.0 (s, together IH); 8.5 (s); 8.52 (s, together IH) ppm.

Examples of use

In the following examples of use, the compound specified below was used as the reference substance:

Known from EP-A 0 327 913.

Example A

Pyrenophora teres test (barley) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkyl aryl polyglycol ether

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.

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. 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%.

Evaluation is carried out 7 days after the inoculation. 0% means one

Efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active substances, active substance concentrations and test results are shown in the following table.

Table A

Pyrenophora teres test (barley) / protective

Example B

Erysiphe test (barley) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

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 dusted with spores from Erysiphe graminis f.sp.hordei.

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means one

Table B

Erysiphe test (barley) / protective

Table B (continued)

Example C

Erysiphe test (wheat) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

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 covered with spores from Erysiphe graminis fsp. tritici pollinated.

Evaluation is carried out 7 days after the inoculation. 0% means one

Table C.

Erysiphe test (wheat) / protective

Example D

Leptosphaeria nodorum test (wheat) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

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 covered with a spore suspension of

Leptosphaeria nodorum sprayed. 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. 15 ° C and a relative humidity of approx. 80%.

Evaluation is carried out 10 days after the inoculation. 0% means one

Table D

Leptosphaeria nodorum test (wheat) / protective

Example E

Pyricularia test (rice) / protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1

Part by weight of active ingredient with the stated amounts of solvent and dilutes the concentrate with water and the stated amount of emulsifier to the desired concentration.

To test for protective efficacy, young rice plants are sprayed with the preparation of active compound to runoff. 4 days after the

Plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are then in a greenhouse at 100% rel. Humidity and 25 ° C.

The disease infestation is evaluated 4 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Table E:

Pyricularia test (rice) / protective

Example F

Sphaerotheca test (cucumber) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, mix 1

Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective efficacy, young plants are sprayed with the preparation of active compound as moist as dew. After the spray coating has dried on, the plants are dusted with conidia of the fungus Sphaerotheca fuliginea.

The plants are then placed in a greenhouse at 23 to 24 ° C and at a relative humidity of approx. 75%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while a

Efficiency of 100% means that no infection is observed.

Table F

Sphaerotheca test (cucumber) / protective

Claims

Oxiranyl-hydroxyethyl-triazoles of the formula

in which

for halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, nitro or optionally single to triple, the same or different halogen substituted phenyl and

m represents the numbers 0, 1, 2 or 3,

as well as their acid addition salts and metal salt complexes.

2. oxiranyl-hydroxyethyl-triazoles of the formula (I) according to claim 1, in which

represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy and ethoxy,

for fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, nitro or for single or double if necessary, similar ι or differently substituted by fluorine and / or chlorine, and

m stands for the numbers 0, 1, 2 or 3, where Z can stand for the same or different radicals if m stands for 2 or 3.

3. Process for the preparation of oxiranyl-hydroxyethyl-triazoles of the formula

(I) according to claim 1 and of their acid addition salts and metal salt complexes,

characterized in that triazolyl-butenols of the formula

in which

X, Z and m have the meanings given above,

reacted with peracids in the presence of a diluent and, if appropriate, then adding an acid or a metal salt to the compounds of the formula (I) thus obtained.

Microbicidal agents, characterized in that they contain at least one oxiranyl-hydroxyethyl-triazole of the formula (I) according to Claim 1 or an acid addition salt or metal salt complex of an oxiranyl-hydroxyethyl-triazole of the formula (I).

Use of oxiranyl-hydroxyethyl-triazoles of the formula (I) according to Claim 1 or of their acid addition salts and metal salt complexes as microbicides in crop protection and in material protection. Process for combating undesirable microorganisms in crop protection and in material protection, characterized in that oxiranyl-hydroxyethyl-triazoles of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes are applied to the microorganisms and / or whose habitat brings out.

7. A process for the preparation of microbicidal agents, characterized gekenn¬ characterized in that oxiranyl-hydroxyethyl-triazoles of formula (I) according to claim 1 or their metal salt compl exe or acid addition salts mixed with extenders and / or surface-active substances.