DE19517722A1 - Oxiranyl-hydroxyethyl-triazoles - Google Patents

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

The present invention relates to new oxiranyl-hydroxyethyl-triazoles, a ver drive to their manufacture and their use as microbicides.

It has already become known that numerous azolyl-methyl-oxiranes and Hydroxyethyl azolyl derivatives have fungicidal properties (cf. EP-OS 0 327 913 and DE-OS 44 19 812). For example, 3,3-dimethyl-2- (2- chlorophenyl) -2- (1,2,4-triazol-1-ylmethyl) oxirane and 2- (2-chlorophenyl) -3- (1- chlor-cyclopropyl) -3-hydroxy-4- (1,2,4-triazol-1-yl) -but-1-en to combat Use mushrooms. The effect of these substances is good, but leaves at low levels Wall quantities left something to be desired in some cases.

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 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, similar or phenyl substituted differently 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 carbons atoms of matter. They can therefore be in the form of diastereomers or optical isomes arises. The present invention relates both to the individual isomers and also their mixtures.

It was also found that oxiranyl-hydroxyethyl-triazoles of the formula (I) as well as their acid addition salts and metal salt complexes, if one 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 Formula (I) and its acid addition salts and metal salt complexes are very good have microbicidal properties and both in crop protection and in Material protection can be used.  

Surprisingly, the substances according to the invention have a better microbi effective as the most structurally similar, known compounds same direction of action. The substances according to the invention thus exceed the 3.3- Dimethyl-2- (2-chlorophenyl) -2- (1,2,4-triazol-1-yl-methyl) -oxirane and the 2- (2- Chlorphenyl) -3- (1-chloro-cyclopropyl) -3-hydroxy-4- (1,2,4-triazol-1-yl -) - but-1-ene in terms of their fungicidal properties.

The oxiranyl-hydroxyethyl-triazoles according to the invention are represented by the formula (I) generally defined.

X preferably represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, Isopropyl, methoxy and ethoxy.

Z preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, trichloromethyl, trifluor methyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluorometh oxy, nitro or for optionally single or double, similar or phenyl differently substituted by fluorine and / or chlorine.

m is preferably the number 0, 1, 2 or 3. If m is 2 or 3 stands, Z can stand for the same or different residues.

Preferred substances according to the invention are also addition products from 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 halogen water Substance acids, such as B. the hydrochloric acid and hydrobromic acid, ins especially hydrochloric acid, also phosphoric acid, nitric acid, Schwe rock acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. B. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, lemons acid, salicylic acid, sorbic acid and lactic acid and sulfonic acids, such as. B. p- Toluenesulfonic acid, 1,5-naphthalenedisulfonic acid, camphorsulfonic acid, saccharin and thiosaccharin.  

Additionally preferred compounds according to the invention are addition products from salts of metals from II. to IV. main and 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 are preferred have the meanings given.

Here are salts of copper, zinc, manganese, magnesium, tin, iron and of nickel is particularly preferred. Anions of these salts come in Considering those derived from those acids that are too physiologically acceptable Lead addition products. Particularly preferred such acids are in this Connection the hydrohalic acids, such as. B. the hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfur acid.

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

Table 1

If 2- (2-chlorophenyl) -3- (1-fluoro-cyclopropyl) -3-hydroxy-4- (1,2,4-tria zol-1-yl) -but-1-ene as starting material and 3-chloro-perbenzoic acid as reaction component, so the course of the method according to the invention by following formula scheme can be illustrated:

The starting materials in carrying out the process according to the invention required triazolyl-butenols are generally defined by the formula (II). In In this formula, X, Z and m preferably have those meanings that already in connection with the description of the substances of the invention Formula (I) was preferably mentioned for these radicals or this index.

The triazolyl-butenols of the formula (II) are known or can be prin Make known known methods (see. DE-OS 44 19 812).

Reaction components used in carrying out the process according to the invention Process all peracids customary for such reactions into consideration. Preferential Perbenzoic acid, 3-chloro-perbenzoic acid and peracetic acid can be used wisely.

Suitable diluents for carrying out the process according to the invention Process all inert, organic solvents customary for such reactions tien in question. Halogenated aliphatic carbons can preferably be used Hydrogen, such as methylene chloride, chloroform or carbon tetrachloride, and also aliphatic carboxylic acids, such as acetic acid or glacial acetic acid.

The reaction temperatures can be carried out when carrying out the process according to the invention Procedure can be varied within a certain range. In general one works at temperatures between -20 ° C and + 60 ° C, preferably between 0 ° C and 40 ° C.  

When carrying out the method according to the invention, one generally works mean under normal pressure. But it is also possible to increase or decrease pressure to work.

When carrying out the process according to the invention, the starting point is 1 mol Triazolyl-butenol of the formula (II) in general 1 to 5 mol, preferably 1.2 up to 2 moles of peracid. The processing takes place according to usual methods. in the the general procedure is to add water to the reaction mixture, several times with a water-immiscible organic solvent extracted, the combined organic phases successively with aqueous alkaline Washed solution and aqueous sodium thiosulfate solution, then dried and concentrated. The remaining residue can, if necessary, according to customary methods Example by chromatography or recrystallization, of any that may be present Impurities are freed.

The oxiranyl-hydroxyethyl-triazoles of the formula (I) according to the invention can be found in Acid addition salts or metal salt complexes are transferred.

For the preparation of acid addition salts of the compounds of the formula (I) those acids that are already related are preferred with the description of the acid addition salts according to the invention as preferred Acids were mentioned.

The acid addition salts of the compounds of formula (I) can in simpler Way according to usual salt formation methods, e.g. B. by loosening a connection of formula (I) in a suitable inert solvent and adding the Acid, e.g. As hydrochloric acid can be obtained and in a known manner, for. B. by filtration, isolated and optionally by washing with an inert organic solvents can be cleaned.

For the preparation of metal salt complexes of the compounds of the formula (I) are preferably those salts of metals that are already in the Connection with the description of the metal salt grain according to the invention plexes were mentioned as preferred metal salts.  

The metal salt complexes of the compounds of formula (I) can in simpler Be obtained by conventional methods, such. B. by solving the Metal salt in alcohol, e.g. B. ethanol and adding to compounds of Formula (I). You can metal salt complexes in a known manner, for. B. by Filter off, isolate and if necessary clean 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 Plasmodio phoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as Xanthomonas oryzae;
Pseudomonas species, such as Pseudomonas lachrymans;
Erwinia species, such as Erwinia amylovora;
Pythium species, such as Pythium ultimum;
Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as Plasmopara viticola;
Peronospora species, such as Peronospora pisi or P. brassicae;
Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera species, such as Podosphaera leucotricha;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as Pyrenophora teres or P. graminea;
(Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as Cochlioboius 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 good plant tolerance of the active ingredients in the fight against Concentrations necessary for plant diseases allow treatment of above-ground parts of plants, of seedlings and 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, Pyreno phora teres, Pseudocercosporella herpotrichoides, Erysiphe and Fusarium species. In addition, the substances according to the invention show 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 infestation and destruction by unwanted Use microorganisms.

Technical materials are not living in the present context Understand materials prepared for use in engineering have been. For example, technical materials through fiction appropriate active substances are protected against microbial change or destruction should be glue, glue, paper and cardboard, textiles, leather, wood, Paints and plastic articles, cooling lubricants and other materials that are attacked or decomposed by microorganisms. As part of the materials to be protected are also parts of production facilities,  For example, cooling water circuits called, by the multiplication of Microorganisms can be affected. As part of the present Er As technical materials, adhesives, glues and papers are preferred and cartons, leather, wood, paints, coolants and heat transfer called liquid wedges, particularly preferably wood.

As microorganisms that break down or change the technical Materials can cause, for example, bacteria, fungi, yeast, algae and called mucus organisms. The ones according to the invention preferably act Active ingredients against fungi, in particular mold, wood-staining and wood destructive pill (Basidiomycetes), as well as against mucous 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, gra nulates, aerosols, ultra-fine encapsulations in polymeric substances and in enveloping masses for seeds and ULV formulations.

These formulations are prepared in a known manner, e.g. B. by Mixing the active ingredients with extenders, i.e. liquid solvents, under Pressurized liquefied gases and / or solid carriers, if necessary  using surface-active agents, ie emulsifiers and / or Dispersing agents and / or foaming agents. In case of use of water as an extender can e.g. B. also organic solvents Auxiliary solvents can be used. As liquid solvents come in essential in question: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylene or methylene chloride, aliphatic carbons Hydrogen, such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as Butanol or glycol and their ethers and esters, ketones, such as acetone, Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solution agents such as dimethylformamide and dimethyl sulfoxide, and water; with ver liquid gaseous extenders or carriers are such liquids meant which are gaseous at normal temperature and pressure, e.g. B. aerosol propellants such as butane, propane, nitrogen and carbon dioxide; as fixed Carriers come into question: z. B. natural stone 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; as solid carriers for granules come into question: z. B. broken chene and fractionated natural rocks such as calcite, marble, pumice, sepiolite, Dolomite and synthetic granules from inorganic and organic flours as well as granules of organic material such as sawdust, coconut shells, corn pistons and tobacco stems; as an emulsifier and / or foam-generating agent come into question: z. B. non-ionic and anionic emulsifiers, such as poly oxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl poly glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethylcellulose, naturally Liche and synthetic powdery, granular or latex-shaped polymers used 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. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal  phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, Copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 weight percent active ingredient, preferably between 0.5 and 90%.

When used in crop protection, the active compounds according to the invention can be used as such or in their formulations also in a mixture with known fungicides, Bactericides, acaricides, nematicides or insecticides are used to so z. B. to broaden the spectrum of activity or to develop resistance bow. In some cases, synergistic effects also occur indicates that the mixture has a higher effect than the sum of the effects 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-carboxanide; 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-cyanophen oxy) 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, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futuberolosil, Futuberfosil , Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, 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, pyr azophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vindozolin,
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, Acephat, 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 carboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinhrhrinhrhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinothrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinothrinothrinophrinothrinophrinothrinophrinothrinophrinothrinophrinothrinophrinothrinophrine , Cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethopro phos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxurosinofionfonfonofionfonofinfonofin, fufenionophonate, fufonoxuroninfonofionfonofionfonofionfonofionfonofionfonofinofinofinfonofinofionofinfonofinofinofinfonofinofinofinfonofinofionofinfonofinofinofionofinfonofinofionofinfonofinofinofinofinofoxinoxinox ,
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Metamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, NI 25, Nitenpyram,
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, Pyrachlophhine, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflub enzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhrononium, Tronomenophoniazonium, Tri
Vamidothione, XMC, xylylcarb, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof prepared application forms such as ready-to-use solutions, suspensions, Wettable powders, pastes, soluble powders, dusts and granules will. The application is done in the usual way, e.g. B. by casting, Ver spraying, spraying, scattering, dusting, foaming, brushing etc. It it is also possible to remove the active ingredients using the ultra-low-volume process bring or the drug preparation or the drug itself into the soil inject. The seeds of the plants can also be treated.

When treating parts of plants, the active substance concentrations can be in the application forms can be varied over a wide range. They are in the generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

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

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

The means used to protect technical materials contain the Active ingredients in general in an amount of 1 to 95%, preferably from 10 to 75%.

The application concentrations of the active compounds according to the invention are directed according to the type and the occurrence of the microorganisms to be controlled and according to the composition of the material to be protected. The optimal one The amount used can be determined by test series. In general, the Application concentrations in the range of 0.001 to 5 wt .-%, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

The effectiveness and spectrum of activity of the material according to the invention protection active ingredients to be used or the means to be produced therefrom, conc  contingent or more general wording can be increased if given if other antimicrobial compounds, fungicides, bactericides, Her bicidal, insecticidal or other active substances to enlarge the range of effects strums or achieving special effects such. B. the additional protection from Insects can be added. These mixtures can have a broader effect spectrum possess as the compounds of the invention. In many cases synergistic effects, d. H. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The manufacture and use of the substances according to the invention are carried out by the following examples illustrate.

Manufacturing examples Example 1

A solution of 5 g (17 mmol) of 2- (2-chlorophenyl) -3- (1-fluorocydopropyl) -3-hydroxy-4- (1,2,4-triazd-1-yl) but-1 8 g (23 mmol) of 3-chloro-perbenzoic acid are added to 100 ml of dichloromethane and the mixture is 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 using ethyl acetate: cyclohexane = 2: 1 as the eluent on silica gel. Concentration of the eluate gives 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, CDCl₃, 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.

Manufacture of starting substances

A solution of 6.2 g (22 mmol) of 1-chloro-2- (1-fluorocydopropyl) -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 chromatographed on silica gel using ethyl acetate: cyclohexane = 2: 1 as the eluent. Concentration of the eluate gives 0.7 g (10% of theory) of (2-chlorophenyl) -3- (1-fluorocyclopropyl) -3-hydroxy-4- (1,2,4-triazol-1-yl) -but-1-en.
1 H-NMR spectrum (200 MHz, CDCl₃, 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 made under an argon atmosphere and with stirring at room temperature in a mixture of 0.85 g (35 mmol) magnesium shavings and 10 ml diethyl ether dropped in. When the addition is complete, the reaction mixture is kept under for 1 hour Reflux heated. The Grignard solution thus obtained is at room temperature with stirring in a solution of 3.8 g (28 mmol) of 1-fluorocyclopropyl chloromethyl ketone added dropwise in 10 ml of diethyl ether. When the addition is complete, it will The mixture was heated under reflux for a further 4 hours. Then you move that Reaction mixture with saturated, aqueous ammonium chloride solution, that pours resulting mixture on water and extracted several times with diethyl ether. The combined organic phases are washed with saturated, aqueous sodium chloride Solution washed and after drying over sodium sulfate by stripping of the solvent concentrated under reduced pressure. 6.2 g (90% of theory) on 1-chloro-2- (1-fluorocyclopropyl) -3- (2-chlorophenyl) but-3-en-2-ol.  

According to the method given in Example 1, those in the following Table 2 substances of formula (I) prepared.

Table 2

Example 2

δ = 0.2-1.0 (m, 4H); 2.94 (d, J = 5Hz); 3.06 (d, J = 4Hz, together 1H); 3.39 (d, J = 4Hz); 3.61 (d, J = 5Hz, together 1H); 4.27 (d, J = 14Hz); 4.52 (d, J = 15Hz, together 1H); 4.86 (d, J = 15Hz); 5.08 (d, J = 14Hz, together 1H); 5.3 (s, 1H); 7.0-7.65 (m, 4H); 8.0 (s); 8.01 (s, together 1H); 8.34 (8s, 1H) 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 1H); 8.08 (s); 8.21 (s) together 1H) ppm.

Example 4

δ = 0.1-0.8 (m, 4H); 2.83 (d, J = 5Hz); 3.0 (d) J = 4Hz, together 1H); 3.12 (d, J = 4Hz); 3.4 (d, J = 5Hz, total 111); 4.13 (d, J = 15Hz); 4.56 (d, J = 14Hz, together 1H); 4.2 (s. 1H); 4.76 (d, J = 14Hz); 4.98 (d, J = 15Hz, together 1H); 7.2-7.8 (m, 5H); 7.92 (s); 8.02 (s, total 1H); 8.27 (s); 8.42 (s, together 1H) ppm.

Example 5

δ = 0.1-1.0 (m, 4H); 2.73 (d, J = 5Hz); 2.97 (d, J = 4Hz, together 1H); 3.11 (d, J = 4Hz); 3.3 (d, J = 5Hz, together 1H); 4.12 (dd, J = 15 and 5Hz); 4.51 (d, J = 14Hz, together 1H); 4.72 (d, J = 14Hz); 4.97 (dd, J = 15 and 1 1Hz, together 1H); 7.2-7.6 (m, 4H); 8.0 (s); 8.01 (s, together 1H); 8.26 (s); 8.27 (s, together 1H) 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 1H); 8.15 (s); 8.19 (s, together 1H) ppm.

Example 7

δ = 0.1-1.0 (m, 4H); 2.64 (d, J = 5Hz); 2.79 (d, J = 5Hz); 2.8 (d, J = 6Hz); 3.39 (d, J = 6Hz, together 2H); 4.35 (dd, J = 14Hz and 1Hz); 4.54 (d, J = 14Hz, together 1H); 4.7 (d, J = 14Hz); 4.7 (dd, J = 14Hz and 1Hz, together 1H); 7.3-7.8 (m, 5H); 7.99 (s); 8.01 (s, together 1H); 8.1 (s); 8.22 (s, together 1H) ppm.  

Example 8

δ = 0.1-1.0 (m, 4H); 3.76 (d, J = 5 Hz); 3.0 (d, J = 5Hz, together 1H); 3.11 (d, J = 5Hz); 3.3 (d, J = 5Hz, together 1H); 4.12 (d, J = 15Hz); 4.52 (d, J = 15Hz, together 1H); 4.72 (d, J = 15Hz); 5.0 (d, J = 15Hz, together 1H); 7.2-7.7 (m, 4H); 8.01 (s, 1H); 8.27 (s, 1H) 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 1H); 8.5 (s); 8.52 (s) together 1H) ppm.  

Examples of use

In the following examples of use, the following was given Compound used as reference substance:

Known from EP-OS 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 alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate.

After the spray coating has dried on, the plants are coated with a conidia sprayed pension from Pyrenophora teres. The plants remain for 48 hours 20 ° C and 100% relative humidity in an incubation cabin.

The plants are grown 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.

In this test, the active ingredient according to the invention listed in Example 1 shows an application rate of 250 g / ha an efficiency of 100%.  

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 prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate. After the The plants are sprayed with spores from Erysiphe graminis f.sp.hordei pollinated.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of about 80% set up the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the inventions listed in Examples 1, 2, 4 to 6 and 8 show Active substances according to the invention have an effect at an application rate of 250 g / ha degree of 100%.  

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 prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active substance preparation in the specified application rate. After the The plants are sprayed with spores from Erysiphe graminis f.sp.tritici pollinated.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of about 80% set up the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the invention shown in Examples 1, 8 and 9 show active ingredients at an application rate of 250 g / ha an efficiency of 100%.  

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 prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate. After the The plants are sprayed with a spore suspension of Leptosphaeria sprayed nodorum. The plants remain at 20 ° C and 100% for 48 hours relative humidity in an incubation cabin.

The plants are grown 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.

In this test, the fiction, listed in Examples 5 and 6 show active ingredients at an application rate of 250 g / ha an efficiency of 100%.  

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 diluted the concentrate with water and the specified amount of emulsifier on the desired concentration.

To test for protective effectiveness, young rice plants are sprayed with the Active ingredient preparation to dripping wet. 4 days after the The plants are sprayed with an aqueous spore suspension of Pyricularia oryzae inoculated. Then the plants are in one Greenhouse at 100% rel. Humidity and 25 ° C.

The disease infestation is evaluated 4 days after the inoculation.

In this test, those listed in Examples 3 to 5 and 8 show Active substances according to the invention at an active substance concentration of 0.05% in the Spray liquid has an efficiency of 70% or more.  

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 one Concentration.

To test for protective effectiveness, young plants are treated with the Active ingredient preparation sprayed dewy. After the spray coating has dried on the plants are dusted with conidia of the fungus Sphaerotheca fuliginea.

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

Evaluation is carried out 10 days after the inoculation.

In this test, those listed in Examples 1 and 2 show Active substances according to the invention at an active substance concentration of 1 ppm in the Spray liquid has an efficiency of over 70%, while the Comparative substance (A) has an efficiency of 22%.

Claims (7)

1. 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 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
X represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy and ethoxy,
Z 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 phenyl which is optionally mono- or disubstituted, identical or different, 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 in which
X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms,
Z 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,
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 an acid or a metal salt is added to the compounds of the formula (I) thus obtained. 4. Microbicidal agents, characterized by a content of at least an oxiranyl-hydroxyethyl-triazole of the formula (I) according to claim 1 or on an acid addition salt or metal salt complex Oxiranyl-hydroxyethyl-triazole of the formula (I). 5. 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 material protection. 6. Process for controlling unwanted microorganisms in the plant Protection and material protection, characterized in that one Oxiranyl-hydroxyethyl-triazoles of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes on the microorgan organisms and / or their habitat. 7. Process for the preparation of microbicidal agents, characterized records that oxiranyl-hydroxyethyl-triazoles of the formula (I) according to Claim 1 or their metal salt complexes or acid addition salts with Extenders and / or surfactants mixed.