DE19521030A1 - Mercapto-triazolylethanols - Google Patents

Abstract

Novel mercapto-triazolyl-ethanols of the formula (I) in which R<1>, R<2>, X, Y and m have the meanings given in the description, and their acid addition salts and metal salt complexes, a process for the production of these substances and their use as microbicides in plant and material protection.

Description

The present invention relates to new mercapto-triazolylethanols, a process for their preparation and their use as microbicides.

It has already become known that numerous azolyl ethanol derivatives are fungicidal Have properties (cf. DE-A 23 24 010 and DE-A 27 37 489). So you can for example 1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutan-2-ol use to combat fungi. The effectiveness of this substance is good but leaves something to be desired in some cases at low application rates.

There have now been new mercapto-triazolylethanols of the formula

in which
R¹ for alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, cycloalkyl with 3 to 7 carbon atoms optionally substituted by halogen and / or alkyl with 1 to 4 carbon atoms, cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, optionally phenyl substituted by halogen or benzyl optionally substituted by halogen,
R² represents hydrogen or alkyl having 1 to 4 carbon atoms,
X represents halogen, nitro, 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 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 represents the numbers 0, 1, 2 or 3 and
Y represents an oxygen atom or a CH₂ group,
as well as their acid addition salts and metal salt complexes.

The substances according to the invention contain two asymmetrically substituted ones Carbon atoms and can therefore in the form of diastereomers (threo form or erythro form) or enantiomers. The present invention relates to both the individual isomers and their mixtures.

It was also found that mercapto-triazolylethanols of the formula (I) as well as their acid addition salts and metal salt complexes, if one Triazolylethanols of the formula

in which
R¹, X, Y and m have the meanings given above,
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

in which
R¹, X, Y and m have the meanings given above,
with halogen compounds of the formula

R³-Hal (III)

in which
R³ represents alkyl having 1 to 4 carbon atoms and
Hal represents chlorine, bromine or iodine,
in the presence of an acid binder and 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 mercapto-triazolylethanols of the formula (I) and their 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 one microbicidal activity as the most constitutionally similar, known  Connections with the same direction of action. So surpass those of the invention Substances that 1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethyl-butan-2-ol regarding the fungicidal properties.

The mercapto-triazolylethanols according to the invention are represented by the formula (I) generally defined.

R¹ preferably represents straight-chain or branched alkyl having 1 to 4 Carbon atoms, fluoroalkyl having 1 to 4 carbon atoms and 1 to 5 Fluorine atoms, optionally single to triple, similar or differently substituted by fluorine, chlorine, bromine, methyl and / or ethyl Cycloalkyl with 3 to 6 carbon atoms, cycloalkylalkyl with 3 to 6 Carbon atoms in the cycloalkyl part and 1 to 3 carbon atoms in the Alkyl part, optionally single to triple, the same or different phenyl substituted by fluorine, chlorine and / or bromine or for if necessary, single to triple, identical or different Fluorine, chlorine and / or bromine substituted benzyl.

R² is preferably hydrogen, methyl or ethyl.

X preferably represents fluorine, chlorine, bromine, nitro, methyl, ethyl, tert.- Butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, Trifluoromethoxy, difluoromethoxy, trifluoromethylthio, optionally single or double, similar or different due to fluorine, chlorine, Bromine and / or methyl substituted phenyl or for optionally single or double, similar or different due to fluorine, chlorine, Bromine and / or methyl substituted phenoxy.

m also preferably represents the numbers 0, 1, 2 or 3, where X is the same or different radicals when m is 2 or 3.

Y also preferably represents an oxygen atom or a CH₂ group.

R¹ particularly preferably represents methyl, isopropyl, tert-butyl, fluoro-tert.- butyl, difluoro-tert-butyl, optionally single to triple, similar or differently substituted by fluorine, chlorine and / or methyl Cyclopropyl, cyclopentyl or cyclohexyl, for cycloalkylalkyl with 3 to 6  Carbon atoms in the cycloalkyl part and 1 or 2 carbon atoms in the Alkyl part, optionally single or double, similar or phenyl or substituted by fluorine, chlorine and / or bromine for optionally single or double, similar or different benzyl substituted by fluorine, chlorine and / or bromine.

R² also particularly preferably represents hydrogen, methyl or ethyl.

X particularly preferably represents fluorine, chlorine, bromine, nitro, methyl, ethyl, tert-butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, Trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl or Phenoxy.

Y also particularly preferably represents an oxygen atom or a CH₂- Group.

m also particularly preferably represents the numbers 0, 1, 2 or 3, where X is the same or different radicals is when m is 2 or 3.

Preferred compounds according to the invention are also addition products from Acids and those mercapto-triazolylethanols of the formula (I) in which R¹, R², X, Y and m have those meanings which are for these substituents and this index was mentioned as preferred.

The acids that can be added preferably include halogen water Substance acids, such as B. the hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as. B. Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, Salicylic acid, sorbic acid and lactic acid, and sulfonic acids, such as. B. p-toluene sulfonic acid and 1,5-naphthalenedisulfonic acid, or 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 Mercapto  triazolylethanols of the formula (I) in which R¹, R², X, Y and m are those Have meanings that are preferred for these radicals and this index were.

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.

The mercapto-triazolylethanols of the formula (I) according to the invention in which R² represents hydrogen, can be in the "mercapto" form of the formula

or in the tautomeric "thiono" form of the formula

available. For the sake of simplicity, only the "Mercapto" shape is used listed.

Examples of substances according to the invention are those in the following table listed mercapto-triazolyl-ethanols called.  

Table 1

If 1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethyl-butan-2-ol is used as raw material, n-butyl lithium as strong base and sulfur powder as reak tion component, the course of the first stage of the invention Procedure can be illustrated by the following formula scheme:

If 1- (4-chlorophenoxy) -1- (5-mercapto-1,2,4-triazol-1-yl) -3,3- is used dimethyl-butan-2-ol as the starting material and methyl iodide as the reaction component, the course of the second stage of the method according to the invention can be carried out the following formula scheme can be illustrated:

The starting materials in carrying out the process according to the invention required triazolylethanols are generally defined by the formula (II). In of this formula, R 1, X, Y and m preferably have those meanings which already in connection with the description of the substances of the invention Formula (I) for these radicals and this index have been mentioned as preferred.

The triazolylethanols of the formula (II) are known or can be reduced produce known processes (cf. DE-A 23 24 010 and DE-A 27 37 489).

The bases used in carrying out the first stage of the invention Process all strong alkali metal bases usual for such reactions in Consideration. N-Butyl-lithium, lithium-diisopropyl are preferably usable amide, sodium hydride, sodium amide and also potassium tert-butoxide in a mixture with Tetramethylethylene diamine (= TMEDA).

When performing the first stage of the method according to the invention come all inert organic solvents customary for such reactions as a diluent. Ethers such as Tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane, more liquid Ammonia or strongly polar solvents, such as dimethyl sulfoxide.

Sulfur is preferably used in the form of powder. For hydrolysis used in the implementation of the first stage of the invention Process water, optionally in the presence of an acid. Come into question all inorganic or organic customary for such reactions Acids. Acetic acid, dilute sulfuric acid and  dilute hydrochloric acid. However, it is also possible to use aqueous hydrolysis Perform ammonium chloride solution.

The reaction temperatures can be carried out when carrying out the first stage of The inventive method varies within a certain range will. In general, temperatures between -70 ° C and + 20 ° C, preferably between -10 ° C and 0 ° C.

When performing all steps of the method according to the invention works one generally under normal pressure.

When carrying out the first stage of the method according to the invention generally 2 to 3 per mole of triazolylethanol of the formula (II) Equivalents, preferably 2.0 to 2.5 equivalents, of strong base and subsequently ßend an equivalent amount or an excess of sulfur. The Implementation can take place under a protective gas atmosphere, e.g. B. under nitrogen or argon, be made. The processing takes place according to usual methods. in the general procedure is such that the reaction mixture with a in water little soluble organic solvent extracted, the combined organic phases dries and evaporates and the remaining residue if necessary Recrystallization and / or chromatography cleans.

The when performing the second stage of the method as Starting substances required compounds of formula (Ia) are fiction appropriate fabrics.

The in the implementation of the method according to the invention in the second stage Halogen compounds required as reaction components are by the Formula (III) generally defined.

R³ is preferably methyl or ethyl.

Hal also preferably represents chlorine, bromine or iodine.

The halogen compounds of the formula (III) are known.  

When carrying out the second stage of the inventions, acid binders are used Process according to the invention in all the usual inorganic or organic bases Question. Alkaline earth or alkali metal hydroxides such as Sodium hydroxide, calcium hydroxide, potassium hydroxide, or ammonium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hy bicarbonate, sodium bicarbonate, alkali or alkaline earth metal acetates such as Sodium acetate, potassium acetate, calcium acetate, and tertiary amines, such as trimethyl amine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methyl piperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabi cyclonones (DBN) or diazabicycloundecene (DBU).

As a diluent when performing the second stage The inventive method all inert for such reactions organic solvents. Ethers such as Diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydro furan and dioxane, also nitriles, such as acetonitrile, and also strongly polar Solvents such as dimethyl sulfoxide or dimethylformamide.

The reaction temperatures can be carried out in the second stage of the the inventive method can be varied within a wide range. In general, temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 100 ° C.

When carrying out the second stage of the method according to the invention per 1 mol of mercapto-triazolylethanol of the formula (Ia) generally 1 to 2 mol of halogen compound of the formula (III) and an equivalent amount or an excess of acid binder. The processing takes place after usual methods. In general, you do that Reaction mixture with aqueous base and a water-immiscible added organic solvent, the organic phase is separated, dried and constricts. The product obtained can optionally by conventional methods, for. B. by recrystallization, from any impurities still present.

The mercapto-triazolyl- obtainable by the process according to the invention Ethanol of formula (I) can be used in acid addition salts or metal salt complexes be 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 called.

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 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 good plant tolerance of the active ingredients in the control of the plant necessary concentrations allows treatment of whether he earthly parts of plants, planting and seeds and 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 Pseudocercosporella, Erysiphe and Fusarium species. In addition, the substances according to the invention are very good against Venturia and  Use Sphaerotheca. They also have a very good 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.

In the present context, technical materials include non-living ones Understand materials prepared for use in engineering have been. For example, technical materials through fiction appropriate active ingredients are protected against microbial change or destruction adhesives, glues, 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 multiplication of micro organisms can be affected. Within the scope of the present invention as technical materials are preferably adhesives, glues, papers and Cardboard boxes, leather, wood, paints, coolants and heat transfer called liquids, 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 fungi (Basidiomycetes) and 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 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, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

The active ingredients can depend on their respective physical and / or chemical properties are converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, Aerosols, ultra-fine encapsulations in polymeric substances and in coating compositions for Seed, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, e.g. B. by Vermi the active ingredients with extenders, i.e. liquid solvents, under pressure standing liquefied gases and / or solid carriers, optionally under Use of surface-active agents, i.e. 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 such as Alcohols can be used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes 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 Solvents such as dimethylformamide and dimethyl sulfoxide, and water; With liquefied gaseous extenders or carriers are such Liquids are meant, which at normal temperature and under normal pressure are gaseous, e.g. B. aerosol propellants such as halogenated hydrocarbons such Butane, propane, nitrogen and carbon dioxide; come in as solid carriers Question: e.g. B. natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic Rock powders such as finely divided silica, aluminum oxide and silicates; as solid carriers for granules are possible: z. B. broken and frak tioned natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well synthetic granules from inorganic and organic flours as well Granules made of organic material such as sawdust, coconut shells, corn cobs  and tobacco stems; come in as emulsifying and / or foaming agents Question: e.g. B. nonionic and anionic emulsifiers, such as polyoxyethylene Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylarylpolygylcol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a disper yaws are possible: B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural 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 phthalalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc can be used.

In crop protection, the formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.

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 can be used, e.g. B. the we broaden the range of products or prevent the development of resistance.

The following substances are suitable for the mixtures, for example.

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, ampro pylfos, 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, Fenpropimorph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futrianolide, Futrianol, Futin 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, pyrazophos, 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, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, 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, Caftap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocytezhrinhrinhrinhrinhrinhrinhrinotin, Clofythrinhrinhrinhrinhrinhrin, Clofythrinhrinhrinhrinhrin, Clofythrinhrinhrinhrin, Clofythrinhrinhrinhrin, Clofythrinhrinhrinotin Cyhexatin, 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, Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin, Lambda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, 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, Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazine, Thuringiensin, Tralomenhrononium, Triomenethriazonium, 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, Spray powder, pastes, soluble powders, dusts and granules are used 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 use the ultra-low-volume method bring or the drug preparation or the drug itself into the soil to 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 in a larger area: 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.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1 wt .-%, preferably from 0.0001 to 0.02 wt .-% required at the site of action Lich.  

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 use quantity can be determined by test series. Generally the applications are concentration in the range of 0.001 to 5% by weight, preferably of 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 that can be produced therefrom, Kon concentrates or more general wording can be increased if given if necessary, other antimicrobial compounds, fungicides, bactericides, Herbicides, insecticides or other active substances to increase the effectiveness spectrum or achieving special effects such. B. the additional protection from Insects can be added. These blends can have a broader impact have spectrum than the compounds of the invention.

The manufacture and use of the substances according to the invention are based on following examples.

Manufacturing examples example 1

A mixture of 1.48 g (5 mmol) of 1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethyl-butan-2-ol and 30 ml of absolute tetrahydrofuran is mixed at -20 ° C with 4 ml (10 mmol) of n-butyl lithium in hexane and stirred at -20 ° C for 30 minutes. Then the reaction mixture is mixed at -20 ° C with 0.19 g (6 mmol) of sulfur powder, then stirred for 1 hour at -20 ° C and then for 2 hours at 0 ° C. 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 (1.9 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 0.7 g (43% of theory) of 1- (4-chlorophenoxy) -1- (5-mercapto-1,2,4-triazol-1-yl) -3,3-dimethyl- butan-2-ol in the form of a solid of melting point 193 to 194 ° C.
MS (ci): 328 (M + H⁺).

Claims (7)

1. Mercapto-triazolylethanols of the formula in which
R¹ is alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, cycloalkyl with 3 to 7 carbon atoms optionally substituted by halogen and / or alkyl with 1 to 4 carbon atoms, cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, optionally phenyl substituted by halogen or benzyl optionally substituted by halogen,
R² represents hydrogen or alkyl having 1 to 4 carbon atoms,
X represents halogen, nitro, 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 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 represents the numbers 0, 1, 2 or 3 and
Y represents an oxygen atom or a CH₂ group,
as well as their acid addition salts and metal salt complexes. 2. mercapto-triazolylethanols of the formula (I) according to claim 1, in which
R¹ for straight-chain or branched alkyl with 1 to 4 carbon atoms, fluoroalkyl with 1 to 4 carbon atoms and 1 to 5 fluorine atoms, optionally single to triple, identical or different by fluorine, chlorine, bromine, methyl and / or ethyl-substituted cycloalkyl with 3 to 6 carbon atoms, cycloalkylalkyl with 3 to 6 carbon atoms in the cycloalkyl part and 1 to 3 carbon atoms in the alkyl part, optionally single to triple, identical or different phenyl substituted by fluorine, chlorine and / or bromine or for optionally single to triple, similar or different by fluorine , Chlorine and / or bromine substituted benzyl,
R² represents hydrogen methyl or ethyl,
X for fluorine, chlorine, bromine, nitro, methyl, ethyl, tert-butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, optionally single or double, identical or different by fluorine, chlorine, bromine and / or Methyl-substituted phenyl or phenoxy which is optionally mono- or disubstituted, identical or different by fluorine, chlorine, bromine and / or methyl,
m 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 represents an oxygen atom or a CH₂ group. 3. A process for the preparation of mercapto-triazolylethanols of the formula (I) according to Claim 1 and of their acid addition salts and metal salt complexes, characterized in that triazolylethanols of the formula in which
R¹, X, Y and m have the meanings given above,
reacted 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 resulting compounds of the formula in which
R¹, X, Y and m have the meanings given above,
with halogen compounds of the formula R³-Hal (III) in which
R³ represents alkyl having 1 to 4 carbon atoms and
Hal represents chlorine, bromine or iodine,
in the presence of an acid binder and in the presence of a diluent,
and optionally then adding an acid or a metal salt to the compounds of formula (I) thus obtained. 4. Microbicidal agents, characterized by a content of at least a mercapto-triazolylethanol of the formula (I) according to claim 1 or on an acid addition salt or metal salt complex of a mercapto triazolylethanols of the formula (I). 5. Use of mercapto-triazolyl ethanols of the formula (I) according to Claim 1 or of their acid addition salts or metal salt Complexes as microbicides in crop protection and material protection. 6. Methods for combating undesirable microorganisms in the Plant protection and material protection, characterized in that one Mercapto-triazolylethanols of the formula (I) according to Claim 1 or the latter Acid addition salts or metal salt complexes on the microorganisms and / or their habitat. 7. Process for the preparation of microbicidal agents, thereby characterized in that mercapto-triazolylethanols of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes with Extenders and / or surfactants mixed.