DE19529091A1 - Mercapto triazolyl ketones - Google Patents

Abstract

New mercapto-triazolyl-ketones have the formula (I), in which R<1>, R<2>, X, Y and m have the meanings given in the description. Also disclosed are their acid addition salts and metal salt complexes, a process for preparing the same and their use as plant-protecting and material-protecting microbicides.

Description

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

It has already become known that numerous azolyl ketone derivatives are fungicidal Have properties (cf. DE-A 22 01 063 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-one 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-triazolyl ketones 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, optionally substituted by halo and / or alkyl with 1 to 4 carbon atoms substituted cycloalkyl with 3 to 7 carbon atoms, cycloalkylalkyl with 3 to 7 carbon atoms in Cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, optionally substituted by halogen-substituted phenyl or optionally substituted by halogen-substituted benzyl,
R² represents hydrogen or alkyl having 1 to 4 carbon atoms,
X represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkyl thio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms or phenoxy optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms,
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 at least one asymmetrically substituted tes carbon atom and can therefore arise in the form of enantiomers. The The present invention relates to both the individual isomers and their Mixtures.

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

in which
R¹, X, Y and m have the meanings given above,
reacted with sulfur in the presence of a high-boiling diluent and then optionally treated with water and optionally with 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.

Finally, it was found that the new mercapto-triazolyl ketones of the formula (I) and their acid addition salts and metal salt complexes very good micro have bicidal properties and both in crop protection and in Material protection can be used.

Surprisingly, the substances according to the invention have a better micro bicidal activity as the most constitutionally similar, known compounds same direction of action. The substances according to the invention thus exceed the 1- (4- Chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutan-2-one with regard to the fungi ziden properties.  

The mercapto-triazolyl-ketones according to the invention are general by the formula (I) my 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, if necessary single to triple, similar or ver separated 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, 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 for optionally single or double, identical or different by 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 ver separated by fluorine, chlorine and / or bromine substituted phenyl or for  optionally single or double, identical or different Fluorine, chlorine and / or bromine substituted benzyl.

R² also particularly preferably represents hydrogen, methyl or ethyl.

X particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, tert.- Butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluor methoxy, 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 when in is 2 or 3.

Preferred compounds according to the invention are also addition products from Acids and those mercapto-triazolyl-ketones of the formula (I) in which R¹, R², X, Y and 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. Vinegar acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicyl acid, sorbic acid and lactic acid, and sulfonic acids, such as. B. p-toluenesulfone 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 triazolyl-ketones of the formula (I) in which R¹, R², X, Y and in those meaning tions that have been mentioned as preferred for these residues and this index.

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-triazolyl-ketones of the formula (I) according to the invention, in which R² is 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 shown guided.

Examples of substances according to the invention are those in the following table led Mercapto-triazolyl-ketones called.  

Table 1

If 1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutan-2-one is used as a starting material, sulfur powder as a reaction component and N-methyl-pyr rolidone as a diluent, so the course of the first stage of it inventive method illustrated by the following formula will:

If 1- (4-chlorophenoxy) -1- (5-mercapto-1,2,4-triazol-1-yl) -3,3-dimeth is used yl-butan-2-one as the starting material and methyl iodide as the reaction component, see above can the course of the second stage of the inventive method by the following formula scheme can be illustrated:

The starting materials in carrying out the process according to the invention required triazolyl ketones 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 triazolyl ketones of the formula (II) are known or can be prepared Manufacture process (cf. DE-A 22 01 063 and DE-A 27 37 489).

When performing the first stage of the method according to the invention come as diluent all usual for such reactions, high boiling organic solvents. Are preferably usable Amides such as dimethylformamide and dimethylacetamide, also heterocyclic Compounds, such as N-methyl-pyrrolidone, and also ethers, such as diphenyl ether.

Sulfur is used when performing the first stage of the invention Process generally used in the form of powder. The implementation can in a protective gas atmosphere, for example under nitrogen or argon men. After the implementation, treatment with Water and optionally with acid. Come into question all common inorganic or organic suitable for hydrolysis Acids. Acetic acid, dilute sulfuric acid and dilute hydrochloric acid. However, it is also possible to use aqueous aftertreatment Perform ammonium chloride solution.

The reaction temperatures can be carried out when carrying out the first stage of the inventive method can be varied within a wide range. In general, temperatures between 150 ° C and 300 ° C, preferably between 180 ° C and 250 ° C.

When performing all steps of the method according to the invention works one generally under atmospheric pressure. But it is also possible under to work under increased or reduced pressure. So comes especially at the Carrying out the first stage of working under increased pressure in question.

When carrying out the first stage of the method according to the invention 1 to 5 moles per 1 mole of triazolyl ketone of the formula (II), preferably 1.5 to 3 moles of sulfur. The processing takes place after usual methods. In general, the procedure is such that the reaction Mix the mixture, mix the remaining residue in a little with water  absorbable organic solvent, the resulting mixture with water, optionally in the presence of an acid, or with aqueous ammonium chloride Shake out the solution, the organic phase dries and concentrates. The received The product can be prepared using conventional methods such as recrystallization or chromato graphic, to be freed of any existing impurities.

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 generally 1 to 2 per 1 mol of mercapto-triazolyl-ketone of the formula (Ia) Mol of halogen compound of the formula (III) and an equivalent amount or also an excess of acid binder. The processing takes place according to methods. In general, the procedure is such that the reaction mixture with an aqueous base and an organic solution which is not very miscible with water medium added, the organic phase is separated off, dried and concentrated. The received Product can optionally by conventional methods such. B. by recrystallization sation, to be freed of any remaining impurities.

The mercapto-triazolyl ketones obtainable by the process according to the invention of the formula (I) can be converted into acid addition salts or metal salt complexes will.

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 Zu connection with the description of the metal salt complexes according to the invention 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 loosening 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 filtering, 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, called:

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;
Sphacrotheca 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 allow treatment of upper 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 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 halogenated hydrocarbons such as butane, propane, stick fabric and carbon dioxide; as solid carriers come into question: B. natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder, how high disperse silica, aluminum oxide and silicates; as solid carriers for Granules are possible: B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as an emulsifier and / or foam-generating agents are possible: z. B. non-ionic and  anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fat alcohol ether, e.g. B. Alkylarylpolygylkol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations 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:

Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cydopropyl-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-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, Methfüroxam, 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, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinhrhrhrinhrhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrhrinhrhrinhrhrinhrhrinhrinhrofhrinophhrinhrinhrinhrinhrinhrinhrinhrinhrinhrhrinhrhrinhrinhrhrinhrhrinhrhrinhrhrinhrofhrine Cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat,
Dimethylvinphos, dioxathione, disulfoton,
Edifenphos, Emamectin, Esfenval erat, 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, M 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 2.93 g (10 mmol) of 1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3- dimethyl-butan-2-one, 0.64 g (20 mmol) sulfur powder and 10 ml absolute N- Methylpyrrolidone is stirred under nitrogen for 8 hours heated to 200 ° C. The reaction mixture is then reduced Concentrated pressure and the remaining residue is dissolved in dichloromethane. The resulting mixture is washed several times with saturated, aqueous ammonium chloride solution shaken out.

The organic phase is dried over sodium sulfate and then under ver reduced pressure. The resulting crude product (2.7 g) is by Chro Matography on silica gel with a mixture of petroleum ether and acetic acid ethyl ester = 1: 1 cleaned as eluent. This gives 2.0 g (62% of theory) on 1- (4-chlorophenoxy) -1- (5-mercapto-1,2,4-triazol-1-yl) -3,3-dimethyl butan-2-one in the form of a solid with a melting point of 134 to 136 ° C.

Claims (7)

1. Mercapto-triazolyl-ketones 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, cycloalkyl alkyl 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, 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-triazolyl-ketones 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, methyl, ethyl, tert. -Butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, di fluoromethoxy, trifluoromethylthio, optionally phenyl substituted once or twice, similarly or differently by fluorine, chlorine, bromine and / or methyl or for optionally monosubstituted or doubly, similarly or differently by fluorine , Chlorine, bromine and / or methyl substituted phenoxy,
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-triazolyl-ketones of the formula (I) according to claim 1 and of their acid addition salts and metal salt complexes, characterized in that triazolyl-ketones of the formula in which
R¹, X, Y and m have the meanings given above,
with sulfur in the presence of a high-boiling diluent and then optionally treated with water and optionally with acid and optionally 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-triazolyl ketone of the formula (I) according to claim 1 or an acid addition salt or metal salt complex of a mercapto triazolyl ketones of the formula (I). 5. Use of mercapto-triazolyl-ketones of the formula (I) according to An saying 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-triazolyl-ketones of the formula (I) according to Claim 1 or their Acid addition salts or metal salt complexes on the microorganisms and / or their habitat. 7. Process for the preparation of microbicidal agents, characterized is characterized in that mercapto-triazolyl-ketones of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes with Extenders and / or surfactants mixed.