WO1997006151A1

WO1997006151A1 - Microbicidal mercapto-triazolyl-ketones

Info

Publication number: WO1997006151A1
Application number: PCT/EP1996/003335
Authority: WO
Inventors: Manfred Jautelat; Ralf Tiemann; Stefan Dutzmann; Klaus Stenzel
Original assignee: Bayer Aktiengesellschaft
Priority date: 1995-08-08
Filing date: 1996-07-29
Publication date: 1997-02-20
Also published as: EP0843668A1; AU6738796A; DE19529091A1; JPH11510799A

Abstract

New mercapto-triazolyl-ketones have the formula (I), in which R1, R2, 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

MICROBICIDAL MERCAPTO TRIAZOLYL KETONES

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 have fungicidal properties (cf. DE-A 2 201 063 and DE-A 2 737 489). For example, l- (4-chlorophenoxy) -l- (1,2,4-triazol-l-yl) -3,3-dimethylbutan-2-one can be used to combat fungi. The effectiveness of this substance is good, but leaves something to be desired in some cases at low application rates.

There have now been new mercapto-triazolyl ketones of the formula

in which

R ¹ for alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 4

Carbon atoms and 1 to 5 halogen atoms, optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, optionally by halogen substituted phenyl or benzyl optionally substituted by halogen,

R ^{2 represents} hydrogen or alkyl having 1 to 4 carbon atoms,

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

Carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkylthio with 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 for optionally halogen and / or alkyl phenoxy substituted with 1 to 4 carbon atoms,

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

Y represents an oxygen atom or a CH ₂ group,

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

The substances according to the invention contain at least one asymmetrically substituted carbon atom and can therefore be obtained in the form of enantiomers. The present invention relates both to the individual isomers and to their mixtures.

Furthermore, it has been found that mercapto-triazolyl ketones of the formula (I) and their acid addition salts and metal salt complexes are obtained if triazolyl ketones of the formula

in which

R ¹ , X, Y and m have the meanings given above,

with sulfur if appropriate in the presence of a high-boiling diluent and then optionally with water and optionally with

Treated acid and optionally the resulting compounds of formula

in which

R ¹ , X, Y and m have the meanings given above,

with halogen compounds of the formula

R ³ - shark (III)

in which

R ^{3 represents} alkyl having 1 to 4 carbon atoms and

Shark 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 have very good microbicidal properties and both in crop protection and in

Material can be used in a protective manner.

Surprisingly, the substances according to the invention have a better microbicidal activity than the constitutionally most similar, known compounds of the same direction of action. Thus, the substances according to the invention outperform l- (4-chlorophenoxy) -l- (1,2,4-triazol-l-yl) -3,3-dimethylbutan-2-one in terms of their fungicidal properties. The mercapto-triazolyl-ketones according to the invention are generally defined by the formula (I).

R ¹ 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 monosubstituted to trisubstituted, similarly or differently, 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, identical or different phenyl substituted by fluorine, chlorine and / or bromine or for optionally single to triple, similar or benzyl substituted differently by fluorine, chlorine and / or bromine.

R ² preferably represents hydrogen, methyl or ethyl.

X preferably represents fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy,

Difluoromethoxy, trifluoromethylthio, optionally mono- or disubstituted, identical or different phenyl substituted by fluorine, chlorine, bromine and / or methyl or phenoxy optionally substituted mono- or disubstituted, identical or different by fluorine, chlorine, bromine and / or methyl.

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

Y also preferably represents an oxygen atom or a CH ₂ group.

R ¹ particularly preferably represents methyl, isopropyl, tert-butyl, fluoro-tert-butyl, difluoro-tert-butyl, optionally single to triple, identical or different, cyclopropyl, cyclopentyl or cyclohexyl substituted by fluorine, chlorine and / or methyl , for cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl part and 1 or 2 carbon atoms in the alkyl part, optionally mono- or disubstituted, identical or different phenyl substituted by fluorine, chlorine and / or bromine or for optionally single or double, identical or different benzyl substituted by fluorine, chlorine and / or bromine.

R ² also particularly preferably represents hydrogen, methyl or ethyl.

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

Y also particularly preferably represents an oxygen atom or a CH ₂ group.

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

Preferred compounds according to the invention are also addition products of acids and those mercapto-triazolyl-ketones of the formula (I) in which R ¹ , R ² , X, Y and m have those meanings which have been mentioned as preferred for these substituents and this index.

The acids that can be added preferably include hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, e.g. Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids, e.g. p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid, or camphorsulfonic acid, saccharin and thiosaccharin.

In addition, preferred compounds according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. And IV. To VIII. Subgroup of the periodic table of the elements and those mercapto-triazolyl-ketones of the formula (I), in those R ¹ , R ² , X, Y and m have those meanings which have been mentioned as preferred for these radicals and this index.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts come in Consideration which are derived from those acids which lead to physiologically tolerable addition products. Particularly preferred acids in this connection are the hydrohalic acids, such as hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulfuric acid.

The mercapto-triazolyl-ketones according to the invention of the formula (I) in which R ^{2 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" form is listed in each case.

The mercapto-triazolyl-ketones listed in the following table may be mentioned as examples of substances according to the invention.

Table 1

151

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

If 1 - (4-chlorophenoxy) - 1 - (1, 2,4-triazol-1-yl) -3,3-dimethylbutan-2-one is used as starting material, sulfur powder as reaction component and N- Methyl pyrrolidone as a diluent, the course of the first stage of the process according to the invention can be illustrated by the following formula:

If one uses l- (4-chlorophenoxy) -l- (5-mercapto-l, 2,4-triazol-l-yl) -3,3-dimeth-yl-butan-2-one as starting material and methyl iodide as Reaction component, the course of the second stage of the process according to the invention can be illustrated by the following formula:

- C (CH ₃ 3) '3 H ₃ 3)' 3

Formula (II) provides a general definition of the triazolyl ketones required as starting materials when carrying out the process according to the invention. In this formula, R ¹ , X, Y and m preferably have those meanings which have already been mentioned as preferred for these radicals and this index in connection with the description of the substances of the formula (I) according to the invention. The triazolyl ketones of the formula (II) are known or can be prepared by known processes (cf. DE-A 2 201 063 and DE-A 2 737 489).

When carrying out the first stage of the process according to the invention, all high-boiling organic solvents customary for such reactions are suitable as diluents. Are preferably usable

Amides, such as dimethylformamide and dimethylacetamide, also heterocyclic compounds, such as N-methyl-pyrrolidone, and also ethers, such as diphenyl ether. However, it is also possible to work in the absence of diluents.

Sulfur is generally used in the form of powder when carrying out the first stage of the process according to the invention. The reaction can be carried out under a protective gas atmosphere, for example under nitrogen or argon. After the reaction, treatment with water and, if appropriate, with acid can optionally be carried out. All the usual inorganic or organic acids suitable for hydrolysis come into question. Acetic acid, dilute sulfuric acid and dilute hydrochloric acid are preferably usable. However, it is also possible to carry out the aftertreatment with aqueous ammonium chloride solution.

The reaction temperatures can be varied within a substantial range when carrying out the first stage of the process according to the invention. In general, temperatures between 150 ° C and 300 ° C, preferably between 180 ° C and 250 ° C.

When carrying out all steps of the process according to the invention, the procedure is generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure. Working under increased pressure is particularly important when carrying out the first stage.

When carrying out the first stage of the process according to the invention, 1 mol to 5 mol, preferably 1.5 to 3 mol, of sulfur are generally employed per mol of triazolyl ketone of the formula (II). The processing takes place according to usual methods. In general, the procedure is that the reaction the mixture is concentrated, the remaining residue is taken up in an organic solvent which is difficult to mix with water, the resulting mixture is shaken out with water, optionally in the presence of an acid, or with aqueous ammonium chloride solution, the organic phase is dried and concentrated. The product obtained can be freed of any impurities which may be present using customary methods, such as recrystallization or chromatography.

The compounds of the formula (Ia) required as starting substances when carrying out the second stage of the process according to the invention are substances according to the invention.

Formula (III) provides a general definition of the halogen compounds required as reaction components in carrying out the process according to the invention in the second stage.

R ³ preferably represents methyl or ethyl.

Shark also preferably represents chlorine, bromine or iodine.

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

Suitable acid binders for carrying out the second stage of the process according to the invention are all customary inorganic or organic bases. Alkaline earth or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, aminate, and trimethyl acetate, as well as terti, are preferably usable - Amine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

Suitable diluents for carrying out the second stage of the process according to the invention are all inert, customary for such reactions organic solvents. Ethers such as diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane, furthermore nitriles such as acetonitrile and also strongly polar solvents such as dimethyl sulfoxide or dimethylformamide can preferably be used.

The reaction temperatures can be varied within a substantial range when carrying out the second stage of the process according to the invention. In general, temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 100 ° C.

When carrying out the second stage of the process according to the invention, 1 to 2 are generally employed per mol of mercapto-triazolyl-ketone of the formula (Ia)

Mole of halogen compound of formula (III) and an equivalent amount or an excess of acid binder. Working up is carried out according to customary methods. In general, the procedure is such that aqueous base and a water-immiscible organic solvent are added to the reaction mixture, the organic phase is separated off, dried and concentrated. The received

If necessary, the product can be prepared by customary methods, e.g. by recrystallization, from any impurities still present.

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

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

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

Be obtained by conventional salt formation methods, for example by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and in a known manner, for example by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent.

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

The metal salt complexes of the compounds of formula (I) can be obtained in a simple manner by conventional methods, e.g. by dissolving the metal salt in alcohol, e.g. Ethanol and adding to compounds of formula (I). Metal salt complexes can be prepared in a known manner, e.g. by filtering, isolating and, if necessary, cleaning by recrystallization.

The active compounds according to the invention have a strong microbicidal action and can be used to protect against undesirable microorganisms, such as fungi and bacteria, in crop protection and in the material.

The undesirable microorganisms include fungi, such as Piasmodi ophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidio-mycetes, Deuteromycetes, and also bacteria, such as Pseudomonadaceae, Rhizobiaceae, Enterobateriaceae and Corynebacteriaceae.

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

The active compounds according to the invention are particularly suitable for controlling Pyricularia oryzae and Pellicularia sasakii on rice and for controlling 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 attack and destruction by undesired microorganisms.

In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked or decomposed by microorganisms can be. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, may also be mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma such as Sclerophoma pityophila, Trichoderma such as Trichoderma viride, Escherichia such as Escherichia coli, Pseudomonas such as Pseudomonas aeruginosa, Staphylococcus such as Staphylococcus aureus.

Depending on their respective physical and / or chemical properties, the active ingredients can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm fog formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. If water is used as an extender, organic solvents such as alcohols can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons, and also butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

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

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

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

When used in crop protection, the active compounds according to the invention can be used in the formulations in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to 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-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phen- oxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S,

Bromuconazole, Bupirimate, Buthiobate,

Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazole, dicloflomolanidol, dicloflomolanidolol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, diclofolomidol, dicloflolonidol, dicloflomolonidol, dicloflolomolonidol , Dinocap, Diphenylamine, Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon, Edifenphos, Epoxyconazole, Ethirimol, Etridiazol, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fentropinimamate, Fefropacimate, Fefropacimate, Fefropimimimone

Fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl aluminum, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion, Isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture, Mancopper, Mancozeb, Maneb, Mepan Mepronil, metalaxyl, metconazole,

Methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickel-dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoat, penconazole, pencycuron, phosicinoxin, phosicinoxin 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:

Bronαpol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alpha-methrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,

Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin,

Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157

419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chl orfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin,

Clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin,

Cyhexatin, cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron,

Diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate,

Dimethylvinphos, dioxathione, 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, flufenprox, fluvalinate, fonophos, formothion, fosthiazat, fubfenprox, furathiocarb, hch, heptenophos, hexaflumuron, hexythiazox, imidacloprid, isofoshrinophone, isofoshrinophosphorosinoxin, isofoshroxin, isofoxin, iodosfosofin, isofoxin, isphosphonosinoxin, isfoshroxin, isotrophin, isfoshroxin Lufenuron,

Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyd, Methacrifos, Methami dophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram Omethoat, Oxofon Moxemyl, Oxamyl, Oxamyl, Oxyd

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos,

RH 5992,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralathenethrin, Triarathenethrin

Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, XMC, Xylylcarb, Zetamethrin.

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

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to prepare the active ingredient or the like Inject active ingredient into the soil yourself. The seeds of the plants can also be treated. In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

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

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

The agents used to protect industrial materials generally contain the active ingredients in an amount of 1 to 95%, preferably 10 to 75%.

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

The effectiveness and the spectrum of action of the active ingredients to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be produced therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or others are used Active ingredients to increase the spectrum of activity or to achieve special effects such as added protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

The preparation and use of the substances according to the invention can be seen from the following examples. Manufacturing examples

example 1

A mixture of 2.93 g (10 mmol) l- (4-chlorophenoxy) -l- (1,2,4-triazol-l-yl) -3,3-dimethylbutane ~ 2-one, 0 , 64 g (20 mmol) sulfur powder and 10 ml absolute N-

Methylpyrrolidone is heated to 200 ° C. for 8 hours under a nitrogen atmosphere and with stirring. The reaction mixture is then concentrated under reduced pressure and the remaining residue is dissolved in dichloromethane. The resulting mixture is shaken out several times with saturated, aqueous ammonium chloride solution.

The organic phase is dried over sodium sulfate and then concentrated under reduced pressure. The resulting crude product (2.7 g) is purified by chromatography on silica gel with a mixture of petroleum ether and ethyl acetate = 1: 1 as the eluent. In this way, 2.0 g (62% of theory) of l- (4-chlorophenoxy) -l- (5-mercapto-l, 2,4-triazol-l-yl) -3,3-dimethyl- butan-2-one in the form of a solid with a melting point of 134 to 136 ° C.

Example A

Cochliobolus sativusTest (barley) / protective

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

Emulsifier: 0.6 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate.

After the spray coating has dried on, the plants are sprayed with a conidia suspension of Cochliobolus sativus.

The plants remain at 20 ° C and 100 ° C rel. 48 hours. Humidity in an incubation cabin.

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.

Evaluation is carried out 7 days after the inoculation. 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

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

Cochliobolus sativusTest (barley) / protective

Claims

claims

1. Mercapto-triazolyl-ketones of the formula

in which

R ¹ for alkyl having 1 to 6 carbon atoms, haloalkyl mitl bis

4 carbon atoms and 1 to 5 halogen atoms, optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, optionally substituted by halogen Phenyl or benzyl optionally substituted by halogen,

R ^{2 represents} hydrogen or alkyl having 1 to 4 carbon atoms,

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

Haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkylthio with 1 to 4 carbon atoms and 1 to 5 halogen atoms, optionally by halogen and / or alkyl with 1 to 4 carbon atoms substituted phenyl 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 CH ₂ 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

R ^{1 is} 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, identical or different, cycloalkyl substituted by fluorine, chlorine, bromine, methyl and / or ethyl 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 by fluorine, chlorine and / or

Bromine-substituted phenyl or benzyl which is optionally monosubstituted to triple, identical or different by fluorine, chlorine and / or bromine,

R ^{2 represents} hydrogen, methyl or ethyl,

X for fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy,

Methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, optionally mono- or disubstituted, identical or different by fluorine, chlorine, bromine and / or methyl-substituted phenyl or optionally mono- or disubstituted, identical or different 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 CH ₂ group.

3. A process for the preparation of mercapto-triazolyl-ketones of the formula (1) according to claim 1 and of their acid addition salts and metal salt complexes, characterized in that triazolyl-ketones of the formula

in which

R ¹ , X, Y and m have the meanings given above,

reacted with sulfur, if appropriate in the presence of a high-boiling diluent, and then optionally treated with water and, if appropriate, with acid and, if appropriate, the compounds of the formula formed in the process

in which

R ¹ , X, Y and m have the meanings given above,

with halogen compounds of the formula

R ³ -Hal (III)

in which

R ^{3 represents} alkyl having 1 to 4 carbon atoms and

Shark represents chlorine, bromine or iodine, in the presence of an acid binder and in the presence of a diluent,

4. Microbicidal agents, characterized in that they contain at least one mercapto-triazolyl ketone of the formula (I) according to Claim 1 or an acid addition salt or metal salt complex of a mercapto-triazolyl ketone of the formula (I).

5. Use of mercapto-triazolyl-ketones of the formula (I) according to Claim 1 or of their acid addition salts or metal salt complexes as microbicides in crop protection and in material protection.

6. A method for controlling undesirable microorganisms in crop protection and in material protection, characterized in that 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 deploys.

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