EP0843669A1

EP0843669A1 - Microbicidal mercapto-triazolyl-nitriles

Info

Publication number: EP0843669A1
Application number: EP96927625A
Authority: EP
Inventors: Manfred Jautelat; Ralf Tiemann; Stefan Dutzmann; Klaus Stenzel
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1995-08-08
Filing date: 1996-07-29
Publication date: 1998-05-27
Also published as: DE19529089A1; WO1997006152A1; JPH11510800A; AU6738896A

Abstract

New mercapto-triazolyl-nitriles have the formula (I), in which R1, R2, X and m have the meanings given in the description. Also disclosed are their acid addition salts and metal salt complexes, as well as a process for preparing the same and their use as plant-protecting and material-protecting microbicides.

Description

MICROBICIDAL MERCAPTO-TRIAZOLYL NITRILE

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

It has already become known that numerous azolyl nitrile derivatives have fungicidal properties (cf. EP-A 0 145 294 and DE-A 3 721 786). For example, 4- (4-chlorophenyl) -2-cyano-2-phenyl- ¹ - (l, 2,4-triazol-l-yl) butane and 2- (4-chlorophenyl) Use -2-cyano-l- (l, 2,4-triazol-l-yl) hexane to combat fungi. The effectiveness of these substances is good, but leaves something to be desired in some cases at low application rates

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

(I)

in which

R ^{1 represents} alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms and 1 to 5 halogen atoms, optionally substituted aryl or for optionally substituted aralkyl,

R ~ 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 with 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 and

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

as well as their acid addition salts and metal salt complexes

The substances according to the invention contain 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.

It has also been found that mercapto-triazolyl-nitriles of the formula (I) and their acid addition salts and metal salt complexes are obtained if triazoyl-nitriles of the formula

(II)

in which

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

with sulfur, if appropriate 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

R ¹ , X 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,

and optionally adding an acid or a metal salt to the compounds of formula (I) thus obtained

Finally, it was found that the new mercapto-triazolyl-nitriles 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 activity. Thus, the substances according to the invention outperform 4- (4-chlorophenyl) -2-cyano-2-phenyl-l- (1,2 , 4-triazol-l-yl) butane and the 2- (4-chloro phenyl) -2-cyano-l- (l, 2,4-triazol-l-yl) -hexane with regard to the fungicidal properties

The mercapto-triazolyl-nitriles 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, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, optionally single to triple, similar or different by halogen, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms with 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms and / or haloalkoxy with 1 or 2

Carbon atoms and 1 to 5 halogen atoms substituted phenyl or for optionally single to triple, identical or different by halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms and / or haloalkoxy with 1 or 2 carbon atoms and

1 to 5 halogen atoms substituted phenylalkyl with 1 to 4 carbon atoms in the alkyl part

, ->

R ~ is preferably 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

R ¹ particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, fluoro-tert-butyl, difluoro-tert-butyl, optionally one or two times, of the same type or different by

Fluorine, chlorine, methyl, ethyl, trifluoromethyl, trichloromethyl, methoxy, Ethoxy, trifluoromethoxy and / or difluoromethoxy substituted phenyl or for phenylalkyl which is monosubstituted or disubstituted in the phenyl part, once or twice, in the same way or differently, by fluorine, chlorine, bromine, methyl, ethyl, trifiuomethyl, trichloromethyl, methoxy, ethoxy, trifluoromethoxy and / or difluoromethoxy 1 or 2 carbon atoms in the alkyl part.

_v 7

R "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

m also particularly preferably stands for the numbers 0, 1, 2 or 3, where X stands for identical or different radicals, if stands for 2 or 3

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

The acids which can be added preferably include halogen acids, such as, for example, the hydrochloric acid and the hydrobromic acid, in particular the hydrochloric acid, furthermore phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example

Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids, such as 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 main groups II to IV and groups I and II and groups IV to VIII of the Periodic Table of the Elements and those mercapto

1 tπazolyl-nitriles of the formula (I) in which R, R, X and m have those meanings which have been mentioned as preferred for these substituents and this index Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to physiologically acceptable addition products. Particularly preferred acids in this context are the hydrohalic acids, such as, for example, the hydrochloric acid and the hydrobromic acid, furthermore phosphoric acid, nitric acid and sulfuric acid

The mercapto-triazolyl nitriles of the formula (I) according to the invention, in which R ^{2 is} hydrogen, can be in the "mercapto" form of the formula

or in the tautomeric "thiono" form of the formula

For the sake of simplicity, only the "mercapto" form is listed

The mercapto-triazolyl-nitriles listed in the following table may be mentioned as examples of substances according to the invention Table 1

Table 1 (continued)

If 4- (4-chlorophenyl) -2-cyano-2-phenyl-l- (l, 2,4-triazol-l-yl) butane is used as the starting material, sulfur powder as the 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 4- (4-chlorophenyl) -2-cyano-2-phenyl-l- (5-mercapto-l, 2,4-triazol-l-yl) butane is used as the starting material and methyl iodide as the reaction component, then can the course of the second stage of the process according to the invention can be illustrated by the following formula:

The Tπazolyl-nitπle required as starting materials when carrying out the process according to the invention are generally defined by the formula (II). In this formula, R ¹ , X and m preferably have those meanings which already exist in connection with the description of the substances of the formula according to the invention

(I) for these residues and this index have been mentioned as preferred

The Tπazolyl-nitπle of formula (II) are known or can be prepared by known processes (see EP-A 0 145 294 and DE-A 3 721 786)

When carrying out the first stage of the process according to the invention, all the high-boiling organic solvents customary for such reactions can be used as diluents. Amides, such as dimethylformamide and dimethylacetamide, and also lactams, such as N-methyl-pyrrohdon, and also ethers, such as, are preferably usable Diphenyl ether It is also possible to work in the absence of diluents

Sulfur is used in carrying out the first stage of the invention

Process generally used in the form of powder. 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 conventional inorganic or suitable for hydrolysis can be used organic acids. Acetic acid, dilute sulfuric acid and dilute hydrochloric acid can preferably be used. 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 nitrile of the formula (II). The processing takes place according to usual methods. In general, the procedure is such that the reaction mixture is concentrated, the remaining residue * is taken up in a ** water-immiscible organic solvent, the resulting mixture is shaken with water, optionally in the presence of an acid, or with aqueous ammonium chloride solution, which organic phase dries and evaporates. The product obtained can be freed of any impurities that may be present using customary methods, such as recrystallization or chromatography.

The when performing the second stage of the method as

Compounds of the formula (Ia) required as starting substances 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 ^" '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 metal 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 - 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 organic solvents which are customary for such reactions. 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 are preferably usable

Solvents such as dimethyl sulfoxide or dimethylformamide.

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 mol of halogen compound of the formula (III) and an equivalent amount or an excess of acid binder are generally employed per mol of mercapto-triazolyl-nitrile of the formula (Ia) on. The processing takes place according to usual 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 product obtained can optionally be processed by conventional methods, e.g. by recrystallization, from any impurities still present.

The mercapto-triazolyl-nitriles 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

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

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

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

Can be obtained 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.

Undesirable microorganisms include fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidomycetes, Deuteromycetes, and also bacteria, such as Pseudomonadaceae,

Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Enterobacteriaceae.

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 permits treatment of above-ground parts of plants, of propagation stock and seeds and of the soil

The active substances 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 can be used very well against Venturia and Sphaerotheca. They also have a very good in-vitro effect.

In the protective material, 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 meaning non-living materials which 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, adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked by microorganisms or can be decomposed. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, may also be mentioned which can be impaired by the multiplication of microorganisms. Within the scope 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 compounds 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, as well as ULV cold and warm mist formulations.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate with

Use of surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. 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, e.g. 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, are strongly polar

Solvents such as dimethylformamide and dimethyl sulfoxide, and water; liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide; come in as solid carriers

Question: eg natural rock powder, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; Solid carrier materials for granules are suitable: 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; suitable emulsifying 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 ethers,

Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; suitable dispersants are: e.g. Lignin sulfitablate and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural ones, can be used in the formulations

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 in general 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 are used, e.g. 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-l, 3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,

Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,

Dichlorophen, diclobutrazol, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, Ditalimfos, dithianon, dodine, Drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, Fenbuconazole, fenfuram, Fenitropan, fenpiclonil, fenpropidin,

Fenpropimorph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl-Aluminum, Fthalide, Fuberidazol, Furalaxyl, Fazinecec, Furmax

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, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,

Methasulf ocarb, methfuroxam, metiram, metsulfovax, myclobutanil,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,

Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb,

Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,

Quintozen (PCNB),

Sulfur and sulfur preparations, tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,

Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon,

Triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforin,

Triticonazole,

Validamycin A, vinclozolin, zineb, ziram. Bactericides:

Bronopoi, 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, 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 41 9, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinhrhrhrinhrhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinothrinothrinothrinhrinhrinhrinhrinhrinhrofhrinothrinhrhrinhrhrinhrhrinhrinhrofhrinothrinothrinhrhrinhrhrinhrofhrinothrinothrinophrinothrinothrinothrinothrinophrinothrinophrine ,

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, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,

Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox,

Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

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

Ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos,

Methamidophos, methidathione, methiocarb, methomyl, metolcarb, milbemectin,

Monocrotophos, moxidectin,

Naled, NC 184, NI 25, Nitenpyram

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, 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 usual way, e.g. 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 inject the active ingredient preparation or the active ingredient into the soil itself . The seeds of the plants can also be treated.

When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and

0.001% by weight.

In the 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 substance 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 activity of the active substances to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be produced therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or others are used Active ingredients to enlarge the spectrum of effects or to achieve special effects such as the additional protection from

Insects can be added. 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 1.68 g (5 mmol) of 4- (4-chlorophenyl) -2-cyano-2-phenyl-l - (1,2,4-tπazol-l-yl) butane, 0.32 g (10 mmol) sulfur powder and 10 ml absolute N-

Methylpyrrolidone is heated to 200 ° C. under a nitrogen atmosphere and with stirring for 47 hours. The reaction mixture is then reduced

Concentrated pressure, and the remaining residue is dissolved in ethyl acetate. The resulting mixture is shaken several times with saturated, aqueous ammonium chloride solution. The organic phase is over

Dried sodium sulfate and then concentrated under reduced pressure. The resulting crude product (1.9 g) is purified by chromatography on silica gel with a mixture of petroleum ether and ethyl acetate = 1 l as eluent. 0.7 g (38% of theory) is obtained in this way an 4- (4-chlorophenyl) -2-cyano-2-phenyl-l- (5-mercapto-l, 2,4-triazol-l-yl) butane in the form of a

Oil

Η NMR spectrum (400 MHz, CDC1 ₃ , TMS) δ = 2.4 (m, 3H), 2.75 (m, 1H), 4.5 (AB, 2H), 7.0 (d, 2H ), 7.2 (d, 2H), 7.4 (m, 3H), 7.55 (m, 2H), 7.8 (s, 1H), 1 1.7 (1H) ppm

Example A

PodosphaeraTest (apple) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl 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 efficacy, young plants are sprayed with the preparation of active compound as moist as dew. After the spray coating has dried on, the plants are dusted with conidia of the apple mildew pathogen

(Podosphaera leucotricha) inoculated.

The plants are then placed in a greenhouse at 23 ° C. and a relative atmospheric humidity of approx. 70%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency which corresponds to that of the untreated 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

PodosphaeraTest (apple) / protective

Claims

claims

1. Mercapto-triazolyl-nitriles of the formula

in which

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

Carbon atoms and 1 to 5 halogen atoms, optionally substituted aryl or optionally substituted aralkyl,

R ~ 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 and

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

as well as their acid addition salts and metal salt complexes. Mercapto-triazolyl-nitriles of the formula (I) according to Claim 1, in which

R ¹ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, optionally single to triple, identical or different by halogen, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms with 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms and / or haloalkoxy with 1 or 2 carbon atoms and 1 to 5 halogen atoms, substituted phenyl or for optionally mono- to triple, identical or different by halogen, Alkyl with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms and / or haloalkoxy with 1 to 2 carbon atoms and 1 to 5 halogen atoms substituted phenylalkyl with 1 to 4 carbon atoms in the alkyl part,

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

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

Methylthio, trichloromethyl, trifluoromethyl, trifiuormethoxy,

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 phenyl and

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

A process for the preparation of mercapto-tπazolyl nitriles of the formula (I) according to claim 1 and of their acid addition salts and metal salt complexes, characterized in that tπazolyl nitriles of the formula (II)

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

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

in which

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

with halogen compounds of the formula

R ³ -Hal (III)

in which

R ^ 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 adding an acid or a metal salt to the compounds of formula (I) thus obtained.

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

Use of mercapto-triazolyl nitriles 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 the material

Process for combating undesirable microorganisms in crop protection and in material protection, characterized in that mercapto-triazolyl-nitriles of the formula (I) according to Claim 1 or their acid addition salts or metal salt complications are applied to the microorganisms and / or their habitat

Process for the preparation of microbicidal agents, characterized in that mercapto-triazolyl-nitriles of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes are mixed with extenders and / or surface-active substances