WO1997005119A1

WO1997005119A1 - Microbicidal 2-phenylethyl-mercapto-triazoles

Info

Publication number: WO1997005119A1
Application number: PCT/EP1996/003221
Authority: WO
Inventors: Manfred Jautelat; Ralf Tiemann; Stefan Dutzmann; Klaus Stenzel
Original assignee: Bayer Aktiengesellschaft
Priority date: 1995-08-02
Filing date: 1996-07-22
Publication date: 1997-02-13
Also published as: JPH11510492A; AU6735596A; EP0842158A1; DE19528300A1

Abstract

New 2-phenylethyl-mercapto-triazoles 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, a process for preparing the same and their use as plant-protecting and material-protecting microbicides.

Description

MICROBICIDES 2-PHENYLETHYL ERCAPT0-TRIAZ0LE

The present invention relates to new 2-phenylethyl-mercapto-triazoles, a process for their preparation and their use as microbicides.

It has already become known that numerous 2-phenylethyl azolyl derivatives have fungicidal properties (cf. DE-A 2 735 872 and EP-A 0 234 242). For example, 2- (2,4-dichlorophenyl) -l- (1,2,4-triazol-l-yl) -pentane and 2- (2,4-dichlorophenyl) -l- (1,2,4 -triazol-l-yl) -3- (l, l, 2,2-tetrafluoroethoxy) propane to combat fungi. The effect of these substances is good, but leaves something to be desired in some cases at low application rates.

There have now been new 2-phenylethyl-mercapto-triazoles of the formula

in which

R ¹ for alkyl with 1 to 10 carbon atoms, haloalkyl with 1 to 6

Carbon atoms and 1 to 5 halogen atoms, fluoroalkoxyalkyl with 1 to 4 carbon atoms in the fluoroalkoxy part and 1 to 4 carbon atoms in the alkyl part, cycloalkyl with 3 to 7 carbon atoms optionally substituted by halogen and / or alkyl with 1 to 4 carbon atoms, cycloalkylalkyl with 3 to 7 carbon atoms in the Cycloalkyl part and 1 to

4 carbon atoms in the alkyl part, phenyl optionally substituted by halogen or phenylalkyl optionally substituted by halogen with 1 to 4 carbon atoms in the alkyl part,

.-.

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 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, 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 was also found that 2-phenylethyl-mercapto-triazoles of the formula

(I) and their acid addition salts and metal salt complexes are obtained when 2-phenylethyl-triazoles of the formula

in which

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

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

in which

R, X 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 2-phenylethyl-mercapto-triazoles of the formula (I) and their acid addition salts and metal salt complexes have very good microbicidal properties and can be used both in crop protection and in protective materials.

Surprisingly, the substances according to the invention have a better microbicidal activity than the structurally most similar, known compounds of the same action. Thus, the substances according to the invention outperform 2- (2,4-dichlorophenyl) -l- (1,2,4-triazol-l-yl) pentane and 2- (2,4-dichlorophenyl) -l - (l, 2,4-triazol-l-yl) -3- (l, l, 2,2-tetrafluoroethoxy) propane with regard to the fungicidal properties.

The 2-phenylethyl-mercapto-triazoles according to the invention are generally defined by the formula (I).

R ¹ preferably represents straight-chain or branched alkyl having 1 to 6

Carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, fluoroalkoxyalkyl having 1 to 3 carbon atoms and _ ^■ - up to 5 fluorine atoms in Fluoralkoxyteil and 1 to 3 carbon atoms in the alkyl part, optionally mono- up to three times, similar or different

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 by fluorine, chlorine and / or Bromine-substituted phenyl or phenylalkyl with 1 or 2 carbon atoms in the alkyl part which is optionally monosubstituted to triple, identical or different 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 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 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, isobutyl, sec-butyl, tert-butyl, haloalkyl with 1 to 4 carbon atoms and 1 to 5 fluorine and chlorine - And / or bromine atoms, fluoroalkoxyalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine atoms in the fluoroalkoxy part and 1 or 2 carbon atoms in the alkyl part, optionally single to triple, identical or different, substituted by fluorine, chlorine and / or methyl, cyclopropyl, cyclopentyl or cyclohexyl, for cycloalkylalkyl with 3 up 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 optionally substituted mono- or disubstituted, similarly or differently by fluorine, chlorine and / or bromine Benzyl.

, 9th

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 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 2-phenylethyl-mercapto-triazoles 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 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 and of the I. and II. And IV

VIII. Subgroup of the Periodic Table of the Elements and Those 2- Phenylethyl-mercapto-triazoles of the formula (I) in which R ¹ , R ² , X 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 such acids in this connection are the hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, as well as phosphoric acid, nitric acid and sulfuric acid.

The 2-phenylethyl-mercapto-triazoles 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 2-phenylethyl-mercapto-triazoles listed in the following table may be mentioned as examples of substances according to the invention. Table 1

- 8th -

Table 1 - continued

- 9 -

Table 1 - continued

X m R ¹ R ²

4-C1 -CH, -O-CF, -CHF, H

2,4-Cl, -CH ₂ -O-CF ₃ H

4-F -CH ₂ -O-CF ₂ -CHF ₂ H

2-C1 -CH ₂ -O-CF ₂ -CHF ₂ H

2,4-Cl, -CH, CH,

2,4-Cl- -C ₂ H ₅ CH,

2,4-CL -CH (CH ₃ ) ₂ CH,

4-C1 -C H CH,

2,4-CL -C ₄ H ₉ -n CH,

2,4-Cl- -CH-C ₂ H ₅ CH,

CH,

2,4-Cl-, -C (CH ₃ ) ₃ CH,

2-C1 -C ₃ H ₇ -n CH ₃

2-OCF, -C ₃ H ₇ -n CH,

4-CF, -C ₃ H ₇ -n CH,

4-CH, -C ₃ H ₇ -n CH,

2,4,6-Cl, -C ₃ H ₇ -n CH,

2,4-Cl, V CH,

Cl

4-F -C ₃ H ₇ CH,

2,4-Cl, CH,

ΣL - 10th

Table 1 - continued

11

Table 1 - continued

12th

If 2- (2,4-dichlorophenyl) -l- (l, 2,4-triazol-l-yl) pentane is used as the starting material, sulfur powder as the reaction component and N-methylpyrrolidone as the diluent, it can be used the course of the first stage of the process according to the invention can be illustrated by the following formula:

If 2- (2,4-dichlorophenyl) -l- (5-mercapto-l, 2,4-triazol-l-yl) pentane is used as the starting material and methyl iodide as the reaction component, the course of the second stage of The method according to the invention can be illustrated by the following formula scheme:

Formula (II) provides a general definition of the 2-phenylethyltriazoles required as starting materials when carrying out the process according to the invention. In this formula, R ¹ , X 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 2-phenylethyl-triazoles of the formula (II) are known or can be prepared by known processes (cf. DE-A 2 735 872 and EP-A 0 234 242).

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, e.g. 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 are preferably usable

Hydrochloric acid. 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 2-phenylethyltriazole of the formula (II). The processing takes place according to usual methods. In general, the reaction mixture is concentrated, the remaining residue is taken up in an organic solvent which is not very miscible with water, the resulting mixture is shaken out with water, optionally in the presence of an acid, or with aqueous ammonium chloride solution, and the organic phase dries and constricts. 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.

The halogen compounds required as reaction components in carrying out the process according to the invention in the second stage are indicated by

Formula (III) generally defined.

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, calcium acetate, and also tertiary amines, such as trimethylamine, 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 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 mol of halogen compound of the formula (III) and an equivalent amount or else an excess are generally employed per mol of 2-phenylethyl-mercapto-triazole of the formula (Ia) of acid binders. The processing takes place according to usual methods. In general, you do that

Reaction mixture with aqueous base and a water-immiscible organic solvent are added, 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 2-phenylethyl-mercapto-triazoles 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 the formula (I), preference is given to those acids which are already preferred in connection with the description of the acid addition salts according to the invention

Acids were called.

The acid addition salts of the compounds of formula (I) can be easily prepared by conventional 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 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

Filter off, isolate and if necessary clean by recrystallization. The active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.

The undesirable microorganisms include fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidio-mycetes, Deuteromycetes, and also bacteria, such as Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomyceae.

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; (Coni form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus;

(Coni 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 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 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 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. 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 break down or change 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, like 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 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 using 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. also organic solvents like

Alcohols can 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, as well as 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 flours, such as kaolins, clays, talc, chalk,

Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and

Granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foaming agents are possible: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; suitable dispersants are: e.g. Lignin sulfite liquor 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 phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.

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 activity spectrum 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-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,

Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxosolidone, edoloxazidololidolol, epidonolol, epidonolol, epidonolol, epidonol, epidonol, epidonol, epidonol

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil,

Flutriafol, folpet, fosetyl aluminum, fthalides, fuberidazole, furalaxyl, furmecyclox, guazatine,

Hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, Iprobefos (IBP), iprodione, isoprothiolan,

Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam _. Metiram, Metsulfovax, Myclobutanil, Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, oxadixyl, oxamocarb, oxycarboxin,

Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,

Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, 5 pyrazophos, pyrifenox, pyrimethanil, pyroquilone,

Quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,

Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, \ ζ> Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin,

Triticonazole,

Validamycin A, vinclozolin,

Zineb, ziram.

Bactericides:

15 Bronopol, 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, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha-20 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, 25 Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Taposulfan, Taposulfan

419, CGA 1 84699, chloethocarb, chlorethoxyfos, chlorfenvinphos,

Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin,

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

Cyhexatin, cypermethrin, cyromazine, 30 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, 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

Omethoat, 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, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyrphroxifen, Pyriproxifen, Pyriproxifen

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, is also possible.

The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions,

Spray powder, pastes, soluble powders, dusts and granules can be used. They are used in a customary manner, for example by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to remove the active ingredients using the ultra-low-volume process. bring or inject the drug preparation or the drug itself into the soil. 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 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 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 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. - 24 -

Manufacturing examples

example 1

A mixture of 1.42 g (5 mmol) of 2- (2,4-dichlorophenyl) -l- (l, 2,4-triazol-l-yl) pentane, 0.32 g (10 mmol) of sulfur Powder and 10 ml of absolute N-methyl pyrrolidone are heated to 200 ° C. under a nitrogen atmosphere and with stirring for 3 hours. The reaction mixture is then concentrated under reduced pressure. The remaining residue is mixed with ethyl acetate and 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 (2.1 g) is purified by chromatography on silica gel using a mixture of petroleum ether and ethyl acetate = 1: 1 as the eluent. In this way 1.5 g (95% of theory) of 2- (2,4-dichlorophenyl) -l- (5-mercapto-l, 2,4-triazol-l-yl) pentane in are obtained Form of a solid with a melting point of 103 ° C.

Example A

Podosphaera test (apple) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, it is mixed

1 part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate 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 inoculated by dusting with conidia of the powdery mildew regulator (Podosphaera leucotricha).

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 one

Efficiency that corresponds to that of some of the untreated controls, whereas an efficiency of 100% means that no infection is observed.

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

T bel le A

Podosphaera test (apple) / protective

Claims

claims

1. 2-phenylethyl-mercapto-triazoles of the formula

in which

R ¹ for alkyl with 1 to 10 carbon atoms, haloalkyl with 1 to 6

Carbon atoms and 1 to 5 halogen atoms, fluoroalkoxyalkyl with 1 to 4 carbon atoms in the fluoroalkoxy part and 1 to 4 carbon atoms in the alkyl part, cycloalkyl with 3 to 7 carbon atoms optionally substituted by halogen and / or alkyl with 1 to 4 carbon atoms, cycloalkylalkyl with 3 to 7 carbon atoms in the Cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, optionally substituted by halogen phenyl or represents optionally substituted by halogen phenylalkyl having 1 to 4 carbon atoms in the alkyl part,

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 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, and

m represents the numbers 0, 1, 2 or 3, as well as their acid addition salts and metal salt complexes

2. 2-phenylethyl-mercapto-triazoles of the formula (I) according to claim 1, in which

R ^{1 is} straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6

Carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, fluoroalkoxyalkyl with 1 to 3 carbon atoms and 1 to 5 fluorine atoms in the fluoroalkoxy part and 1 to 3 carbon atoms in the alkyl part, 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 by fluorine, chlorine and / or Bromine-substituted phenyl or phenylalkyl with 1 or 2 carbon atoms in the alkyl part which is optionally monosubstituted to trisubstituted, in the same way or differently, 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 is 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

3 Process for the preparation of 2-phenylethyl-mercapto-triazoles of the formula (I) according to Claim 1 and of their acid addition salts and Metal salt complexes, characterized in that 2-phenylethyltriazoles of the formula

in which

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 optionally treated with water and, if appropriate, with acid and, if appropriate, the resulting compounds of the formula

in which

R, X 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 subsequent to the compounds thus obtained

Formula (I) added an acid or a metal salt.

4. Microbicidal agents, characterized by a content of at least one 2-phenylethyl-mercapto-triazole of the formula (I) according to claim 1 or of an acid addition salt or metal salt compl ex of a 2-phenylethyl-mercapto-triazole of the formula (I).

5. Use of 2-phenylethyl-mercapto-triazoles 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 the material, characterized in that 2-

Phenylethyl-mercapto-triazoles 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 in that 2-phenylethyl-mercapto-triazoles of the formula (I) according to

Claim 1 or their acid addition salts or metal salt complexes mixed with extenders and / or surface-active substances.