WO1997001547A1 - Benzazole derivatives with microbiocidal properties - Google Patents

Abstract

The present invention concerns novel benzazole derivatives, a method of preparing them and their use as microbiocides for protecting plants and materials.

Description

 BENZAZOLE DERIVATIVES WITH MICROBIOCID PROPERTIES

The present invention relates to new benzazole derivatives, a process for their preparation and their use as microbicides in crop protection and in

Protect material.

It has already become known that certain benzazole derivatives have insecticidal and acaricidal properties (cf., for example, DE A 2334356). However, microbicidal properties of these compounds have hitherto not been known.

There have now been new benzazoles of the formula (I)

in which

n represents 1 or 2,

R ¹ , R ² , R ³ and R ⁴ individually independently of one another for hydrogen, halogen, cyano, nitro, in each case optionally substituted alkyl, cycloalkyl,

Alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aryl or heterocyclyl, or

R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ together with the carbon atoms to which they are attached form a further, optionally substituted, carbocyclic or heterocyclic ring,

stands for oxygen or sulfur and

X represents hydrogen or halogen, found, the compound 6-chloro-2-difluoromethylsulfonylbenzthiazol is excluded.

In the definitions, the hydrocarbon chains, such as alkyl, are in each case straight-chain or branched, also in combination with heteroatoms, such as in alkoxy, alkylthio or alkylamino.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular chlorine or bromine.

Aryl is exemplary and preferably aromatic, mono or polycyclic hydrocarbon rings, e.g. Phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl.

Heterocyclyl is an example and preferably for saturated or unsaturated, as well as aromatic, ring-shaped compounds, in which at least one ring member is a heteroatom, i. H. is an atom other than carbon. If the ring contains several heteroatoms, these can be the same or different. Heteroatoms are preferably oxygen, nitrogen or sulfur. If appropriate, the ring-shaped compounds together with other carbocyclic or heterocyclic, fused or bridged rings together form a polycyclic ring system. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems.

Cycloalkyl is an example and preferably for saturated, carbocyclic, ring-shaped compounds which, if appropriate, form a polycyclic ring system with further carbocyclic, fused or bridged rings.

It was also found that the benzazoles of the formula (I) are obtained if thioethers of the general formula (II)

in which

R ¹ , R ² , R ³ , R ⁴ , Q and X have the meanings given above,

with an oxidizing agent, if appropriate in the presence of a diluent, if appropriate in the presence of a catalyst and if appropriate in the presence of a phase transfer catalyst.

Finally, it was found that the benzazoles of the formula (I) have very good microbicidal properties and can be used in material protection and in crop protection.

The compounds according to the invention can optionally be in the form of mixtures of various possible isomeric forms, in particular stereoisomers, such as e.g. optical isomers. Both the R and the S isomers and any mixtures of these isomers are claimed.

The invention preferably relates to compounds of the formula (I) in which

n represents 1 or 2,

R ¹ , R ² , R ³ and R ⁴ individually independently of one another for hydrogen, fluorine, chlorine, bromine, cyano, nitro, alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms, haloalkyl haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 8 carbon atoms and 1 to 5 identical or different halogen atoms, for each in the phenyl or heteroaryl part, if appropriate, simply to triple, identical or different by Ha¬ logenous, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, straight-chain or branched haloalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms substituted Phenyl, pyridyl or pyrimidyl, or R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ together with the carbon atoms to which they are attached, for another, optionally by halogen, cyano, nitro, alkyl having 1 to 8 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each with 1 to 8 carbon atoms, haloalkyl

Halogenalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 8 carbon atoms and 1 to 5 identical or different halogen atoms substituted, six-membered, aromatic ring, or

R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ for an alkylene chain with 3 which is optionally monosubstituted to tetrasubstituted by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms or 4 members in which one or two (non-adjacent) carbon atoms can be replaced by oxygen atoms,

Q stands for oxygen or sulfur and

X represents hydrogen or halogen,

the compound 6-chloro-2-difluoromethylsulfonylbenzthiazol is excluded.

The invention relates in particular to compounds of the formula (I) in which

n represents 1 or 2,

R ¹ , R ² , R ³ and R ⁴ individually independently of one another for hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Cyclopropyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio ,

Methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluoromethloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylfluoromethyl, trifluoromethyl, trifluoromethyl for each in the phenyl or heteroaryl part, if appropriate, from one to three times, identical or different by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, Cyclopropyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, Methylsulfinyl,

Ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoro ethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, chloromethylthio difluoromethyl, are trifluoromethylsulphinyl or trifluoromethylsulphonyl substitutable tuiertes phenyl, pyridyl or pyrimidyl, or

R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ together with the carbon atoms to which they are attached, for a further one, optionally by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-

Butylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorethoxy, difluoromethylthio, trifluoromethylthio, difluoromethyltrifluoromifluoromifluoromifluoromifluoromifluoromethylsifluoromethylsifluoromethylsifluoromethylsifluoromethylsifluoromethyl

R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ together for an optionally single to quadruple, identical or different, substituted by fluorine, chlorine, methyl, trifluoromethyl or ethyl alkylene chain with 3 or 4 links, in one or two (non-adjacent) carbon atoms can be replaced by oxygen atoms,

Q stands for oxygen or sulfur and

X represents hydrogen or bromine,

the compound 6-chloro-2-difluoromethylsulfonylbenzthiazol is excluded.

These radical definitions can be combined with one another as desired, that is to say also between the specified ranges of preferred compounds. Examples of the compounds of the formula (I) according to the invention are listed in Table 1:

Table 1:

Formula (II) provides a general definition of the thioethers required as starting materials for carrying out the process according to the invention. In this formula (II) R ¹ , R ² , R, R ⁴ , Q and X preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred were preferably given for R ¹ , R ² , R ³ , R ⁴ , Q and X.

The starting materials of the formula (II) are known and / or can be prepared by processes which are known per se (cf., for example, DE A 2334356).

The process according to the invention is carried out using an oxidizing agent. Hydrogen peroxide, its salts and its adducts with z. B. urea, t-butyl peroxide, peracids or their salts, such as performic acid, peracetic acid, perpropionic acid, perbenzoic acid, 3-

Chloroperbenzoic acid, potassium hydrogen persulfate, potassium peroxodisulfate, sodium perborate, sodium percarbonate or sodium peroxodisulfate, also also potassium permanganate, or sodium perrhenate, also also chlorous or hypochlorous acid or their metal salt solutions in water.

The process according to the invention is optionally carried out using a catalyst. Salts of metals of IV., V. and VI. Are preferred as catalysts. Subgroup of the Periodic Table of the Elements. Examples include sodium (meta) vanadate, sodium molybdate and sodium tungstate.

The process according to the invention is optionally also carried out in a two-phase system, such as water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst. Examples of such catalysts are: tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tributylmethylphosphonium bromide, trimethyl-C ₁₃ / C _{] 5-} alkylammonium chloride, trimethyl-C ₁₃ / C ₁₅ -alkylammonium bromide, dibenzylmethyl sulfonate , Dimethyl-C ₁₂ / C _{] 4} -alkyl-benzylammonium chloride, dimethyl-C ₁₂ / C ₁₄ -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5 or 18-crown-6-ammonium chloride Tris [2- (2-methoxy ethoxy) ethyl] amine.

Suitable diluents for carrying out the process according to the invention are all inert organic solvents. This includes preferably aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane or trichloroethane; Ethers, such as diethyl ether,

Diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Acids such as formic acid, acetic acid or propionic acid; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-

Dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or Hexamethyl¬ phosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with Water or pure water.

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.

To carry out the process according to the invention for the preparation of the compounds of the formula (I), in the event that n is 1, 1 to 1.5 equivalents, preferably 1 to, are generally employed per mole of the thioether of the formula (II) 1.2 equivalents of oxidizing agent.

To carry out the process according to the invention for the preparation of the compounds of the formula (I), in the event that n is 2, 2 to 10 equivalents, preferably 2 to 5 equivalents, are generally employed per mole of the thioether of the formula (II) of oxidizing agent.

The process according to the invention is generally carried out under normal pressure. It is also possible, however, under increased or reduced pressure

- generally between 0.1 bar and 10 bar - to work. 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.

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 that 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 that can be attacked or decomposed by microorganisms.

Parts of are also within the scope of the materials to be protected

Production plants, such as cooling water circuits, called by

Propagation of microorganisms can be affected. 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 called.

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 or agents according to the invention preferably act against fungi, in particular mold, 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 versucorum, Polyporusicol, Polyporusicol , 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.

Fungicidal agents in crop protection are used to combat plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes. Some pathogens of fungal diseases which fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or

Pseudoperonospora cubense;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora pisi or Peronospora brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or Pyrenophora graminea (conidial form: Drechslera, synonym: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, 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 and also treatment of plants and seeds and the soil.

Depending on their respective physical and / or chemical properties, the active compounds of the formula (I) can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances.

These formulations or agents 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 foaming agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, 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 or 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 and butane, propane, nitrogen and carbon dioxide; solid carriers are possible: e.g. 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; 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 as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; emulsifying and / or foaming agents are possible: e.g. non-ionic 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; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers, 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, ferrocyanin 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.

The effectiveness and the spectrum of activity of the active compounds of the formula (I) or the agents, precursors or very generally formulations which can be prepared therefrom can be increased if, if appropriate, further antimicrobial agents Compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients to increase the spectrum of action or to achieve special effects such as, for example, additional protection against insects are added. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

In many cases, synergistic effects are obtained, i. H. the effectiveness of the mixture is greater than the effectiveness of the individual components. Particularly favorable mix partners are e.g. the following connections:

Triazoles such as: Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole,

Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazole, Isozofos, Myclobutanil, Metconazole, Epoxyconazole, Paclobutrazol, Penconazole, Propioconazole, (+) - cis-l- (4-chlorophenyl) -2, (l -triazol-l-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.

Imidazoles such as:

Imazalil, pefurazoate, prochloraz, triflumizole, 2- (1-tert-butyl) - l- (2-chlorophenyl) - 3- (l, 2,4-triazol-l-yl) -propan-2-ol, thiazolecarboxanilide as 2 ', 6'-dibromo-2-methyl ^ -trifluoromethoxy ^' - trifluoromethyl-l ^ -thiazole-S-carboxanilide, 1-

Imidazolyl-l- (4'-chlorophenoxy) -3,3-dimethylbutan-2-one and their metal salts and acid adducts.

Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylate, methyl (E) -2- [2- [6- (2-thioamidophenoxy) pyrimidine -4-yloxy] phenyl] -3- methoxyacrylates, methyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3- m ethoxy acrylates, methyl (E) - 2- [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy acrylate, methyl (E) -2- [2- [3 - (pyrimidin-2- yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl- (E) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dimethylbenzoyl) pyrrol-l-yl] -3- methoxyacrylate, methyl (E) -2- [2- (3-methoxyphenoxy) phenyl] -3-methoxyacrylates, methyl (E) -2- [2- (2-phenylethen-l-yl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl (E) -2- (2- (3- (1,1,2,2-tetrafluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate, methyl (E) -2- (2- [3 - (alpha-hydroxybenzyl) phenoxy] pheny l) -3-methoxy acrylate, methyl (E) -2- (2- (4-phenoxy pyridin-2-yloxy) phenyl) -3-methoxyacrylate, methyl ( E) -2- [2- (3-n-propyloxyphenoxy) phenyl] -3-methoxy acrylate, methyl (E) -2- [2- (3-isopropyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxy acrylates, methyl (E) -2- [2- (3-ethoxyphenoxy) phenyl] - 3-methoxy acrylates, methyl (E) -2- [2- (4-tert-butyl pyridin-2-y 1 oxy) phenyl] -3-methoxy acrylates, methyl (E) -2- [2- [ 3 - (3-cyanophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3-methylpyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl (E) -2 - [2- [6- (2-methylphenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- (5-bromopyridin-2-yloxyme thyl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, (E), (E) methyl-2- [2- (5,6-dimethylpyr∑ιzin-2- ylmethyloximinomethyl) phenyl] -3-methoxyacrylate, (E) -methyl- 2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, (E), ( E) methyl-2- {2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methyl-2- {2- (6- (2-azidophenoxy) pyrimidin-4-yloxy] phenyl} 3-methoxyacrylates, (E), (E) methyl-2- {2- [6-phenylpyrimidin-4-yl) methyloximinomethyl] phenyl} -3-methoxyacrylates, (E), (E) methyl-2- {2 - [(4-chlorophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methyl-2- {2- [6- (2-n-propylphenoxy) -l, 3,5-triazine-4 -yloxy] phenyl} -3-methoxyacrylate, (E), (E) methyl-2- {2 - [(3-nitrophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate;

Succinate dehydrogenase inhibitors such as:

Fenfuram, furcarbanil, cyclafiuramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (moncut);

Naphthalene derivatives such as terbinafine, naftifine. Butenafine, 3-chloro-7- (2-aza-

2,7,7-trimethyl-oct-3-en-5-in); Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;

Benzimidazoles, such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate methyl, thiabendazole or their salts; Morpholine derivatives, such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph, aldimorph, fenpropidine and their aryl sulfonic acid salts, such as, for example, p-toluene sulfonic acid and p-dodecylphenyl sulfonic acid;

Dithiocarbamates such as Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram;

Benzothiazoles such as 2-mercaptobenzothiazole;

Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide;

Boron compounds such as boric acid, boric acid esters, borax;

Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poly) hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide,

Paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;

Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) - tributyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper;

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylene isothiazolinones,

4,5-benzisothiazolinone, N-methylolchloroacetamide;

Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde;

Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc;

quaternary ammonium compounds, such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride;

Iodine derivatives, such as diiodomethyl p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodallyl alcohol, 3 -Bromine-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl-cyclohexyl carbamate, 3 Iodine-2-propynylphenyl carbamate; Phenol derivatives, such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali and alkaline earth metal salts;

Microbicides with activated halogen group, such as chloroacetamide, bronopol,

Bronidox, tectamers such as 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxyacetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4 -dicyanobutane, ß- B rom-ß-nitrosty rol;

Pyridines, such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mri, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, 1-

Hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1H) pyridine;

Metal soaps, such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;

Metal salts, such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate,

Copper fluorosilicate;

Oxides such as tributyltin oxide, Cu ₂ O, CuO, ZnO;

Dialkyldithiocarbamates, such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;

Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;

Quinolines such as 8-hydroxyquinoline and their Cu salts;

Mucochloric acid, 5-hydroxy-2 (5H) furanone;

4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-dichloro- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetrahydro-l, 3, 5-thiadiazin-2-thione,

N- (2-p-chlorobenzoylethyl) hexaminium chloride, potassium N-hydroxymethyl-N'-methyl-dithiocarbamate, 2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride, Phenyl- (2-chloro-cyanovinyl) sulfone, phenyl- (1,2-dichloro-2-cyanovinyl) sulfone; Zeolites containing Ag, Zn or Cu alone or included in polymeric active substances.

Mixtures with azaconazole, bromuconazole, cy proconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl- (E) -methoximino [α- (o-tolyloxy) -otolyl) are very particularly preferred ] acetate, methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yl-oxy] phenyl} -3- methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4- (2.2 -Difluoro-l, 3-benzodi- oxol-4-yl) -lH-pyrrole-3-carbonitrile, butenafine, imazalil, methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N- Octylisothiazolin-3-one, dichloro-N-octylisothiazolin-3-one, benzisothiazolinone, N- (2-hydroxypropyl) amino-methanol,

Benzyl alcohol (hemi) formal, glutaraldehyde, omadine, dimethyl dicarbonate, and / or 3-iodo-2-propynyl-n-butyl carbamate.

Furthermore, well-effective mixtures with the following active ingredients are also produced:

Fungicides:

Acypetacs, 2-aminobutane, Ampropylfos, anilazine, benalaxyl, Bupirimate, chinomethionat, chloroneb, chlozolinate, cymoxanil, dazomet, Diclomezine, Dichloram, diethofencarb, dimethirimol, Diocab, dithianon, dodine, Drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl,

Fthalides, Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal -isopropyl, Nuarimol, Ofurace, Oxadiyl, Perflurazoate, Pencycuron, Phosdiphen, Pimaricin, Proponymone, Pyonoxone, Pyronoxin, Proamonoxyrin, Proamonoxyrin, Proconoxinone, Proamonoxin, Proamonoxin, Proamonoxin, Proamon, Pyronoxin Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide,

Trichlamide, Tricyclazole, Triforine, Vinclozolin.

Insecticides:

Phosphoric acid esters, such as azinphos-ethyl, azinphos-methyl, α-l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, Chloφyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos , Dimethoate, Ethoate, Ethoprophos,

Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphone; Carbamates such as aldicarb, bendiocarb, α-2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxy carboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarbox;

Organosilicon compounds, preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether, such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethylether or [(phenyl) -3- (3-phenoxyphenyl) -propyl] (dimethyl) -silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenylpropyl] dimethyl silane, silafluofen;

Pyrethroids, such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro- 2-trifluoro-methyl-vinyl) -cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;

Nitroimines and nitromethylenes, such as imidacloprid, N - [(6-chloro-3-pyridyl) methyl-] N2-cyano-N 1 -methyl acetamide (NI-25);

Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thunngiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos,

Pyrethrins, Pyridaben, Pyridafenthion, Pyriproxyfen, Quinalphos, RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphhrin, Tetrachlorvinphhrin, Tetruf Butyl-pyrimidin-5-yl-o-isopropyl-phosphorothiate, thiocyclam, thiofanox, thiometone, tralomethrin, triflumuron, trimethacarb,

Vamidothion, Verticillium Lacanii, XMC, Xylylcarb, Benfuracarb, Bensultap, Bifenthrin, Bioallethrin, MERbioallethrin (S) -cyclopentenyl isomer, Bromophos, Bromophos-ethyl, Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothomonfluoride, Chlorophenothomethane, Carchloride Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha- cypermethrin, Cyophenothrin, Cyromazine, Dazomet, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinosofos, Doxanobin, Dulfanos, Doxanos, Doxanos, Doxanos, Doxanos, Doxanos, Deoxanos EPN, Esfenvalerate, Ethiofencarb, Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogenofyanos, Hydrogen Cyanophene, Hydrogen Cyanophene, Hydrogen Cyanophosphone, Hydrogen Cyanophosphone , Isoxathion, Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam,

Mephosfolan, Mercurous, chloride, Metam, Metarthizin, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Pentometholone, Ometholone, Ometholone, Ometholone, Ometholone oils, phenothrin, phenthoates, phorates;

Molluscicide:

Fentin acetates, metaldehydes, methiocarb. Niclosamide, thiodicarb, trimethacarb.

Algicide:

Coppersulfate, dichlororphen, Endothal, Fentinacetate, Quinoclamine.

Herbicides: acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfonon, benzenesulfuron, benzenesulfuron, benzenesulfonon, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinosebomobomilomomolomomom butachlor, butamifos, fuenachlor, butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen, chloramben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone, clomeprop, clopyralid, cyanamide, cyanazine, dinoseb acetate, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuronamp, flamp -M, flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluoroxypyr, cycloate, cycloxydim, 2,4-D, daimuron, dalapon, DBomet, dazomet , desmedipham, desmetryn, dicamba, dichlorobenzil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluamuriton, metam, metazaziazuride, metam, metazaziazole methazole, methoproptryne, methyldymron, methylisothiocyanate, metobromuron, fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, pyynidol, pyrazidolate, pyazidolate, pyazidolate, pyazidolate, pyabrazolate, pyabrazolate, pyabrazole, pyabrazole, pyrazolate, pyobenzolate, pyroxylate, pyrazole , quinclorac, quinmerac, quinocloamine, quizalofop, quzizalofop-P, S-23121, sethoxydim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils,

TCA, metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide, monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadlorone, pentahlorophenone, oxyfluenthophenone petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodiamine, proglinazine, propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifarbi-carboxilonium, thifarbi-chloro-thioblimi, thifarbazoximilil , triasulfuron, tribenzuron, triclopyr, tridiphane, trietazine, trifluralin, IBI-C4874 vernolate, propanil, propaquizafop, propazine, propham.

The weight ratios of the active ingredients in these active ingredient combinations can be varied within relatively large ranges.

The active substance combinations preferably contain 0.1 to 99.9%, in particular 1 to 75%, particularly preferably 5 to 50% of the active substance, the rest being filled 100% by one or more of the above-mentioned mixing partners.

The microbicidal agents or concentrates used to protect the industrial materials contain the active ingredient or combination of active ingredients in a concentration of 0.01 and 95% by weight, in particular 0.1 to 60% by weight.

The application concentrations of the active substances to be used or the active substance combinations 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 can be determined by test series become. 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 active substances or agents according to the invention advantageously make it possible to replace the microbicidal agents available to date with more effective ones. They show good stability and advantageously have a broad spectrum of activity.

The following examples serve to illustrate the invention. The invention is not limited to the examples.

Preparation Examples:

example 1

^ SO - CHF-

Cl

A solution of 5.03 g (20 mmol) of 7-chloro-2-difluoromethylthiobenzthiazol in 50 ml of glacial acetic acid is mixed with 50 mg of sodium tungstate, warmed to 40-50 ° C. and then 2.3 g (20 mmol) of 30% strength Hydrogen peroxide too. After stirring at 40-50 ° C. for 12 hours, the mixture is poured into 250 ml of water and extracted with dichloromethane. The organic phase is dried over sodium sulfate, concentrated in vacuo and the residue is chromatographed on silica gel using dichloromethane. 1.8 g (33.6% of theory) of 7-chloro-2-difluoromethylsulfinylbenzothiazole of melting point 100 ° C. are obtained.

Example 2

A solution of 5.03 g (20 mmol) of 7-chloro-2-difluoromethylthiobenzthiazol in 50 ml of glacial acetic acid is mixed with 50 mg of sodium tungstate, warmed to 40-50 ° C. and then 6.8 g (50 mmol) of 30% strength Hydrogen peroxide too. After stirring at 40-50 ° C. for 18 hours, the mixture is poured into 250 ml of water, the product precipitating. This is suctioned off, dissolved in dichloromethane and chromatographed on silica gel with dichloromethane. 3.0 g (52.8% of theory) of 7-chloro-2-difluoromethylsulfonylbenzthiazole of melting point 101 ° C. are obtained.

Analogously to Examples (1) and (2) and in accordance with the general description of the production processes according to the invention, the compounds of the formula (I) according to the invention listed in Table 2 below are also obtained: Table 2:

Examples of use

The minimum Heram concentrations (MIC) of agents according to the invention are determined to demonstrate the effectiveness against fungi:

Active ingredients according to the invention are added to an agar which is produced using malt extract in concentrations of 0.1 mg / l to 5,000 mg / l. After the agar solidifies, it is contaminated with pure cultures of the test organisms listed in Table 1. After 2 weeks of storage at 28 ° C and 60 to 70% relative humidity, the MIC is determined. MIC is the lowest concentration of active ingredient at which no growth occurs due to the type of microbe used, it is shown in Table 2 below.

Table 2

Minimum inhibitory concentrations (ppm) of compounds of the formula (I) according to the invention

Example No. 9 3 11 12

Penicillium <50 <50 <50 <50 brevicaule

Chaetomium <50 <50 <50 <50 globosum

Aspergillus <50 <50> 50> 50 niger

Coriolus <20 * <20 ^{! |} <20 * <20 * versi color

Giant colony test (radial mycelium growth)

The procedure for testing emulsion paint coatings for mold resistance is as follows:

The paint to be tested is coated on both sides on a suitable surface. In order to obtain practical results, some of the test specimens are leached with running water (24 hours; 20 ° C) before the test for mold resistance; another part is treated with a warm fresh air flow (7 days; 40 ° C).

The test specimens prepared in this way are placed on an agar culture medium. Test specimens and culture medium are contaminated with fungal spores. After 2 to 3 weeks

Storage at 29 + 1 ° C and 80 to 90% clean. Humidity is checked. The paint is permanently mold-resistant if the test specimen remains free of fungi or if at most a slight edge infestation can be seen.

Fungus spores of the following molds, which are known as paint destroyers or are often found on paints, are used for contamination:

1. Alternaria tenuis

2. Aspergillus flavus

3. Aspergillus niger

4. Aspergillus ustus 5. Cladosporium herbarum

6. Paecilomyces variotii

7. Penicillium citrinum

8. Aureobasidium pullulans

9. Stachybotrys atra Corda

Coatings are resistant to mold according to recipe A (even after leaching and

Wind tunnel exposure) if they contain, for example, 0.6% (based on solids) of compound 9.

Recipe A:

EXTERNAL emulsion paint based on Acronal 290 D (styrene acrylate)

Trade name Chemical name Parts

Bayer Titan RKB2 40 titanium dioxide

Talc V58 new 10 magnesium silicate containing water

Durcal 5 45 Calcite CaCO3

Walsroder MC 3000 S 2% 30 methyl cellulose

H2O 6.5 dist. water

Calgon N 10% 3 polyphosphate

Pigment distributor A 10% 1 polyacrylic acid salt

Agitan 281.1: 1 in Texanol 1

White spirit 5 different aliphatic carbons and hydrogens

Butyl glycol acetate 1.5 butyl glycol acetate

Acronal 290 D (binders.) 71 polyacrylic acid esters

Total 219.0

Solids content: 135.5 = 61.6%

Claims

claims

1. Compounds of formula (I)

in which

n represents 1 or 2,

R ¹ , R ² , R ³ and R ⁴ individually independently of one another represent hydrogen, halogen, cyano, nitro, in each case optionally substituted alkyl, cycloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aryl or heterocyclyl, or

R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ together with the carbon atoms to which they are attached form a further, optionally substituted, carbocyclic or heterocyclic ring,

Q stands for oxygen or sulfur and

X represents hydrogen or halogen,

the compound 6-chloro-2-difluoromethylsulfonylbenzthiazol is excepted.

Compounds of formula (I) according to claim 1, in which

represents 1 or 2,

R ¹ , R ² , R ³ and R ⁴ individually independently of one another for hydrogen, fluorine, chlorine, bromine, cyano, nitro, alkyl having 1 to 8 carbon atoms, Cycloalkyl with 3 to 6 carbon atoms, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each with 1 to 8 carbon atoms, haloalkyl haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each with 1 to 8 carbon atoms and 1 to 5 identical or different Haiogen¬ atoms, for each in the phenyl or heteroaryl part, in each case single to triple, identical or different by halogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 5 same or different halogen atoms, straight-chain or branched alkoxy with 1 to 4 carbon atoms, straight-chain or branched haloalkoxy with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms substituted phenyl, pyridyl or pyrimidyl, or

R ¹ and R ² or R ² and R ^J or R ³ and R ⁴ together with the carbon atoms to which they are attached, for another, optionally by halogen, cyano, nitro, alkyl having 1 to 8 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms, haloalkyl haloalkoxy, halogenoalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 8 carbon atoms and 1 to 5 identical or different halogen atoms substituted, six-membered, aromatic ring stand, or

R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ for an optionally one to four times by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 9

Halogen atoms substituted alkylene chain with 3 or 4 links, in which one or two (not adjacent) carbon atoms by

Oxygen atoms can be replaced,

Q stands for oxygen or sulfur and

X represents hydrogen or halogen, the compound 6-chloro-2-difluoromethylsulfonylbenzthiazol is excluded.

3. Compounds of formula (I) according to claim 1, in which

n represents 1 or 2,

R ¹ , R ² , R ³ and R ⁴ individually independently of one another for hydrogen, fluorine,

Chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, methoxy, ethoxy, n- or i-propoxy, n-, i- , s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, Trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, each optionally in the phenyl or heteroaryl part, single to triple, identical or different, by fluorine, chlorine, the same, or different, by fluorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine or carbonate

Nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t- Butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, difluorochloromethoxy Difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl substituted phenyl, pyridyl or pyrimidyl, or

R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ together with the carbon atoms to which they are attached for a further one, optionally by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-

Butylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, Trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl-substituted, six-membered, aromatic ring, or

R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ together for one in each case optionally up to fourfold, identically or differently

Fluorine, chlorine, methyl, trifluoromethyl or ethyl substituted alkylene chain with 3 or 4 links, in which one or two (non-adjacent) carbon atoms can be replaced by oxygen atoms,

Q stands for oxygen or sulfur and

X represents hydrogen or bromine,

the compound 6-chloro-2-difluoromethylsulfonylbenzthiazol is excepted.

4. pesticide, characterized by a content of at least one compound of the formula (I) according to claim 1.

5. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.

6. A process for the preparation of compounds of formula (I) according to claim l. characterized in that compounds of the formula (II)

in which R ¹ , R ² , R ³ , R ⁴ , Q and X have the meanings given in Claim 1.

with an oxidizing agent, optionally in the presence of a diluent, optionally in the presence of a catalyst and optionally in the presence of a phase transfer catalyst.

7. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims 1 to 3 are mixed with plug-in agents and / or surface-active agents.

Use of compounds of the formula (I)

in which

n represents 1 or 2,

R ¹ , R ² , R ³ and R ⁴ individually independently of one another represent hydrogen, halogen, cyano, nitro, in each case optionally substituted alkyl, cycloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aryl or heterocyclyl, or

R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ together with the carbon atoms to which they are attached form a further, optionally substituted, carbocyclic or heterocyclic ring,

Q stands for oxygen or sulfur and

X represents hydrogen or halogen, to control microorganisms on plants and technical materials.