EP0975611A1

EP0975611A1 - 3-alkoxy isothiazoles

Info

Publication number: EP0975611A1
Application number: EP98916926A
Authority: EP
Inventors: Hermann Uhr; Martin Kugler; Peter Wachtler
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1997-03-25
Filing date: 1998-03-12
Publication date: 2000-02-02
Also published as: DE19712409A1; AU7034298A; JP2001518105A; CA2284821A1; WO1998042689A1

Abstract

The invention relates to novel 3-alkoxy isothiazoles, their application as microbicides and methods for the production thereof.

Description

3-alkoxyisothiazoIe

The invention relates to new 3-alkoxyisothiazoles, their use as microbicides and processes for their preparation.

3-alkoxyisothiazoles which have a biocidal action are already known (US Pat. No. 3,957,808, US Pat. No. 5,384,326). However, their effective range and depth do not reach the required level, or the compounds are not sufficiently stable to hydrolysis, which makes them of limited use for material protection agents.

New 3-alkoxyisothiazoles of the general formula (I) have now been found

in which

R ^{1 represents} optionally substituted alkyl, alkenyl or alkynyl,

R ^{2 represents} optionally substituted alkyl, alkenyl, alkynyl or phenyl and

R ^{3 represents} hydrogen or halogen.

It has also been found that the new 3-alkoxyisothiazoles of the formula (I) have an activity which is superior to the prior art and are very stable to hydrolysis, which makes them particularly suitable for use in material protection agents.

Furthermore, new processes for the preparation of 3-alkoxyisothiazoles of the general formula (I) have been found. The new and 3-alkoxyisothiazoles according to the invention are generally defined by the formula (I). Compounds of the formula (I) in which

R ^{1 stands} for straight-chain and branched alkyl with 1 is 10 carbon atoms, straight-chain or branched alkenyl with 2 to 10 carbon atoms or straight-chain or branched alkynyl with 2 to 10 carbon atoms, which are each optionally substituted one or more times by the same or different substituents by halogen, alkoxy with 1 to 6 carbon atoms, haloalkoxy with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, alkylthio with 1 to 6 carbon atoms, haloalkylthio with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, acyl with 1 to 6 carbon atoms, Acyloxy with 1 to 6 carbon atoms, (alkoxy) carbonyl with 1 to 6 carbon atoms, amino which is optionally substituted identically or differently by alkyl or aryl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano,

R ^{2 represents} straight-chain and branched alkyl having 1 is 10 carbon atoms, straight-chain or branched alkenyl having 2 to 10 carbon atoms or straight-chain or branched alkynyl having 2 to 10 carbon atoms, which are each optionally substituted one or more times by the same or different substituents by halogen, alkoxy with 1 to 6 carbon atoms, haloalkoxy with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, alkylthio with 1 to 6 carbon atoms, haloalkylthio with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, acyl with 1 to 6 carbon atoms, Acyloxy having 1 to 6 carbon atoms, (alkoxy) carbonyl having 1 to 6 carbon atoms, amino, which is optionally substituted identically or differently by alkyl or aryl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano, or stands for aryl,

which is optionally mono- to pentasubstituted by halogen, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms,

Alkoxy with 1 to 10 carbon atoms, haloalkoxy with 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, alkylthio with 1 to 10 carbon atoms, haloalkylthio with 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, amino, monoalkylamino with straight-chain or branched alkyl radicals with 1 to 6 carbon atoms, dialkylamino with the same or different, straight-chain or branched alkyl radicals with 1 to 6 carbon atoms each, cycloalkyl with 1 to 6 carbon atoms, methylenedioxy, dichloromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylene dioxy, nitro or cyano , and

R ^{3 represents} halogen or hydrogen.

Compounds of the formula (I) in which

R ^{1 represents} straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms or straight-chain or branched alkynyl having 2 to 8 carbon atoms, which are in each case optionally substituted one to four times by identical or different substituents by fluorine, chlorine , Alkoxy with 1 to 5 carbon atoms,

Haloalkoxy with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, alkylthio with 1 to 5 carbon atoms, haloalkylthio with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, acyl with 1 to 5 carbon atoms, acyloxy with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms, Amino which is optionally substituted identically or differently by alkyl having 1 to 4 carbon atoms and / or phenyl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano,

represents straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms or straight-chain or branched alkynyl having 2 to 8 carbon atoms, which in each case are substituted one to four times in the same way or differently by fluorine, chlorine, alkoxy with 1 to 5 carbon atoms,

Haloalkoxy with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, alkylthio with 1 to 5 carbon atoms, haloalkylthio with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, acyl with 1 to 5 carbon atoms, acyloxy with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms,

Amino, which is optionally substituted identically or differently by alkyl having 1 to 4 carbon atoms and / or phenyl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano, or for

represents phenyl, which is optionally mono- to tetrasubstituted by fluorine, chlorine, alkyl having 1 to 8 carbon atoms, haloalkyl having 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, alkoxy having 1 to 8 carbon atoms, haloalkoxy 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, alkylthio with 1 to 8

Carbon atoms, haloalkylthio with 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, amino, monoalkylamino with alkyl radicals of 1 to 4 carbon atoms, dialkylamino with the same or different alkyl radicals each with 1 to 4 carbon atoms, cycloalkyl with 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylenedioxy, nitro or cyano, and

R ^{3 represents} chlorine, bromine or hydrogen.

R ¹ is preferably methyl, ethyl, n- and i-propyl, n-, s-, i- and t-butyl, allyl and propargyl, which are each optionally substituted and are substituted by fluorine and / or chlorine, methoxy or methylthio, in particular R ^{1 represents} methyl, ethyl or n-propyl.

R ³ preferably represents chlorine and in particular hydrogen.

R ² preferably represents methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, which are each optionally substituted by methoxy, ethoxy, methylthio, ethylthio, methoxycarbonyl, ethylcarbonyl, cyano or phenyl . R ² furthermore preferably represents phenyl. Phenyl in the meanings given above is optionally mono- or disubstituted by methyl, ethyl, fluorine, chlorine, methoxy, ethoxy or trifluoromethyl.

The radical definitions specified for these radicals in the respective combinations or preferred combinations of radicals are independently replaced by radical definitions of other preferred ranges, regardless of the combination specified in each case.

It has also been found that the 3-alkoxyisothiazoles can be obtained by

Hydroxyisothiazoles of the general formula (II),

where R ^{3 has} the meaning given above, either with compounds of the formula (III)

wherein R ¹ and R ^{3 have} the meaning given above and

R ^{4 can} independently have the same meaning as R ¹ , but is preferably identical to R ¹ , optionally reacted in the presence of catalysts,

or with compounds of the general formula (IV),

where R ¹ and R ^{3 have} the meanings given above and X is chlorine or

Bromine stands, optionally in the presence of acid-binding agents.

In the reaction of hydroxyisothiazoles of the formula (II) with compounds of the general formula (III), the reaction temperatures can be varied within a substantial range. Generally one works between 0 ° C and 200 ° C, preferably between 20 ° C and 150 ° C. If appropriate, the reactions can be carried out in the presence of diluents. All solvents which do not react with the starting materials are suitable as diluents. It is preferred to use hydrocarbons such as toluene, xylene or hexane, chlorinated hydrocarbons such as chlorobenzene, chloroform, methylene chloride, ethers such as methyl tert-butyl ether, nitriles such as acetonitrile, ketones such as acetone, and DMSO or DMF. The ratio of the starting materials can be varied within a wide range. In general, one works in equimolar amounts of (II) and (III) or uses (III) in up to 10-fold excess.

All catalysts which promote the transacetalization can be used as catalysts. Acids or Lewis acids are generally used. Inorganic acids such as Hcl, H2SO4, H3PO4, organic acids such as formic acid, acetic acid, p-toluenesulfonic acid or Lewis acids such as A1C1 ₃ , ZnCl ₂ , TiCl _{4 are} preferably used.

In the reaction of the hydroxyisothiazoles of the formula (II) with compounds of the formula (IV), the reaction temperatures can be varied within a substantial range. Generally one works between -20 ° C and + 150 ° C, preferably between -10 ° C and + 80 ° C.

If appropriate, the reactions can be carried out in the presence of diluents. All solvents which cannot react with the starting materials are suitable as diluents. Hydrocarbons such as toluene, xylene or hexane, chlorinated hydrocarbons such as chlorobenzene, chloroform, methylene chloride, ethers such as e.g. Methyl tert-butyl ether, nitriles such as acetonitrile, ketones such as acetone, and DMSO or DMF.

If appropriate, the reactions will be carried out in the presence of acid-binding agents; all customary acid-binding agents can be used here. These preferably include tertiary amines such as triethylamine and pyridine; Alkali hydroxides such as sodium and potassium hydroxide and alkali carbonates and hydrogen carbonates such as potassium carbonate and sodium hydrogen carbonate.

The hydroxyisothiazoles of the formula (II) are known and can be prepared according to literature regulations (for example Crow et al., J. Org. Chem. 30, 2660 (1965)). The compounds of the formula (III) are known or can be prepared by methods known from the literature (for example W. Kantlehner et al., Just. Leisip Ann. Chemie 1974, 690).

The compounds of the formula (IV) are likewise known or can be prepared according to literature instructions (for example McLeod, JK, Tetrahedron. 23, 2095 (1967); Pihlaja, Kalevi et al., Acta Chem. Scand. Ser. B. 40, 196 (1986)).

The active compounds of the formula (I) have a strong microbicidal action and can be used practically to combat unwanted microorganisms. The active compounds of the formula (I) are suitable for protecting industrial 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 from microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked or decomposed by microorganisms can be. As part of the to be protected

Materials are also parts of production systems, such as cooling water circuits, that can be affected by the proliferation 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.

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 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 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 foam-generating 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, Chlorethylene, 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, 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 butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Solid carriers for granules are possible: for example 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 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; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers, 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, for example iron oxide, titanium oxide, ferocyanine blue and organic dyes such as alizarin, azo and metal phthalocya Nine 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 further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active compounds to enlarge the spectrum of action or Achieving special effects such as added protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

In many cases, synergistic effects are obtained, i.e. 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:

Azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, epoxyconazole, etaconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol,

Furconazole, Hexaconazole, Imibenconazole, Ipconazole, Isozofos, Myclobutanil, Metconazole, Paclobutrazol, Penconazole, Propioconazole, (+) - cis-l- (4-chlorophenyl) -2- (lH-l, 2,4-triazole-l -yl) -cycloheptanol, 2- (l-tert-butyl) -l- (2-chlorophenyl) -3- (l, 2,4-triazol-l-yl) -propan-2-ol, tebuconazole, tetraconazole, Triadimefon, Triadimenol, Triapenthenol, Triflumizole, Triticonazole, Uniconazole and their

Metal salts and acid adducts;

Imidazoles such as:

Clotrimazole, Bifonazole, Climbazole, Econazole, Fenapamil, Imazalil, Isoconazole, Ketoconazole, Lombazole, Miconazole, Pefurazoate, Prochloraz, Triflumizoles, thiazole car l-imidazolyl-l- (4'-chlorophenoxy) -3,3-dimethylbutan-2-one and their metal salts and acid adducts;

Pyridines and pyrimidines such as: ancymidol, buthiobate, fenarimol, nuarimol, triamirol;

Succinate dehydrogenase inhibitors such as:

Benodanil, Carboxim, Carboximsulfoxid, Cyclafluramid, Fenfuram, Flutanil, Furcarbanil, Furmecyclox, Mebenil, Mepronil, Methfuroxam, Metsulfovax, Pyrocarbolide, Oxycarboxin, Shirlan, Seedvax;

Naphthalene derivatives such as:

Terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-yne);

Sulfenamides such as:

Dichlorfluanide, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;

Benziniidazoles such as:

Carbendazim, benomyl, fuberidazole, thiabendazole or their salts;

Morpholine derivatives such as:

Aldimorph, Dimethomorph, Dodemorph, Falimorph, Fenpropidin Fenpropimorph, Tridemorph, Trimorphamid and their arylsulfonic acid salts, e.g. p-

Toluenesulfonic acid and p-dodecylphenyl sulfonic acid;

Benzthiazoles such as:

2-mercaptobenzothiazole; Benzothiophene dioxides such as:

Benzo [b] thiophene-S, S-dioxide-carboxylic acid cyclohexylamide;

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

Boron compounds such as:

Boric acid, boric acid ester, borax;

Formaldehyde and formaldehyde releasing compounds such as:

Benzyl alcohol mono- (poly) hemiformal, n-butanol hemiformal, Dazomet, ethylene glycol hemiformal, hexa-hydro-S-triazine, hexamethylenetetramine, N-hydroxymethyl-N '-methylthiourea, N-methylolchloroacetamide, oxazolidine, Parafor - maldehyde, tauroline, tetrahydro-l, 3-oxazine, N- (2-hydroxypropyl) amine-methanol;

Isothiazolinones such as:

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, 5-chloro-N-octylisothiazolinone, N-octyl-isothiazolin-3- on, 4,5-trimethylene-isothiazolinone, 4,5-benzisothiazolinone;

Aldehydes such as:

Cinnamaldehyde, formaldehyde, glutardialdehyde, ß-bromocinnamaldehyde;

Thiocyanates such as: thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate;

quaternary ammonium compounds such as:

Benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, dichlorobenzyldimethylalkylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium chloride,

N-hexadecyl trimethyl ammonium chloride, 1-hexadecyl pyridinium 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-

Bromo-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-iodo 2-propynylphenyl carbamate;

Phenols such as:

Tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, 2-benzyl-4-chlorophenol, 5-chloro-2- (2,4-dichlorophenoxy) phenol, Hexachlorophene, p-hydroxybenzoic acid ester, o-phenylphenol, m-phenylphenol, p-phenylphenol and their alkali and alkaline earth metal salts; Microbicides with activated halogen group such as:

Bronopol, Bronidox, 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxy-acetophenone, l-bromo-3-chloro-4,4,5,5-tetramethyl-2 -imidazoldinone, ß-bromo-ß-nitrostyrene, chloroacetamide, chloramine T, l, 3-dibromo-4,4,5,5-tetrametyl-2-imidazoldinone, dichloramine T, 3,4-dichloro- (3H) -l , 2-dithiol-3-one, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, halanes, halazones, mucochloric acid, phenyl- (2-chloro-cyano- vinyl) sulfone, phenyl- (1,2-dichloro-2-cyanovinyl) sulfone, trichloroisocyanuric acid;

Pyridines such as: l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, l-hydroxy-4-methyl-6- ( 2, 4, 4-tr imethylpentyl) -2 (1 H) pyridine;

Methoxyacrylates or similar like:

Methyl (E) methoximino [alpha- (o-tolyloxy) -o-toly 1] acetate,

(E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide,

(E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, O-methyl-2 - [([3-methoximino-2-butyl) imino] oxy ) o-tolyl] -2-methoximinoacet imidates,

2 - [[[[[1- (2,5-dimethylphenyl) ethylidene] amino] oxy] methyl] -. Alpha .- (methoximino) - N-methyl 1-benzeneacetamide, alpha- (methoxyimino) -N-methyl-2 - [[[[l- [3- (trifluoromethyl) phenyl] ethylidene] amino] oxy] methyl] benzene acetamides, alpha- (methoxyimino) -2 - [[[[l- [3- (trifluoromethyl) phenyl] - ethy 1 idene] amino] oxy] methyl 1] -benzeneaceticacid methyl ester, alpha- (methoxymethylene) -2 - [[[[[1 - [3- (trifluoromethyl) phenyl] ethylidene] amino] oxy] methyl] -benzeneaceticacid- methyl ester, 2 - [[[5-chloro-3- (trifluoromethyl) -2-pyridinyl] oxy] methyl] -. Alpha .- (methoxyimino) - N-methyl-benzeneacetamide,

2 - [[[cyclopropyl [(4-ethoxyphenyl) imino] methyl] thio] methyl] -. Alpha.- (methoxyimino) -benzeneaceticacid-methyl ester, alpha- (methoxyimino) -N-methyl-2- (4-methyl- 5-phenyl-2,7-dioxa-3,6-diazaocta-

3, 5 -dien- 1 -y 1) -benzeneacetamide, alpha- (methoxymethylene) -2- (4-methyl-5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-dien- l -yl) -benzeneaceticacid-methyl ester, alpha- (methoxyimino) -N-methyl-2 - [[[l- [3- (trifluoromethyl) phenyl] ethoxy] imino] methyl] -benzeneacetamide,

2 - [[(3,5-dichloro-2-pyridinyl) oxy] methyl] -. Alpha .- (methoxyimino) -N-methylbenzeneacetamide,

2- [4,5-dimethyl-9- (4-morpholinyl) -2,7-dioxa-3,6-diazanona-3,5-dien-l-yl] -. Alpha.-

(methoxymethylene) benzene aceticacid methyl ester;

Metal soaps like:

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, CU2O, CuO, ZnO; Dithiocarbamates such as:

Cufraneb, ferban, potassium-N-hydroxymethyl-N'-methyl-dithiobarbamate, Na- or K-dimethyldithiocarbamate, Macozeb, Maneb, Metam, Metiram, Thiram, Zineb, Ziram;

Nitriles such as:

2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;

Quinolines such as: 8-hydroxyquinoline and their Cu salts;

other fungicides and bactericides such as:

5-hydroxy-2 (5H) furanone; 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, N- (2-p-chlorobenzoylethyl) hexaminium chloride, 2-oxo-2- (4-hydroxyphenyl) acethydroximic acid chloride, Tris-N- (cyclohexyldiazeniumdioxy) -aluminium, N- (cyclohexyldiazeniumdioxy) -tributyltin or K salts, bis-N- (cyclohexyldiazenium-dioxy) copper;

Zeolites containing Ag, Zn or Cu alone or enclosed in polymeric materials.

Mixtures with are very particularly preferred

Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole,

Hexaconazole, Metaconazole, Penconazole, Propiconazole, Tebuconazole, Dichlofluanid, Tolylfluanid, Fluorfolpet, Methfuroxam, Carboxin, Benzofb] - thiophene-S, S-dioxid-carboxylic acid cyclohexylamide, Fenpiclonil, 4- (2,2-Difluodioxol-l 4-yl) -IH-pyrrole-3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, dichloro -N-octylisozhiazolinone, mercaptobenthiazole, thiocyanatomethylthiobenzothiazol benzisothiazolinone, N- (2-hydroxypropyl) -amino-methanol, benzyl alcohol- (hemi) formal, N-methylolchloroacetamide, N- (2-hydroxypropyl) amine-methanol, glutaraldehyde, omadine, dimethyldicarbonate, and / or 3-iodo-2-propynyl-n-butylcarbamate.

In addition to the above-mentioned fungicides and bactericides, effective mixtures with other active ingredients are also produced:

Insecticides / acaricides / nematicides:

Abamectin, Acephat, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Aldrin, Allethrin, Alpha-cypermethrin, Amitraz, Avermectin, AZ 60541,

Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, Barthrin, 4-Bromo-2 (4-chlorophenyl) -l- (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3-carbonitrile, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, Bioresmethrin, Bioallethrin Bromophos A, Bromophos M, Bufencarb, Buprofezin, Butathiophos, Butocarboxin, Butoxycarboxim,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chinomethionate, Cloethocarb, Chlordane, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl -ethanimidamide, chlorpicrin, chlorpyrifos A, chlorpyrifos M, cis- resmethrin, clocythrin, cypophenothrin clofentezin, coumaphos, cyanophos,

Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin, Decamethrin, Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Dialiphos, Diazinon, l, 2-Dibenzoyl-l (l, l-dimethyl) , DNOC, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diflubenzuron, dimethoate, dimethyl- (phenyl) -silyl-methyl-3-phenoxybenzylether, dimethyl- (4-

Ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether, dimethylvinphos, dioxathione, disulfoton,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, EPN, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenfluthrin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fensulfothion, Fenthion, Fenvalerate, Fipronil, Fluazuron, Flucycloxuron, Flxthroxinphonate, Floxethrinifurinate, Flucythrinolanate, Flucythrininone, Flucythrininate, Flucythrininone, Flucythrininate, Flucythrininate, Flucythrininate, Flucythrininate, Flucythrininone, Fosthiazat, Fubfenprox, Furathiocarb,

HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydramethylnon, Hydroprene, Imidacloprid, Iodfenfos, Iprobefos, Isazophos, Isoamidophos, Isofenphos, Isoprocarb, Isoprothiolane, Isoxathion, Ivermectin, Lama-cyhalothrinadhronuronuronurinuronurinuronurinuronurinuronuronurinurluronurinurluronurinurluronurinurluronurinurluronurinurlhronurinurlhrinuronurinurlhronurinurluronuronuroluronuronuroluronuronuroluronurinurluronurinuroluronurinurlhronurinuroluronurinuroluronurinuroluronurinurluronurinuroluronuroluronuronuroluronuroluronuroluronuroluronuroluronuroluronuroluronuroluronuroluronurinhrinuronurol

Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metalcarb, Milbemectin, Monocrotophos, Moxiectin, Naled, NC 184, NI 125, Nicotine, Nitenpyram, Moxydydonethoxate, Oxamate, Oxamate, Oxam

Parathion A, Parathion M, Penfluron, Permethrin, 2- (4-phenoxyphenoxy) ethyl ethyl carbamate, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Prallethrin, Profenophos, Promecarb, Propaphos Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,

Quinalphos,

Resmethrin, RH-7988, Rotenone, Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tau fluvalinate, Taroils, Tebufenozide, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terblorufos, Terbamufos

Tetramethrin, Tetramethacarb, Thiafenox, Thiapronil, thiodicarb, thiofanox, Thiazophos, thiocyclam, Thiomethon, Thionazin, thuringiensin, tralomethrin, Triarathen, triazophos, Triazamate, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, Zetamethrin; Molluscicides:

Fentin acetates, metaldehydes, methiocarb. Niclosamide;

Herbicides and algicides

Acetochlor, Acifluorfen, Aclonifen, Acrolein, Alachlor, Alloxydim, Ametryn, Amidosulfuron, Amitrole, Ammonium sulfamate, Anilofos, Asulam, Atrazine, Aziptrotryne, Azimsulfuron, Benazolin, Benfluralin, Benfuresate, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Bensulfuron, Benzenesulfonon , Bromacil, bromobutide,

Bromofenoxim, Bromoxynil, Butachlor, Butamifos, Butralin, Butylate, Bialaphos, Benzoyl-prop, Bromobutide,

Carbetamides, chloromethoxyfen, chloramben, chlorbromuron, chlorflurenol, chloridazon, chlorimuron, chloronitrofen, chloroacetic acid, chlorotoluron, chloroxuron, chlorpropham, chlorosulfuron, chlororthhal, chlorothiamide,

Cinmethylin, Cinofulsuron, Clethodim, Clomazone, Chlomeprop, Clopyralid, Cyanamide, Cyanazine, Cycloate, Cycloxydim, Chloroxynil, Clodinafop-propargyl, Cumyluron, CGA 248757, Clometoxyfen, Cyhalofop, Clopyrasuluron, Dichlopylamopluryl, Dichloroplamoplurop, dichlorophenyl, dichlorophenyl, dichlorophenyl, dichlorophenyl, dichlorophenol Difenoxuron, difenzoquat,

Diflufenican, Dimefuron, Dimepiperate, Dimethachlor, Dimethipin, Dinitramine, Dinoseb, Dinoseb Acetate, Dinoterb, Diphenamid, Dipropetryn, Diquat, Dithiopyr, Diduron, DNOC, DSMA, 2,4-D, Daimuron, Dalapon, Dazomet, 2,4-DB , Desmedipham, Desmetryn, Dicamba, Dichlobenil, Dimethamid, Dithiopyr, Dimethametryn,

Eglinazine, Endothal, EPTC, Esprocarb, Ethalfluralin, Ethidimuron, Ethofumesate, Ethobenzanid, Ethoxyfen, ET 751, Ethametsulfuron, Fenoxaprop, Fenoxaprop-P, Fenuron, Flamprop, Flamprop-M, Flazasulfuron, Fluazifop, Fazloronlorum, Fluazifalin-Fluaziflorop, Fluaziflorop, Fluazifalin-Fluaziflorum-F, , Fluorocglycofen, Fluoronitrofen, Flupropanate, Flurenol, Fluridone, Flurochloridone, Fluroxypyr, Fomesafen, fosamine, flamprop-isopropyl, flamprop-isopropyl-L, flumiclorac-pentyl, flumipropyn, flumioxzim, flurtatone, flumioxzim,

Glyphosate, glufosinate-ammonium

Haloxy fop, Hexazinone, Imazamethabenz, Isoproturon, Isoxaben, Isoxapyrifop, Imazapyr, Imazaquin,

Imazethapyr, ioxynil, isopropalin, imazosulfuron,

KUH 911, KUH 920

Lactofen, Lenacil, Linuron, LS830556,

MCPA, MCPA-thioethyl, MCPB, Mecoprop, Mecoprop-P, Mefenacet, Mefluidide, Metam, Metamitron, Metazachlor, Methabenzthiazuron, Methazole,

Methoroptryne, methyldymron, methylisothiocyanate, metobromuron, metoxuron,

Metribuzin, Metsulfuron, Molinate, Monalide, Monolinuron, MSMA,

Metolachlor, metosulam, metobenzuron,

Naproanilide, Napropamide, Naptalam, Neburon, Nicosulfuron, Norflurazon, Sodium Chlorate,

Oxadiazon, oxyfluorfen, orbencarb, oryzalin, quinchlorac, quinmerac,

Propyzamides, prosulfocarb, pyrazolates, pyrazolesulfuron, pyrazoxyfen,

Pyributicarb, pyridate, paraquat, pebulate, pendimethalin, pentachlorophenol,

Pentanochlor, Petroleum oils, Phenmedipham, Picloram, Piperophos, Pretilachlor, Primisulfuron, Prodiamine, Prometryn, Propachlor, Propanil, Propaquizafob,

Propazine, Propham, Pyrithiobac,

Quinmerac, Quinocloamine, Quizalofop, Quizalofop-P,

Rimsulfuron

Sethoxydim, Sifuron, Simazine, Simetryn, Sulfometuron, Sulfentrazone, Sulcotrione, Sulfosate,

Tar oils, TCA, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine,

Terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil,

Tralkoxydim, Triallate, Triasulfuron, Tribenuron, Triclopyr, Tridiphane,

Trietazine, Trifluralin, Tycor, Thdiazimin, Thiazopyr, Triflusulfuron, Vernolate. The weight ratios of the active ingredients in these active ingredient combinations can be varied within relatively large ranges.

The active compound combinations preferably contain the active compound at 0.1 to

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

The microbicidal agents used to protect the technical materials or

Concentrates 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. 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 action.

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

example 1

3 g (30 mmol) of hydroxyisothiazole are placed in 20 ml of xylene, with 20 mg of p-

Toluene sulfonic acid and 3.2 g (36 mmol) acetaldehyde dimethyl acetal were added and the mixture was stirred at 115 ° C. for 15 h.

It is washed with water, dried over Na SO and evaporated. The oily residue is chromatographed on silica gel (ethyl acetate / toluene = 10: 1).

Yield: 1.1 g (23% of theory). For physical data, see Table 1.

The example compounds mentioned in Table 1 were prepared analogously.

Table 1 3-alkoxy-isothiazole derivatives of the formula (I)

Example of use A

The minimum inhibitory concentrations (MIC) of agents according to the invention are determined to demonstrate the activity against bacteria:

A defined candy agar is mixed with active substances according to the invention in concentrations of 0.1 mg / 1 to 5000 mg / 1. After the agar has solidified, it is contaminated with pure cultures of the test organisms listed in Table 2. After 3 days 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 concentration (ppm) of compounds of the formula (I) according to the invention

Example No. 7 from US 3,957,808:

Example No. 1 from US 5,384,326:

Claims

claims

1. Compounds of formula (I)

in which

R ^{1 represents} optionally substituted alkyl, alkenyl or alkynyl,

R ^{2 represents} optionally substituted alkyl, alkenyl, alkynyl or phenyl and

R ^{3 represents} hydrogen or halogen.

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

R ^{1 stands} for straight-chain and branched alkyl with 1 is 10 carbon atoms, straight-chain or branched alkenyl with 2 to 10 carbon atoms or straight-chain or branched alkynyl with 2 to 10 carbon atoms, which are each optionally substituted one or more times by the same or different substituents by halogen, alkoxy with 1 to 6 carbon atoms, haloalkoxy with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, alkylthio with 1 to 6 carbon atoms,

Haloalkylthio with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, acyl with 1 to 6 carbon atoms, acyloxy with 1 to 6 carbon atoms, (alkoxy) - carbonyl having 1 to 6 carbon atoms, amino, which is optionally identical or differently substituted by alkyl or aryl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano,

straight-chain and branched alkyl having 1 is 10 carbon atoms, straight-chain or branched alkenyl having 2 to 10 carbon atoms or straight-chain or branched alkynyl having 2 to 10 carbon atoms, which are in each case optionally substituted one or more times by the same or different substituents

Halogen, alkoxy with 1 to 6 carbon atoms, haloalkoxy with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, alkylthio with 1 to 6 carbon atoms, haloalkylthio with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, acyl with 1 to 6 carbon atoms, acyloxy with 1 to 6 carbon atoms, (alkoxy) carbonyl with 1 to 6 carbon atoms, amino, which is optionally substituted identically or differently by alkyl or aryl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or Cyano, or

stands for aryl,

which is optionally mono- to pentasubstituted by halogen, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, alkoxy having 1 to 10 carbon atoms, haloalkoxy having 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, alkylthio with 1 to 10 carbon atoms, haloalkylthio with 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, amino, monoalkylamino with straight-chain or branched alkyl radicals with 1 to 6 carbon atoms, dialkylamino with identical or different, straight-chain or branched alkyl radicals with 1 to 6 carbon atoms each, cycloalkyl with 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy , Chlorofluoromethylene dioxy, dichloromethylene dioxy, nitro or cyano, and

R ^{3 represents} halogen or hydrogen.

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

R ^{1 represents} straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms or straight-chain or branched alkynyl having 2 to 8 carbon atoms, which are in each case mono- to tetrasubstituted or substituted by fluorine or chlorine , Alkoxy with 1 to 5 carbon atoms, haloalkoxy with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, alkylthio with 1 to 5 carbon atoms, haloalkylthio with 1 to

5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, acyl with 1 to 5 carbon atoms, acyloxy with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms, amino, which is optionally substituted identically or differently by alkyl having 1 to 4 carbon atoms and / or phenyl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano,

R ^{2 is} straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms or straight-chain or branched alkynyl having 2 to 8 carbon atoms, which are in each case substituted one to four times in the same way or differently by fluorine, chlorine, alkoxy with 1 to 5 carbon atoms, haloalkoxy with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms,

Alkylthio with 1 to 5 carbon atoms, haloalkylthio with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, acyl with 1 to 5 carbon atoms, acyloxy with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms, amino, which may be the same or is differently substituted by alkyl having 1 to 4 carbon atoms and / or phenyl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano, or for

represents phenyl, which is optionally mono- to tetrasubstituted by fluorine, chlorine, alkyl having 1 to 8 carbon atoms, haloalkyl having 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, alkoxy having 1 to 8 carbon atoms, haloalkoxy 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, alkylthio with 1 to 8 carbon atoms,

Haloalkylthio with 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, amino, monoalkylamino with alkyl radicals of 1 to 4 carbon atoms, dialkylamino with identical or different alkyl radicals each with 1 to 4 carbon atoms, cycloalkyl with 1 to 6 carbon atoms, methylenedioxy, Difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylenedioxy, nitro or cyano, and

represents chlorine, bromine or hydrogen.

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

R ^{3 represents} chlorine or in particular hydrogen.

5. Microbicidal agents, characterized by a content of at least one

A compound of formula (I) according to claim 1.

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

7. Use of compounds of formula (I) or agents according to claims 1 to 5 for combating microorganisms.

8. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims 1 to 4 are mixed with extenders and / or surface-active agents.

9. A process for the preparation of compounds of the formula (I) as defined in claim 1, characterized in that hydroxyisothiazoles of the general formula (II),

wherein R ^{3 has} the meaning given in claim 1, either with

Compounds of formula (III)

wherein R ¹ and R ^{3 have} the meanings given in claim 1 and

R ^{4 can} independently have the same meaning as R ¹ , if appropriate in the presence of catalysts,

or with compounds of the general formula (IV),

wherein R ¹ and R ^{3 have} the meanings given in claim 1 and X represents chlorine or bromine, optionally in the presence of acid-binding agents.

10. A method for protecting industrial materials from attack and destruction by microorganisms, characterized in that the technical materials with compounds of the formula (I) as defined in claim 1, added or treated.