EP1335909A1 - 3-nitroisoxazoles and their use in the protection of materials - Google Patents

Abstract

The partly known 3-nitroisoxazoles of formula (I), wherein R?1 and R2¿ have the meanings given in the description, are excellently suited to use as biocides for protecting technical materials.

Description

3-nitroisoxazoles and their use in material protection

The present invention relates to new 3-nitroisoxazoles, processes for their preparation and the use of new and known 3-nitroisoxazoles as biocides for protecting industrial materials.

Some 3-nitro-isoxazoles with alkyl, aryl, hetaryl, alkynyl and alkoxycarbonyl radicals are known, a biological effect has not been described for the compounds mentioned (K. Baum. J. Org. Chem. 1985, 50, 2736; K. Kim, Tetrahedron

Lett. 1996, 37, 7791; K. Eiter, Natural Sciences 1972, 59, 468; E. Duranti, Tetrahedron Lett. 1973, 7, 485).

3,5-dinitroisoxazoles are known, an antibacterial effect is also not described here (D.T. Corner, Acta Crystallogr., Sect. C. Cryst. Struct. Commun. 1987,

43, 2011). Specially substituted 3-nitro-isoxazole-5-carboxaldehyde derivatives are known and in some cases have weak to moderate antibacterial effects (E. Duranti II Farmaco Ed. Sc. 1987, 42, 299).

It has now been found that 3-nitroisoxazoles of the general formula (I)

in which

R ¹ and R ² independently of one another represent hydrogen, halogen, nitro, cyano or each optionally substituted alkyl, alkenyl, alkynyl or aryl, have excellent bactericidal activity. In particular, the compounds of the formula (I), individually or as a mixture with one another, are suitable for combating microorganisms in and on industrial materials on account of their antibacterial and antifungal activity.

In addition, the compounds of formula (I) have good long-term activity and stability in industrial materials.

The compounds which can be used according to the invention are generally defined by the formula (I). Preferred is the use of compounds of formula (I) in which

R ¹ and R ² are each independently hydrogen, halogen, cyano, nitro, or represents in each case straight-chain or branched Cι-C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂ -C ₈ - alkynyl are, which in each case optionally a - or is substituted several times, identically or differently, by halogen, nitro, cyano, aryl, aryloxy, C ₁ -C ₆ -alkoxy which is optionally substituted 1 to 9 times, identically or differently by halogen, CrCβ-alkylthio which is optionally 1- up to 9-fold, the same or different is substituted by halogen, -C-C ₆ -acyl, dC ₆ -acyloxy, -C-C ₆ -alkoxy-carbonyl, amino which is optionally 1 or 2 times, identical or differently substituted by are CRG _f alkyl or aryl, or C _ö -Cio-aryl which is optionally substituted 1 or more times, identically or differently, _1. by halogen, cyano, nitro, C -C ₅ - alkyl which is optionally substituted from 1 to 6 -fold, identical or different substituted by halogen, CrCs-alkoxy which g optionally 1 to 6 times, identical or different, is substituted by halogen, d-Cs-alkylthio which is optionally 1 to 6 times, identical or differently substituted by halogen, amino, monoalkylamino with straight-chain or branched C ₁ -C ₆ -Alkyl radicals, dialkylamino with the same or different, straight-chain or branched C ₁ -C ₆ -alkyl radicals. Particular preference is given to the use of compounds of the formula (I) in which R ¹ and R ² independently of one another are hydrogen, fluorine, chlorine, bromine, cyano, nitro or in each case straight-chain or branched C ₁ -C ₆ -alkyl, C ₂ -C ₆ - alkenyl, C ₂ -C ₆ - alkynyl, which are each optionally mono- to tetrasubstituted, identically or differently, by fluorine, chlorine, bromine, nitro, cyano,

Is phenyl, naphthyl, phenyloxy, naphthyloxy, Cι-C ₄ alkoxy fold 7 which is optionally substituted 1 to identical or different manner by fluorine, chlorine or bromine, C ₁ -C ₄ -alkylthio which is optionally substituted from 1 to 7 -fold, identical or differently substituted by fluorine, chlorine or bromine, -CC ₄ -acyl, QQ-alkoxy-carbonyl, amino, which is optionally 1 or 2 times, identical or differently substituted by C1-C ₄ - alkyl, phenyl or naphthyl, or represent phenyl or naphthyl, which is in each case optionally substituted 1 to 4 times by fluorine, chlorine, bromine, cyano, nitro, QG alkyl which may be 1 to 4 times, identical or is differently substituted by fluorine, chlorine or bromine, C 1 -C 4 -alkoxy which is optionally 1- to 4-fold, identical or differently substituted by fluorine, chlorine or bromine, C 1 -C ₄ -alkylthio which may be 1- up to 4-fold, identical or different, substituted by fluorine, chlorine or bromine, amino, monoalkyl amino with straight-chain or branched C 1 -C ₄ -alkyl radicals or dialkylamino with the same or different, straight-chain or branched -Q-alkyl radicals.

It is very particularly preferred to use compounds of the formula (I) in which R ¹ and R ² independently of one another are hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n- Butyl, iso-butyl, sec-butyl, tert-butyl, for each isomer of pentyl, hexyl, heptyl and octyl, allyl, vinyl, propargyl, where the alkyl radicals mentioned are each optionally substituted one to four times, identically or differently by Fluorine, chlorine, bromine, nitro, cyano, phenyl, phenoxy, 2,4-dichlorophenoxy, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, trifluoromethoxy, Methyl thio, ethylthio, n-propylthio, iso-propylthio, trifluoromethylthio, C 1 -C ₄ -acyl, C 1 -C ₄ -acyloxy, - -alkoxycarbonyl, amino, which is optionally substituted identically or differently by C _! -C ₄ - alkyl, phenyl or naphthyl, furthermore for Phenyl or naphthyl, which are each optionally. 1- to 4-fold substituted the same or different by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, trifluoromethyl, methoxy, ethoxy, n -Propoxy, iso-propoxy, trifluoromethoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, trifluoromethylthio, amino, methylamino, ethylamino, n-propylamino, iso-propylamino, dimethylamino, diethylamino, methylethylamino, di-n -propylamino or di-iso-propylamino.

Particular preference is given to the use of compounds of the formula (I)

in which

R ¹ for hydrogen, fluorine, bromine, cyano, nitro, methyl, trifluoromethyl, difluoromethyl, methoxymethyl, ethoxymethyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl , n-pentyl, n-hexyl, n-heptyl, n-octyl, allyl,

Vinyl, propargyl, phenoxymethyl, 2,4-dichlorophenoxymethyl or phenyl, which is optionally substituted one to three times by the same or different substituents by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, trifluoromethyl , Methoxy, ethoxy, n-propoxy, iso-propoxy, trifluoromethoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, trifluoromethylthio, amino, methylamino, ethylamino, n-propylamino, iso-propylamino, dimethylamino, diethylamino , Methylethylamino, di-n-propylamino or di-iso-propylamino

and

R ² for hydrogen, fluorine, bromine, cyano, nitro, methyl, trifluoromethyl, difluoromethyl, methoxymethyl, ethoxymethyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl , n-pentyl, n-hexyl, n-heptyl, n-octyl, allyl, vinyl, propargyl, phenoxymethyl, phenyl. Also particularly preferred is the use of compounds of the formula (I) in which

R ¹ for hydrogen, fluorine, bromine, cyano, nitro, methyl, trifluoromethyl, difluoromethyl, methoxymethyl, ethoxymethyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl , n-pentyl, n-hexyl, n-heptyl, n-octyl, allyl, vinyl, propargyl, phenoxymethyl, 2,4-dichlo henoxymethyl or phenyl, which is optionally substituted one to three times by the same or different fluorine, chlorine , Bromine, cyano, nitro, methyl, ethyl, n-propyl, iso-propyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, trifluoromethoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, trifluoromethylthio , Amino, methylamino, ethylamino, n-propylamino, iso-propylamino, dimethylamino, diethylamino, methylethylamino, di-n-propylamino or di-iso-propylamino

and

R> 2 represents hydrogen.

The radicals specified in the respective definitions or preferred and particularly preferred definitions can be replaced as desired by radical definitions of other combinations, regardless of the combination specified in each case. In addition, residual definitions from any preferred area can also be omitted.

1

The optionally substituted aryl radicals mentioned in the definition of R and R represent in particular each optionally substituted phenyl and naphthyl radicals. The term halogen means in particular fluorine, chlorine and bromine.

The compounds of the formula (I) are new and likewise a subject of the present invention, with the exception of the compounds

3-nitro-isoxazole-5-carboxylic acid methyl ester (CAS-RN: 40995-06-0)

3-nitro-isoxazole-5-carboxylic acid ethyl ester (Beilstein RN: 6598833)

3-nitro-5-phenylisoxazole (CAS-RN: 6455-30-7) 3-nitro-5-methylisoxazole (CAS-R: 750097-82-2)

3- (3-nitro-isoxazol-5-yl) prop-2-yn-l-ol (Beilstein RN: 1106231)

3,5-dinitro-isoxazole (CAS-RN: 42216-62-6)

4-methyl-3,5-dinitro-isoxazole (CAS-RN: 42216-63-7)

3-nitro-5- (3-nitro-ρrop-l-ynyl) -isoxazole (Beistein RN: 1119643) 3-nitroisoxazole (CAS-RN: 39485-31-9)

4-chloromethyl-3-nitro-isoxazole (Beilstein RN: 6594348)

4-methyl-3-nitro-isoxazole (Beilstein RN: 6593345)

5-butyl-3-nitro-isoxazole (CAS-RN: 40995-04-8)

3-nitro-5-hydroxymethyl-isoxazole (CAS-RN: 75079-83-3) 5- (bromoprop-1-ynyl) -3-nitro-isoxazole (CAS-RN: 40995-02-6)

3-nitro-l-ρhenyl-isoxazole (Beilstein RN: 6596756)

(3-nitro-isoxazol-4-yl) phenyl methanone (Beilstein RN: 6599593)

4- (4-methoxy-ρhenyl) - 3-nitro-isoxazole (Beilstein RN: 6600205)

3-nitro-4- (2-nitro-phenyl) isoxazole (Beilstein RN: 6604179) 3-nitro-4- (4-nitrophenyl) isoxazole (Beilstein RN: 6604546)

3-nitro-4- (2,4-dinitrophenyl) isoxazole (Beilstein RN: 6612177)

3-nitro-isoxazole-5-carbaldehyde (CAS-RN: 108802-81-9)

3-nitro-5-acetyl-isoxazole (CAS-RN: 54468-91-6).

The new and known 3-nitroisoxazoles of the formula (I) which can be used according to the invention are obtained by compounds of the formula (II),

in which

R ¹ and R ^{2 have} the meaning given above

with tetranitroethylene, optionally in the presence of diluents, (see also K. Baum, J. Org. Chem. 1985, 50, 2736).

All organic solvents are suitable as diluents which can be used. These preferably include hydrocarbons such as toluene, xylene or hexane, chlorinated hydrocarbons such as chlorobenzene, methylene chloride or chloroform, ketones such as acetone, ethers such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether and dioxane, nitriles such as acetonitrile, and DMSO, DMF and

NMP.

The reaction temperatures can be varied over a wide temperature range in this process. Generally one works between -30 ° C and + 150 ° C, preferably between -10 ° C and + 50 ° C.

Tetranitroethylene can be prepared from hexanitroethane in a known manner.

The compounds of formula (II) used are known or can be prepared by generally known processes.

Nitroisoxazoles of the general formula (I),

in which

R ^{1 has} the meaning given above and R ^{2 represents} hydrogen,

can alternatively also be prepared by reacting compounds of the general formula (III)

X-CHz-C≡CR ¹ (III)

in which

R ^{1 has} the meaning given above and

X represents a leaving group, preferably bromine, iodine, chlorine, tosylate or mesylate,

with metal nitrites, preferably sodium or potassium nitrite, optionally in the presence of diluents.

In this process, the reaction temperatures can be varied over a wide range of temperatures. Generally one works between -30 ° C and

+ 150 ° C, preferably between -10 ° C and + 80 ° C.

Possible diluents that can be used are both water and all organic solvents. These preferably include hydrocarbons such as toluene, xylene or hexane, chlorinated hydrocarbons such as

Chlorobenzene, methylene chloride or chloroform, ketones such as acetone, ethers such as tefrahydrofuran, diethyl ether, methyl tert-butyl ether and dioxane, nitriles such as acetonitrile, and DMSO, DMF and NMP. This process is suitable both for the preparation of the known compounds and of the novel compounds of the formula (I) according to the invention with the stated meaning of the radical R ¹ .

The substances of the formula (I) which can be used according to the invention have a strong microbicidal action and can be used for controlling undesired microorganisms, such as fungi and bacteria, in crop protection and in material protection.

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

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basiidiomycetes) and against mucus organisms and bacteria. For example, microorganisms of the following genus are 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.

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following mixing partners have proven to be particularly favorable:

Triazoles such as:

Azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, epoxyconazole, etacazazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafolazol , Penconazole, propioconazole, (±) -cis-l- (4-chlorophenyl) -2- (lH-l, 2,4- triazol-1 -yl) -cycloheptanol, 2- (l-tert.-butyl) - 1 - (2-chlorophenyl) -3- (l, 2,4-triazol-1 -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, Trifluomizole, Thiazolcar, l-Imidazolyl-l- (4'-chlorophenoxyutan) as well as their metal salts and acid adducts;

Pyridines and pyrimidines such as:

Ancymidol, buthiobate, fenarimol, mepanipyrin, nuarimol, pyroxyfor, triamirol;

Succinate dehydrogenase inhibitors such as: benodanil, carboxime, carboxime sulfoxide, cyclafluramide, fenfuram, flutanil, furcananil, furmecyclox, mebenil, mepronil, methfüroxam, 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-in);

Sulfenamides such as:

Dichlofluanid, tolylfluanid, folpet, fluorfolpet, captan, captofol;

Benzimidazoles such as:

Carbendazim, benzomyl, fuberidazole, thiabendazole or their salts; Morpholine derivatives such as:

Aldimoφh, Dimethomoφh, Dedemoφh, Falimoφh, Fenpropidin, Fenpropimoφh, Tridemoφh, Trimoφhamid and their arylsulfonic salts, e.g. p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid;

Benzothiazoles 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-glycolhemiformal, hexa-hydro-S-triazine, hexamethylenetetramine, N-hydroxymethyl-N'-methylthiourea, N-methylolchloroacetamide, oxazolidine, paraformaldehyde , 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-octylisothiazolines, N-octyl-isothiazoline -3-one, 4,5-trimethylene-isothiazolinone, 4,5-benzisothiazolinone;

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

Thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate;

Quaternary ammonium compounds and guanidines such as: benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, dichlorobenzyldimethylalkylammonium chloride, di-decyldimethylammmonium chloride, dioctyldimethylammonium chloride, N-hexadecyldimidiumchloride Iminoctadinetris (albesilate);

Iodine derivatives such as:

Diiodomethyl-p-tolyl sulfone, 3-iodo-2-ρropinyl alcohol, 4-chloro-phenyl-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;

Phenols such as:

Tribromophenol, tetrachloφhenol, 3-methyl-4-chloro-phenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichloro-phenol, 2-benzyl-4-chloro-phenol, 5-chloro-2- (2,4-dichloro-phenoxy) - 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:

Bronidox, 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 1-bromo-3-chloro-4,4,5,5-tetramethyl-2-imidazolinone, ß -Brom-ß-nitrostyrene, chloroacetamide, chloramine T, l, 3-dibromo-4,4,5,5-tetramethyl-2-imidazolinone, dichloramine T, 3, 4-dichloro- (3H) - 1, 2 dithiol-3-one, 2,2-dibromo-3-nitrile-propionamide, 1, 2-dibromo-2,4-dicyanobutane, halanes, halazones, mucochloric acid, phenyl- (2-chloro-cyanovinyl) 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 -

'ι (2,4,4-trimethylpentyl) -2 (1H) pyridine;

Methoxyacrylates or similar like:

azoxystrobin,

Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] 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)] imino] oxy) o-tolyl] -2-methoximinoacetimidate,

2 - [[[[l- (2,5-dimethylphenyl) ethylidene] amino] oxy] methyl] -alpha- (methoximino) -N-methylbenzeneacetamide, alpha- (methoxyimino) -N-methyl-2 - [[[[ 1- [3- (trifluoromethyl) phenyl] ethylidene] amino] oxy] methyl] benzene acetamides,

Trifluoxystrobin, alpha- (methoxymethylene) -2 - [[[[l- [trifluoromethyl) phenyl] ethylidene] amino] - oxy] methyl] benzeneaceticacid methyl ester,

2 - [[[5-chloro-3- (trifluoromethyl) -2-pyridinyl] oxy] methyl] -alpha- (methoxyimino) -N-methylbenzeneacetamide,

2 - [[[cyclopropyl [(4-ethoxyphenyl) imino] methyl] thio] methyl] -alpha- (methoxy-imino) -benzeneaceticacid-methyl ester, alpha- (methoxyimino) -N-methyl-2-) 4-methyl- 5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-diene-1-yl) -benzeneacetamide, alpha- (methoxymethylene) -2- (4-methyl-5-phenyl-2,7- dioxa-3,6-diazaocta-3,5-diene

1-yl-benzeneaceticacid methyl ester, alpha (-methoximino) -N-methyl-2 - [[[l- [3-trifluoromethyl) phenyl] ethoxy] imino] - methyl] -benzeneacetamide, 2 - [[(3,5-dichloro-2-pyridinyl) -oxy] methyl] -alpha- (methoxyimino) -N-methyl-benzeneacetamide,

2- [4,5-dimethyl-9- (4-moφholinyl) -2,7-dioxa-3,6-diazanona-3,5-dien-l-yl] -alpha- (methoxymethylene) -benzeneaceticacid-methyl ester, kresoxim-methyl;

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, Cu ₂ O, CuO, ZnO;

Dithiocarbamates such as:

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

Nitriles such as:

2,4,5,6-tetrachloroisophthalodinitrile, 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) acetyroxy acid chloride, tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) tri-butyltin or K salts, bis-N- (cyclohexyldiazeniumdi- oxy) copper, iprovalicarb, fenhexamide, spiroxamine, Caφropamid, diflumetorin, quinoxyfen, famoxadone, polyoxorim, acibenzolar-S-methyl, furametpyr, thifluzamide, methalaxy-M, AgN, Zn or Cu-containing zeolites or alone enclosed in polymeric materials.

Mixtures of compounds of the formula (I) with one or more of the following active compounds are very particularly preferred:

Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, dichlofluanid,

Tolylfluanid, Fluorfolpet, Methfüroxam, Carboxin, Benzo [b] thiophene-S, S-dioxid-Carbonsäurecyclohexylamid, Fenpiclonil, 4- (2,2-Difluoro-l, 3-benzodioxol-4-yl) -lH-pyrrol-3- carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, dichloro-N-octylisothiazolinone, mercaptobenthiazole, thiocyanatomethylthiobenzothiazole, benzisothiazolinone,

(2-hydroxypropyl) amino-methanol, benzyl alcohol (hemi) formal, N-methylolchloroacetamide, N- (2-hydroxypropyl) amine methanol, glutaraldehyde,

Omadine, dimethyl dicarbonate, 2-bromo-2-nitro-l, 3-propanediol and / or 3-iodo-2-propynyl-n-butyl carbamate.

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

Insecticides / acaricides / nematicides: Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb,

Aldrin, Allethrin, Alpha-cypermethrin, Amitraz, Avermectin, AZ 60541, Azadirachin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, Barthrin, 4-Bromo-2 (4-chlθφhenyl) -l- (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3-carbonitrile, Bendiocarb, Benfüracarb, Bensultap, Betacyfluthrin, Bifenthrin, Bioresmethrin, Bio Bromophos A, Bromophos

M, Bufencarb, Buprofezin, Butathiophos, Butocarboxim, Butoxycarboxim, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chinomethionat, Chloethocarb, Chlordane, Chlorethoxyf s, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-3-pyridinyl) -methyl] -N '- cyano-N-methyl-ethanimidamide, Chloφicrin, Chloφyrifos A, Chloφyrifos 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 -hydrazine, DNOC, dichlofenthion, dichlorvos, dicliphos, dicrotophos, difethialone, diflubenzuron, dimethoate, dimethyl- (phenyl) -silyl-methyl-3-phenoxybenzylether, dimethyl- (4-ethoxyphenyl), -silylmethy 1-3, -phenoxybenzyl Dimethylvinphos, dioxathione, disulfoton,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, EPN, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etrimphos, Etoxazole, Etobenzanid, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenfluthrin, Fenitrothion, Fenobucarb,

Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fensulfothion, Fenthion, Fenvalerate, Fipronil, Fluazuron, Flucycloxuron, Flucythrinate, Flufenoxuron, Flupyrazofos, Flufenzine, Flumenthrin, Flufenproxate, Fonophion, Fofionosphonate, Fofionosulfonate, Fofionosphonate, Fylphonium, Ffionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fofionosphonate, Fonophone, Fonophone, Fonfosolate, Fonophone, Fonophionate Furathiocarb, Halofenocid, HCH, heptenophos, Hexaflumuron, Hexythiazox, Hydramethylnon,

hydroprene,

Imidacloprid, Imiprothrin, Indoxycarb, Iodfenfos, Iprinomectin, Iprobefos, Isaophos, Isoamidophos, Isofenphos, Isoprocarb, Isoprothiolane, Isoxathion, Ivermectin, Lamacyhalothrin, Lufenuron, Kadedrin,

Lambda-cyhalothrin, lufenuron,

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

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos, Parathion A, Parathion M, Penfluron, Permethrin, 2-4-Phenoxyphenoxy) ethyl ethyl carbamate, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimi- carb, Pirimiphos M, Pirimiphos A, Prallethrin, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Pyrithiobac-sodium,

quinalphos,

Resmethrin, RH-7988, Rotenone,

Salithion, Sebufos, Silafluofen, Spinosad, Sulfotep, Sulprofos, Tau-fluvalinate, Taroils, Tebufenozide, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorethrin, Tetrachlorethrin

Tetramethacarb, thiacloprid, Thiafenox, thiamethoxam, Thiapronil, thiodicarb, thiofanox, methrin Thiazophos, thiocyclam, Thiomethon, Thionazin, thuringiensin, Tralo-, ron transfluthrin, Triarathen, triazophos, Triazamate, trichlorfon, Triflumu-, trimethacarb, vamidothion, XMC, xylylcarb, Zetamethrin;

molluscicides:

Fentin acetates, metaldehydes, methiocarb, niclosamides;

Herbicides and algicides:

Acetochlor, Acifluorfen, Aclonifen, Acrolein, Alachlor, Alloxydim, Ametryn, Amidosulfüron, Amitrole, Ammonium sulfamate, Anilofos, Asulam, Atrazine, Azafenidin, Aziptrotryne, Azimsulfuron, Benazolin, Benfluralin, Benfuresate, Bensulfuron, Bensulfuron, Bensulfonate - cap, benzthiazuron, bifenox, bispyribac, bispyribac sodium, bispyribac methyl,

Borax, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butamifos, butralin, butylates, bialaphos, benzoyl-prop, bromobutide, butroxydim, carbetamides, carfentrazone-ethyl, carfenstrole, chlomethoxyfen, chloramben, chlorbromuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronurluronuronuronuronurluronuronurluronurluronurluronuryluronurl Chloroacetid acid, chlorosulam-methyl, cinidon-ethyl, chlorotoluron, chloroxuron,

Chloφropham, Chlorsulfuron, Chlorthal, Chlorthiamid, Cinmethylin, Cinofulsuron, Clefoxydim, Clethodim, Clomazone, Chlomeprop, Clopyralid, Cyanamide, Cyana- zine, Cycloate, Cycloxydim, Chloroxynil, Clodinafop-propargyl, Cumyluron, Clometoxyfen, Cyhalofop, Cyhalofop-butyl, Clopyrasuluron, Dicyclofo-phyllo, Cyclosulfoflurlo, Cyclosulfofluramon, Cyclosulfofluramon, Cyclosulflosulamon, Cyclosulflosulamon, Cyclosulflosulamon, Cyclosulflosulamon, Cyclosulflosulamon, Cyclosulflosulamon, Cyclosulflosulamon, Cyclosulflosulamon, Cyclosulflosulamon, Cyclosulflosulamonon Diethatyl, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor,

Dimethipin, Dinitramine, Dinoseb, Dinoseb Acetate, Dinoterb, Diphenamid, Dipro-petryn, Diquat, Dithiopyr, Diduron, DNOC, DSMA, 2,4-D, Daimuron, Dalapon, Dazomet, 2,4-DB, Desmedipham, Desmetryn, Dicamba , Dichlobenil, dimethamide, dithiopyr, dimethametryn, Eglinazine, Endothal, EPTC, Esprocarb, ethalfluralin, ethidimuron, ethofumesate,

Ethobenzanide, ethoxyfen, ethametsulfuron, ethoxysulfuron,

Fenoxaprop, Fenoxaprop-P, Fenuron, Flamprop, Flamprop-M, Flazasulfüron, Fluazifop, Fluazifop-P, Fuenachlor, Fluchloralin, flufenacet, Flumeturon, Fluorocglycofen, Fluoronitrofen, Flupropanate, Flurenol, Fluridone, Flurafenoxamine, Flurafenoxamine Flamprop-isopropyl, flamprop-isopropyl-L, flumiclorac-pentyl, flumipropyn, flumioxzim, flurtamone, flumioxzim, flupyrsulfuron-methyl, fluthiacet-methyl, glyphosate, glufosinate-ammonium, haloxyfop, hexazinone, isazamopyronezone imazaquin,

Imazethapyr, Ioxynil, Isopropalin, Imazosulfüron, Imazomox, Isoxaflutole, Imazapic, Lactofen, Lenacil, Linuron,

MCPA, MCPA-thioethyl, MCPB, Mecoprop, Mecoprop-P, Mefenacet, Mefluidide, Metam, Metamitron, Metazachlor, Methäbenzthiazuron, Methazole, Methoropytryne, Methyldymron, Methylisothiocyanate, Metobromuron, Metoxinon, Metribuzon

Metsulfuron, Molinate, Manolide, Monolinuron, MSMA, Metolachlor, Metosulam, Metobenzuron,

Naproanilide, Napropamide, Naptalam, Neburon, Nicosulfuron, Norflurazon, Sodium Chlorate, Oxadiazon, Oxyfluorfen, Oxysulfuron, Orbencarb, Oryzalin, Oxadiargyl, Propyzamide, Prosulfocarb, Pyrazolate, Pyrazolsulfuron, Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Paraquat, Pebulate, Pendimethalin, Pentachlorophenol, Pentoxazone, Pentanochlor, Petroleum oils, Phenmedipham, Picloram, Piperophan, Prodililonloron, Prodililonloron , Propazine, Propham, Propisochlor, Pyriminobac-methyl, Pelargonic acid, Pyrithiobac, Pyraflufen-ethyl, Quinmerac, Quinocloamine, Quizalofop, Quizalofop-P, Quinchlorac, Rimsulfuron, Sethoxydim, Sifuron, Simazine, Simetryn, Sulfomra Sulfuron, Sulfosulfuron , Sulcotrione, sulfosate,

Tar oils, TCA, tebutam, tebuthiuron, terbacil, terbumeton, Terbuthylazine, terbutryn, Thiazafluoron, thifensulfuron, thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, Tribenzuron, triclopyr, Tridiphane, Trietazine, Trifluoralin, Tycor, Thdiazimin, thiazopyr, triflusulfuron, vernolate.

Depending on their physical properties 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.

The formulations or agents are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents or other carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. Possible emulsifiers and / or foam-generating agents are: for example non-ionogenic and anionogenic 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; The following may be used as dispersants: for example lignin sulfite leaching and methyl cellulose. In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic Tables, powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

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

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

Preparation Examples

example 1

3-Nitroisoxazol

20.7 g (0.3 mol) of sodium nitrite are placed in 100 ml of DMF and 22.3 g (0.15 mol) of an 80% solution of propargyl bromide are added dropwise with cooling. The reaction solution turns dark purple. After stirring for 24 h at room temperature, the mixture is poured into 300 ml of water, extracted twice with ether, washed with saturated NaCl solution, dried over sodium sulfate and concentrated. The brown residue is chromatographed on silica gel (toluene). 1.66 g of 3-nitroisoxazole were obtained as a slightly yellow oil with the physical data given in Table 1.

Analogously to the method mentioned in Example 1 and analogously to the method mentioned in the description, compounds mentioned in Table 1 were prepared.

Table 1 Compounds of the general 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 Landy Agar is mixed with active substances according to the invention in concentrations of 0.1 mg / ml to 5000 mg / ml. 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 substance at which no growth occurs due to the type of microbe used, it is shown in the table below.

Table 2 Minimum inhibitory concentration (ppm) of compounds of the formula (I) according to the invention

Example of use B

The minimal inhibitory concentrations (MIC) of agents according to the invention are determined to demonstrate the activity 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 / 1 to 5,000 mg / 1. After the agar solidifies, it is contaminated with pure cultures of the test organisms listed in Table 3. 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 3 below.

Table 3 Minimum hemin concentration (ppm) of compounds of the formula (I) according to the invention

Claims

Patentansprtiche

1. A method for combating microorganisms, characterized in that at least one compound of the formula (I)

in which

R ¹ and R ² independently of one another represent hydrogen, halogen, nitro, cyano or each optionally substituted alkyl, alkenyl, alkynyl or aryl,

affects microbes or their living space.

2. The method according to claim 1, characterized in that in formula (I)

R and R independently represent hydrogen, halogen, cyano, nitro, or represents in each case straight-chain or branched Cι-C ₈ alkyl, C ₂ -C ₈ - alkenyl or C ₂ -C ₈ - alkynyl stand, which is optionally monosubstituted or in each case is substituted several times, identically or differently by halogen, nitro, cyano, aryl, aryloxy, C ₁ -C ₆ -alkoxy which is optionally 1- to 9-fold, is identical or differently substituted by halogen, dC _ö -alkylthio which is optionally 1- up to 9-fold, identical or different, is substituted by halogen, dC ₆ -

Acyl, Ci-C _ö acyloxy, dC ₆ -alkoxy-carbonyl, amino which is optionally 1- or 2-fold, the same or differently substituted by -CC ₄ alkyl or aryl, or are C ₆ -Cιo-aryl which is optionally substituted one or more times, identically or differently is by halogen, cyano, nitro, C ₁ -C 5 alkyl which is optionally substituted 1 to 6 times, identically or differently by halogen, Ci-d-alkoxy which is optionally 1 to 6 times, identical or different by halogen is is substituert, d-Cs-alkylthio which is optionally 6-fold 1 to identical or different substituents chosen from halogen, amino, monoalkylamino having straight-chain or branched dC _ö alkyl radicals, dialkylamino having identical or different straight-chain or branched dC ₆ - alkyl ,

Process according to claims 1 and 2, characterized in that in formula (I)

R ¹ and R ² independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, or each straight-chain or branched dC ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, which in each case optionally substituted one to four times, identically or differently, by fluorine, chlorine, bromine, nitro, cyano, phenyl, naphthyl, phenyloxy, naphthyloxy, dC ₄ -alkoxy which may be 1- to 7-fold, identical or different, by fluorine, Chlorine or bromine is substituted, C 1 -C ₄ -alkylthio which is optionally substituted 1 to 7 times, identically or differently, by fluorine, chlorine or bromine, dC ₄ - acyl, dC ₄ -alkoxy-carbonyl, amino, which is optionally substituted 1 or 2 times, identically or differently, by dC ₄ -alkyl, phenyl or naphthyl, or represents phenyl or naphthyl, which is in each case optionally substituted 1 to 4 times by fluorine, chlorine,

Bromine, cyano, nitro, dC ₄ -alkyl which is optionally substituted 1 to 4 times, identically or differently by fluorine, chlorine or bromine, dC ₄ -alkoxy which is optionally 1 to 4 times, identical or different by Fluorine, chlorine or bromine is substituted, d- C ₄ -alkylthio which is optionally 1- to 4-fold, identical or differently substituted by fluorine, chlorine or bromine, amino, Monoalkylamino having straight-chain or branched C ₁ -C ₄ alkyl radicals or dialkylamino having identical or different straight-chain or branched Cι-C ₄ alkyl radicals.

4. Use of compounds of formula (I) according to claim 1 as a microbicide for protecting industrial materials and plants.

5. Use according to claim 4 for the protection of industrial materials against fungi and bacteria.

Microbicidal agents for the protection of materials, comprising at least one compound according to claim 1, solvents or diluents and, if appropriate, processing aids and, if appropriate, further active ingredients.

7. A process for the preparation of microbicidal compositions according to claim 6, characterized in that at least one compound according to claim 1 is mixed with solvents or diluents and, if appropriate, with processing aids and, if appropriate, with further active ingredients.

8. Technical materials containing at least one compound according to claim 1.

9. Compounds of formula (I)

in which R ¹ and R ² independently of one another represent hydrogen, halogen, nitro, cyano or in each case optionally substituted alkyl, alkenyl, alkynyl or aryl,

with the ecxeption of

3-nitro-isoxazole-5-carboxylic acid methyl ester (CAS-RN: 40995-06-0) 3-nitro-isoxazole-5-carboxylic acid ethyl ester (Beilstein RN: 6598833) 3-nitro-5-phenylisoxazole (CAS-RN: 6455-30 -7)

3-nitro-5-methylisoxazole (CAS-RN: 750097-82-2) 3- (3-nitro-isoxazol-5-yl) prop-2-yn-l-ol (Beilstein RN: 1106231) 3.5 -Dinitro-isoxazole (CAS-RN: 42216-62-6) 4-methyl-3,5-dinitro-isoxazole (CAS-RN: 42216-63-7) 3-nitro-5- (3-nitro-ρrop- l-ynyl) -isoxazole (Beistein RN: 1119643)

3-nitroisoxazole (CAS-RN: 39485-31-9) 4-chloromethyl-3-nitro-isoxazole (Beilstein RN: 6594348) 4-methyl-3-nitro-isoxazole (Beilstein RN: 6593345) 5-butyl-3- nitro-isoxazole (CAS-RN: 40995-04-8) 3-nitro-5-hydroxymethyl-isoxazole (CAS-RN: 75079-83-3)

5- (bromo-proρ-l-ynyl) -3-nitro-isoxazole (CAS-RN: 40995-02-6) 3-nitro-l-phenyl-isoxazole (Beilstein RN: 6596756) (3-nitro-isoxazole- 4-yl) phenylmethanone (Beilstein RN: 6599593) 4- (4-methoxyphenyl) -3-nitro-isoxazole (Beilstein RN: 6600205) 3-nitro-4- (2-nitro-phenyl) isoxazole (Beilstein RN: 6604179)

3-nitro-4- (4-nitrophenyl) isoxazole (Beilstein RN: 6604546) 3-nitro-4- (2,4-dinitrophenyl) isoxazole (Beilstein RN: 6612177) 3-nitro-isoxazole-5-carbaldehyde ( CAS-RN: 108802-81-9) 3-nitro-5-acetyl-isoxazole (CAS-RN: 54468-91-6).

10. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that compounds of formula (II),

R ² -C≡CR ¹ (II)

in which

R ¹ and R ^{2 have} the meaning given in claim 1

with tetranitroethylene, optionally in the presence of diluents.

11. Process for the preparation of compounds of formula (I)

in which

R ^{1 has} the meaning given in claim 1, and

R ^{2 represents} hydrogen,

characterized in that compounds of the general formula (HI)

X-CH ₂ -0≡CR ¹ (III)

in which R ^{1 has} the meaning given above and

X represents a leaving group, preferably bromine, iodine, chlorine, tosylate or mesylate,

with metal nitrites, preferably sodium or potassium nitrite, optionally in the presence of diluents.