EP1904464A1 - 1-cycloalkyl-5-iodotetrazoles - Google Patents

Abstract

Disclosed are compounds of formula (I), wherein R1 represents cycloalkyl, and the stereoisomers and any mixtures thereof. Said compounds are excellent microbicides used for protecting plants and materials.

Description

l-CvcloaIkyl-5-Iod.etrazole

The invention relates to novel 1-cycloalkyl-5-iodotetrazoles, processes for their preparation and their use as biocides for the protection of plants and technical materials.

The literature already discloses some 5-iodotetrazoles and ways of preparing them. A biological effect is not mentioned in any of the above cases. 1-Cycloalkyl-5-iodotetrazoles are not known in the literature.

5-iodo-tetrazoles can be obtained by reacting 1-substituted 5-tetrazolyllithium compounds with iodine at low temperatures (see R. Raap, Can. J. Chem., 1971, 49, 2139, Satoh, Yoshitaka, Tetrahedron Lett. , 1995, 36, 1759; Satoh, Yoshitaka, Synlett 1998, 528).

Another process for preparing 1-alkyl-5-iodo-tetrazoles is based on 1-alkyltetrazoles which are treated with iodine in glacial acetic acid containing KMnO ₄ and H ₂ SO ₄ (compare PN Gaponik, Khimiya Geterotsiklicheskikh Soedinenii 1988 , 1699).

There have been found new 5-iodo-tetrazoles substituted in the 1-position by cycloalkyl, which are very well suited as microbicides for the protection of plants and technical materials.

The present invention therefore relates to novel compounds of the formula (I)

in which

R ^{1 is} cycloalkyl.

Preference is given to compounds of the general formula (I) in which

R ^{1 represents} optionally bridged, unsubstituted or mono- or polysubstituted by identical or different substituted C ¹ -C 8 -cycloalkyl,

wherein the substituents for the mono- or polysubstituted or differently substituted cycloalkyl radicals are selected from the group halogen; nitro; cyano; hydroxy; unsubstituted Q-Cg-alkyl; Ci-Cg-alkyl, which is 1 to 9 times, the same or different substituted by halogen; C ₂ -C ₈ alkynyl; unsubstituted QC ₈ alkoxy; C _r C ₈ -

Alkoxy which is substituted 1 to 9 times, identically or differently by halogen; unsubstituted C _r C ₈ alkylthio; C 1 -C ₈ -alkylthio which is substituted 1 to 9 times, same or different by halogen; C ₃ -C ₈ cycloalkyl; amino; Monoalkylamino having straight-chain or branched CrQ-alkyl radicals; Dialkylamino having the same or different, straight-chain or branched C _r C ₈ -alkyl radicals; dC ₈ acyl; Ci-Cg-acyloxy; Cj-Cg alkoxycarbonyl; carboxyl; unsubstituted phenyl; Phenyl which is one to five times, identically or differently substituted by halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, acyl, acyloxy, alkoxycarbonyl, carboxyl, amino, monoalkylamino or dialkylamino.

Particular preference is given to compounds of the general formula (I) in which

R ^{1 represents} optionally bridged, unsubstituted or mono- to disubstituted, identical or differently substituted C ₃ -Cg -cycloalkyl,

wherein the substituents for the mono- to 6-fold, identically or differently substituted C ₃ -C ₈ - cycloalkyl radicals are selected from the series fluorine; Chlorine; Bromine; iodine; nitro; cyano; hydroxy; unsubstituted C ₁ -C ₆ -alkyl; C _r C ₆ alkyl, which is 1- to 6-fold, substituted by identical or different fluorine, chlorine or bromine; C ₂ -C ₈ -alkyl; C ₁ -C ₆ -alkoxy;

C 1 -C 6 -alkoxy which is substituted 1 to 6 times, identically or differently by fluorine, chlorine or bromine; unsubstituted C ₁ -C ₆ -alkylthio; C ₁ -C ₆ -alkylthio which is substituted 1 to 6 times, same or different by fluorine, chlorine or bromine; C ₃ -C ₀ -cycloalkyl; amino; Monoalkylamino having straight-chain or branched C 1 -C 6 -alkyl radicals; Dialkylamino having the same or different, straight-chain or branched C _r

C ₆ alkyl radicals; Ci-Cβ-acyl; QC _ό acyloxy; CRQ-alkoxy-carbonyl; carboxyl; unsubstituted phenyl; Phenyl which to 4-fold, identical or different substituents Ci-C is substituted by fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxy, ₄ alkyl, Ci-C ₄ - halogenoalkyl which 1- to 5-fold identical or is substituted by fluorine, chlorine or bromine, Ci-C ₄ -alkoxy, Ci-C ₄ -haloalkoxy which is 1 to 5 times the same or different substituted by fluorine, chlorine or bromine, Q -C ₄ - alkylthio, Ci -C ₄ - haloalkylthio which is substituted 1- to 5 fold by identical or different fluorine, chlorine or bromine, Ci-C ₆ acyl, QC _ß acyloxy, Ci-Q-alkoxycarbonyl, carboxyl, amino, monoalkylamino having straight-chain or branched C 1 -C ₄ -alkyl radicals, dialkylamino having the same or different, straight-chain or branched C 1 -C ₄ -alkyl radicals

Alkyl radicals.

Very particular preference is given to compounds of the formula (I) in which R ^{1 represents} optionally bridged, unsubstituted or mono- to disubstituted, identically or differently substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl,

wherein said cycloalkyl radicals are each optionally substituted one to four times, identically or differently by fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxy,

Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, trifluoromethyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, methoxy, ethoxy, n- Propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, trifluoromethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, trifluoromethylthio, cyclopropyl, cylobutyl, cyclopentyl, cyclohexyl, amino, Methylamino, ethylamino, n-

Propylamino, iso-propylamino, dimethylamino, diethylamino, methylethylamino, di-n-propylamino di-iso-propylamino, acetyl, acetyloxy, methoxycarbonyl, carboxyl, unsubstituted phenyl, phenyl which one to three times by fluorine, chlorine, bromine, iodine , Nitro, cyano, hydroxy, methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-

Butoxy, sec-butoxy, tert-butoxy, trifluoromethoxy, methylthio, ethylthio, n-propylthio, iso-propylthio, trifluoromethylthio, formyl, acetyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, carboxy, amino, methylamino, ethylamino, n-propylamino, iso- Propylamino, dimethylamino, diethylamino, methylethylamino, di-n-propylamino di-iso-propylamino substituted.

The radicals given in the respective definitions or preferred, particularly preferred and very particularly preferred definitions can, irrespective of the particular combination given, also be replaced as desired by radical definitions of other combinations. In addition, remainder definitions from any preferred area can be omitted.

The compounds of formula (I) may also be chiral depending on the substitution. The invention also includes the optionally occurring stereoisomers and any mixtures thereof. In the context of the invention, the terms stereoisomerically enriched (enantiomerically enriched or diastereomerically enriched) mean stereoisomerically pure (enantiomerically pure or diastereomerically pure) compounds or mixtures of stereoisomers (enantiomers or diastereomers) in which a stereoisomer (enantiomer or diastereomer) is present in a relatively large proportion as another or the other. By way of example, stereoisomerically enriched means and preferably has a content of a stereoisomer of from 50% to 100% by weight, more preferably from 70% to 100% by weight and very preferably from 90 to 100% by weight, based on the sum of the respective stereoisomers. The enrichment and separation of the racemates and / or diastereomeric mixtures may be accomplished by physical methods making use of optionally optically active support materials having a preferred affinity with one of the enantiomers or diastereomers. For example, inclusion compounds may be mentioned. Furthermore, it is possible to carry out the enrichment and separation of the racemates and / or diastereomer mixtures by chromatographic methods on optionally optically active adsorbents, for example cyclodextrins, starch or modified silica gels. Furthermore, it is possible to carry out the enrichment and separation of the racemates by adding an optically active auxiliary.

Under optionally bridged C ₃ -C ₈ -CyC loalkyl in the definition of R is to be understood that optionally at least 2 C-atoms of the C ₃ -C ₈ cycloalkyl are part of at least one further attached ring.

In the definition of R ¹ , optionally bridged C ₃ -C ₈ -cycloalkyl is to be understood as meaning that optionally at least 2 C-atoms of the C ₃ -C ₈ -cycloalkyl radical are part of up to three further attached rings, the attached rings optionally each have a size of 3 to 10 carbon atoms.

Particular preference is given by optionally bridged C ₃ -C ₈ -cycloalkyl to understand that optionally at least 2 C-atoms of the C ₃ -C ₈ -cycloalkyl are part of up to three other attached rings, wherein the attached rings optionally each have a size of Have 3 to 6 carbon atoms.

The novel compounds of the general formula (I) can be prepared by reacting tetrazoles of the general formula (II)

in which

R ^{1 has} the general or preferred meaning given above,

treated with iodine, optionally in the presence of a base or a diluent. In general, the processes can vary the temperature over a wide range. In general, the reaction is between 50 ⁰ C and -100 ⁰ C, preferably at 30 ⁰ C to -90 ⁰ C, most preferably is carried out in a range of 10 ⁰ C and -80 ⁰ C.

As bases, in principle all common bases can be used. Strong bases have proven to be particularly advantageous, such as alkali metal amides and alkali metal alkyl compounds. Very particularly preferred are: lithium diisopropylamide, methyllithium, ethyllithium, propyllithium, n-butyllithium, tert-butyllithium, sodium hexamethyl disilazide, lithium hexamethyldisilazide.

As diluents, it is possible to use all solvents which themselves do not react with iodine or the base which may be used. These preferably include hydrocarbons such as toluene, xylene or hexane, chlorinated hydrocarbons such as chlorobenzene, methylene chloride or chloroform, ethers such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether and dioxane, nitriles such as acetonitrile, and DMSO, DMF and NMP.

Furthermore, the compounds of the general formula (I) can be obtained if tetrazoles of the general formula (H) in which R ^{1 has} the meaning given,

optionally treated with iodine in the presence of an acid and optionally in the presence of an oxidizing agent.

In general, one works here between 0 ⁰ C and 150 ⁰ C, preferably between 20 ⁰ C and 130 ⁰ C and particularly preferably between 80 ⁰ C and 110 ⁰ C.

As acids all common acids can be used. Preference is given to using acetic acid or sulfuric acid.

As oxidizing agent it is possible to use all customary oxidizing agents, preference is given to using KMnO ₄ , HNO ₃ , H ₂ O ₂ or peroxyacetic acid, most preferably KMnO _{4 is} used.

The preparation processes provide the compounds of general formula (I) as a racemate, provided that the compounds of general formula (II) has a stereogenic center or, if the compounds of general formula (II) has more than one stereogenic center as a mixture of diastereomers. The racemates and diastereomeric mixtures may be used as such or enriched by methods known to those skilled in the art and converted to the enantiomers or diastereomerically pure compounds. The compounds of the general formula (II) with the exception of the compounds with the following CAS number are also novel and a further subject of the present invention:

[280131 -31 -9]: 5H-cyclopenta [c] pyridine-1-amine, 6,7-dihydro-6- (1H-tetrazol-1-yl) -;

[280131-30-8]: 5H-cyclopenta [c] pyridine-1-amines, 6,7-dihydro-5- (1H-tetrazol-1-yl) -; [280131-27-3]: 5H-cyclopenta [c] pyridine-1-amines, 6,7-dihydro-7- (1H-tetrazol-1-yl) -;

[207729-97-3]: cyclopentanamine, 2- (4-fluorophenyl) -3- (1H-tetrazol-1-yl) -, (1R, 2S, 3R);

[190270-66-7]: cyclopentanamine, 2- (4-fluorophenyl) -3- (1H-tetrazol-1-yl) -, (1α, 2α, 3β) -;

[190270-65-6]: 1H-tetrazoles, 1- [3-azido-2- (4-fluorophenyl) cyclopentyl] -, (1α, 2β, 3β) -;

[190270-64-5]: cyclopentanol, 2- (4-fluorophenyl) -3- (1H-tetrazol-1-yl) -, (1R, 2S, 3S); [190270-63 ^ t]: 1H-tetrazoles, 1 - [(1R, 2R, 3S) -2- (4-fluorophenyl) -3- (phenylmethoxy) cyclopentyl] -;

[103312-35-2]: 1H-tetrazoles, 1- (6-chloro-2,3-dihydro-5-methyl-1H-inden-1-yl) -;

[103294-76-4]: 1H-tetrazoles, 1- (5,6-dichloro-2,3-dihydro-1H-inden-1-yl) -;

[720721-24-4]: Carbamic acid, [(1R, 2S _> 5S) -2 - [[[(5-chloro-2-pyridinyl) amino] oxoacetyl] amino] -5-

(1H-tetrazol-1-yl) cyclohexyl], 1,1-dimethylethyl ester; [720721-23-3]: Carbamic acid, [(IS, 2R, 4S) -2 - [[(1,1-dimethylethoxy) carbonyl] amino] -4- (1H-tetrazol-1-yl) cyclohexyl] - , phenylmethyl ester;

[160698-27-1]: 1H-tetrazoles, 1 - (1, 2,3,4-tetrahydro-1-naphthalenyl) -;

[160698-25-9]: 1H-tetrazoles, 1- (1-ethyl-1,2,3,4-tetrahydro-1-naphthalenyl) -;

[50987-42-3]: 1H-tetrazoles, 1-tricyclo [3.3.1.13,7] dec-2-yl; (Adamantyl) [50987-38-7]: 1H-tetrazoles, 1-tricyclo [3.3.1.13,7] dec-1-yl; (Adamantyl)

[24281-91-2]: 1H-tetrazoles, 1- (5α-cholestan-3β-yl) -;

[24281-90-1]: 1H-tetrazoles, 1- (5α-cholestan-3α-yl) -;

[24281-82-1]: 1H-tetrazoles, 1- (5α-cholestan-6β-yl) -;

[24211-56-1]: 1H-tetrazoles, 1- (5α-cholestan-6α-yl) -; [18102-76-6]: 1H-tetrazoles, 1-cyclohexyl-.

The compounds of general formula (H) can be prepared by those skilled in the art according to generally known methods, for example by reacting a primary amine with triethyl orthoformate and sodium azide in acetic acid (see, e.g., Science of Synthesis, Volume 13, page 864).

The compounds of the formula (I) in which R ^{1 has} the abovementioned general and preferred meanings have pronounced activity against plant and material protection-relevant microorganisms and can be used as microbicides for the protection of plants and industrial materials. Another object of the present invention is therefore the use of the compounds of formula (I) for the protection of plants and technical materials against attack and / or destruction by microorganisms.

The compounds of formula (I) have potent microbicidal activity and can be used to control undesirable microorganisms, e.g. Fungi, bacteria and algae are used. The compounds of general formula (I) are preferably used for controlling unwanted microorganisms in the protection of materials.

In the protection of materials, the substances according to the invention can be used to protect industrial materials against infestation and destruction by undesired microorganisms.

Technical materials as used herein mean non-living materials that have been prepared for use in the art. For example, the technical materials are adhesives, glues, paper and cardboard, textiles, leather, wood, wood-based materials, wood composites, paints and plastics, coolants and other materials that may be infested or decomposed by microorganisms. Furthermore, technical materials in the context of the present invention also mean parts of production plants, for example cooling water circuits, which can be impaired by the multiplication of microorganisms. Preferred technical materials to be protected are adhesives, glues, papers and boards, leather, wood, wood-based materials, wood composites, paints, plastics, coolants and heat transfer fluids.

In particular, the compounds of the general formula (I) according to the invention are suitable for protecting wood, wood-based materials, wood composites, plastics, cooling lubricants, aqueous and / or solvent-borne organic or inorganic dispersions and coating systems such as paints, varnishes or plasters from infestation by microorganisms.

As microorganisms that can cause degradation or a change in the technical materials, for example, bacteria, fungi, yeasts, algae and mucus organisms may be mentioned. The active compounds according to the invention preferably act against fungi, in particular molds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime 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 such as Trichoderma viride, Escherichia, like Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus.

The compounds (I) according to the invention can be used individually or in any desired mixture with one another for the protection of industrial materials.

Furthermore, the compounds of the invention or mixtures thereof, depending on their physical and / or chemical properties in the conventional formulations can be converted, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and Feinstverkapselungen in polymeric materials.

These formulations can be prepared in a known manner, for example by mixing the individual active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents , In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, eg petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. By liquefied gaseous diluents or carriers are meant those liquids which are at normal temperature and below Normal pressure gaseous, for example, aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. As solid carriers for granules are: for example, broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corncobs and tobacco stalks. Suitable emulsifiers and / or foam-formers are: for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. Suitable dispersants are: for example lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient or active ingredient mixture, preferably between 2 and 75 percent by weight.

The present invention therefore furthermore relates to microbicidal compositions based on the compounds of the formula (I) according to the invention, comprising at least one solvent or diluent and, if appropriate, processing auxiliaries and, if appropriate, further antimicrobial substances. Here, the active ingredients may be present either in dissolved form or as suspensions or emulsions. The solvents or diluents are either water or all common organic solvents.

The compositions according to the invention can be prepared by mixing at least one compound of the formula (I) with at least one solvent or diluent and, if appropriate, with auxiliaries and additives and, if appropriate, further antimicrobial substances.

The efficacy and the spectrum of action of the active compounds of the formula (I) or the agents, precursors or, more generally, formulations which can be prepared therefrom can be increased, if necessary, further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients are added to increase the spectrum of action or to achieve particular effects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

In many cases synergistic effects, i. E. the effectiveness of the mixture is greater than the effectiveness of the individual components. Particularly favorable mixing 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, paclobutrazole, penconazole, propioconazole, prothioconazole,

S imeoconazole, (±) -cis-1 - (4-chlorophenyl) -2- (IH-1, 2,4-triazol-1-yl) -cycloheptanol, 2- (1-tert-butyl) -l- (2-chloro-phenyl) -3- (l, 2,4-triazol-1-yl) -propan-2-ol, tebuconazole, tetraconazole, triadimefon, triadimol, tri-pentenol, triflumizole, triticonazole, uniconazole and their metal salts and

acid adducts;

Imidazoles like:

Clotrimazole, bifonazole, climbazole, econazole, fenapamil, imazalil, isoconazole, ketoconazole, lombazole, miconazole, pefurazoate, prochloraz, triflumizole, thiazol-1-l-imidazolyl-1- (4'-chlorophenoxy) -3,3-dimethylbutan-2-one and the like their metal salts and acid adducts;

Pyridines and pyrimidines such as:

Ancymidol, buthiobate, fenarimol, mepanipyrine, nuarimol, pyroxyfur, triamirole;

Succinate dehydrogenase inhibitors such as:

Benodanil, Carboxim, Carboximsulfoxide, Cyclafluramid, Fenfuram, Flutanil, Furcarbanil, Furmecyclox, Mebenil, Mepronil, Methfuroxam, Metsulfovax, Nicobifene, Pyrocarbolide, Oxycarboxine, Shirlan, Seedvax;

Naphthalene derivatives such as:

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

Sulphenamides like: Dichlorofluidide, tolylfluanid, folpet, fluorfolpet; Captan, Captofol; Benzimidazoles such as:

Carbendazim, benomyl, fuberidazole, thiabendazole or their salts;

Morpholine derivatives such as:

Aldimorph, dimethomorph, dodemorph, falimorph, fenpropidin, fenpropimorph, tridemorph, trimorphamide and their arylsulfonic acid salts, e.g. p-toluenesulfonic acid and p-dodecylphenylsulfonic acid;

Benzothiazoles such as:

2-mercaptobenzothiazole; Benzothiophene dioxides such as:

Benzofblthiophen-S, S-dioxide-carboxylic acid cyclohexylamide;

Benzamides like:

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, 1,3-bis (hydroxymethyl) -5,5-dimethylimidazolidine-2,4-diones (DMDMH), bisoxazolidines, n-butanol hemiformal, cis 1- (3-chloroallyl) -3 , 5,7-triaza-1-azoniaadamantane chloride, 1- [1,3-bis (hydroxymethyl-2,5-dioxoimidazolidin-4-yl] -l, 3-bis (hydroxymethyl) urea, dazomet, dimethylolurea, 4, 4-dimethyl-oxazolidines, ethylene glycol hemiformal, 7-ethylbicyclooxazolidines, hexa-hydro-S-triazines, hexamethylenetetramine, N-hydroxymethyl-N'-methylthiourea, methylenebismorpholine, sodium N- (hydroxymethyl) glycinate, N-methylolchloroacetamide, oxazolidines , Paraformaldehyde, tauroline, tetrahydro-1,3-oxazine, N- (2-hydroxypropyl) -amine-methanol, tetramethylol-acetylene-diurea (TMAD);

Isothiazolinones such as:

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

Aldehydes such as: Cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde, o-phthaldialdehyde;

Thiocyanates such as:

Thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate; quaternary ammonium compounds and guanidines such as: benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, dichlorobenzyldimethylalkylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium chloride, N-hexadecyltrimethylammonium chloride, 1-hexadecylpyridinium chloride, iminoctadine tris (albesilate);

Iodine derivatives such as:

Diiodomethyl-p-tolylsulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3,3-triiodoallylalcohol, 3-bromo- 2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate, 3-iodo-2-propynylcyclohexylcarbamate, 3-iodo-2- propynyl phenylcarbamate;

Phenols like:

Tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, dichlorophene, 2-benzyl-4-chlorophenol, triclosan, diclosan, hexachlorophene, p-hydroxybenzoic acid methyl ester, p-hydroxybenzoic acid ethyl ester, p- Propyl hydroxybenzoate, butyl p-hydroxybenzoate, octyl p-hydroxybenzoate, o-phenylphenol, m-phenylphenyl, p-phenylphenol, 4- (2-tert-butyl-4-methyl-phenoxy) -phenol, 4- (2-isopropylbenzene) 4-methylphenoxy) phenol, 4- (2,4-dimethylphenoxy) phenol and their alkali and alkaline earth metal salts;

Microbicides with activated halogen group such as:

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

Pyridines like: l-hydroxy-2-pyridinethione (and its Cu, Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrrithione, 1-hydroxy-4-methyl-6- ( 2,4,4-trimethylpentyl) -2 (1H) -pyridine;

Methoxyacrylates or similar such as:

Azoxystrobin, Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Trifloxystrobin, 2,4-dihydro-5-rnethoxy-2-methyl-4- [2 - [[[[l- [3- (trifluoromethyl ) phenyl] ethylidenes] amino] oxy] methyl] phenyl] -3H-l, 2,4-triazol-3-ones (CAS No. 185336-79-2);

Metal soaps like:

Salts of the metals tin, copper and zinc with higher fatty, resinous, naphthenic and phosphoric acid e.g. Tin, copper, zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;

Metal salts like:

Salts of the metals tin, copper, zinc, as well as chromates and dichromates such. Copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;

Oxides like:

Oxides of the metals tin, copper and zinc, e.g. Tributyltin oxide, CU2O, CuO, ZnO; Oxidizing agents such as: hydrogen peroxide, peracetic acid, potassium persulfate; Dithiocarbamates such as:

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

Nitriles like:

2,4,5,6-tetrachloroisophthalodinitrile, disodium cyanodithioimidocarbamate; Chinolins like:

8-hydroxyquinoline and its Cu salts;

other fungicides and bactericides such as:

Bethoxazine, 5-hydroxy-2 (5H) -furanone; 4,5-benzdithiazolinone, 4,5-trimethylenedithiazolinone, N- (2-p-chlorobenzoylethyl) -hexaminium chloride, 2-oxo-2- (4-hydroxyphenyl) -aceto-hydroximic acid chloride, tris-N- (cyclohexyldiazeniumdioxy) -aluminum , N- (cyclohexyldiazeniumdioxy) -tributyl-tin or K-salts, bis-N- (cyclohexyldiazenium-dioxy) -copper, iprovalicarb, fenhexamide,

Spiroxamine, Carpropamid, Diflumetorin, Quinoxyfen, Famoxadone, Polyoxorim, Acibenzolar-S-methyl, Furametpyr, Thifluzamide, Methalaxyl-M, Benthiavalicarb, Metrafenone, Cyflufenamid, Tiadinil, Tea Tree Oil, Phenoxyethanol,

Ag, Zn or Cu-containing zeolites alone or included in polymeric materials.

Very particular preference is given to mixtures with

Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, diuron, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, dichlofluanid, tolylfluanid, fluorfolpet, methfuroxam, carboxin, benzofblthiophene-SS-dioxide-carboxylic cyclohexylamide, fenpiclonil, 4- (2,2-difluoro -l, 3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile, butenafine, imazalil, N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazoline 3-one, dichloro-N-octylisozhiazolinone, mercaptobenzothiazole, thiocyanatomethylthiobenzothiazole, thiabendazole, benzisothiazolinone, N- (2-hydroxypropyl) amino methanol, benzyl alcohol (hemi) formal, N-methylolchloroacetamide, N- (2-hydroxypropyl) - amine-methanol, glutaraldehyde, omadine, Zn-omadine, dimethyldicarbonate, 2-bromo-2-nitro-1,3-propanediol, 3-iodo-2-propynyl-n-butylcarbamate, bethoxazine, o-phthalaldehyde, 2,2- Dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, 1,3-bis (hydroxymethyl) -5,5-dimethylimidazolidine-2,4-dione (DMDMH), tetramethylol-acet ylenediurea (TMAD), ethylene glycol hemiformal, p-hydroxybenzoic acid, carbendazim, chlorophene, 3-methyl-4-chlorophenol, o-phenylphenol.

Furthermore, in addition to the above-mentioned fungicides and bactericides, also effective mixtures with other active ingredients are prepared: Insecticides / acaricides / nematicides:

Abamectin, Acephate, Acetamiprid, Acetoprole, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Aldrin, Allethrin, Alpha-cypeπnethrin, Amidoflumet, Amitraz, Avermectin, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, barthrin, 4-bromo-2 (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, bioresmethrin, bioallethrin, Bistrifluron, Bromophos A, Bromophos M, Bufencarb, Buprofezin, Butathiophos, Butocarboxine, Butoxycarboxime,

Cadusafos, carbaryl, carbofuran, carbophenothione, carbosulfan, cartap, quinomethionate, cocoethocarb, 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone

(CAS-RN: 120955-77-3), chlorodanes, chloroethoxyfos, chlorfenapyr, chlorfenvinphos,

Chlorofluorazuron, Chlormephos, N-tCo-chloro-S-pyridyl-O-methyl-N'-cyano-N-methyl-ethanimidamide, Chloropyrine, Chlorpyrifos A, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clothiazoben,

Cypophenothrin Clofentezine, Coumaphos, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazine,

Decamethrin, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, dialiphos, diazinon, 1,2-dibenzoyl-l (1,1-dimethyl) -hydrazine, DNOC, dichlorofenthione, dichlorvos, dicliphos, dicrotophos, difethialone , Diflubenzuron, dimethoate, 3,5-dimethylphenyl-methylcarbamate, dimethyl (phenyl) -silyl-methyl-3-phenoxybenzyl ether, dimethyl (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzyl ether, dimethylvinphos, dioxathione, disulfone,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, EPN, Esfenvalerate, Ethiofencarb, Ethion, Ethofenprox, Etrimphos, Etoxazole, Etobenzanide,

Fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fensulfothion, fenthione, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flupyrazofos, fluffine, flumethrin flufenprox , Fluvalinate, Fonophos, Formethanates, Formothion, Fosmethilan Fosthiazat, Fubfenprox, Furathiocarb,

Halofenocide, HCH (CAS RN: 58-89-9), heptenophos, hexaflumuron, hexythiazox, hydramethylnone, hydroprene,

Imidacloprid, imiprothrin, indoxycarb, iodoffen, iprinomectin, Iprobenfos, isazophos, isoamidophos, isofenphos, isoprocarb, isoprothiolanes, isoxathion, ivermectin, Kadedrin

Lambda-Cyhalothrin, Lufenuron,

Malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathione, methiocarb, methomyl, metalcarb, milbemectin, monocrotophos, moxiectin,

Naled, NI 125, nicotine, nitenpyram, noviflumuron,

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, parathion M, penfluron, permethrin, 2- (4-phenoxyphenoxy) ethyl-ethylcarbamate, phenthoate, phorate, phosalone, phosmet, phosphamidone, phoxim, pirimicarb, pirimiphos M, pirimiphos A, prallethrin, profenophos, promecarb, propaphos, Propoxur, Prothiophos, Prothoate, Pymetrozine, Pyrachlophos, Pyridaphenthione, Pyresmethrin, Pyrethrum, Pyridaben, Pyridalyl, Pyrimidifen, Pyriproxifen, Pyrithiobac Sodium

quinalphos,

Resmethrin, Rotenone,

Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfotep, Sulprofos,

Tau fluvalinate, Taroils, Tebufenozide, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Tetramethrin, Tetramethacarb, Thiacloprid, Thiafenox, Thiamethoxam, Thiapronil, Thiodicarb, Thiofanox, Thiazophos, Thiocyclam, Thiomethone, Thionazine, Thuringiensin, Tralomethrin, transfluthrin, triarathene, triazophos, triazamates, triazuron, trichlorfon, triflumuron, trimethacarb,

Vamidothione, xylylcarb, zetamethrin;

molluscicides:

Fentin acetate, metaldehyde, methiocarb, niclosamide;

Herbicides and algicides:

Acetochlor, Acifluorfen, Aclonifen, Acrolein, Alachlor, Alloxydim, Ametryn, Amidosulfuron, Amitrole, Ammonium sulfamate, Anilofos, Asulam, Atrazine, Azafenidine, Aziptrotryn, Azimsulfuron, Benazoline, Benfluralin, Benfuresat, Bensulfuron, Bensulfide, Bentazone, Benzofencap, Benzthiazuron, Bifenox, Bispyribac, Bispyribac sodium, Borax, Bromacil, Bromobutide, Bromofenoxime, Bromoxynil, Butachlor, Butamifos, Butraline, Butylate, Bialaphos, Benzoyl-prop, Bromobutide, butroxydim,

Carbetamido, carfentrazone-ethyl, carfenstrol, chlomethoxyfen, chloramphene, chlorobromuron, chloroflorene, chloridazon, chlorimuron, chloronitrofen, chloroacetic acid, chloransulam-methyl, cinidon-ethyl, chlorotoluron, chloroxuron, chlorpropham, chlorosulfuron, chlorothal, chlorthiamide, cinmethylin, cinofulsuron, clefoxydim, Clethodaz, clomazone, chlomeprop, clopyralid, cyanamide, cyanazine, cycloate, cycloxydim, chloroxynil, clodinafop-propargyl, cumyluron, clometoxyfen, cyhalofop, cyhalofop-butyl, clopyrasuluron, cyclosulfamuron,

Diclosulam, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, difluufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethipine, dinitramine, dinoseb, dinoseb acetates, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, DSMA , 2,4-D, daimurone, dalapon, dazomet, 2,4-DB, desmedipham, desmetryne, dicamba, dichlobenil, dimethamide, dithiopyr, dimethametryn,

Eglinazine, Endothal, EPTC, Esprocarb, Ethalfluralin, Ethidimuron, Ethofumesate, Ethobenzanide, Ethoxyfen, Ethametsulfuron, Ethoxysulfuron,

Fenoxaprop, Fenoxaprop-P, Fenuron, Flamprop, Flamprop-M, Flazasulfuron, Fluazifop, Fluazifop-P, Fuenachlor, Fluchloralin, Flufenacet Flumeturon, Fluorocglycofen, Fluoronitrofen, Flupropanate, Flurenol, Fluridone, Flurochloridone, Fluroxypyr, Fomesafen, Fosamine, Fosametine, Flamprop -isopropyl, flamprop-isopropyl-L, flufenpyr, flumiclorac-pentyl, flumipropyne, flumioxzim, flurtamone, flumioxime, flupyrsulfuron-methyl, fluthiacet-methyl,

Glyphosate, glufosinate-ammonium

Haloxyfop, hexazinone,

Imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, imazosulfuron, imazomox, isoxaflutole, imazapic,

ketospiradox,

Lactofen, Lenacil, Linuron,

MCPA, MCPA hydrazide, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron, metam, metamifop, metamitron, metazachlor, methabenzthiazuron, Methazol, Methoropyrene, Methyldymrone, Methylisothiocyanate, Metobromuron, Metoxuron, Metribuzin, Metsulfuron, Molinate, Monalid, Monolinuron, MSMA, Metolachlor, Metosulam, Metobenzuron,

Naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, sodium chlorate,

Oxadiazon, oxyfluorfen, oxysulfuron, orbencarb, oryzalin, oxadiargyl,

Propyzamide, Prosulfocarb, Pyrazolates, Pyrazolesulfuron, Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Paraquat, Pebulate, Pendimethalin, Pentachlorophenol, Pentoxazone, Pentanochlor, Petroleum Oils, Phenmedipham, Picloram, Piperophos, Pretilachlor, Primisulfuron, Prodiamine, Profoxydim, Prometryn, Propachlor, Propanil, Propaquizafob, propazine, prophyne, propisochlor, pyriminobac-methyl, pelargonic acid, pyrithiobac, pyraflufen-ethyl,

Quinmerac, quinocloamine, quizalofop, quizalofop-P, quinchlorac,

rimsulfuron

Sethoxydim, sifuron, simazine, simetryn, sulfosulfuron, sulfometuron, sulfentrazone, sulcotrione, sulfosate,

Tar oils, TCA, TCA sodium, tebutam, tebuthiuron, terbacil, terbumetone, terbutylazine, terbutryn, thiazafluorone, thifensulfuron, thiobencarb, thiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron, triclopyr, tridiphane, trietazine, trifluralin, tycor, thdiazimine, thiazopyr, triflusulfuron,

Vernolate.

The weight ratios of the active ingredients in these drug combinations can be varied in relatively large areas.

The active compound combinations preferably contain the active substance at from 0.1 to 99.9%, in particular from 1 to 75%, particularly preferably from 5 to 50%, the remainder being filled to 100% by one or more of the abovementioned mixing partners.

The microbicidal agents or concentrates used for the protection of the technical materials contain the active substance or the active substance combination in a concentration of 0.01 and 95 percent by weight, in particular 0.1 to 60 percent by weight.

The use concentrations of the active substances or the active ingredient combinations to be used depends on the nature and the occurrence of the animals to be controlled Microorganisms and after the composition of the material to be protected. The optimum amount used can be determined by test series. In general, the use concentrations are in the range of 0.001 to 5 weight percent, preferably from 0.05 to 2.5 weight percent, based on the material to be protected.

The active compounds or compositions according to the invention advantageously make it possible to replace the previously available microbicidal agents with more effective ones. They show good stability, low tendency to discoloration and advantageously have a broad spectrum of activity.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The application is done in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing etc.

The following examples are intended to illustrate the present invention without limiting it in any way.

example 1

l-Cyclopentyl-5-iodtetrazol

In an inert gas atmosphere was added to a cooled -75 ° C solution of 8.68 mmol (1.20g) of 1-Cyclopentyltetrazol in 27 ml of anhydrous tetrahydrofuran, 10:42 mmol of butyllithium (1.6M in hexane) was added dropwise so that the temperature of the reaction mixture -70 ⁰ C. not exceeded. The mixture was stirred for 30 minutes at this temperature and then added dropwise 8.68 mmol (2 2 g) of iodine in 4 ml of anhydrous tetrahydrofuran. The reaction mixture was heated to 23 ⁰ C after stirring for 30 minutes at this temperature and cautiously mixed with water. The solvent was extracted with ethyl acetate, the combined organic phase washed with sodium thiosulfate solution and saturated sodium chloride solution and dried over sodium sulfate. The solid obtained after distilling off the solvent under reduced pressure was stirred with diisopropyl ether to give 1.55 g (68%) of 1-cyclopentyl-5-iodo-tetrazole having a melting point of 119 ° C. Analogously to Example 1, the compounds mentioned in Table 1 were prepared:

Table 1 (Example Compounds of Formula 1)

Application Example A

To demonstrate the effectiveness against fungi, the minimum inhibitory concentrations (MIC) of active compounds according to the invention were determined:

An agar prepared using malt extract was admixed with active compounds according to the invention in concentrations of 0.1 mg / 1 to 5 000 mg / l. After solidification of the agar, contamination took place with pure cultures of the test organisms listed in Table 3. After storage for 2 weeks at 28 ^° C. and 60 to 70% relative humidity, the MIC was determined. The MIC is the lowest concentration of active substance in which no growth occurs due to the microbe species used. The determined MIC values are given in Table 3 below.

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

Application Example B

The following procedure was used to test dispersion paints for mildew resistance:

The paint to be tested was painted on both sides on a suitable surface. In order to obtain practical results, a portion of the test pieces before the test for mold resistance with running water (24 h, 2O ⁰ C) leached; another part was treated with a warm fresh air stream (7 days, 40 ^° C.).

The prepared samples were then placed on an agar medium and contaminated both samples and medium with fungal spores. After 2-3 weeks of storage (29 ± 1 ° C, 80-90% relative humidity) was scrapped.

The paint is then classified as permanently resistant to scumming if the sample remains fungus-free or at most detects a slight edge infestation. For contamination, fungal spores of the following molds known as painting destroyers or commonly found on paints have been used:

Alternaria tenuis Aspergillus flavus Aspergillus niger Aspergillus ustus Cindosporum herbarum Paecilomyces variotii Penicillium citrium Aureobasidium pullulans Stachybotrys chartarum

Molds are paints according to formula A (even after leaching and wind tunnel exposure) if they contain, for example, 1.0% (based on solids) of the example compounds 2.

Formulation A: External dispersion paint based on Acroal 290 D (styrene acrylate)

Solids content 135.5 = 61.6%.

Claims

claims

1. Compounds of the formula (I)

in which

R ^{1 is} cycloalkyl,

their stereoisomers and any mixtures thereof.

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

R ^{1 represents} optionally bridged, unsubstituted or mono- or polysubstituted by identical or different substituents C ₃ -Cg -cycloalkyl,

where the substituents for the mono- or polysubstituted or differently substituted

Cycloalkyl radicals are selected from the group halogen; nitro; cyano; hydroxy; unsubstituted Ci-Cg-alkyl; Ci-Cg-alkyl, which is 1 to 9 times, the same or different substituted by halogen; C ₂ -C ₈ alkynyl; unsubstituted C 1 -C ₈ -alkoxy; C ₁ -Cg alkoxy which is monosubstituted to disubstituted by halogen, unsubstituted C ₁ -C ₈ -alkylthio; Ci-Q-alkylthio which is 1 to 9 times, the same or different substituted by halogen; C ₃ -C ₈ cycloalkyl; amino; Monoalkylamino having straight-chain or branched C 1 -C 6 -alkyl radicals; Dialkylamino having the same or different, straight-chain or branched CrQ-alkyl radicals; dQ-acyl; C ₁ -Cg acyloxy; Ci-Cg-alkoxycarbonyl; carboxyl; unsubstituted phenyl; Phenyl which is one to five times, identically or differently substituted by halogen, nitro, cyano, alkyl,

Haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, acyl, acyloxy, alkoxycarbonyl, carboxyl, amino, monoalkylamino or dialkylamino.

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

R ^{1 represents} optionally bridged, unsubstituted or mono- to 6-fold, identically or differently substituted C ₃ -C ₈ -cycloalkyl,

wherein the substituents for the mono- to 6-fold, identically or differently substituted C ₃ -C ₈ - cycloalkyl radicals are selected from the series fluorine; Chlorine; Bromine; iodine; nitro; cyano; hydroxy; unsubstituted C ₁ -C ₆ -alkyl; C _r C ₆ alkyl, which is 1- to 6-fold, substituted by identical or different fluorine, chlorine or bromine; C ₂ -C ₈ alkynyl; C ₁ -C ₆ -alkoxy; dQ-alkoxy which is substituted 1 to 6 times, identically or differently by fluorine, chlorine or bromine; unsubstituted C ₁ -C ₆ -alkylthio; C 1 -C ₆ -alkylthio which is substituted 1 to 6 times, the same or different by fluorine, chlorine or bromine; C ₃ -Q-

cycloalkyl; amino; Monoalkylamino having straight-chain or branched QC ₆ -alkyl radicals; Dialkylamino having the same or different, straight-chain or branched C _r C ₆ alkyl radicals; Ci-Q-acyl; QQ acyloxy; C _r C ₆ alkoxycarbonyl; carboxyl; unsubstituted phenyl; Phenyl which is substituted one to four times, identically or differently by fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, C 1 -C ₄ -alkyl, C 1 -C ₄ -

Haloalkyl which tray 5-1 to equal to or different fluorine, chlorine or bromine, is Ci-C ₄ alkoxy, _{Ci-C4-haloalkoxy} which 1- to 5-fold identical or different fluorine, chlorine or bromine is Ci-C ₄ alkylthio, Ci-G ₁ - halogenoalkylthio which 1- to 5-times in an identical or different manner by fluorine, chlorine or bromine, QQ-acyl, Ci-C ₆ - acyloxy, Ci-C ₆ - Alkoxycarbonyl, carboxyl,

Amino, monoalkylamino having straight-chain or branched Ci-C ₄ alkyl radicals, dialkylamino having identical or different straight-chain or branched Ci-C ₄ - alkyl radicals.

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

R ^{1 represents} optionally bridged, unsubstituted or mono- to disubstituted, identically or differently substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl,

wherein said cycloalkyl groups are each optionally substituted one to four times, identically or differently by fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxy, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso Butyl, sec-butyl, tert-butyl, pentyl,

Hexyl, trifluoromethyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, trifluoromethoxy, methylthio, ethylthio, n-propylthio, iso -propylthio, trifluoromethylthio, cyclopropyl, cylobutyl, cyclopentyl, cyclohexyl, amino, methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, diethylamino, methylethylamino, di-n-propylamino di-iso-propylamino, acetyl , Acetyloxy, methoxycarbonyl, carboxyl, unsubstituted phenyl, phenyl which is one to three times by fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxy, methyl, ethyl, n-propyl, i-propyl, n-butyl, iso Butyl, sec-butyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, trifluoromethoxy, methylthio, ethylthio, n- propylthio, isopropylthio, trifluoromethylthio, formyl, acetyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, carboxy, amino, methylamino, ethylamino, n-propylamino, iso-propylamino, dimethylamino, diethylamino, methylethylamino, di-n-propylamino diisopropylamino is substituted.

5. A microbicidal composition containing at least one compound of formula (I) according to claim 1 and at least one solvent or diluent and optionally processing aids and optionally other antimicrobial substances.

6. Use of compounds of formula (I) according to at least one of claims 1 to 4 or a microbicidal agent according to claim 5 for the protection of plants and industrial materials against attack and / or destruction by microorganisms.

7. Use according to claim 6, characterized in that the technical materials are wood, wood-based materials, wood composites, plastics, cooling lubricants, aqueous and / or solvent-borne organic or inorganic dispersions and coating systems.

8. Process for the preparation of compounds of the general formula (I) according to claim 1, characterized in that tetrazoles of the general formula (II)

in which

R ^{1 is} cycloalkyl,

treated with iodine, optionally in the presence of a base or a diluent.

9. Compounds of the formula (II)

Wonn R ^{1 is} cycloalkyl,

except the connections

5H-cyclopenta [c] pyridine-1-amines, 6,7-dihydro-6- (1H-tetrazol-1-yl) -;

SH-cyclopentafc-pyridin-1-amine, 6,7-dihydro-5- (1H-tetazazol-1-yl) -; 5H-cyclopenta [c] pyridine-1-amines, 6,7-dihydro-7- (1H-tetrazol-1-yl) -;

Cyclopentanamines, 2- (4-fluorophenyl) -3- (1H-tetrazol-1-yl) -, (1R, 2S, 3R);

Cyclopentanamine, 2- (4-fluorophenyl) -3- (1H-tetrazol-1-yl) -, (1α, 2α, 3β) -;

1H-tetrazoles, 1- [3-azido-2- (4-fluorophenyl) cyclopentyl] -, (1ct, 2β, 3β) -;

Cyclopentanol, 2- (4-fluorophenyl) -3- (1H-tetrazol-1-yl) -, (1R, 2S, 3S); 1H-tetrazoles, 1 - [(1R, 2R, 3S) -2- (4-fluorophenyl) -3- (phenylmethoxy) cyclopentyl] -;

1H-tetrazoles, 1- (6-chloro-2,3-dihydro-5-methyl-1H-inden-1-yl) -;

1H-tetrazoles, 1- (5,6-dichloro-2,3-dihydrot-1H-inden-1-yl) -;

Carbamic acid [(1R, 2S, 5S) -2 - [[[(5-chloro-2-pyridinyl) amino] oxoacetyl] amino] -5- (1H-tetrazol-1-yl) cyclohexyl] -, 1,1 dimethyl-ethyl ester; Carbamic acid [(IS, 2R, 4S) -2 - [[(1,1-dimethylethoxy) carbonyl] amino] -4- (1H-tetrazol-1-yl) cyclohexyl], phenylmethyl ester;

1H-tetrazoles, 1- (1,2,3,4-tetrahydro-1-naphthalenyl) -;

1H-tetrazoles, 1- (1-ethyl-1,2,3,4-tetrahydro-1-naphthalenyl) -;

1H-tetrazoles, 1-tricyclo [3.3.1.13,7] dec-2-yl; (Adamantyl) 1H-tetrazoles, 1-tricyclo [3.3.1.13,7] dec-1-yl; (Adamantyl)

1H-tetrazoles, 1- (5α-cholestan-3β-yl) -;

1H-tetrazoles, 1- (5α-cholestan-3α-yl) -;

1H-tetrazoles, 1- (5α-cholestaπ-6β-yl) -;

1H-tetrazoles, 1- (5α-cholestan-6α-yl) -; 1H-tetrazoles, 1-cyclohexyl-.

10. Technical materials containing at least one compound of the formula (I) according to claim 1.