DE3942333A1 - New azolyl:methyl-oxirane cpds. fungicides - Google Patents

Abstract

Azolylmethyl-oxiranes of formula (I) and their acid addn. salt and metal complexes are new, with the exception of 2-(imidazol-1-ylmethyl) 2-(4-fluorophenyl)-3 (pyrid-3-yl) oxirane. A,B = 5- or 6-membered heteroaryl, 1-8C alkyl, 3-8C cycloalkyl, tetrahydropyranyl, tetrahydrothiopyranyl, phenyl, biphenyl, naphthyl or benzyl, all opt. substd. by an NO2 or NH2 gp. or by 1-3 halo, 1-4C alkyl, 1-4C haloalkyl, 1-4C alkyl or phenoxy; with the proviso that 1 of A or B is heteroaryl unless B is O-methylphenyl; Z = CH or N. Also claimed are oxiranes of formula (III).

Description

The present invention relates to new azolylmethyloxiranes of the formula I.

in which the substituents have the following meaning:

A, B: 5- or 6-membered heteroaryl, C₁-C₈-alkyl, C₃-C₈-cycloalkyl, tetrahydropyranyl, tetrahydrothiopyranyl, phenyl, biphenyl, naphthyl or benzyl, these substituents also having a nitro or amino group or up to three of the following radicals can carry: halogen, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl, C₁-C₄-alkoxy or phenoxy, with the proviso that at least one of the substituents A or B represents one of the heteroaryl groups defined above;
Z CH or N

as well as the plant-compatible mineral acid salts I-HX and metal complexes from I, except 2- (imidazol-1-ylmethyl) -2- (4-fluorophenyl) -3- (pyrid-3-yl) oxirane.

The invention also relates to processes for the preparation of these compounds, their use as fungicides and fungicidal agents which these Contain compounds as active substances.

The invention further relates to oxirane intermediates of the formula III

where L is halogen or a radical R-SO₂-O- and R C₁-C₆-alkyl, partially or fully halogenated C₁-C₄ alkyl or phenyl which is substituted by halogen, C₁-C₄ alkyl or nitro may be substituted.

In EP-A 3 32 073 are azolylmethyloxiranes of the compound I type mentions that on the oxirane ring in the 2-position an imidazolylmethyl and 4-fluorophenyl group and in the 3-position u. a. carry a pyridyl group.

The fungicidal effects of these compounds can, however, especially with small amounts and concentrations, only partially satisfactory.

The invention was therefore based on the object of new fungicidal activity To find substances.

Accordingly, the azolylmethyloxiranes of the formula I defined at the outset found. Intermediates of formula III were also used in the preparation found this azolylmethyloxirane.

Specifically, the substituents in the compounds of the invention I and III have the following meaning:

A, B

• 5- or 6-membered heteroaryl, in particular pyrrol-2-yl, Pyrrol-3-yl, furan-2-yl, thien-2-yl, thien-3-yl, pyrid-2-yl, Pyrid-3-yl, pyrid-4-yl, 1,3-diazol-2-yl, oxazol-4-yl, Oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, Thiazol-4-yl, thiazol-5-yl, imidazol-4-yl, 1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl. These substituents can still a nitro or amino group or one on each carbon atom of the following residues: halogen such as fluorine, chlorine and Bromine, C₁-C₄-alkyl such as methyl, ethyl, n-butyl and tert-butyl, partially or completely by fluorine, chlorine and / or Bromine halogenated C₁-C₄ alkyl such as trifluoromethyl, pentafluoroethyl and 2-chloro-1,1,2-trifluoroethyl, C₁-C₄ alkoxy such as Methoxy, ethoxy and tert-butoxy or phenoxy;
• - Branched or unbranched C₁-C₈ alkyl, which is a nitro or amino group or up to three of those in the heteroaryl group can carry said radicals, preferably C₁-C₆ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and neopentyl;
• - C₃-C₈-cycloalkyl, which is a nitro or amino group or up contribute to three of the residues mentioned in the heteroaryl group can, preferably cyclopropyl, cyclobutyl, cyclopentyl and Cyclohexyl;  
• - tetrahydropyranyl or tetrahydrothiopyranyl, each a nitro or amino group or up to three of the at Can carry heteroaryl groups,
• - Phenyl, which is a nitro or amino group or up to three which can carry the radicals mentioned in the heteroaryl group, preferably phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-4-fluorophenyl, 2-chloro-6-fluorophenyl, 3-nitrophenyl, 4-nitrophenyl, 3-aminophenyl, 4-aminophenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2-chloro-6-methylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 3,4-dimethoxyphenyl, 3-phenoxyphenyl and 4-phenoxyphenyl;
• - Biphenyl, naphthyl or benzyl, each a nitro or Amino group or up to 3 of the heteroaryl group can carry said residues;

L

• - Halogen such as fluorine, chlorine, bromine and iodine, preferably chlorine and Bromine;
• - A radical R-SO₂-O-, where R has the following meaning:
  • - Branched or unbranched C₁-C₆ alkyl, in particular C₁-C₄ alkyl such as methyl, ethyl, n-butyl and tert-butyl;
  • - Partially or fully halogenated C₁-C₄-alkyl such as trifluoromethyl, trichloromethyl, pentafluoroethyl and 2-chloro-1,1,2-trifluoroethyl;
  • - Phenyl, which can be substituted by halogen such as fluorine, chlorine and bromine, C₁-C₄-alkyl such as methyl, ethyl and tert-butyl or nitro.

Particularly preferred compounds I and III are in Tables A and B, respectively remove.  

The intermediate III is produced in a very advantageous manner Way by known oxidation of α-haloalkene of the formula Va or substituted propenals of the formula Vb (cf. G. Dittus in Houben-Weyl-Müller, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart, 1965, Vol. VI / 3, page 385 ff.) And - in the case of the propenale - subsequent reduction and esterification of the formyl group:

The oxidation of the olefins Va and Vb is preferably carried out in inert solution or diluents such as acetic acid, ethyl acetate, acetone, methyl tert-butyl ether and dimethylformamide, especially in chlorinated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride.

If desired, you can work in a buffered medium. As Buffers are suitable for. B. sodium acetate, sodium carbonate, disodium hydrogen phosphate and benzyltrimethylammonium hydroxide (Triton B).

Peroxycarboxylic acids such as perbenzoic acid, 3-chloroperbenzoic acid, 4-nitroperbenzoic acid, monoperphthalic acid are advantageously used as oxidizing agents. Peracetic acid, perpropionic acid, permaleic acid, monoper succinic acid, Perpelargonic acid and trifluoroperacetic acid.

The oxidation can be catalyzed if desired, e.g. B. with iodine, Sodium tungstate or light.

In general, the temperature is between 10 and 100 ° C, especially at the boiling point of the solvent used.

Alkyl hydroperoxides such as tert-butyl hydroperoxide are also suitable for the oxidation using a catalyst such as sodium tungstate, tungstic acid, Molybdenum hexacarbonyl and vanadylacetylacetonate, as well as alkaline Solutions from e.g. B. 30% hydrogen peroxide in methanol, ethanol, acetone or acetonitrile. When using one of these oxidizing agents temperatures of 20 to 30 ° C are recommended.  

The oxidizing agent is generally in equimolar amounts or in a slight excess, up to about 20 to 50%, based on the olefins Va and Vb.

The reaction is advantageously carried out at normal pressure. Lesser or higher pressure is possible, but generally has no advantages.

After epoxidation and subsequent reduction, e.g. B. with sodium borohydride at about 20 ° C, the alcohols Vb according to known methods converted into their esters (cf. Houben-Müller-Weyl, methods of organic chemistry, Georg-Thieme-Verlag Stuttgart, 1955, Vol. 9, Pages 388, 663 and 671). Examples of suitable esters are methanesulfonic acid esters, Trifluoromethanesulfonic acid ester, 2,2,2-trifluoroethanesulfonic acid ester, Nonafluorobutanesulfonic acid esters, benzenesulfonic acid esters, 4-methylbenzenesulfonic acid ester, 4-bromobenzenesulfonic acid ester and 4-nitrobenzenesulfonic acid ester.

The Propenale Vb can e.g. B. by known condensation of two Aldehydes can be obtained.

The reaction is advantageously carried out in an inert solvent and diluent at temperatures between 10 and 50 ° C, especially 20 to 30 ° C carried out.

With regard to printing, the information given above applies.

The olefins Va are corresponding, for example, by chlorination known per se Propene derivatives CH₃-CA = CHB available in the allyl position.

As halogenating reagents such. B. N-chloro and N-bromosuccinimide in halogenated hydrocarbons such as carbon tetrachloride, trichloroethane and methylene chloride are suitable. The temperature is generally between 20 and 100 ° C.

The propene derivatives to be halogenated are themselves known Methods of olefin synthesis available (cf. Houben-Weyl-Müller, methods of organic chemistry, Georg-Thieme Verlag Stuttgart, 1972, Vol. V / 1b).

The intermediates III according to the invention contain two centers of asymmetry. They are used as racemates like those used in most manufacturing processes may be incurred, however, if desired, according to the usual methods, e.g. B. by chromatography on an optically active Adsorbent into which pure isomers are separated.  

The Azolylmethyloxirane I are available in various ways, namely preferably using the following methods:

• a) Preparation from an Azole and an Oxirane: The reaction is preferably carried out in a solvent or diluent, particularly preferably with the addition of an organic or inorganic base.
  Suitable solvents or diluents are ketones such as acetone, methyl ethyl ketone and cyclohexanone, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, isopropanol, n-butanol and glycol, esters such as methyl acetate, ethyl acetate and butyl acetate, ethers such as tetrahydrofuran, diethyl ether , Dioxane and diisopropyl ether, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and mixtures of the solvents mentioned.
  Suitable bases are, for example, alkali metal hydroxides such as lithium, sodium and potassium hydroxide, alkali carbonates such as sodium and potassium carbonate, hydrogen carbonates such as sodium and potassium hydrogen carbonate, pyridine and 4-dimethylamine pyridine.
  The reaction proceeds particularly advantageously in the presence of a reaction accelerator. For this purpose, z. B. metal halides such as sodium and potassium iodide, quaternary ammonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride and bromide or crown ethers such as [12] crown-4, [15, [15] 18] -6 and dicyclohexanol [18] crown-6.
  The starting compounds IIa and III are expediently used in a stoichiometric ratio, but in some cases an excess of one or the other component, for example up to 10%, may be advisable.
  The reaction normally proceeds at a sufficient rate above 10 ° C. In general, the temperature is between 10 and 150 ° C, in particular between 20 and 120 ° C, preferably at the boiling point of the solvent used.
  Since the reaction is not dependent on pressure, it is advantageous to work at normal pressure.
• b) reaction of an azolyl anion with an oxirane M⊕ means an alkali metal cation, especially lithium, sodium or potassium.
  As a rule, the reaction is carried out in a solvent or diluent, preferably with the addition of a strong inorganic or organic base.
  Amides such as dimethylformamide, diethylformamide, dimethylacetamide and diethylacetamide, N-methylpyrrolidone, hexamethylphosphorus triamide, sulfoxides such as dimethyl sulfoxide and sulfolane can be used as solvents or diluents.
  Suitable bases are, for example, alkali metal hydrides such as lithium, sodium and potassium hydride, alkali amides such as sodium and potassium amide and alkali metal alcoholates such as sodium and potassium tert-butoxide.
  The reaction generally proceeds at a sufficient rate above (-10) ° C. In general, the temperature is between (-10) and 120 ° C, in particular between 0 and 100 ° C, particularly preferably between 20 and 80 ° C.
  With regard to the stoichiometric conditions and the pressure, the information for method a) applies.
• c) Epoxidation of a 3-azolylprop-1-ene The epoxidation of the olefins IV to the azolylmethyloxiranes I takes place according to methods known per se (cf. G. Dittus in Houben-Weyl-Müller, Methods of Organic Chemistry, Georg-Thieme-Verlag Stuttgart, 1965, Vol. VI / 3, page 385ff ).
  The reaction is advantageously carried out in a solvent or diluent, for example in nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, formamides such as dimethylformamide, ketones such as acetone, ethers such as diethyl ether and tetrahydrofuran, and in mixtures of the solvents mentioned. Chlorinated hydrocarbons such as methylene chloride and chloroform are particularly preferred.
  In general, the reaction temperature is between 0 and 100 ° C, preferably between 20 and 80 ° C. It is particularly preferred to work at the boiling point of the solvent used.
  With regard to the oxidizing agent and the pressure, the information applies to the production of intermediate II.

The compounds I according to the invention contain two centers of asymmetry. they act as racemates, as they occur in most manufacturing processes, can if desired also according to the usual for this Methods, e.g. B. by chromatography on an optically active adsorbent, be separated into the pure isomers.

Suitable acid addition salts are the salts of those acids which do not impair the fungicidal activity of I, e.g. B. the Hydrochlorides and bromides, sulfates, nitrates, phosphates, oxalates or the Dodecylbenzenesulfonates.

The complexes of copper, zinc, tin, manganese, Iron, cobalt or nickel. Preferably you put the Complexes of the free bases I and mineral acid salts, for example the chlorides or sulfates, the metals.

Manufacturing example cis-2- (1,2,4-triazol-1-ylmethyl) -2-phenyl-3- (3-pyridyl) oxirane Intermediate 1 2-phenyl-3- (3-pyridyl) propenal

To a mixture of 54 g (0.50 mol) pyridine-3-carbaldehyde in 300 ml Water and 8.4 g (0.21 mol) of sodium hydroxide in 40 ml of water were added 10 g of 60 g (0.50 mol) of phenylacetaldehyde were added dropwise in the manner that the temperature of the solution remained below 30 ° C. After stirring for 2 hours at about 20 ° C 300 ml of water were added, the resulting emulsion with Methyl tert-butyl ether extracted and the organic phase on the Refurbished product. The raw substance was cleaned distillation at 160 ° C and 0.6 mbar. Oil; Yield 70.5%.

Intermediate 2 cis-2-hydroxymethyl-2-phenyl-3- (3-pyridyl) oxirane

To a mixture of 32.2 g (0.152 mol) of 2-phenyl-3- (3-pyridyl) propenal in 150 ml of methanol and 1.7 ml of conc. Sodium hydroxide solution became slow at 0 ° C 13.5 g of 30% hydrogen peroxide solution was added dropwise in such a way that the The temperature of the mixture remained below 30 ° C. After stirring for 6 hours 20 ° C., 6 g (0.158 mol) of sodium borohydride, dissolved in a little 10% strength, were added Sodium hydroxide solution, and the mixture was stirred for a further 18 hours. Subsequently 100 ml of water were added, the resulting emulsion with methylene chloride shaken out and the organic phase towards the product worked up. M.p .: 108-110 ° C; Yield 82%.  

Intermediate 3 (= intermediate of formula II)

17.2 g (0.15 mol) of methanesulfonic acid chloride were at about 20 ° C in a Solution of 28.6 g (0.12 mol) of cis-2-hydroxymethyl-2-phenyl-3- (3-pyridyl) oxirane stirred in 120 ml of methylene chloride and 26 g of triethylamine. After this this mixture had been stirred for 24 hours, it became more aqueous Sodium bicarbonate solution and water washed and on the product worked up. Yield: 69%.

Production of the end product

A mixture of 7.8 g (0.11 mol) of 1,2,4-triazole in 150 ml of N, N-dimethylformamide and 26.3 g (0.19 mol) of potassium carbonate was at 50 ° C for 30 minutes heated, then cooled to about 20 ° C and added dropwise with a Solution of 28.2 g (0.09 mol) of cis-2- (methylsulfonyloxymethyl-2-phenyl-3- (3-pyridyl) oxirane added in 50 ml of N, N-dimethylformamide. After 12 hours Stirring at room temperature was mixed with 100 ml of water, the mixture extracted several times with methyl tert-butyl ether and the organic phase worked up for the product. Mp: 75 ° C; Yield 65% cis-2- (1,2,4- Triazol-1-yl-methyl) -2-phenyl-3- (3-pyridyl) oxirane.

In Table A there are further intermediates III, in Table B more Azolylmethyloxirane I contain, which are analogous to the example compounds have it made.  

Table A

Table B

The Azolylmethyloxirane I are characterized by an excellent effectiveness against a wide range of phytopathogenic fungi, in particular from the class of Ascomycetes and Basidiomycetes. you are partly systemically effective and can be used as leaf and soil fungicides be used.

They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, Corn, grass, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers, beans and squashes, as well on the seeds of these plants.

They are particularly suitable for combating the following plant diseases:
Erysiphe graminis (powdery mildew) in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,
Podosphaera leucotricha on apples,
Uncinula necator on vines,
Puccinia species on cereals,
Rhizoctonia species on cotton and lawn,
Ustilago species on cereals and sugar cane,
Venturia inaequalis (scab) on apples,
Helminthosporium species on cereals,
Septoria nodorum on wheat,
Botrytis cinerea (gray mold) on strawberries, vines,
Cercospora arachidicola on peanuts,
Pseudocercosporella herpotrichoides on wheat, barley,
Pyricularia oryzae on rice,
Phytophthora infestans on potatoes and tomatoes,
Fusarium and Verticillium species on different plants,
Plasmopara viticola on vines,
Alternaria species in vegetables and fruits.

The compounds are applied by treating the plants with the active ingredients sprayed or dusted or the seeds of the plants with the active ingredients treated. It is used before or after infection Plants or seeds through the mushrooms.

They can be converted into the usual formulations, such as Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend on the purposes; You should in any case a fine and even distribution of the azolylmethyloxirane guarantee. The formulations are known in  Made way, e.g. B. by stretching the active ingredient with solvent and / or carriers, if desired using Emulsifiers and dispersants, being in the case of water as a diluent also other organic solvents as auxiliary solvents can be used. For this purpose, essentially come in as auxiliary substances Consider: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. Methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, Dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. finely divided silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ether, Alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite waste liquors and methyl cellulose.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% active ingredient.

Depending on the type of effect desired, the application rates are between 0.02 and 3 kg of active ingredient per ha. The new compounds can also in Material protection can be used, e.g. B. against Paecilomyces variotti.

The agents or the ready-to-use preparations made from them such as solutions, emulsions, suspensions, powders, dusts, pastes or granules are applied in a known manner, for example by spraying, Nebulizing, dusting, scattering, pickling or pouring.

Examples of such preparations are:

• I. a solution of 90 parts by weight of compound no. B.001 and 10 parts by weight of N-methyl-α-pyrrolidone for use in the form smallest drop is suitable;
• II. A mixture of 20 parts by weight of compound no. B.100, 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide in 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the adduct and 40 moles of ethylene oxide to 1 mole Castor oil; by finely distributing the solution in water a dispersion.  
• III. an aqueous dispersion of 20 parts by weight of the compound B.001, 40 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 20 parts by weight of the adduct of 40 mol Ethylene oxide in 1 mol castor oil;
• IV. An aqueous dispersion of 20 parts by weight of the compound B.100, 25 parts by weight of cyclohexanol, 65 parts by weight of one Mineral oil fraction with a boiling point of 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole Castor oil;
• V. a mixture of 80 parts by weight ground in a hammer mill Compound No. B.001, 3 parts by weight of the sodium salt of Diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt a lignosulphonic acid from a sulphite waste liquor and 7 parts by weight of powdered silica gel; through fine distribution a spray mixture is obtained from the mixture in water;
• VI. an intimate mixture of 3 parts by weight of compound no. B.100 and 97 parts by weight of finely divided kaolin; this dusts contains 3% by weight of active ingredient;
• VII. An intimate mixture of 30 parts by weight of compound no. B.001, 92 parts by weight of powdered silica gel and 8 parts by weight Paraffin oil that is on the surface of this silica gel was sprayed; this preparation gives the active ingredient a good one Adherence;
• VIII. A stable aqueous dispersion of 40 parts by weight of the compound No. B.001, 10 parts by weight of the sodium salt of a phenosulfonic acid urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which can be further diluted;
• IX. a stable oily dispersion of 20 parts by weight of the compound No. B.100, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic Mineral oil.

The agents according to the invention can also be used together in these forms of use with other active ingredients, e.g. B. with herbicides, insecticides, Growth regulators, fungicides or even with fertilizers.  

When mixed with fungicides, you get one in many cases Enlargement of the fungicidal spectrum of activity:

The following list of fungicides with which the compounds of the invention The possible combinations can be used together explain, but not limit:

Sulfur,
Dithiocarbamates and their derivatives, such as
Ferridimethyldithiocarbamate,
Zinc dimethyldithiocarbamate,
Zinc ethylene bisdithiocarbamate,
Manganese ethylene bisdithiocarbamate,
Manganese-zinc-ethylenediamine-bis-dithiocarbamate,
Tetramethylthiuram disulfide,
Ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate),
Ammonia complex of zinc (N, N-propylene-bis-dithiocarbamate),
Zinc (N, N'-propylene-bis-dithiocarbamate),
N, N'-polypropylene bis (thiocarbamoyl) disulfide;

Nitroderivatives, such as
Dinitro- (1-methylheptyl) phenylcrotonate,
2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate,
2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate;
5-nitro-isophthalic acid di-isopropyl ester

heterocyclic substances, such as
2-heptadecyl-2-imidazoline acetate,
2,4-dichloro-6- (o-chloroanilino) -s-triazine,
O, O-diethyl phthalimidophosphonothioate,
5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,
2,3-dicyano-1,4-dithioanthraquinone,
2-thio-1,3-dithiolo [4,5-b] quinoxaline,
1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester,
2-methoxycarbonylamino-benzimidazole,
2- (furyl- (2)) - benzimidazole,
2- (thiazolyl- (4)) - benzimidazole,
N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide,
N-trichloromethylthio-tetrahydrophthalimide,
N-trichloromethylthio-phthalimide,
N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenyl-sulfuric acid diamide,
5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,
2-rhodanmethylthiobenzthiazole,
1,4-dichloro-2,5-dimethoxybenzene,
4- (2-chlorophenylhydroazano) -3-methyl-5-isoxazolone,
Pyridine-2-thio-1-oxide,
8-hydroxyquinoline or its copper salt,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,
2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid aniline,
2-methyl-furan-3-carboxylic acid anilide,
2,5-dimethyl-furan-3-carboxylic acid anilide,
2,4,5-trimethyl-furan-3-carboxylic acid anilide,
2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide,
N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide,
2-methylbenzoic acid anilide,
2-iodo-benzoic acid anilide,
N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,
Piperazin-1,4-diylbis- (1- (2,2,2-trichloro-ethyl) -formamide,
1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane,
2,6-dimethyl-N-tridecyl-morpholine or its salts,
2,6-dimethyl-N-cyclodedecyl-morpholine or its salts,
N- [3- (p-tert-butylphenyl) -2-methylpropyl] cis-2,6-dimethylmorpholine,
N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine,
1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-t-riazole,
1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole,
N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl-urea,
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, -
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol, -
α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidine-methanol,
5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine,
Bis- (p-chlorophenyl) -3-pyrimidinemethanol,
1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene,
1,2-bis (3-methoxycarbonyl-2-thioureido) benzene,

as well as various fungicides such as
Dodecylguanidine acetate,
3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide,
Hexachlorobenzene,
DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) -alaninate,
DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester,
N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone,
DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester,
5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine,
3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] -1,3-oxazolidine-2,4-d-ion,
3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin,
N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, -
2-cyano- [N- (ethylaminocarbanoyl) -2-methoximino] acetamide,
1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole,
2,4-difluoro-α- (1H-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol,
N- (3-chloro-2,6, dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-c-chloro-2-aminopyridine,
1 - ((bis- (4-Fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

Claims (6)

1. Azolylmethyloxirane of the formula I. in which the substituents have the following meaning:
A, B: 5- or 6-membered heteroaryl, C₁-C₈-alkyl, C₃-C₈-cycloalkyl, tetrahydropyranyl, tetrahydrothiopyranyl, phenyl, biphenyl, naphthyl or benzyl, these substituents also having a nitro or amino group or up to three of the following radicals can carry: halogen, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl, C₁-C₄-alkoxy or phenoxy, with the proviso that at least one of the substituents A or B represents one of the heteroaryl groups defined above;
Z CH or N
and the plant-compatible mineral acid salts I-HX and metal complexes of I, with the exception of 2- (imidazol-1-ylmethyl) -2- (4-fluorophenyl) -3- (pyrid-3-yl) oxirane. 2. A process for the preparation of the Azolylmethyloxirane I according to claim 1, characterized in that either

• a) an azole of the formula IIa with an oxirane of formula III where L represents a nucleophilic leaving group, or
• b) an azolyl anion of the formula IIb wherein M represents an alkali metal atom, with an oxirane of the formula III, or
• c) a 3-azolylprop-1-ene of the formula IV epoxidized,
  and, if desired, convert the compounds obtained into their salts or metal complexes.

3. Use of the Azolylmethyloxirane I, their plant-compatible Salts and metal complexes according to claim 1 as fungicides. 4. Fungicidal composition containing at least one azolylmethyloxirane Formula I, its plant-compatible salt or its metal complex according to claim 1 and a liquid or solid carrier. 5. A method of combating fungi, characterized in that a fungicidally effective amount of an azolylmethyloxirane of the formula I, its plant-compatible salt or metal complex, according to claim 1, on fungi, plants threatened by fungal attack, their habitat or affects the seeds of the endangered plants. 6. Oxiranes of the general formula III in which the substituents A and B have the meaning given in claim 1 and
L is halogen or a radical R-SO₂-O- and R is C₁-C₆-alkyl, partially or completely halogenated C₁-C₄-alkyl or phenyl, which can be substituted by halogen, C₁-C₄-alkyl or nitro.