DE4010068A1 - New N-oxo-azolyl-methyl derivs. - useful as plant growth regulators and fungicides effective against e.g. Erysiphe graminis and Botrytis cinerea - Google Patents

Abstract

N-oxo-azolyl methyl derivs. of formula (I) are new. R = -CH2R1 or -CHR2R3, R1 = -CA1B1Z1, -SiA3B3Me or cpd. of formula (i); R2 = -X1A4; R3 = Z2-tert.butyl; A1, A3, B1 and B3 = each 1-8C alkyl, phenylethyl or Ph, each gp. opt. mono-, di- or tri-substd. by halogen, 1-4C alkyl or 1-4C haloalkyl; A2 and B2 = each H, 1-8C alkyl or Ph; each gp. opt. mono- di- or tri-substd. by halogen, 1-4C alkyl or 1-4C haloalkyl; A4 = Ph opt. substd. by halogen; Z1 = H or OH; Z2 = CO or CHOH; X = CH or N; and X1 = O, S or CH2. USE/ADVANTAGE - (I) are fungicides and plant growth regulators. (I) have a broad spectrum of activity against phyto pathogenic fungi esp. Ascomycetes and Basidiomycetes. They are partially systemic and can be used as leaf and soil fungicides. (I) are effective against e.g. Erisiphe gramines in cereals, Verturia inaequatis on apples, Botrytis unerea on strawberries and vines, Pyricularia oryzae on rice etc. (I) also influence practically all stages of plant development.

Description

The present invention relates to new N-oxo-azolylmethyl derivatives, these contains fungicides and growth regulators and control methods of fungi and to regulate plant growth.

From the publications EP 1 48 026, DE 34 06 993, EP 2 52 875, EP 2 37 483, EP 2 54 857, DE 37 16 559, EP 2 75 013, EP 2 33 714, DE 30 42 302 and EP 15 756 it is known to use azolylmethyl compounds as fungicides or Use growth regulators.

It has now been found that N-oxo-azolylmethyl derivatives of the formula I

in the R -CH₂-R¹ or

means R¹

R² -X¹-A⁴,
R³ denotes -Z²-tert-butyl,
A¹, A³, B¹ and B³ are the same or different and are C₁-C₈-alkyl, phenylethyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl ,
A² and B² are the same or different and are hydrogen, C₁-C₈-alkyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A⁴ is phenyl optionally substituted by halogen,
Z¹ is hydrogen or OH,
Z² C = O or CHOH,
X CH or N and
X¹ is O, S or CH₂, have a better fungicidal activity than the known azolylmethyl compounds and are suitable for regulating plant growth.

In particular, the substituents have the following preferred meanings:
A¹, A², A³, B¹, B², B³ independently of each other
unbranched or branched C₁-C₈-alkyl, especially C₁-C₄-alkyl such as methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl,
Phenyl
Phenethyl.
The radicals mentioned can be mono- to trisubstituted by
Halogen such as fluorine, chlorine or bromine,
C₁-C₄-alkyl as mentioned above in detail,
C₁-C₄ haloalkyl with 1 to 3 halogen atoms such as fluorine, chlorine or bromine.

The following radicals are particularly preferred: methyl, ethyl, isopropyl, n-propyl, butyl, sec.-butyl, tert.-butyl, n-pentyl, phenyl, 2-chlorophenyl, 2-fluorophenyl, 2-bromophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2-methylphenyl, 4-methylphenyl, 2-trifluoromethylphenyl, 4-trifluoromethylphenyl, phenylethyl, 4-chlorophenylethyl, 2,4-dichlorophenylethyl, 4-fluorophenylethyl, 2-fluorophenylethyl, 4-bromophenylethyl, 4-methylphenylethyl, 2-methylphenylethyl.  

Particularly preferred compounds are:
1- (4-chlorophenyl) -3- (1,2,4-triazol-4-oxo-1-ylmethyl) -4,4-dimethyl-pentan-3-ol

1- (1,2,4-Triazol-4-oxo-1-yl) -2- (4-fluorophenyl) -2- (2-fluorophenyl) eth-an-2-ol

1- (1,2,4-triazol-4-oxo-1-yl) -2- (2,4-dichlorophenyl) hexan-2-ol

1- (1,2,4-triazol-4-oxo-1-yl) -2- (4-chlorophenyl) -3-cyclopropylbutan-2-ol

1- (1,2,4-triazol-4-oxo-1-yl) -2- (2,4-dichlorophenyl) pentane

1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl] -1H-4-oxo-1-, 2,4-triazole

1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-4-oxo - 1,2,4- triazole

1- (4-chlorophenyl) -2- (1,2,4-triazol-4-oxo-1-yl) -3-hydroxy-4,4-dimethy-l- pentane

1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-4-oxo-1-yl) -3-hydroxy-4,4-dimethyl pentane

1- (4-chlorophenoxy) -1- (1,2,4-triazol-4-oxo-1-yl) -3,3-dimethylbutan-2-ol

1- (4-biphenyloxy) -1- (1,2,4-triazol-4-oxo-1-yl) -3,3-dimethylbutan-2-ol

(1,2,4-triazol-4-oxo-1-ylmethyl) bis (4-fluorophenyl) methylsilane

The compounds of formula I can contain and become chiral centers generally in the form of racemates or as diastereomer mixtures receive. The diastereomers can be in the inventive Connections in the usual way, for example due to their different Solubility or separate by column chromatography and in pure Isolate form. Such an isolated diastereomer can be used to known methods receive uniform enantiomers. As a fungicidal agent and growth regulators, one can use both the uniform diastereomers or enantiomers as well as their mixtures obtained in the synthesis use.

The N-oxo-azole derivatives of the formula I can, for. B. are produced by the corresponding azole compounds of the formula II with peroxycarboxylic acids, H₂O₂ or alkyl hydroperoxides implemented and in known per se Way isolated.

Suitable peroxycarboxylic acids are e.g. B. perbenzoic acid, 3-chloroperbenzoic acid, 4-nitroperbenzoic acid, monoperphthalic acid, peracetic acid, Perpropionic acid, permaleic acid, monoper succinic acid, perpelargonic acid or trifluoroperacetic acid.  

The peroxycarboxylic acids can also be generated in situ from the corresponding Acid anhydride and hydrogen peroxide can be produced. For example permaleic acid can be obtained from maleic anhydride and hydrogen peroxide, e.g. B. a 30 to 50 wt .-% aqueous hydrogen peroxide solution, produce. In general, the molar ratio of anhydride to H₂O₂ e.g. B. at about 1.5 to 10 in particular 2 to 4.

The oxidation with peracids takes place e.g. B. in aprotic polar solvents, preferably chlorinated hydrocarbons, e.g. B. methylene chloride, Chloroform, carbon tetrachloride, dichloroethane, but optionally also in acetic acid, ethyl acetate, acetone or dimethylformamide.

In some cases it may be advantageous to add one to the reaction mixture usual buffers such as sodium acetate, sodium carbonate, disodium hydrogen phosphate or add benzyltrimethylammonium hydroxide (Triton B).

The reaction temperature is e.g. B. at 10 to 100, especially 20 to 80 ° C.

The oxidation can take place in the absence or in the presence of a catalyst Iodine, pyridine-n-oxide, sodium tungstate or light can be made.

Alkaline solutions of hydrogen peroxide are also suitable as oxidizing agents, e.g. B. 30 to 50 wt .-% aqueous solutions. In this case come as solvents alcohols such as methanol or ethanol and acetone or Acetonitrile in question. The reaction temperature is usually lower than in the case of peracids as the oxidizing agent and is, for example about 10 to 50, e.g. B. 25-30 ° C.

Furthermore, alkyl hydroperoxides, e.g. B. tert-butyl hydroperoxide or Cyclohexyl hydroperoxide can be used as an oxidizing agent. In this In case it is advisable to add a catalyst such. B., sodium tungstate, Tungsten acid, molybdenum hexacarbonyl or vanadylacetylacetonate. The abovementioned aprotic-polar solvents can be used Solvents are used such as. B. chlorinated hydrocarbons.

Preferred oxidizing agents are peroxycarboxylic acids, in particular Permaleic acid and m-chloroperbenzoic acid.

The oxidizing agents can e.g. B. in amounts of about 1 to 10, in particular 2 to 8 moles in the case of peroxycarboxylic acids, from about 1 to 20 moles in the case of hydrogen peroxide and about 1 to 20 moles in the case of alkyl hydroperoxides are used, the information being based on 1 mol of starting material II.  

The N-oxides are isolated from the reaction mixture in a conventional manner Way, e.g. B. by using a chromatographic reaction mixture Subjected to cleaning on silica gel.

The starting materials II are by known methods, for. B. as in EP 1 48 026, DE 34 06 993, EP 2 52 875, EP 2 33 714, EP 2 54 857, EP 2 75 013 or EP 15 756 described, accessible.

The following examples illustrate the preparation of the active ingredients.

Example 1.1 1- (4-chlorophenyl) -3- (1,2,4-triazol-4-oxo-1-ylmethyl) -4,4-dimethyl-pentan-3-ol

To a solution of 19.9 g (0.06 mol) of 1- (4-chlorophenyl) -3- (1,2,4-triazole- 1-ylmethyl) -4,4-dimethyl-pentan-3-ol and 0.5 ml pyridine-N-oxide in 150 ml 1,2-dichloroethane are 63 g maleic anhydride at room temperature (20 ° C) given. The reaction mixture is cooled to 0 ° C and slowly with 17.6 g (0.25 mol) hydrogen peroxide (approx. 50%) added. After the addition is complete is stirred for two hours at 40-50 ° C and the formation of the N-oxide Thin layer chromatography followed. Then the failed Aspirated maleic acid and the filtrate with sodium bicarbonate solution and water washed, dried over sodium sulfate and in vacuo evaporated. The following chromatographic purification of the remaining Residue on silica gel (ethyl acetate to isolate the starting product; Methanol to isolate the N-oxide) provides 5.0 g (26%) 1- (4-chlorophenyl) - 3- (1,2,4-triazol-4-oxo-1-ylmethyl) -4,4-dimethyl-pentan-3-ol with the melting point higher than 250 ° C.

According to Example 1.1, those listed in the tables can Connections are made.  

Example 4.1 (1,2,4-triazol-4-oxo-1-ylmethyl) bis (4-fluorophenyl) methylsilane

To a solution of 19.6 g (0.062 mol) (1,2,4-triazol-1-ylmethyl) - bis- (4-fluorophenyl) methylsilane and 0.5 ml pyridine-N-oxide in 150 ml Dichloroethane are given 60.6 g of maleic anhydride at room temperature. The reaction mixture is cooled to 0 ° C and slowly with 16.9 g (0.25 mol) hydrogen peroxide (approx. 50%) added. After the addition is complete is stirred for two hours at 40-50 ° C and by the formation of the N-oxide Thin layer chromatography followed. Then the failed Aspirated maleic acid and the filtrate with sodium bicarbonate solution and water washed, dried over sodium sulfate and in vacuo evaporated. The following chromatographic purification of the remaining Residue on silica gel (ethyl acetate / n-hexane = 4: 1 to isolate the Starting product; Ethyl acetate / methanol = 1: 1 to isolate the N-oxide) provides 1.9 g (9%) (1,2,4-triazol-4-oxo-1-ylmethyl) -bis- (4-fluorophenyl) - methylsilane.

According to Example 4.1, the compounds listed in Table 4 can getting produced.  

Table 1

Table 2

Table 2

Table 4

Generally speaking, the new compounds are characterized by a excellent effectiveness against a wide range of phytopathogenic agents Mushrooms, in particular from the classes of the Ascomycetes and Basidiomycetes, out. They are partially systemic and can be used as leaf and Soil fungicides are used.

The fungicidal compounds are particularly interesting for combating a variety of fungi on different crops or their Seeds, especially wheat, rye, barley, oats, rice, corn, lawn, Cotton, soy, coffee, sugar cane, fruit and ornamental plants in horticulture, Viticulture and vegetables - such as cucumbers, beans and squashes -.

The new compounds are particularly suitable for controlling 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 on 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. It will be the mushrooms or the ones before Fungi to protect plants, seeds, materials or the Soil treated with an effective amount of the active ingredient.

The new compounds can cover virtually all stages of development Influence plants in various ways and are therefore used as growth regulators  used. The variety of effects of plant growth regulators depends above all

• a) the plant species and variety,
• b) from the time of application, based on the development stage the plant and the season,
• c) the place and method of application (seed dressing, soil treatment or leaf application),
• d) climatic factors, e.g. B. temperature, rainfall, also day length and light intensity,
• e) the soil conditions (including fertilization),
• f) the formulation or application form of the active ingredient and in the end
• g) the concentrations of active substance used.

From the range of different applications of the Plant growth regulators according to the invention in plant cultivation some mentioned below.

A. With the compounds which can be used according to the invention, the vegetative Strongly inhibit plant growth, which is particularly evident in a Reduction in length growth expresses. The treated plants show accordingly a stubborn growth; also a darker leaf color to observe.

As an advantage in practice, z. B. the reduction of Grass growth on roadsides, hedges, canal embankments and on lawns like parks, sports and orchards, ornamental lawns and airfields, so that the labor and costly grass clippings can be reduced.

Increasing stability is also of economic interest of crops prone to storage such as cereals, corn, rice, sunflowers and Soy. Reduce the resulting shortening and strengthening of the straw or eliminate the danger of "storing" (twisting) plants under unfavorable weather conditions before harvest.

It is also important to use growth regulators to inhibit the Growth in length and the temporal change in the maturation process Cotton. This is a fully mechanized harvesting of this important crop.

By using growth regulators, the lateral Branching of the plants can be increased or inhibited. There is Interest if e.g. B. in tobacco plants the formation of side shoots (Stinginess) should be inhibited in favor of leaf growth.  

Growth regulators can also be used, for example, in winter rape Increase frost resistance considerably. On the one hand, the length growth and developing one too lush (and thereby special leaf or plant mass susceptible to frost.

On the other hand, the young rapeseed plants are planted after sowing and before Onset of winter frosts despite favorable growth conditions in the vegetative stage of development held back. This also makes the Frost risk of such plants eliminated, which leads to the premature degradation of the Inhibit flowering and tend to transition to the generative phase. Also at other cultures, e.g. B. Winter cereals, it is advantageous if the Stocks by treatment with compounds according to the invention in autumn well stocked, but not too lavishly into the winter. This can increase the sensitivity to frost and - because of the relative low leaf and plant mass - infestation with various Diseases (e.g. fungal disease) can be prevented. The inhibition of vegetative growth also enables the cultivation of many crops denser planting of the soil, so that an additional yield, based on the Floor area can be achieved.

B. With the new funds, additional yields can be obtained both on plant parts and also achieve plant ingredients. For example, it is possible the growth of large quantities of buds, flowers, leaves, fruits, Grains, roots and tubers induce the sugar content in Sugar beets, sugar cane as well as citrus fruits increase the protein content to increase in cereals or soybeans or rubber trees to increase the flow of latex to stimulate.

The compounds of formula I can increase yields Interventions in the plant metabolism or through promotion or Inhibit vegetative and / or generative growth.

C. Finally, with the plant growth regulators both Shortening or lengthening the development stages as well Accelerating or decelerating the ripeness of the harvested plant parts or reach after harvest.

Ease of harvest, for example, is of economic interest, caused by the temporally concentrated falling or decreasing of the Adhesion to the tree with citrus fruits, olives or other types and varieties of pome, stone and shell fruit is made possible. The same  Mechanism, that is, the promotion of the formation of separating tissue between fruit or leaf and shoot part of the plant is also for a well controlled defoliation of crops essential.

D. With growth regulators the water consumption of plants can continue be reduced. This is particularly important for agricultural Usable areas that are artificially irrigated at a high cost need to be, e.g. B. in arid or semi-arid areas. Because of the engagement the intensity of the irrigation of the substances according to the invention reduce and thus perform a more cost-effective management. Under the influence of growth regulators, there is a better one Exploitation of the existing water because u. a.

• - the opening width of the stomata is reduced,
• - a thicker epidermis and cuticle are formed,
• - the root penetration of the soil is improved,
• - The microclimate in the crop due to a more compact growth is influenced favorably.

The active compounds to be used according to the invention can be used in crop plants both from the seed (as a seed dressing) and via the soil, d. H. through the root and through the leaf.

Due to the high plant tolerance, the application rate can be as Growth regulators can be varied widely.

In the seed treatment, amounts of active ingredient are generally 0.001 up to 50 g, preferably 0.01 to 10 g per kilogram of seed is required.

For leaf and soil treatment, doses are generally from 0.01 to 10 kg / ha, preferably 0.02 to 3 kg / ha, should be considered sufficient.

The new substances can be converted into the usual formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and Granules. The application forms depend entirely on the purposes; in any case, they should have a fine and even distribution ensure the effective substance. The wording is in manufactured in a known manner, e.g. B. by stretching the active ingredient with Solvents and / or carriers, optionally using Emulsifiers and dispersants, where in the use of Water as a diluent other than optical solvents Auxiliary solvents can be used. As auxiliaries come for it  essentially in question: 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 like natural Rock flours (e.g. kaolins, clays, talc, chalk) and synthetic Rock flour (e.g. highly disperse silica, silicates); Emulsifier, such as nonionic and anionic emulsifiers (e.g. polyoxyethylene Fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants, such as lignin, lye 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 or more per hectare. The new compounds can can also be used in material protection (wood protection), e.g. B. against Paecilomyces variotii. When treating seeds, in general Amounts of active ingredient from 0.001 to 50 g, preferably 0.01 to 10 g, each Kilogram of seeds required.

The agents or the ready-to-use preparations made therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or Granules are used in a known manner, for example by Spraying, atomizing, dusting, scattering, pickling or pouring.

Examples of such preparations are:

• I. 90 parts by weight of compound no. 1 are mixed with 10 parts by weight. Share N-methyl-α-pyrrolidone and get a solution for Application in the form of tiny drops is suitable.
• II. 20 parts by weight of compound no. 1 are in a mixture dissolved, the 80 parts by weight of xylene, 10 parts by weight of Addition product of 8 to 10 moles of ethylene oxide with 1 mole Oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt Dodecylbenzenesulfonic acid and 5 parts by weight of the adduct and 40 moles of ethylene oxide with 1 mole of castor oil. Obtained by pouring and finely distributing the solution in water an aqueous dispersion.
• III. 20 parts by weight of compound no. 1 are dissolved in a mixture, that from 40 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 20 parts by weight of the adduct of 40 moles There is ethylene oxide in 1 mol of castor oil. By pouring and  finely distributing the solution in water gives an aqueous Dispersion.
• IV. 20 parts by weight of compound No. 1 are mixed dissolved, the 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 is made up. By pouring and finely distributing the Solution in water gives an aqueous dispersion.
• V. 80 parts by weight of compound no. 1 are mixed with 3 parts by weight of the Sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a Sulfite waste liquor and 7 parts by weight of powdered silica gel are good mixed and ground in a hammer mill. By fine Distributing the mixture in water gives a spray mixture.
• VI. 3 parts by weight of compound no. 1 with 97 parts by weight of finely divided Kaolin mixed intimately. You get one in this way Dusts containing 3% by weight of the active ingredient.
• VII. 30 parts by weight of compound no. 1 are mixed with a mixture of 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, mixed intimately. You get one in this way Preparation of the active ingredient with good adhesiveness.
• VIII. 40 parts by weight of compound no. 1 with 10 parts by weight Sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water intimately mixed. A stable aqueous dispersion is obtained. By diluting an aqueous dispersion is obtained with water.
• IX. 20 parts by weight of compound no. 1 are mixed with 2 parts by weight of calcium salt dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenolsulfonic acid urea-formaldehyde condensate and 68 parts by weight of one paraffinic mineral oil intimately mixed. You get one stable oily dispersion.

The agents according to the invention can also be used together in these forms of use with other active ingredients, such as. B. herbicides, insecticides, Growth regulators and fungicides, or also with fertilizers  are mixed and applied. When mixed with fungicides in many cases an increase in the fungicidal activity Spectrum.

The following list of fungicides with which the compounds of the invention can be combined, the possible combinations explain, but not limit.

Fungicides which are combined with the compounds according to the invention can include:

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

heterocyclic substances, such as
N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide,
N-trichloromethylthio-tetrahydrophthalimide,
2-heptadecyl-2-imidazoline acetate,
2,4-dichloro-6- (o-chloroanilino) -s-triazine,
0,0-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-phenylsulfuric acid amide,
5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,
2-rhodanmethylthiobenzthiazole,
1,4-dichloro-2,5-dimethoxybenzene,
4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone,
Pyridine-2-thio-1-oxide,
8-hydroxyquinoline or its copper salt,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,
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-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-cyclododecyl-morpholine or its salts,
N- [3- (p-tert-butylphenyl) -2-methylpropyl] cis-2,6-dimethylmorpholine,
N- [3- (p-tert-butylphenyl) -2-methylpropal] piperidine,
2- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole,
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) pyridine methanol,
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- (ethylaminocarbonyl) -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-chloro-2-aminopyridine,
1 - ((bis- (4-Fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

Claims (8)

1. N-oxo-azolylmethyl derivatives of the general formula I in the R -CH₂-R¹ or means R¹ R² -X¹-A⁴,
R³ denotes -Z²-tert-butyl,
A¹, A³, B¹ and B³ are the same or different and are C₁-C₈-alkyl, phenylethyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A² and B² are the same or different and are hydrogen, C₁-C₈-alkyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A⁴ is phenyl optionally substituted by halogen,
Z¹ is hydrogen or OH,
Z² C = O or CHOH,
X CH or N and
X¹ is O, S or CH₂. 2. A process for the preparation of the N-oxo-azolylmethyl derivatives of the formula I according to claim 1, characterized in that azolylmethyl derivatives of the formula II in which R has the meaning given in claim 1, with peroxycarboxylic acids, H₂O₂ or alkyl hydroperoxides in the presence of a solvent to give the N-oxides of the formula I. 3. Fungicidal composition comprising a carrier and a fungicidally effective amount of an N-oxo-azolylmethyl derivative of the formula I. in the R-CH₂-R¹ or means R¹ R² -X¹-A⁴,
R³ denotes -Z²-tert-butyl,
A¹, A³, B¹ and B³ are the same or different and are C₁-C₈-alkyl, phenylethyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A² and B² are the same or different and are hydrogen, C₁-C₈-alkyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A⁴ is phenyl optionally substituted by halogen,
Z¹ is hydrogen or OH,
Z² C = O or CHOH,
X CH or N and
X¹ is O, S or CH₂. 4. Process for combating fungi, characterized in that an fungicidally effective amount of an N-oxo-azolylmethyl derivative of the formula I in the R -CH₂-R¹ or means R¹ R² -X¹-A⁴,
R³ denotes -Z²-tert-butyl,
A¹, A³, B¹ and B³ are the same or different and are C₁-C₈-alkyl, phenylethyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A² and B² are the same or different and are hydrogen, C₁-C₈-alkyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A⁴ is phenyl optionally substituted by halogen,
Z¹ is hydrogen or OH,
Z² C = O or CHOH,
X CH or N and
X¹ is O, S or CH₂, can act on the fungi or materials, surfaces, plants, seeds or the soil threatened by fungal attack. 5. Agent for the purification of plant growth, comprising a carrier and a plant-regulating amount of an N-oxo-azolylmethyl derivative of the formula I. in the R -CH₂-R¹ or means R¹ R² -X¹-A⁴,
R³ denotes -Z²-tert-butyl,
A¹, A³, B¹ and B³ are the same or different and are C₁-C₈-alkyl, phenylethyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A² and B² are the same or different and are hydrogen, C₁-C₈-alkyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A⁴ is phenyl optionally substituted by halogen,
Z¹ is hydrogen or OH,
Z² C = O or CHOH,
X CH or N and
X¹ is O, S or CH₂. 6. A process for regulating plant growth, characterized in that the soil, the seed or the plants are treated with an amount of an N-oxo-azolylmethyl derivative of the formula I which regulates the plant growth in the R -CH₂-R¹ or means R¹ R² -X¹-A⁴,
R³ denotes -Z²-tert-butyl,
A¹, A³, B¹ and B³ are the same or different and are C₁-C₈-alkyl, phenylethyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A² and B² are the same or different and are hydrogen, C₁-C₈-alkyl or phenyl, these radicals being unsubstituted or mono- to trisubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
A⁴ is phenyl optionally substituted by halogen,
Z¹ is hydrogen or OH,
Z² C = O or CHOH,
X CH or N and
X¹ is O, S or CH₂. 7. A compound of formula I according to claim 1, characterized in that R is -CH₂-R¹,
R¹ A¹ tertiary butyl,
B¹ 2- (4-chlorophenyl) ethyl,
Z¹ OH and
XN mean. 8. A compound of formula I according to claim 1, characterized in that R is -CH₂-R¹,
R¹ A³ 4-fluorophenyl,
B³ 4-fluorophenyl and
XN mean.