MXPA99010519A

MXPA99010519A - Fungicidal mixture

Info

Publication number: MXPA99010519A
Application number: MXPA/A/1999/010519A
Authority: MX
Inventors: Ammermann Eberhard; Muller Bernd; Schelberger Klaus; Sauter Hubert; Lorenz Gisela; Leyendecker Joachim; Hampel Manfred; Saur Reinhold; Birner Erich
Original assignee: Basf Aktiengesellschaft
Priority date: 1997-06-04
Filing date: 1999-11-16
Publication date: 2000-05-01

Abstract

The invention relates to fungicidal mixtures containing a synergetically effective quantity of a.1) a carbamate of formula (I.a), wherein X means CH and N, n stands for 0, 1 or 2, and R means halogen, alkyl, and alkyl halide or a.2) the oxime ether carboxylic acid amide of formula (I.b), and b.1) 4-[2-methyl-3-(4-tert.-butylphenyl)-propyl]-2, 6-dimethylmorpholine of formula (II.a) or b.2) 4-(C10-C13-alkyl)-2,6-dimethylmorpholine of formula (II.b) or b.3) (RS)-1-[3-(4-tert-butyl phenyl)-2-methyl-propyl]-piperidine of formula (II.c) and c) an active agent from the group of azole fungicides (III).

Description

FUNGICIDE MIXES.

Description The present invention relates to a fungicidal mixture which contains to. D n carbamate of the formula I, wherein X means CH and N, n is 0, 1 or 2 and R means halogen, C, -C 4 -alkyl and C 4 -Chaloalkyl, the radicals R being different when n is 2, or a.2) Oxymether carboxamide of formula I.b as well as b.l) 4- [2-methyl-3- (4-tert.-butylphenyl) -propyl] -2,6-dimethylmorpholine or b. 2) 4- (C? 0-Ci3-alkyl) -2,6-dimethylmorphine b.3) (RS) -l- [3- (4-fcerc-butylphenyl) -2-methyl-propyl] -piperidine CHg CH3 H3C- c- < Á? - CH2- CH- II.C CH3 c) an active substance from the group of azole (III) fungicides, in an active synergetic quantity.

Mixtures are particularly preferred, in which the azole fungicide is one of compounds III.1 to III.33: III.1 l-. { [2- (2,4-dichlorophenyl) -l, 3-dioxolan-2-yl] -lH-l, 2,4-tri- azole III.2 1- (biphenyl-4-yloxy) -3,3-dimethyl-1- (lH-1, 2,4-triazol-1-yl) -butan-2-ol HO CH C (CH 3) 3 III.3 1 - [(2RS, 4RS; 2RS, 4SR) -4-Brom-2- (2, -dichlorofenyl) tetrahydrof urf uryl] -1H-1, 2, 4 -triazol III.4 (2RS, 3RS, 2RS, 3SR) -2- (4-chlorofenyl) -3-cyclopro-pyl-1- (lH-1, 2,4-triazol-1-yl) -butan-2 ol III.5 (2RS, 3RS) -l- (2,4-dichlorophenyl) -4,4-diphenyl-2- (lH-1, 2,4-triazol-1-yl) -pentan-3 -ol HO-CH- C (CH3) 3 III.6 cis, _rans-3-chloro-4- [4-methyl-2- (lH-1, 2,4-triazol-1-ylmethyl) 1, 3- dioxolan-2-yl] -f-enyl-4-chlorophenylether III.7 ("_?) - (R, S) -1- (2,4-dichlorofenyl) -4,4-dimethyl-2- (lH-1, 2,4-triazol-1-yl) ) -pent-l-en-3-ol III.8 C2 - ???, 3RS) -1- [3- (2-chlorophenyl) -2,3-epoxy-2- (4-fluorophenyl) -propyl] -1H-1,2,4-triazole III.9 (±) -1- [2- (2,4-dichlorofenyl) -4-ethyl-l, 3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole III, 10 (RS) -4- (4-chloro-enyl) -2-f-enyl-2- (1H-1,2,4-triazol-1-ylmethyl) -butyronitrile III.113- (2,4-dichlorofenyl) -6-f luoro-2- (1H-1, 2,4-triazol-1-yl) -guinazolin-4 (3H) -one III.12 bis- (4-fluorophenyl) - (methyl) - (1H-1,2,4-triatol-1-ylmethyl) -silane III.13 alcohol (RSj-2,4 '-dif luoro-a- (lH-l, 2,4-triazol-l-ylmethylbenzhydryl III .14 (RS) -2- (2,4-dichlorofenyl) -1- (1H-1,2-triazol-1-yl) -hexan-2-ol III .15 (±) -1- (ß-allyloxy-2,4-dichlorophenyl-ethyl) -imidazole III.164-chlorobenzyl N- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -thioacetamidate III.17 (1RS, 2SR, 5RS, 1RS, 2SR, 5SR) -2- (4-chlorobenzyl) -5-isopropyl-1- (1H-1,2,4-triazol-1-ylmethyl) -cyclopentanol III.18 (1RS, 5RS, 1RS, 5SR) -5- (4-chlorobenzyl) -2, 2-dimethyl-l- (1H-1,2,4-triazol-1-ylmethyl) -cyclopentanol III.192- (4-chlorophenyl) -2-cyano-l- (lH-1, 2,4-triazol-1-yl) -hexane III.202- (4-chlorophenyl) -3-hydroxy-4,4-dimethyl-1- (lH-1, 2,4-triazol-1-yl) -pentane III.21 N-Furfuryl-N-imidazol-1-ylcarbonyl-DL-homoalanin-pent-4-enyl ester H3CCH2 - CH COz-CH2) 3-CH = CH2 III.222- (2,4-dichlorophenyl) -l- (1 H-1,2,3-triazol-1-yl) -pentane III.23 N-propyl-N- [(2,4,6-trichloro-phenoxy) -ethyl] -imidazole-1-carboxamide 11.24 (±) -l-. { [2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolan-2-yl] -methyl} -lH-1, 2,4-triazole III.253- (2,4-dichlorofenyl) -2- (1 H-1,2,4-triazol-1-yl) -guinazolin-4 (3H) -one III.26 (±) -cis) -1- (4-chloro-enyl) -2- (1H-1,2,4-triazol-1-yl) -cycloheptanol III.27 l- (4-chlorophenyl) -4,4-dimethyl-3- (lH-1, 2,4-triazol-1-yl) -pentan-3-ol III.28 (_xS; -2- (2,4-dichlorophenyl) -3- (lH-l, 2,4-triazol-l-yl) -propyl-1,2, 2-tetraf luoroethylether III.29 l- (4-Chlorophenoxy) -3,3-dimethyl-1- (lH-1, 2,4-triazol-1-yl) -butan-2-one Q __ = c C (CH3) 3 III.30 (1RS, 2RS, 1RS, 2SR) -1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1, 2,4-triazole- 1-yl) -butan-2-ol III.31 (_?; - 4-chloro-, a, a-trifluoro-N- (l-imidazol-l-yl-2-propoxyethylidene) -o- toluidine III.32 (±) - (, _?) - 5- (4-chlorobenzylidene) -2,2-dimethyl-l- (lH-l, 2, -tri-azol-l-ylmethyl) -cyclopentanol 111.33 (E) - (RS) -1- (4-chlorophenyl) -4,4-di.methyl-2- (lH-1, 2,4-triazol-1-yl) -pent-1 -in-3-ol Furthermore, the invention relates to a process for controlling harmful fungi with mixtures of the compounds I (I. and Ib), II (II.a, II.b and II.c) and III (III.1-III.33). ).

The compounds of the formula I, their preparation and action against harmful fungi are known from the literature (EP-A 477 631, WO-A 96 / 01,256, O-A 96 / 01,258).

The compounds of formula II are also known: • II. a (common name: fenpropimorph): CAS RN [67564-91-4], US-A 4,202,894; • II.b (common name: tridemorph): CAS RN [81412-43-3], DE-A 11 64 152; • II. c (common name: fenpropidin): CAS RN [67306-00-7], US-A 4,202,894.

Also compounds III are described in the literature as active substances for controlling harmful fungi: 10 111.1 (common name: azaconazole): CAS RN [60207-31-0]; 111.2 (common name: biteranol): CAS RN [70585-36-3], DE-A 23 24 010; 111.3 (common name: bromuconazole): CAS RN [116255-48-2]; 111. (common name: cyproconazole): CAS RN [94361-06-5], US-A 4,664,696; 111.5 (common name: diclobutrazol): CAS RN [75736-33-3]; 111.6 (common name: diphenconazole): CAS RN [119446-68-3], EP-A 65 485; 111.7 (common name: diniconazole): CAS RN [83657-24-33; 111.8 (proposed common name: epoxiconazole): CAS RN [106325-08-0]; 111.9 (common name: etaconazole): CAS RN [60207-93-4]; 111.10 (common name: fenbuconazole): CAS RN [114369-43-6]; 111.11 (common name: fluquinconazole): CAS RN 25 [136426-54-5]; 111.12 (common name: flusilazole): CAS RN [85509-19-9]; 111.13 (common name: flutriafol): CAS RN [76674-21-0], EP- A 15 756; 111.14 (common name: hexaconazole): CAS RN [79983-71-4]; 111.15 (common name: imazalil): CAS RN [73790-28-0]; 111.16 (common name: imibenzconazole): CAS RN [86598-92-7]; -? H • III.17 (common name: ipconazole): CAS RN [125225-28-7], EP-A 267 778; 111.18 (common name: metconazole): CAS RN [125116-23-6]; 111. 19 (common name: myclobutanil): CAS RN [88671-89-0]; 111. 20 (common name: paclobutrazol): CAS RN [76738-62-0], US-A 1,595,697; 111.21 (common name: pefurazoate): CAS RN [101903-30-4]; 111. 22 (common name: penconazole): CAS RN [66246-88-6], GB-A 1 589 852; 111.23 (common name: prochloroaz) CAS RN [67747-09-5], US-A 4,080,462; 111.24 (common name: propiconazole): CAS RN [60207-90-1], GB-A 1 522 657; 111.25 (common name: quinconazole): CAS RN [103970-75-8]; 111. 26 (code yam: SSF 109): CAS RN [129586-32-9]; 111.27 (common name: tebuconazole): CAS RN [107534-96-3], EP-A 40 345; 111.28 (common name: tetraconazole): CAS RN [112281-77-3], EP-A 234 242; 111.29 (common name: triadimefon): CAS RN [43121-43-3], US-A 3,912,752; 111.30 (common name: triadi enol): CAS RN [55219-65-3], DE-A 23 24 010; 111.31 (common name: triflumizole): CAS RN [99387-89-0], JP-A 79 / 119,462; 111.32 (common name: triticonazole): CAS RN [131983-72-7]; 111. 33 (common name: uniconazole): CAS RN [83657-22-1]. Synergistic mixtures of the compounds I. with active substances II. up to II. c are described in the above patent application DE P 19 616 724.8 and synergistic mixtures of the compounds I. with active substances III.1 to III.33 are described in the oldest patent application DE P 19 618 676.5.

Furthermore, synergistic mixtures of compound I.b with active substances II are known from EP-A 645,087. up to II. c, and EP-A 645 091 discloses synergistic mixtures of compound I.b with a part of active substances III.1 to III.33.

In order to reduce the amounts of aliquot and improve the spectrum of action of the known compounds, the present invention was aimed at finding mixtures which, with the application of a lower total content of the active substances, had a better effect against harmful fungi (synergistic mixtures). ).

Therefore, the mixtures defined above were found. In addition, it was found that by simultaneously applying the compounds I, II and III together or separately, or by applying the compounds I, II and III successively, it is better to fight off harmful fungi than by applying the compounds alone.

Formula I.a represents, in particular, carbamates, in which the combination of substituents is equivalent to one of the lines in the following table: fifteen twenty Compounds la.12, la. Are especially preferred. 3, la.32 and la.38.

Thanks to their basic nature of the nitrogen atoms contained therein, compounds I, II and III are capable of forming salts or adducts with inorganic or organic acids or with metal ions.

Examples of inorganic acids are the hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid and the alkanoic acids, such as acetic acid, trifluoroacetic acid and propionic acid, as well as glycolic acid, thiocyanuric acid, lactic acid, succinic acid, citric acid, benzoic acid, acid cinnamic, oxalic acid, alkylsulfonic acids (sulfonic acids with linear or branched alkyl radicals having 1 to 20 carbon atoms), arylsulfonic or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl carrying one or two sulphonic acid groups), alkylphosphonic acids (phosphonic acids with linear or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonic or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl carrying one or two phosphoric acid radicals), whose alkyl or aryl radicals they can carry other substituents, eg p-toluenesulf acid nico, 2-phenoxybenzoic salicylic acid, p-aminosalicylic acid, 2-aceto? i-benzoic etc.

Suitable metal ions are, in particular, the ions of the elements of the second main group, especially calcium and magnesium, of the third and fourth main groups, especially aluminum, tin and lead, as well as of the eighth secondary group, especially chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. Especially preferred are the metal ions of the elements of the secondary groups of the fourth period. The metals can be present in the different valences that correspond to them.

In the production of mixtures of pure active substances I, II and III, to which, if appropriate, other active substances are added against harmful fungi or other parasites, such as insects, arachnids or nematodes, or else active substances. growth regulators or fertilizers.

The mixtures of compounds I, II and III or the combined or separate use of compounds I, II and III provide an excellent effect against a broad spectrum of phytopathogenic fungi, especially of the class of ascomycetes, deu-teromycetes , phycomycetes and basidiomice os. In part they have systemic action, so they can also be used as foliar and soil fungicides.

They are especially important for combating a myriad of fungi in different crop plants, such as cotton, legumes (eg cucumbers, beans and cucurbits), barley, turf, oats, coffee, corn, rice, rye, soy, vine, barley, ornamental plants, sugar cane and countless seeds.

They are especially suitable for combating the following phytopathogenic fungi: Erysiphe gra inis (mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucur-bitaces, Podosphaera leucotricha in apples, Uncinula ñecator in the vine, Puccinia species in cereals, Rhizoctonia species in cotton, rice and grass, Ustilago species in cereals and sugar cane, Venturia inaequalis in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis ciñera (gray rot) in strawberries, legumes, ornamental plants and vine, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudoperonospora species in cucurbitas and hops, Plasmopara viticulture in the vine, Alternate species in legumes and fruits, as well as Fusarium species and of Verticillium.

In addition, they can be used in the protection of materials (eg wood preservation), for example against Paecilomyces variotii.

The compounds I, II and III can be applied simultaneously together or separately or successively; in the separate application, generally, the order in which the compounds are applied has no effect on the success of the treatment.

Compounds I and II are usually applied in a weight ratio of 10: 1 to 0.01: 1, preferably 5: 1 to 0.05: 1, especially 1: 1 to 0.05: 1. Compounds I and III are usually applied in a weight ratio of 10: 1 to 0.01: 1, preferably 5: 1 to 0.05: 1, especially 1: 1 to 0.05: 1.

The application rates of the mixtures according to the invention vary, especially in agricultural growing areas, according to the desired effect of 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, especially 0.2 up to 3.0 kg / ha.

The application rates of compounds I vary from 0.01 to 2.5 kg / ha, preferably 0.05 to 2.5 kg / ha, especially 0.1 to 1.0 kg / ha.

The application rates of compounds II vary, in correspondingly, from 0.01 to 10 kg / ha, preferably 0.05 to 5 kg / ha, especially 0.05 to 2.0 kg / ha.

The application rates of the compounds III vary, correspondingly, from 0.01 to 10 kg / ha, preferentially 0.05 to 5 kg / ha, especially 0.05 to 2.0 kg / ha. xjp; In the treatment of the seeds, the mixtures are applied in amounts of 0.001 to 250 g / kg of seeds, preferably 0.01 to 100 g / kg, especially 0.01 to 50 g / kg.

Whenever the plants are to combat phytopathogenic fungi, the separate or joint application of compounds I, II and III or mixtures of compounds I, II and III by spraying or spraying the seeds is carried out. , plants or soils before or after the planting of the plants, or before or after the emergence of the plants.

The synergistic fungicidal mixtures of the invention or the compounds I, II and III can be used in the form of solutions, powders, suspensions or dispersions, emulsions, oil dispersions, spraying agents, sprays, directly sprayable granules, by spraying nebulization , atomization, spray or watering. The forms of application depend entirely on the respective application purposes; in all cases, the finest possible distribution of the mixtures of the invention should be ensured.

The formulations are prepared in known manner, eg by the addition of solvents and / or support substances. The formulations are usually added inert additives, such as emulsifiers or dispersants.

Suitable surfactants are: alkali metal, alkaline earth metal, ammonium salts of lignin sulphonic acid, naphthalene sulphonic acid, phenylsulfonic acid and dibuylthiaphthalene sulfonic acid, alkylaryl sulphonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulphates, and fatty acids, alkaline and alkaline earth metal salts, sulphated fatty alcohol glycol ethers, naphthalene condensates and naphthalene derivatives with formaldehyde, naphthalene or naphthalene sulfonic acid condensates with phenol and formaldehyde, polyoxyethylene-ethylphenol ethers , isooctylphenol, octyl-phenol or nonylphenol ethoxylates, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol-ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, polyoxypropylene , the po-liglicoléter aceta l of lauryl alcohol, sorbitol esters, sulphite residual liquors and methylcellulose.

The powders, spraying and spraying agents can be obtained by mixing or grinding together the compounds I or II or the mixture from the compounds I and II with a solid support.Granules (eg coated, impregnated or homogeneous granules) are usually prepared by joining the active substance or active substances with a solid support.

As solids or solid supports, for example, mineral earths, such as silica gel, silicic acid, silica gel, silicates, talc, kaolin, limestone, lime, bolus, loess, clay, dolomite, diatomaceous earth, sulfate, can be used. of calcium and magnesium sulphate, magnesium oxide, plastics, as well as fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and mineral products, such as cereal flour, cutting powders, wood and nut shells, cellulose powders or other solid supports.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of one of the compounds I, II and III, or of the mixture of the compounds I, II and III . The active substances are used here in a purity of 90 to 100%, preferably 95 to 100% (according to NMR / HPLC spectrum).

Compounds I, II and III, or the corresponding mixtures or formulations are used, treating the harmful fungi, plants, seeds, soils, surfaces, materials or enclosures to be kept free of them, with a active fungicidal quantity of the mixture, or of the compounds I, II and III in the separate application. The application can be made before or after the infestation by the harmful fungi.

The application can be made before or after infection by harmful fungi.

Application examples The synergistic effect of the mixtures according to the invention can be demonstrated by the following tests: The active substances, used separately or together, are formulated as a 10% emulsion in a mixture from 63% by weight of cyclohexanone and 27% by weight of an emulsifier, and are diluted in water to the desired concentration.

Action against Erysiphe graminis var. tri tici (wheat mildew) The leaves of wheat seedlings (variety "Frühgold") are treated, first, with the aqueous preparation of the active substances. After approx. 24 hours the plants are sprayed with spores of the trio mite (_.rysiphe graminis var. Tritici). The plates thus treated are incubated, then, for 7 days at 20-22 ° C and a relative air humidity of 75-80%. Next, the extent of the development of the fungus is evaluated.

The evaluation is done, determining the area of the leaves infested in percent. These percentage values are converted into degrees of action. The degree of action (W) is determined by means of the formula of Abbot in the following way: = (1 - a) -100 / ß a is equivalent to the fungal infection of the plants treated in% and ß is equivalent to the fungal infection of the untreated (control) plants in%.

Given a degree of action equal to O, the infestation of the treated plants is equivalent to that of the untreated control plants; in the case of a 100% action grade, the treated plants do not show any infestation.

The expected degrees of action of the mixtures of active substances are determined by the formula of Colby [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed degrees of action.

Colby's formula: E = x + y -? -y / 100 E means the expected degree of action, translated in% of the untreated control, when using the mixture from the active substances A and B in the concentrations a and b; x is the degree of action, translated in% of the untreated control, by using the active substance A in the concentration a; and it is the degree of action, translated in% of the untreated control, by using the active substance B in the concentration b.

Application example 1 - Effect against wheat mildew The leaves of wheat seedlings grown in pots of the variety "Frühgold" are sprayed until they drip with an aqueous solution of active substance, consisting of a stock solution from 10% active substance, 63% cilcohe-xanone and 27%. % of emulsifier and 24 hours after drying the sprayed layer are sprayed with spores of wheat mildew (x_r sip e graminis forma specialis tritici). Next, the plants are placed in the greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity of the air. After 7 days, the spread of mildew development is determined visually by the entire leaf surface in%.

The values for the percentage of the infected leaf surface are converted into action degrees as% of the untreated control, an action degree equal to 0 equals the same infection of the untreated control, a degree of action equal to 100 means 0 % infection The expected degrees of action for combinations of active substance are determined according to Colby's formula (Colby, SR (Calculating synergistic and antagonistic responses of herbi-cide Combinations, eeds, 15, S. 20-22, 1967) and compared with the observed degrees of action. *) calculated according to the formula of Colby From the results of the test it is clear that the degree of action observed is with all the mixing ratios higher than the degree of action calculated according to Colby's formula.

Application example 2 - Curative action against Puccinia retinitis in wheat (brown royo of wheat) The leaves of wheat seedlings grown in vase pots "Frühgold" are sprinkled with spores of brown royo. { Puccinea recóndi ta). Afterwards, the pots are placed for 24 hours in a chamber with high humidity (90 to 95%) and 20 to 22 ° C. During this time the spores germinate and the germ tubes penetrate the leaves of the leaf. The day si¬ Next, the infected plants are sprayed until they are dripped with an aqueous solution of active substance, which consists of a stock solution from 10% active substance, 63% cilcohexanone and 27% emulsifier. After drying the sprayed layer, the test plants are grown by days in the greenhouse at temperatures between 20 and 22 ° C and 65 to 70% relative humidity. Then the extent of the development of the fungus on the leaves is evaluated.

Values for the percentage of sheet surfaces in¬ fectada are converted into degrees of action as% of untreated control. A degree of action equal to 0 equals the same infection of the untreated control, a degree of action equal to 100 means 0% infection. The expected degrees of action for combinations of active substance are completed according to Colby's formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbi- -x cide Combinations ", eeds, 15, S. 20 - 22, 1967) and compared to the observed degrees of action. *) calculated according to Colby's formula From the results of the test it can be deduced that the degree of action observed is with all the mixing ratios higher than the degree of action calculated according to the Colby formula.

Claims

1. Fungicide mixture containing a.Dun carbamate of the formula I, wherein X means CH and N, n is 0, 1 or 2 and R means halogen, C, -C4-alkyl and C, -C4-haloalkyl, the radicals R being able to be different when n is 2, or a.2) Oxymether carboxamide of formula I.b as well as b.l) 4- [2-methyl-3- (4-tert.-butylphenyl) -propyl] -2,6-dimethylmorpholine or b .2) 4- (C? o-Ci3-alkyl) -2,6-dimethylmorphine [n = 10, 11,12 (60-70%), 13] b.3) (, i? 5) -l- [3- (4-tert-butylphenyl) -2-methyl-propyl] -piperidine c) an active substance from the group of fungicides of 15 azol (III), in an active synergetic quantity. Fungicidal mixture according to claim 1, characteri¬ 20 because the azole (III) fungicide is selected from the group of compounds III .1 1-. { [2- (2,4-dichloro-enyl) -1, 3-dioxolan-2-yl] -1H-1, 2,4-triazole 30 III.2 l- (biphenyl-4-yloxy) -3,3-dimethyl-1- (lH-1, 2,4-triazol-1-yl) -butan-2-ol HO CH C (CH3) 3 111.3 1 - [(2RS, 4RS; 2RS, 4SR) -4-Brom-2- (2,4-dichlorofonyl) tetrahydrofurfuryl] -1H-1,2,4-triazole

111. 4 (2RS, 3RS, 2RS, 3SR) -2- (4-chloro-enyl) -3-cyclopro-pyl-1- (1H-1,2-triazol-1-yl) -butan-2-ol 15 Cl _rfJ-, 111.4 III.5 (2RS, 3RS) -l- (2,4-dicorophenyl) -4,4-dimethoxy-2- (lH-1, 2,4-triazol-1-yl) -pentan-3 ol HO-CH C (CH 3) 3 25 III.6 cis, fcrans-3-chloro-4- [4-methyl-2- (lH-1, 2,4-triazol-1-ylmethyl) l, 3 dioxolan-2-yl] -phenyl-4-chlorophenylether III.7 (E) - (R, S) -1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1H-1, 2,4-triazol-1-yl) -pent -l-in-3-ol III.8 (2RS, 3RS) -1- [3- (2-chlorophenyl) -2,3-epoxy-2- (4-f luorofenyl) -propyl] -lH-1, 2,4-triazole III .9 (±) -1- [2- (2,4-dichlorofenyl) -4-ethyl-l, 3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole 20 III .10 (RS) -4- (4-chloro-enyl) -2-f-enyl-2- (1H-1, 2, -triazol-1-ylmethyl) -butyronitrile i! N III.113- (2,4-dichlorophenyl) -6-fluoro-2- (lH-l, 2,4-triazol-l-yl) -quinazolin- (3H) -one III.12 bis- (4-fluorophenyl) - (methyl) - (1H-1,2,4-tria-tol-1-ylmethyl) -silane III.13 alcohol (RS) -2,4 '-difluoro-a- (1H-1, 2, - riazol-1-ylmethyl) benzhydryl III.14.!? _. ~ 2- (2,4-dichlorophenyl) -l- (lH-l, 2,4-tria-15-yl-l-yl) -hexan-2-ol 20 III .15 (±) -1- (ß-allyloxy-2,4-dichlorofenyl-ethyl) -imidazole

111. 15 25 III.164-Chlorobenzyl N- (2,4-dichlorofonyl) -2- (1H-1,2,4-triazol-1-yl) -thioacetamidate 30 III.17 (1RS, 2SR, 5RS, 1RS, 2SR, 5SR) -2- (4-chlorobenzyl) -5-isopropyl-1- (1H-1,2,4-triazol-1-ylmethyl) ) -cyclopentanol til-1- (1H-1, 2,4-triazol-l-ylmethyl) -cyclopentanol III, 19 2- (4-chlorofenyl) -2-cyano-l- (1H-1, 2, -tria-15-yl-1-yl) -hexane III. 2- (4-chlorophenyl) -3-hydroxy-4,4-dimethyl-1-tyl-1- (1H-1,2,4-triazol-1-yl) -pentane III. 21 N-Furfuryl-N-imidazol-1-ylcarbonyl-DL-homoalanin-25 pent-4-enyl ester H3CCH2 - CH - CO_-. { CH2) 3-CH = CH2 30 III.222- (2,4-dichlorophenyl) -l- (lH-l, 2,3-triazol-l-yl) -pentane III.23 N-propyl-N- [(2,4,6-trichloro-phenoxy) -ethyl] -imidazole-1-carboxamide III .24 (±) -1-. { [2- (2,4-dichlorofenyl) -4-propyl-l, 3-dioxolan-2-yl] -methyl} -1H-1, 2, -triazole III.253- (2, -dichlorofonyl) -2- (1H-1, 2,4-triazol-1-yl) -chenazolin- (3H) -one 30 III.26 (±) -cis) -1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -cycloheptanol III.271- (4-chlorophenyl) -4, -dimethyl-3- (1H-1, 2,4-triazol-1-yl) -pentan-3-ol III.28 .R £ ?. -2- (2,4-dichlorophenyl) -3- (lH-l, 2,4-triazol-l-yl) -propyl-1,1,2,2-tetrafluoroethylether III .29 1- (4-Chlorophenoxy) -3,3-dimethyl-1- (1 H-1,2,4-triazol-1-yl) -butan-2-one 0 = C C (CH3) 3 III. 30 (1RS, 2RS, 1RS, 2SR) -1- (4-chlorophenoxy) -3,3-dimethyl-1- (1 H-1,2,4-triazol-1-yl) -butan-2-ol 30 III.31 ._?) - 4-chloro-a, a, a-trifluoro-N- (l-imidazol-l-yl-2-propoxy tylidene) -o-toluidine 111.32 (±) - C _) - 5- (4-chlorobenzylidene) -2,2-dimethyl-1- (1H-1, 2,4-tri-azol-l-ylmethyl) -cyclopentanol III .33 (E) - (RS) -1- (4-chlorofenyl) -4, -dimethyl-2- (1H-1, 2,4-triazol-1-yl) -pent-1-en -3-ol Fungicide mixture according to claim 1, characterized in that the weight ratio between the compound I, its salt or adduct and the compound II amounts to 10: 1 to 0.01: 1. 25

4. Fungicidal mixture according to claim 1, characterized in that the weight ratio between the compound I, its salt or adduct and the compound III amounts to 10: 1 to 0.01: 1.

A method for controlling harmful fungi, characterized in that the harmful fungi, their environment or the seed plants, the soil, the materials or areas to be kept free thereof are treated with a compound of the formula I, one of its salts or adducts according to claim 1, a compound of the formula II according to claim 1 and a compound of the formula II according to claim 1.

Process according to claim 5, characterized in that a compound I, or one of its salts or adducts according to claim 1 and the compound II according to claim 1 and the compound III according to claim 1 is applied simultaneously together or separately, or successively .

7. Process according to claim 5 or 6, characterized in that compound I, one of its salts or adducts according to claim 1, is applied in an amount of 0.01 to 2.5 kg / ha.

8. Process according to claims 5 to 7, characterized in that the compound II according to claim 1 is applied in an amount of 0.01 to 10 kg / ha.

9. Process according to claims 5 to 8, characterized in that the compound III according to claim 1 is applied in an amount of 0.01 to 10 kg / ha.

10. Product according to claim 1, which is conditioned in two parts, the first part containing a compound of the formula I according to claim 1 and a solid or liquid support and the second part a compound of the formula II according to claim 1 and a support solid or liquid, and one additionally gives a compound III according to claim 1.

11. Product according to claim 1, which is conditioned in three parts, the first part containing a compound of the formula I according to claim 1 and a solid or liquid support and the second part a compound 10 of the formula II according to claim 1 and a solid or liquid support, and the third part a compound III according to claim 1 and a solid or liquid support. fifteen twenty 25 30 SUMMARY OF THE INVENTION. Fungicidal mixtures containing a. D a carbamate of formula I, wherein X means CH and N, n is 0, 1 or 2 and R means halogen, C, -C 4 -alkyl and C, -C 4 -haloalkyl, the radicals R being able to be different when n fes 2, or a.2) Oxymether carboxamide of formula I.b as well as b.l) 4- [2-methyl-3- (4-tert.-butylphenyl) -propyl] -2,6-dimethylmorpholine H3C - 11.a or well b .2) 4- (C_o-Ci3-alkyl) -2, ß-dimethylmorpholine CH3 H3C - (CH2) n- O ll.b "CH3 [n = 10, 11, 12 (60- 70%), 13] b.3) (RS) -l- [3- (4-fcerc-butylphenyl) -2-methyl-propyl] -piperidine c) an active substance from the group of azole (III) fungicides, in an active synergetic quantity.