Fungicide mixtures

Abstract

Fungicidal mixtures, comprisinga) a carbamate of the formula I ##STR1## where T is CH or N, n is 0, 1 or 2 and R is halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -haloalkyl, it being possible for the radicals R to be different when n is 2, and/orb) an oxime ether of the formula II ##STR2## where the substituents have the following meaning: X is oxygen or amino (NH);Y is CH or N;Z is oxygen, sulfur, amino (NH) or C.sub.1 -C.sub.4 -alkylamino (N--C.sub.1 -C.sub.4 -alkyl);R' is C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -haloalkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.2 -C.sub.6 -haloalkenyl, C.sub.3 -C.sub.6 -alkynyl, C.sub.3 -C.sub.6 -haloalkynyl, C.sub.3 -C.sub.6 -cycloalkylmethyl, or is benzyl which can be partially or fully halogenated and/or have attached to it one to three of the following radicals: cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy, and C.sub.1 -C.sub.4 -alkylthio; andc) an acaricide selected from the group of the compounds III.a to III.d ##STR3## in a synergistically active amount.

Description

The present invention relates to a fungicidal mixture which comprises

a) a carbamate of the formula I ##STR4## where T is CH or N, n is 0, 1 or 2 and R is halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -haloalkyl, it being possible for the radicals R to be different when n is 2, and/or b) an oxime ether of the formula II ##STR5## where the substituents have the following meaning: X is oxygen or amino (NH); Y is CH or N; Z is oxygen, sulfur, amino (NH) or C.sub.1 -C.sub.4 -alkylamino (N--C.sub.1 -C.sub.4 -alkyl); R' is C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -haloalkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.2 -C.sub.6 -haloalkenyl, C.sub.3 -C.sub.6 -alkynyl, C.sub.3 -C.sub.6 -haloalkynyl, C.sub.3 -C.sub.6 -cycloalkylmethyl, or is benzyl which can be partially or fully halogenated and/or have attached to it one to three of the following radicals: cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy, and C.sub.1 -C.sub.4 -alkylthio; and c) an acaricide selected from the group of the compounds III.a to III.d ##STR6## in a synergistically active amount.

Moreover, the invention relates to methods of controlling harmful fungi with mixtures of the compounds I and/or II and III and to the use of the compound I and/or II and the compounds III for the preparation of such mixtures.

The compounds of the formula I, their preparation and their action against harmful fungi have been disclosed in the literature (WO-A 96/01,256 and WO-A 96/01,258).

The compounds of the formula II, their preparation and their action against harmful fungi have been described in WO-A 95/21,153, WO-A 95/21,154 and DE-A 1 95 28 651.0.

The acaricides III, their preparation and their use against arachnids have also been disclosed (III.a: CAS RN 120928-09-8, common name: fenazaquin; III.b: EP-A 289 879, common name: tebufenpyrad; III.c: CAS RN 111812-58-9, common name: fenpyroxymate; III.d: CAS RN 96489-71-3, common name: pyridaben).

It was an object of the present invention to provide mixtures which have an improved activity gainst harmful fungi combined with a reduced total amount of active ingredients applied (synergistic mixtures) with a view to reducing the rates of application and to improving the spectrum of action of the known compounds.

Accordingly, we have found that this object is achieved by the mixtures defined at the outset. Moreover, we have found that better control of the harmful fungi is possible by applying a compound I and/or II and the compounds III simultaneously together or separately or by applying a compound I and/or II and the compounds III in succession than when the individual compounds are used.

In particular, the formula I represents carbamates in which the combination of the substituents corresponds to one line of the table which follows:

______________________________________No. T R.sub.n______________________________________I.1 N 2-FI.2 N 3-FI.3 N 4-FI.4 N 2-ClI.5 N 3-ClI.6 N 4-ClI.7 N 2-BrI.8 N 3-BrI.9 N 4-BrI.10 N 2-CH.sub.3I.11 N 3-CH.sub.3I.12 N 4-CH.sub.3I.13 N 2-CH.sub.2 CH.sub.3I.14 N 3-CH.sub.2 CH.sub.3I.15 N 4-CH.sub.2 CH.sub.3I.16 N 2-CH(CH.sub.3).sub.2I.17 N 3-CH(CH.sub.3).sub.2I.18 N 4-CH(CH.sub.3).sub.2I.19 N 2-CF.sub.3I.20 N 3-CF.sub.3I.21 N 4-CF.sub.3I.22 N 2,4-F.sub.2I.23 N 2,4-Cl.sub.2I.24 N 3,4-Cl.sub.2I.25 N 2-Cl, 4-CH.sub.3I.26 N 3-Cl, 4-CH.sub.3I.27 CH 2-FI.28 CH 3-FI.29 CH 4-FI.30 CH 2-ClI.31 CH 3-ClI.32 CH 4-ClI.33 CH 2-BrI.34 CH 3-BrI.35 CH 4-BrI.36 CH 2-CH.sub.3I.37 CH 3-CH.sub.3I.38 CH 4-CH.sub.3I.39 CH 2-CH.sub.2 CH.sub.3I.40 CH 3-CH.sub.2 CH.sub.3I.41 CH 4-CH.sub.2 CH.sub.3I.42 CH 2-CH(CH.sub.3).sub.2I.43 CH 3-CH(CH.sub.3).sub.2I.44 CH 4-CH(CH.sub.3).sub.2I.45 CH 2-CF.sub.3I.46 CH 3-CF.sub.3I.47 CH 4-CF.sub.3I.48 CH 2,4-F.sub.2I.49 CH 2,4-Cl.sub.2I.50 CH 3,4-Cl.sub.2I.51 CH 2-Cl, 4-CH.sub.3I.52 CH 3-Cl, 4-CH.sub.3______________________________________ The compounds I.12, 1.23, I.32 and I.38 are especially preferred.

The formula II represents, in particular, oxime ethers where X is oxygen and Y is CH or X is amino and Y is N.

Also preferred are compounds I where Z is oxygen.

Equally preferred are compounds II where R' is alkyl or benzyl.

Particularly preferred with a view to their use in the synergistic mixtures according to the invention are the compounds I compiled in the tables which follow.

Table 2.

Compounds of the formula IIA, where ZR' for each compound corresponds to one line of Table A

TABLE 2______________________________________Compounds of the formula IIA, where ZR' for each compoundcorresponds to one line of Table A______________________________________ (IIA) ##STR7##______________________________________ Table 3.

Compounds of the formula IIB, where ZR' for each compound corresponds to one line of Table A

TABLE 3______________________________________Compounds of the formula IIB, where ZR' for each compoundcorresponds to one line of Table A______________________________________ (IIB) ##STR8##______________________________________ TABLE A______________________________________No. ZR'______________________________________II.1 O--CH.sub.2 CH.sub.2 CH.sub.3II.2 O--CH(CH.sub.3).sub.2II.3 O--CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3II.4 O--CH(CH.sub.3)CH.sub.2 CH.sub.3II.5 O--CH.sub.2 CH(CH.sub.3).sub.2II.6 O--C(CH.sub.3).sub.3II.7 S--C(CH.sub.3).sub.3II.8 O--CH (CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3II.9 O--CH.sub.2 C(CH.sub.3).sub.3II.10 O--CH.sub.2 C(Cl).dbd.CCl.sub.2II.11 O--CH.sub.2 CH.dbd.CH--Cl(trans)II.12 O--CH.sub.2 C(CH.sub.3).dbd.CH.sub.2II.13 O--CH.sub.2 -(cyclopropyl)II.14 O--CH.sub.2 --C.sub.6 H.sub.5II.15 O--CH.sub.2 --[4-F--C.sub.6 H.sub.4 ]II.16 O--CH.sub.2 CH.sub.3II.17 O--CH(CH.sub.2 CH.sub.3).sub.2______________________________________

Relative to the C=Y double bond, the compounds of the formula II can exist in the E or the Z configuration (relative to the carboxylic acid function). Accordingly, they can be used in the mixture according to the invention in each case either as the pure E or Z isomers or as an E/Z isomer mixture. Preferred is in each case the E/Z isomer mixture or the E isomer, the E isomer of the compound II being especially preferred.

The C.dbd.N double bonds of the oxime ether groups in the side chain of the compounds II can exist in each case as pure E or Z isomers or as E/Z isomer mixtures. The compounds II can be used in the mixtures according to the invention both as isomer mixtures and as pure isomers. Preferred with a view to their use are, in particular, compounds II where the terminal oxime ether group in the side chain is in the cis configuration (OCH.sub.3 group to ZR').

Due to their basic character, the compounds I and II are capable of forming adducts or salts with inorganic or organic acids or with metal ions.

Examples of inorganic acids are 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 alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals having from 1 to 20 carbon atoms), arylsulfonic acids or -disulfonic acids (aromatic radicals such as phenyl and naphthyl which have attached to them one or two sulfo groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals of from 1 to 20 carbon atoms), arylphosphonic acids or -diphosphonic acids (aromatic radicals such as phenyl and naphthyl which have attached to them one or two phosphoric acid radicals), it being possible for the alkyl or aryl radicals to have attached to them further substituents, eg. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc.

Suitable metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, and of the third and fourth main group, in particular aluminum, tin and lead, and of the first to eighth sub-group, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Especially preferred are the metal ions of the elements of the sub-groups of the fourth period. The metals can in this case be in the various valences which they can assume.

When preparing the mixtures, it is preferred to employ the pure active ingredients I and/or II and III, with which further active ingredients against harmful fungi or other pests such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be admixed, if so desired.

The mixtures of the compounds I and/or II and III, or the simultaneous joint or separate use of the compounds I and/or II and III, are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically and can therefore be employed as foliar- and soil-acting fungicides.

They are especially important for controlling a large number of fungi in a variety of crop plants such as cotton, vegetable species (eg. cucumbers, beans and curcubits), barley, grass, oats, coffee, maize, fruit species, rice, rye, soybeans, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.

They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on curcubits, Podosphaera leucotricha on apples, Puccinia species on cereals, Rhizoctonia species on cotton, rice 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, vegetables, ornamentals and grapevines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora species on cucurbits and hops, Plasmopara viticola on grapevines, Pseudoperonospora species on cucurbits and hops, Alternaria species on vegetables and fruit, and Fusarium and Verticillium species.

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

The compounds I and/or II and III can be applied simultaneously together or separately or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.

The compounds I and III or II and III are normally used in a weight ratio of from 200:1 to 0.1:1, preferably 100:1 to 1:1, in particular 50:1 to 5:1 (III:I or III:II).

In the case of the compounds I and/or II, the application rates of the mixtures according to the invention are in general from 0.005 to 0.5 kg/ha, preferably 0.01 to 0.5 kg/ha, in particular 0.01 to 0.3 kg/ha, depending on the nature of the desired effect.

Correspondingly, in the case of the compounds III, the application rates are normally from 0.1 to 10 kg/ha, preferably 0.5 to 5 kg/ha, in particular 1 to 4 kg/ha.

For seed treatment, the application rates of the mixture used are generally from 0.001 to 100 g/kg seed, preferably 0.01 to 50 g/kg, in particular 0.01 to 10 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and/or II and III or of the mixtures of the compounds I and/or II and III is effected by spraying or dusting the seeds, the plants or the soils before or after sowing of the plants, or before or after plant emergence.

The fungicidal synergistic mixtures according to the invention, or the compounds I and/or II and III, can be formulated for example in the form of ready-to-spray solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, and applied by spraying, atomizing, dusting, spreading or pouring. The use form depends on the intended purpose; in any case, it should guarantee as fine and uniform as possible a distribution of the mixture according to the invention.

The formulations are prepared in a manner known per se, eg. by adding solvents and/or carriers. It is usual to admix inert additives, such as emulsifiers or dispersants, with the formulations.

Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol polyglycol ethers or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, or lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing or jointly grinding the compounds I and/or II or III or the mixture of the compounds I and/or II and III with a solid carrier.

Granules (eg. coated granules, impregnated granules or homogeneous granules) are normally prepared by binding the active ingredient, or active ingredients, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths such as silica gel, silicas, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.

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

The compounds I and/or II or III, or the mixtures, or the corresponding formulations, are applied by treating the harmful fungi or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally active amount of the mixture, or of the compounds I and/or II and III in the case of separate application. Application can be effected before or after infection by the harmful fungi.

The fungicidal activity of the compounds and of the mixtures is demonstrated by the following experiments:

The active ingredients, separately or together, are formulated as a 10% emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil.RTM. LN (Lutensol.RTM. AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Emulphor.RTM. EL (Emulan.RTM. EL, emulsifier based on ethoxylated fatty alcohols) and diluted with water to give the desired concentration.

Evaluation is carried out by determining the infected leaf areas in percent. These percentages are converted into efficacies. The expected efficacies of the mixtures of the active ingredients are determined using Colby's formula [R. S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficacies.

Colby's formula:

E=x+y=x.multidot.y/100 E expected efficacy, expressed in % of the untreated control, when using the mixture of the active ingredients A and B at concentrations of a and b x efficacy, expressed in % of the untreated control, when using active ingredient A at a concentration of a y efficacy, expressed in % of the untreated control, when using active ingredient B at a concentration of b

The efficacy (W) is calculated as follows using Abbot's formula:

W=(1-.alpha.).multidot.100/.beta. .alpha. is the fungal infection of the treated plants in % and .beta. is the fungal infection of the untreated (control) plants in %

An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants are not infected.

EXAMPLES 1-14

Efficacy against Botrytis cinerea on peppers

After 4-5 leaves had developed properly, pepper seedlings cv. "Neusiedler Ideal Elite" were sprayed to run-off with an aqueous preparation of active ingredient made with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. Next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7.times.10.sup.6 spores/ml in a 2% strong aqueous Biomalz solution. The test plants were subsequently placed in a controlled-environment cabinet at 22 to 24.degree. C. at high atmospheric humidity. After 5 days, the extent of fungal infection on the leaves was determined visually in %.

The visually determined values for the percentage of diseased leaf area were converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control, an efficacy of 100 is a disease level of 0%. The expected efficacies for combinations of active ingredients were determined using Colby's formula (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, p. 20-22, 1967) and compared with the observed efficacies.

TABLE 4______________________________________ Concentration of active ingredient Efficacy in % of in the spray mix- the untreated con-Ex. Active ingredient ture in ppm trol______________________________________1V Control (untreated) (disease level 70%) 02V Compound No. I.38 of 63 44 Table 1 = A3V IIIa = fenazaquin 125 86 63 794V IIIb = tebufenpyrad 125 72 63 585V IIIc = fenpyroxymate 125 0 63 06V IIId = pyridaben 125 16 63 16______________________________________ TABLE 5______________________________________ Concentration of active ingredient in the spray calculatedEx. mixture in ppm observed efficacy efficacy*______________________________________7 63 A 99 88 + 63 IIIa8 63 A 99 92 + 125 IIIa9 63 93 77 + 63 IIIb10 63 A 100 84 + 125 IIIb11 63 A 96 44 + 63 IIIc12 63 A 98 44 + 125 IIIc13 63 A 99 53 + 63 IIId14 63 A 99 53 + 125 IIId______________________________________ *calculated using Colby's formula

EXAMPLES 15-35

Efficacy against Pyricularia oryzae (protective)

Leaves of rice seedlings cv. "Tai-Nong 67" in pots were sprayed to run-off with an aqueous preparation of active ingredient made with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. Next day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were subsequently placed for 6 days in controlled-environment cabinets at 22-24.degree. C. and relative atmospheric humidity of 95-99%. The extent of the disease development on the leaves was then determined visually.

The visually determined values for the percentage of diseased leaf area were converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control, an efficacy of 100 is a disease level of 0%. The expected efficacies for combinations of active ingredients were determined using Colby's formula (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, p. 20-22, 1967) and compared with the observed efficacies.

TABLE 6______________________________________ Concentration of Efficacy in active ingredient % of the in the spray mix- untreatedEx. Active ingredient ture in ppm control______________________________________15V Control (untreated) (disease level 86%) 016V Compound No. 1.38 from 63 65 Table 1 = A 31 65 16 6517V IIIa = fenazaquin 125 7 63 718V IIIb = tebufenpyrad 125 53 63 019V IIIc = fenpyroxymate 125 7 63 020V IIId = pyridaben 125 7 63 0______________________________________ TABLE 7______________________________________ Concentration of active ingredient in the spray calculatedEx. mixture in ppm observed efficacy efficacy*______________________________________21 63 A + 99 67 125 IIIa22 31 A 99 67 + 125 IIIa23 16 A 99 67 + 63 IIIa24 63 A 99 65 + 63 IIIb25 63 A 99 84 + 125 IIIb26 31 A 97 84 + 125 IIIb27 16 A 99 65 + 63 IIIb28 63 A 94 65 + 63 IIIc29 63 A 99 67 + 125 IIIc30 31 A 97 67 + 125 IIIc31 16 A 80 65 + 63 IIIc32 63 A 94 67 + 63 IIId33 63 A 97 65 + 125 IIId34 31 A 94 65 + 125 IIId35 16 A 88 67 + 63 IIId______________________________________ *calculated using Colby's formula

EXAMPLES 36-53

Efficacy against Botrytis cinerea on peppers

After 4-5 leaves had developed properly, pepper seedlings cv. "Neusiedler Ideal Elite" were sprayed to run-off with an aqueous preparation of active ingredient made with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. Next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7.times.10.sup.6 spores/ml in a 2% strong aqueous Biomalz solution. The test plants were subsequently placed in a controlled-environment cabinet at 22 to 24.degree. C. at high atmospheric humidity. After 5 days, the extent of fungal infection on the leaves was determined visually in %.

The visually determined values for the percentage of diseased leaf area were converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control, an efficacy of 100 is a disease level of 0%. The expected efficacies for combinations of active ingredients were determined using Colby's formula (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, p. 20-22, 1967) and compared with the observed efficacies.

TABLE 8______________________________________ Concentration of Efficacy in active ingredient % of the in the spray mix- untreatedEx. Active ingredient ture in ppm control______________________________________36V Control (untreated) (disease level 70%) 037V B = Tab. 2A, No. 2 63 30 16 1638V C = Tab. 2A, No. 4 31 44 16 4439V IIIa = fenazaquin 125 86 63 7940V IIIb = tebufenpyrad 63 5841V IIIc = fenpyroxymate 125 0 63 042V IIId = pyridaben 125 16 63 16______________________________________ TABLE 9______________________________________ Concentration of active ingredient in the spray calculatedEx. mixture in ppm observed efficacy efficacy*______________________________________43 16 B + 98 82 63 IIIa44 63 B + 93 85 63 IIIa45 16 B + 80 65 63 IIIb46 63 B + 92 70 63 IIIb47 16 B + 44 16 63 IIIc48 63 B + 50 30 125 IIIc49 63 B + 100 41 125 IIId50 16 B + 58 30 63 IIId51 31 C + 100 92 125 IIIa52 16 C + 100 88 63 IIIa53 16 C + 93 77 63 IIIb______________________________________ *calculated using Colby's formula

EXAMPLES 54-74

Efficacy against Pyricularia oryzae (protective)

Leaves of rice seedlings cv. "Tai-Nong 67" in pots were sprayed to run-off with an aqueous preparation of active ingredient made with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. Next day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were subsequently placed for 6 days in controlled-environment cabinets at 22-24.degree. C. and relative atmospheric humidity of 95-99%. The extent of the disease development on the leaves was then determined visually.

The visually determined values for the percentage of diseased leaf area were converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control, an efficacy of 100 is a disease level of 0%. The expected efficacies for combinations of active ingredients were determined using Colby's formula (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, p. 20-22, 1967) and compared with the observed efficacies.

TABLE 10______________________________________ Concentration of Efficacy in active ingredient % of the in the spray mix- untreatedEx. Active ingredient ture in ppm control______________________________________54V Control (untreated) (disease level 86%) 055V B = Tab. 2A, No. 2 63 83 31 77 16 1856V C = Tab. 2A, No. 4 31 83 16 3057V IIIa = fenazaquin 125 7 63 758V IIIb = tebufenpyrad 63 059V IIIc = fenpyroxymate 125 7 63 060V IIId = pyridaben 125 7 63 0______________________________________ TABLE 11______________________________________ Concentration of active ingredient in the spray calculatedEx. mixture in ppm observed efficacy efficacy*______________________________________61 63 B 99 84 + 125 IIIa62 31 B 94 78 + 125 IIIa63 16 B 77 24 + 63 IIIa64 63 B 99 63 + 63 IIIb65 16 B 77 18 + 63 IIIb66 31 B 91 78 + 125 IIIc67 63 B 97 83 + 63 IIIc68 16 B 83 18 + 63 IIIc69 63 B 99 84 + 125 IIId70 31 B 99 79 + 125 IIId71 16 B 77 18 + 63 IIId72 31 C 100 84 + 125 IIIa73 16 C 99 35 + 63 IIIa74 16 C 88 30 + 63 IIIb75 31 C 99 84 + 125 IIIc76 16 C 88 30 + 63 IIIc77 31 C 98 83 + 125 IIId78 16 C 65 35 + 63 IIId______________________________________ *calculated using Colby's formula

The results of experiments 1-78 reveal that the observed efficacy in all mixing ratios exceeds the efficacy precalculated using colby's formula.

Claims

1. A fungicidal composition comprising

a) a carbamate I ##STR9## where T is CH or N, n is 0, 1 or 2 and R is halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -haloalkyl, it being possible for the radicals R to be different if n is 2, and

c) an acaricide III selected from the group consisting of the compounds III.a to III.d ##STR10## in a synergistically active amount.

2. The composition defined in claim 1 comprising the compound III.a.

3. The composition defined in claim 1 comprising the compound III.b.

4. The composition defined in claim 1 comprising the compound III.c.

5. The composition defined in claim 1 comprising the compound III.d.

6. The composition defined in claim 1, wherein the weight ratio of the acaricide III to the carbamate I is from 200:1 to 0.1:1.

7. The composition defined in claim 1, further comprising an oxime ether II ##STR11## wherein the substituents have the following meaning: X is oxygen or amino (NH);

Y is CH or N;

Z is oxygen, sulfur, amino (NH) or C.sub.1 -C.sub.4 -alkylamino (N-C.sub.1 -C.sub.4 -alkyl);

R' is C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -haloalkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.2 -C.sub.6 -haloalkenyl, C.sub.3 -C.sub.6 -alkynyl, C.sub.3 -C.sub.6 -haloalkynyl, C.sub.3 -C.sub.6 -cycloalkylmethyl, or benzyl which may be partially or fully halogenated and/or may carry one to three of the following radicals: cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy and C.sub.1 -C.sub.4 -alkylthio.

8. The composition defined in claim 7 comprising the compound III.a.

9. The composition defined in claim 7 comprising the compound III.b.

10. The composition defined in claim 7 comprising the compound III.c.

11. The composition defined in claim 7 comprising the compound III.d.

12. The composition defined in claim 7, wherein the weight ratio of the acaricide III to the carbamate I is from 200:1 to 0.1:1.

13. The composition defined in claim 7, wherein the weight ratio of the acaricide III to the oxime ether II is from 200:1 to 0.1:1.

14. A method for controlling harmful fungi, which comprises treating the harmful fungi, their environment, or the plants, seeds, soils, areas, materials or spaces to be kept free from said fungi with synergistically active amounts of a carbamate I and an acaricide III as set forth in claim 1.

15. The method defined in claim 14, wherein the carbamate I and the acaricide III are applied simultaneously together or separately or in succession.

16. The method defined in claim 14, wherein from 0.005 to 0.5 kg/ha of the carbamate I are applied.

17. The method defined in claim wherein from 0.1 to 10 kg/ha of the acaricide III are applied.

18. The method defined in claim 7, further comprising treating the harmful fungi, their environment, or the plants, seeds, soils, areas, materials or spaces to be kept free from said fungi with a synergistically effective amount of an oxime ether II ##STR12## wherein the substituents have the following meaning: X is oxygen or amino (NH);

Y is CH or N;

z is oxygen, sulfur, amino (NH) or C.sub.1 -C.sub.4 -alkylamino (N--C.sub.1 -C.sub.4 -alkyl);

R' is C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -haloalkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.2 -C.sub.6 -haloalkenyl, C.sub.3 -C.sub.6 -alkynyl, C.sub.3 -C.sub.6 -haloalkynyl, C.sub.3 -C.sub.6 -cycloalkylmethyl, or benzyl which may be partially or fully halogenated and/or may carry one to three of the following radicals: cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy and C.sub.1 -C.sub.4 -alkylthio.

19. The method defined in claim 18, wherein the carbamate I and the acaricide III are applied simultaneously together or separately or in succession.

20. The method defined in claim 18, wherein from 0.005 to 0.5 kg/ha of the carbamate I are applied.

21. The method defined in claim 18, wherein from 0.005 to 0.5 kg/ha of the oxime ether II are applied.

22. The method defined in claim 18, wherein from 0.1 to 10 kg/ha of the acaricide III are applied.