Furthermore, the invention relates to methods of controlling harmful fungi 
using mixtures of the compounds I and II, and to the use of the compound I 
and of the compounds II for the preparation of such mixtures. 
The compounds of the formula I, their preparation and their action against 
harmful fungi are known from the literature (WO-A 95/18,789). Also known 
are the azole derivatives II, their preparation and their action against 
harmful fungi: 
II.1: common name: bromuconazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 
5-6, 439 (1990); 
II.2: common name: cyproconazole, U.S. Pat. No. 4,664,696; 
II.3: common name: difenoconazole, GB-A 2,098,607; 
II.4: common name: diniconazole, CAS RN [83657-24-3]; 
II.5: common name (proposed): epoxiconazole, EP-A 196 038; 
II.6: common name: fenbuconazole (proposed), EP-A 251 775; 
II.7: common name: fluquinconazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 
5-3, 411 (1992); 
II.8: common name: flusilazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 1, 
413 (1984); 
II.9: common name: hexaconazole, CAS RN [79983-71-4]; 
II.10: common name: metconazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 
5-4, 419 (1992); 
II.11: common name: prochloraz, U.S. Pat. No. 3,991,071; 
II.12: common name: propiconazole, GB-A 1,522,657; 
II.13: common name: tebuconazole, U.S. Pat. No. 4,723,984; 
II.14: common name: tetraconazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 
1, 49 (1988); 
II.15: common name: triflumizole, JP-A 79/119,462 
II.16: common name: flutriafol, CAS RN [76674-21-0] 
II.17: common name: myclobutanil, CAS RN [88671-89-0]. 
With the view of reducing the rates of application and improving the 
spectrum of action of the known compounds, it was an object of the present 
invention to provide mixtures which have an improved action against 
harmful fungi combined with a reduced total amount of active ingredients 
applied (synergistic mixtures). 
Accordingly, we have found that this object is achieved by the mixtures 
defined at the outset. Moreover, we have found that, when using the 
compound I and the compounds II simultaneosuly together or separately or 
when using the compound I and the compounds II in succession, a better 
control of the harmful fungi can be achieved than with the individual 
compounds. 
R in formula I is hydrogen or a halogen atom, such as fluorine, chlorine, 
bromine and iodine, especially hydrogen, fluorine and chlorine, in 
partiuclar hydrogen or fluorine. 
Relative to the C.dbd.N double bond, the compounds of the formula I can be 
present 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, either as the pure E or Z isomer or as an E/Z isomer mixture. 
The E/Z isomer mixture or the E isomer is preferably used, the E isomer 
being especially preferred. 
The C.dbd.N double bonds of the oxime ether groups in the side chain of the 
compounds I can in each case be present as pure E or Z isomers or E/Z 
isomer mixtures. The compounds I can be used, in the mixtures according to 
the invention, as isomer mixtures, but also as pure isomers. With a view 
to their use, particularly preferred compounds I are those where both 
oxime ether groups are present in the side chain or in the E configuration 
(E/E). 
Due to the basic character of the nitrogen atoms which the compounds I and 
II contain, they are capable of forming salts or adducts 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 hydriodic 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 of 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 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 other 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, 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 be 
present at the various valency levels which they can assume. When 
providing the mixtures, it is preferred to employ the pure active 
ingredients I and II, with which other 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 desired. 
The mixtures of the compounds I and II, or the simultaneous joint or 
separate use of the compounds I and II, are distinguished by an 
outstanding action against a wide spectrum of phytopathogenic fungi, in 
particular from the classes of the Ascomycetes and Basidiomycetes. Some of 
them act systemically and can therefore also 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 cucurbits), barley, grass, oats, coffee, maize, fruit species, 
rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a large 
number of seeds. 
In particular, they are suitable for controlling the following 
phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, 
Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, 
Podosphaera leucotricha in apples, Uncinula necator in grapevines, 
Puccinia species in cereals, Rhizoctonia species in cotton, rice and 
lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis 
(scab) in apples, Helminthosporium species in cereals, Rhynosporium 
Secalis, Septoria nodorum in wheat, Botrytis cinera (gray mold) in 
strawberries and grapevines, Cercospora arachidicola in groundnuts, 
Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia 
oryzae in rice, Phytophthora infestans in potatoes and tomatoes, 
Plasmopara viticola in grapevines, Alternaria species in vegetables and 
fruit, and Fusarium and Verticillium species. 
They can furthermore be used in the protection of materials (eg. in the 
protection of wood), for example against Paecilomyces variotii. 
The compounds I and II can be applied simultaneously together or separately 
or in succession, the sequence in which they are used when being applied 
separately generally having no effect on the result of the control 
measure. 
The compounds I and II are usually used in a weight ratio of 10:1 to 0.1:1, 
preferably 10:1 to 0.2:1, in particular 5:1 to 0.2:1 (II:I). 
Depending on the nature of the desired effect, the rates of application in 
the mixtures according to the invention are, in the case of the compounds 
I, 0.005 to 0.5 kg/ha, preferably 0.005 to 0.3 kg/ha, in particular 0.01 
to 0.3 kg/ha. In the case of the compounds II, the rates of application 
are, accordingly, 0.01 to 1 kg/ha, preferably 0.05 to 1 kg/ha, in 
particular 0.05 to 0.5 kg/ha. 
The application rates generally used for seed treatment are from 0.001 to 
50 g of mixture/kg of seed, preferably 0.001 to 10 g/kg, in particular 
0.01 to 5 g/kg. 
If phytopathogenic harmful fungi ate to be controlled, the separate or 
joint application of the compounds I and II or of the mixtures of the 
compounds I and II is effected by spraying or dusting the seeds, the 
plants or the soils before or after sowing the plants or before or after 
plant emergence. 
The fungicidal synergistic mixtures according to the invention or the 
compounds I and II can be applied, 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, by means of spraying, atomizing, dusting, spreading or pouring. 
The use form depends on the intended use; in any case, it should guarantee 
as fine and uniform a distribution of the mixture according to the 
invention as possible. 
The formulations are prepared in a manner known per se, eg. by adding 
solvents and/or carriers. Inert additives, such as emulsifiers or 
dispersants, are conventionally admixed 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, 
alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol 
sulfates, and salts of sulfated hexa-, hepta- and octadecanols or of 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 
octylphenol 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 alkyl ethers or 
polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol 
esters, lignosulfite waste liquors or methylcellulose. 
Powders, materials for spreading and dusts can be prepared by mixing or 
jointly grinding of the compounds I or II or of the mixture of the 
compounds I and II with a solid carrier. 
Granules (eg. coated granules, impregnated granules or homogeneous 
granules) are conventionally prepared by binding the active ingredient, or 
active ingredients, to a solid carrier. 
Suitable fillers or solid carriers are, for example, mineral earths, such 
as silica gel, silicic acids, silica gel, silicates, talc, kaolin, 
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, 
calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic 
materials, and also 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 
powder, or other solid carriers. 
In general, the formulations comprise from 0.1 to 95% by weight, preferably 
0.5 to 90% by weight, of one of the compounds I or II or of the mixture of 
the compounds I and II. The active ingredients are employed in a purity of 
from 90% to 100%, preferably 95% to 100% (according to NMR or HPLC 
spectrum [sic]). 
The compounds I or II, or the mixtures or the formulations in question are 
used by treating the harmful fungi, or the plants, seeds, soils, areas, 
materials or spaces to be kept free from them, with a fungicidally 
effective amount of the mixture, or of the compounds I and II in the case 
of separate application. Application can be effected before or after 
infection by the harmful fungi. 
Examples of the synergistic action of the mixtures according to the 
invention against harmful fungi The fungicidal action of the compounds and 
the mixtures was demonstrated by the following experiments: 
The active ingredients were formulated separately or jointly 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 based on ethoxylated 
alkylphenols, having emulsifying and dispersing action) 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. 
The experiments were evaluated [lacuna] determining the infected leaf areas 
in percent. These percentages were transformed into degrees of action. The 
expected degrees of action of the active ingredient mixtures were 
determined by Colby's formula [R.S. Colby, Weeds 15, 20-22 (1967)] and 
compared with the observed degrees of action. 
Colby's formula: 
EQU E=x+y-x.multidot.y/100 
E expected degree of action, expressed in % of the untreated control, when 
using the mixture of the active ingredients A and B at concentrations of a 
and b 
x degree of action, expressed in % of the untreated control, when using 
active ingredient A at a concentration of a 
y degree of action, expressed in % of the untreated control, when using 
active ingredient B at a concentration of b 
If the degree of action is 0, the infection level of the treated plants 
corresponds to that of the untreated control plants; if the degree of 
action is 100, the treated plants were free from infection. 
Activity against Erysiphe graminis var. tritici (powdery mildew of wheat) 
Leaves of wheat seedlings (3-leaf stage; cultivar "Kanzler") were 
inoculated in parallel with triazole-resistant and triazole-sensitive 
powdery mildew of wheat (Erysiphe graminis var. tritici) and treated with 
the aqueous preparation of the active ingredients when the fungal 
infection had reached a level of approximately 5%. After approximately 24 
hours, the plants were dusted with spores of [lacuna]. The plants treated 
in this manner were subsequently incubated for 20 days at 18-22.degree. C. 
The extent of fungal development was then determined. 
The test results are compiled in the tables which follow: 
Activity of the active ingredients when applied separately 
(triazole-resistant): 
______________________________________ 
Rate of Degree of action 
Active ingredient application [%] [%] 
______________________________________ 
I.1 (R = H) 0.05 2 
I.2 (R = F) 0.05 7 
II.5 0.05 2 
untreated control --/-- 0 
______________________________________ 
Activity of the synergistic mixtures according to the invention 
(triazole-resistant) 
______________________________________ 
Synergistic mixture Degree of 
Active action 
ingredients [%] Ratio observed 
______________________________________ 
I.1 + II.5 
0.03 + 0.01 3/1 15 
I.2 + II.5 0.03 + 0.01 3/1 21 
______________________________________ 
Activity of the active ingredients when applied separately 
(triazole-sensitive) 
______________________________________ 
Rate of Degree of action 
Active ingredient application [%] [%] 
______________________________________ 
I.1 (R = H) 0.05 1 
I.2 (R = F) 0.05 4 
II.5 0.05 1 
untreated control --/-- 0 
______________________________________ 
Activity of the synergistic mixtures according to the invention 
(triazole-sensitive) 
______________________________________ 
Synergistic mixture 
Active Degree of action 
ingredients 
[%] Ratio observed 
calculated 
______________________________________ 
I.1 + II.5 
0.03 + 0.01 
3/1 15 1.99 
I.2 + II.5 0.03 + 0.01 3/1 21 4.96 
______________________________________