Fungicidal agents

A synergistic fungicidal composition comprising a fungicidally effective amount of PA0 (a) 1-(4-phenyl-phenoxy)-1-(1,2,4-triazol-1-yl)-3,3-dimethyl-butan-2-ol of the formula ##STR1## (b) plus another fungicidally active derivative of 1,2,4-triazole of the formula ##STR2## in which A is the keto group of the CH(OH) group.

The present invention relates to new fungicidal synergistic active compound 
combinations of (a) the known compound 
1-(4-phenyl-phenoxy)-1-(1,2,4-triazol-1-yl)-3,3-dimethyl-butan-2-ol and 
(b) the other known fungicidally active derivatives of 1,2,4-triazole. 
It is already generally known that mixtures containing 1,2,4-triazole 
derivatives, such as, for example, 
1-(4-chloro-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone, in 
combination with other known fungicides have a considerably higher action 
than the individual components (compare, for example, German 
Offenlegungsschrift (German Published Specification) 2,552,967. However, 
the activity of these active compound mixtures is not always completely 
satisfactory in all areas of use. 
It has now been found that new specific active compound combinations of 
(a) 1-(4-phenyl-phenoxy)-1-(1,2,4-triazol-1-yl)-3,3-dimethyl-butan-2-ol of 
the formula 
##STR3## 
and (b) other fungicidally active derivatives of 1,2,4-triazole having 
the formula 
##STR4## 
in which A represents the keto group or the CH(OH) group, have a 
particularly high fungicidal activity. 
Surprisingly, the fungicidal action of the active compound combinations 
according to the invention is considerably higher than the action of the 
individual components and also than the sum of the individual components 
(synergistic effect). In particular, the expert could not predict that a 
mixture containing the active compound of the formula (I) and active 
compounds of the formula (II) having a very similar structure has a 
synergistic effect. The discovery of this specific combination represents 
a valuable enrichment of the art. 
The above formulae (I) and (II) provide definitions of the active compounds 
to be used for the specific combinations according to the invention. These 
are the following compounds: 
(I): short name BITERTANOL 
(IIa): A=CO; short name TRIADIMEFON 
(IIb): A=CH(OH); short name TRIADIMENOL 
The compounds mentioned are generally known (in this context, compare 
German Patent Specifications 2,201,063 and 2,324,010 and the corresponding 
U.S. Pat. Nos. 3,912,752 and 3,952,002). 
Other active compounds can also be added (for example as a third component) 
to an active compound combination of the active compound of the formula 
(I) and the active compounds of the formula (II). 
The weight ratios of the groups of active compounds in the active compound 
combinations can vary within relatively wide limits. In general, 0.001 to 
50 parts by weight of active compound of the formula (II), preferably 0.01 
to 20 parts by weight of the latter and particularly preferably 0.1 to 10 
parts by weight, are present per part by weight of active compound of the 
formula (I). 
The active compounds according to the invention exhibit a powerful 
microbicidal action and can be employed in practice for combating 
undesired micro-organisms. The active compounds are suitable for use as 
plant protection agents. 
Fungicidal agents in plant protection are employed for combating 
Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, 
Ascomycetes, Basidiomycetes and Deuteromycetes. 
The good toleration, by plants, of the active compounds in the 
concentrations required for combating plant diseases permits treatment of 
above-ground parts of plants, of vegetative propagation stock and seeds 
and of the soil. 
The active compound combinations according to the invention have a very 
broad action spectrum and can be used against parasitic fungi which affect 
the above-ground parts of plants or attack the plants from the soil, as 
well as seed-borne causative organisms. Such active compound combinations 
have particularly practical imporatnce as seed dressing agents against 
phytophatogenic fungi which are transferred with the seed or occur in the 
soil and attack the crop plants from there. The diseases in question are 
damping off diseases, root rot and diseases of the stalk, stem, leaf, 
blossom, fruit and seed, which are caused, in particular, by species of 
Tilletia, Urocystis, Ustilago, Septoria, Typhula, Rhynchosporium, 
Helminthosporium and Fusarium. As a result of the systemic action of the 
partners in the mixture, the plants are frequently still protected, for a 
relatively long time after dressing, from causative organisms which can 
attack various parts of the shoot, for example powdery mildew fungi and 
rust fungi. In addition, the active compound combinations can also be used 
as soil treatment agents against phytopathogenic fungi, and they act 
against root rot and tracheomycoses, which are caused, for example, by 
causative organisms of the genera Pythium, Verticillium, Phialophora, 
Rhizoctonia, Fusarium and Thielaviopsis. 
However, when applied directly to the above-ground parts of plants, the 
active compound combinations according to the invention also exhibit an 
outstanding action against causative organisms on various crop plants, 
such as powdery mildew fungi (species of Erysiphe, Uncinula, Sphaerotheca 
and Podosphaera, and Leveillula taurica), rust fungi, Venturia species, 
Cercospora species, Alternaria species, Botrytis species, Phytophthora 
species, Peronospora species, Pyricularia oryzae and Pellicularia sasakii. 
The active compounds can be converted to the customary formulations, such 
as solutions, emulsions, suspensions, powders, foams, pastes, granules, 
aerosols, natural and synthetic materials impregnated with active 
compound, very fine capsules in polymeric substances and in coating 
compositions for seed, and formulations used with burning equipment, such 
as fumigating cartridges, fumigating cans, fumigating coils and the like, 
as well as ULV cold mist and warm mist formulations. 
These formulations are produced in a known manner, for example by mixing 
the active compounds with extenders, that is, liquid solvents, liquefied 
gases under pressure, and/or solid carriers, optionally with the use of 
surface-active agents, that is, emulsifying agents and/or dispersing 
agents, and/or foam-forming agents. In the case of the use of water as an 
extender, organic solvents can, for example, also be used as auxiliary 
solvents. As liquid solvents, there are suitable in the main: aromatics, 
such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or 
chlorinated aliphatic hydrocarbons, such as chlorobenzenes, 
chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as 
cyclohexane or paraffins, for example mineral oil fractions, alcohols, 
such as butanol or glycol as well as their ethers and esters, ketones, 
such as acetone, methyl ethyl ketone, methyl isobutyl ketone or 
cyclohexanone, strongly polar solvents, such as dimethylformamide and 
dimethylsulphoxide, as well as water; by liquefied gaseous extenders or 
carriers are meant liquids which are gasesous at normal temperature and 
under normal pressure, for example aerosol propellants, such as 
halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon 
dioxide; as solid carriers there are suitable: for example ground natural 
minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, 
montmorillonite or diatomaceous earth, and ground synthetic minerals, such 
as highly-dispersed silicic acid, alumina and silicates; as solid carriers 
for granules there are suitable: for example crushed and fractionated 
natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as 
well as synthetic granules of inorganic and organic meals, and granules of 
organic material such as sawdust, coconut shells, corn cobs and tobacco 
stalks; as emulsifying and/or foam-forming agents there are suitable: for 
example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty 
acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl 
polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as 
well as albumin hydrolysis products; as dispersing agents there are 
suitable: for example lignin-sulphite waste liquors and methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulations. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, 
and trace nutrients such as salts of iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. 
The formulations in general contain between 0.1 and 95 percent by weight 
of active compound, preferably between 0.5 and 90%. 
The active compounds according to the invention can be present in the 
formulations or in the various use forms as a mixture with other known 
active compounds, such as fungicides, bactericides, insecticides, 
acaricides, nematicides, herbicides, bird repellents, growth factors, 
plant nutrients and agents for improving soil structure. 
The active compounds can be used as such or in the form of their 
formulations or the use forms prepared therefrom by further dilution, such 
as ready-to-use solutions, emulsions, suspensions, powders, pastes and 
granules. They are used in the customary manner, for example by watering, 
immersion, spraying, atomizing, misting, vaporizing, injecting, foaming, 
brushing on, dusting, scattering, dry dressing, moist dressing, wet 
dressing, slurry dressing or encrusting. 
In the treatment of parts of plants, the active compound concentrations in 
the use forms can be varied within a substantial range. They are, in 
general, between 1 and 0.0001 percent by weight, preferably between 0.5 
and 0.001%. 
In the treatment of seed, amounts of active compound of 0.001 to 50 g per 
kilogram of seed, preferably 0.01 to 10 g, are generally required. 
For the treatment of soil, active compound concentrations of 0.00001 to 
0.1% by weight, preferably 0.0001 to 0.02%, are required at the place of 
action.

The Use Examples which follow are for illustration. 
EXAMPLE A 
Venturia test (apple)/protective 
Solvent: 4.7 parts by weight of acetone 
Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. 
To test for protective activity, young plants are sprayed with the 
preparation of active compound until dripping wet. After the spray coating 
has dried on, the plants are inoculated with an aqueous conidia suspension 
of the apple scab causative organism (Venturia inaequalis) and then remain 
in an incubation cabinet at 20.degree. C. and 100% relative atmospheric 
humidity for 1 day. 
The plants are then placed in a greenhouse at 20.degree. C. and a relative 
atmospheric humidity of about 70%. 
Evaluation is carried out 12 days after the inoculation. 
TABLE A 
______________________________________ 
Venturia test (apple)/protective 
Infestation in % at 
an active compound 
Active compound concentration of 
______________________________________ 
BITERTANOL (I) 0.0001% 62 
(known) 
TRIADIMEFON (IIa) 0.000012% 72 
(known) 
Mixture of (I) and (IIa) 
0.0001% 30 
(mixing ratio 1:0.12) 
+0.000012% 
______________________________________ 
EXAMPLE B 
Drechslera graminea test (barley)/seed treatment (syn. Helminthosporium 
gramineum) 
The active compounds are used as dry dressings. These are prepared by 
extending the particular active compound with a ground mineral to give a 
finely pulverulent mixture, which ensures uniform distribution on the seed 
surface. 
To apply the dressing, the infected seed is shaken with the dressing in a 
closed glass flask for 3 minutes. 
The seed is embedded in sieved, moist standard soil and is exposed to a 
temperature of 4.degree. C. in closed Petri dishes in a refrigerator for 
10 days. Germination of the barley, and possibly also of the fungus 
spores, is thereby initiated. 2 batches of 50 grains of the pregerminated 
barley are subsequently sown 3 cm deep in standard soil and are cultivated 
in a greenhouse at a temperature of about 18.degree. C., in seedboxes 
which are exposed to light for 15 hours daily. 
About 3 weeks after sowing, the plants are evaluated for symptoms of stripe 
disease. 
TABLE B 
______________________________________ 
Drechslera graminea test (barley)/seed treatment 
(syn. Helminthosporium gramineum) 
Amount of 
active com- 
pound 
applied in Diseased plants in % 
mg/kg of of the total plants 
Active compound 
seed emerged 
______________________________________ 
No dressing -- 28.8 
BITERTANOL (I) 
500 11.1 
(known) 
TRIADIMENOL (IIb) 
200 12.3 
(known) 
Mixture of (I) and 
500 0.0 
(IIb) 
(mixing ratio 2.5:1) 
+200 
______________________________________ 
It is understood that the specification and examples are illustrative but 
not limitative of the present invention and that other embodiments within 
the spirit and scope of the invention will suggest themselves to those 
skilled in the art.