Note: Descriptions are shown in the official language in which they were submitted.
CA 02290519 1999-11-16
0050/48028
Fungicidal mixture
The present invention relates to a fungicidal mixture which
comprises
a) a phenyl benzyl ether derivative of the formula I.a or I.b
CH3 CH3
O \ O
H3CO \ N, OCH3 I/ H3CO OCH3
I.a O CH3 Lb O
and
b) ( )-(2-chlorophenyl)(4-chlorophenyl)(pyrimidin-5-yl)methanol
CI
OH CI
i" II
N~N
in a synergistically effective amount.
Moreover, the invention relates to methods for controlling
harmful fungi using mixtures of the compounds I(I.a and I.b)
and II and to the use of the compounds I and II for the
preparation of such mixtures.
The compounds I, their preparation and their activity against
harmful fungi are disclosed in the literature (EP-A 253 213,
EP-A 254 426).
Also disclosed is the compound II (GB-A 1,218,623; common name:
Fenarimol), its preparation and its activity against harmful
fungi.
It is an object of the present invention to provide mixtures
which have an improved activity against harmful fungi combined
with a reduced total amount of active ingredients applied
(synergistic mixtures), with a view to reducing the application
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rates and to improving the activity spectrum of the known
compounds.
We have found that this object is achieved by the mixture
defined at the outset. Moreover, we have found that better
control of harmful fungi is possible by applying the compound I
and the compound II simultaneously, either together or
separately, or by applying the compound I and the compounds II
in succession then when the individual compounds are used on
their own.
Owing to their basic character, the compounds I and the compound
II 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, and furthermore 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 aryldisulfonic acids (aromatic radicals, such as phenyl
and naphthyl, which carry 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 aryldiphosphonic acids (aromatic radicals, such as
phenyl and naphthyl, which carry one or two phosphoric acid
radicals), it being possible for the alkyl or aryl radicals to
carry further substituents, e.g. 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. Particular preference is given to the metal ions of the
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elements of the sub-groups of the fourth period. The metals can
exist in the various valences which they can assume.
When preparing the mixtures, it is preferred to employ pure
active ingredients I and II, to which further active ingredients
against harmful fungi of other pests, such as insects, arachnids
or nematodes, or else herbicidal or growth-regulating active
ingredients or fertilizers can be admixed, if so required.
The mixtures of compounds I and II, or the simultaneous joint or
separate use of the compounds I and II, exhibit outstanding
activity against a wide range of phytopathogenic fungi, in
particular from the classes of the Ascomycetes, Basidiomycetes,
Phycomycetes and Deuteromycetes. 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 (e.g. cucumbers, beans, tomatoes, potatoes and
cucurbits), barley, grass, oats, bananas, coffee, maize, fruit
species, rice, rye, soya, grapevine, wheat, ornamentals, sugar
cane, and a variety of seeds.
They are oarticularly 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, Septoria nodorum in wheat, Botrytis cinera
(gray mold) in strawberries, vegetables, ornamentals 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,
Pseudoperonospora species in hops and cucumbers, Alternaria
species in vegetables and fruit, Mycosphaerella species in
bananas and Fusarium and Verticillium species.
Furthermore, it can be used in the production of materials (e.g.
in the protection of wood), for example against Paecilomyces
variotii.
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The compounds I and II can be applied simultaneously, either
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 II are usually used in a weight ratio of
10:1 to 0.1:1, preferably 5:1 to 0.2:1, in particular 3:1 to
0.3:1.
Depending on the kind of effect desired, the application rates
of the mixtures according to the invention are, in particular in
agricultural crops, from 0.01 to 8 kg/ha, preferably 0.1 to
5 kg/ha, in particular 0.2 to 3.0 kg/ha.
The application rates of the compounds I are from 0.005 to
0.5 kg/ha, preferably 0.05 to 0.5 kg/ha, in particular 0.05 to
0.3 kg/ha.
Correspondingly, in the case of compounds II, the application
rates are from 0.05 to 0.5 kg/ha, preferably 0.1 to 0.5 kg/ha,
in particular 0.1 to 0.3 kg/ha.
For seed treatment, the application rates of mixture are
generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100
g/kg, in particular 0.01 to 50 g/kg.
If phytopathogenic harmful fungi are 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 of the plants, or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention,
or the compounds I and II, 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 broadcasting or granules, and applied by
spraying, atomizing, dusting, broadcasting or watering. 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.
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The formulations are prepared in a manner known per se, e.g. by
adding solvents and/or carriers. It is usual to admix inert
additives, such as emulsifiers or dispersants, with the
formulations.
5
Suitable surfactants are the alkali metal salts, alkaline earth
metal salts and ammonium salts of aromatic sulfonic acids, e.g.
lignin-, 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 octyl phenol ether, ethoxylated isooctyl-,
octyl- or nonylphenol, alkylphenol polyglycol ethers,
tributylphenyl polyglycol ethers, alkylaryl polyether alcohols,
isotridecyl alcohol, fatty alcohols/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 broadcasting and dusts can be prepared by
mixing or joir-t grinding of the compounds I or II or the mixture
of the compounds I and II with a solid carrier.
Granules (e.g. coated granules, impregnated granules or
homogeneous granules) are usually 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, silica gels, 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 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 spectrum or HPLC).
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The compounds I or II, or the mixtures, or the corresponding
formulations, are applied by treating the harmful fungi, their
habitat, 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 II in the case of
separate application.
Application can be effected before or after infection by the
harmful fungi.
Use example
The synergistic activity of the mixtures according to the
invention was demonstrated by the following experiments:
The active ingredients, separately or together, were formulated
as a 10% emulsion in a mixture of 63% by weight of cyclohexanone
and 27% by weight of emulsifier, and diluted with water to a
desired concentration.
Use example 1 - Activity against Puccinia recondita on wheat
(wheat leaf rust)
Leaves of potted wheat seedlings of the variety "Fruhgold" were
dusted with spores of the wheat leaf rust (Puccinia recondita).
Thereafter, the pots were kept in a chamber of high atmospheric
humidity (90 to 95%) and 20 to 22 C for 24 hours. During this
time, the spores germinated and the germ tubes penetrated into
the leaf tissue. The next day, the infected plants were sprayed
to runoff point with an aqueous preparation of active ingredient
which had been prepared from a stock solution comprising 10% of
active compound, 63% of cyclohexanone and 27% of emulsifier.
After the spraycoating had dried on, the test plants were
cultivated for 7 days in a greenhouse at 20-22 C and 65-70%
relative atmospheric humidity. Thereafter, the extent of the
rust fungus development on the leaves was determined.
Evaluation was carried out by determining the infected leaf
areas in percent. These percentages were converted into
efficacies. The efficacy (K) was calculated as follows using
Abbot's formula:
E=(1-a/p)=100
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a corresponds to the fungal infection of the treated plants in
% and
corresponds to 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 were not infected.
The expected efficacies of the mixtures of the active
ingredients were determined using Colby's formula [R.S. Colby,
Weeds ]j,.5, 20-22 (1967)] and compared with the observed
efficacies.
Colby's formula: E= x + y - x=y/l00
E expected efficacy, expressed in % of the untreated control,
when using the mixture of the active ingredients A and B at
the concentrations 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 results are shown in Tables 2 and 3 below.
Table 2
Ex. Active ingredient Concentration of Efficacy in % of
active ingredient the untreated
in the spray control
liquor in ppm
1 C Control (100% infection) 0
(untreated)
2 C Ia 200 20
100 20
50 0
3 C II 20 0
10 0
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Table 3
Ex. Mixtures Observed Calculated
according to efficacy efficacy*)
the invention
4 200 ppm Ia 65 20
+
20 ppm II
(mixture 10:1)
5 100 ppm Ia 70 20
+
ppm II
(mixture 5:1)
6 50 ppm Ia 35 0
15 10 ppm Ib
(mixture 5:1)
*) calculated using Colby's formula
20 The test results show that the observed efficacy in all mixing
ratios is higher than the efficacy which had been calculated
beforehand using Colby's formula.
