Note: Descriptions are shown in the official language in which they were submitted.
CA 02289677 1999-11-15
VV,/Vl '~V Vi. I
Fungicidal mixture
The present invention relates to a fungicidal mixture which
comprises
a) a phenyl benzyl ether derivative of the formula I.a, I.b or
I.c,
CH3 ~ CH3 \
/ ~. O I /
/ H3C0 ~ N/ OCH3 I / H3C N ~ N/ OCH3
I
La O CH3 Lb O
CH3 \
\ o ~ /
H3C / OCH3
I ~N
CH3 Lc O
and
b) a carboxamide II selected from the group of the compounds
IIa and IIb
CI
O
C= CH-C-N O (ila)
U
CH30 OCH3
O
ii CH3
~ CH2CH3
(11b)
CH30 OCH3
in a synergistically effective amount.
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Moreover, the invention relates to methods for controlling
harmful fungi using mixtures of the compounds I (I.a, I.b or
I.c) and II (II.a or II.b) and to the use of the compound I and
of the compound II for the preparation of such mixtures.
The compounds of the formula I, their preparation and their
activity against harmful fungi are disclosed in the literature
(EP-A 253 213; EP-A 254 426; EP-A 398 692).
Also disclosed are the carboxamides II [IIa: common name:
Dimethomorph, EP-A 120 321; IIb: proposed common name:
Flumetover, AGROW No. 243 (1995), 22), their preparation and
their 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
rates and to improving the activity spectrum of the known
compounds.
We have found that this object is achieved by the mixtures
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 together or separately, or by
applying the compounds I and the compounds II in succession than
when the individual compounds are used.
Owing to the basic character, the compounds I and 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
hydroiodic 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
CA 02289677 1999-11-15
vu.rvi ~uur ~
3
and naphthyl, which carry one or two sulfo groups),
alkylphosphonic acids (phosphoric 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, 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. Particular preference is given to the metal ions of the
elements of the sub-groups of the fourth period. The metals can
exist in the various valencies which they can assume.
When preparing the mixtures, it is preferred to employ the pure
active ingredients I and II, to 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 mixed, if so required.
The mixtures of the compounds I and II, or the simultaneous
joint or separate use of the compounds T 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 folio- 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, tomatoes, potatoes and
cucurbits), barley, grass, oats, bananas, coffee, maize, fruit
species, rice, rye, Soya, grapevine, wheat, ornamentals,
sugarcane, and a variety of seeds.
They are particularly suitable for controlling the following
phytophathogenic fungi: Erysiphe graminis (powdery mildew) on
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
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sugarcane, 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 ground
nuts, Pseudocercosporella herpotrichoides in wheat and barley,
Pyricularia oryzae in rice, Phytophthora infestans in potatoes
and tomatoes, Plasmopara viticola in grapevines,
Pseudocercosporella species in hops and cucumbers, Alternaria
species in vegetables and fruit, Mycosphaerella species in
bananas 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 II can be applied simultaneously, either
together. or separately, or in succession, the sequence, in the
case of separate application, generally not having an effect on
the result of the control measures.
The compounds I and II are usually used in a weight ratio of
20:1 to 0.005:1, preferably 10:1 to 0.01:1, in particular
5:1 to 0.2:1.
30
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 0.5 to 3.0 kg/ha.
Application rates of the compounds I are from 0.01 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 the compounds II, the
application rates are from 0.005 to 1 kg/ha, preferably 0.1 bis
0.5 kg/ha, in particular 0.1 to 0.3 kg/ha.
For seed treatment, the application rates of the 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 fungi are to be controlled, the separate or
joined application of the compounds I and II or of the mixtures
of the compounds I and II is affected by spraying or dusting the
CA 02289677 2006-07-31
seeds, the plants or the soils before the sowing of the plants,
or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention,
5 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 as 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
formlations~.
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 ethers, alkylaryl polyether alcohols, isotridecyl
alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated
castor oil, polyoxyethylene alkyl ether 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 jointly grinding the compounds I or II or the mixture
of the compounds I and II with a solid carrier.
Granules (eg. coated granules, impregnated granules or
homogeneous granules) are usually prepared by binding the active
ingredient, or active ingredients, to a solid carrier.
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Fillers or solid carriers are, for example, mineral earths, such
as silica gel, silicic acids, 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 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).
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 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.
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~ strength emulsion in a mixture of 63~ by weight of
c:yclohexanone and 27~ by weight of emulsifier, and diluted with
water to the desired concentration.
Use example 1 - activity against Phytophthora infestans on
tomatoes
Leaves of potted plants of the cultivar "Grolie Fleischtomate"
were sprayed to runoff point with an aqueous suspension made
from a stock solution of 10~ of active compound, 63$ of
cyclohexanone and 27~ of emulsifier. The next day, the leaves
were infected with an aqueous zoospore suspension of
Phytophthora infestans. The plants were subsequently placed in a
water-vapor-saturated chamber at 16-18~C. After 6 days, the
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tomato blight on the untreated, but infected control plants had
developed to such an extent that the infection could be
determined visually in $.
Evaluation was carried out by determining the infected leaf
areas in percent. These percentages were converted into
efficacies. The efficacy (E) was calculated as follows using
Abbot's formula:
E=(1-a/(3)~100
a corresponds to the fungal infection of the treated plants in
~ and
15 ~ corresponds to the fungal infection of the untreated
(control) plants in $
An efficacy of 0 means that the infection level of the treated
20 plants corresponds to that of the untreated control plants; an
efficacy of 100 means that the treated plants were not infected.
The expected efficacy of the mixtures of the active ingredients
were determined using Colby's formula [R.S. Colby, Weeds 15,
25 20-22 (1967)] and compared with the observed efficacies.
Colby's formula: E = x + y - x~y/100
30 E expected efficacy, expressed in ~ of the untreated control,
when using the mixture of the active ingredients A and B at
the concentrations of a and b
x efficacy, expressed in $ of the untreated control, when
using active ingredient A at a concentration of a
35 y efficacy, expressed in ~ of the untreated control, when
using active ingredient B at a concentration of b
The test results are shown in Tables 2 and 3 below.
CA 02289677 1999-11-15
"...."~ -~.,"....
Table 2
8
Ex. Active ingredient Concentration Efficacy in ~ of
of
active ingredientthe untreated con-
s in the spray trol
liquor in ppm
1 C Control (100 infection) 0
(untreated)
2 C :La 1.25 20
0.31 p
3 C Ib 0.08 0
4 C IIa = dimethomorph1.25 80
0.31 40
0.08 40
155 C IIb = flumetover 1.25 10
0.31 0
0.08 0
Table 3
Mixtures according Observed Calculated
to the invention efficacy efficacy*)
1.25 ppm I:a 95 84
1,25 ppm IIa
(mixture 1 . 1)
0.31 ppm Ia 70 40
0.31 ppm IIa
30(mixture 1 . 1)
1.25 ppm Ia 75 28
1.25 ppm IIb
(mixture 1 . 1)
350.31 ppm Ia 40 0
0.31 ppm IIb
(Mischung 1 . 1)
0.08 ppm Ib 90 76
400.08 ppm ITa)
(mixture 1 . 1)
0.08 ppm Ib 95 60
0.08 ppm IIb
(mixture 1 . 1)
45
*:~
calculated
using
Colby's
formula
. CA 02289677 1999-11-15
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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.
10
20
30
40
