Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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30517-124D
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Plant Protection Agents
This application is a divisional application of copending application
2,274,654, filed
December 11, 1997.
The present invention relates to new plant-protecting active ingredient
mixtures having
synergistically increased activity, containing at least two active ingredient
components, and
a process for the application of such mixtures in plant protection, especially
in the control
and prevention of disease outbreaks.
Component I is the compound
2-[a-{[(a-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl] -glyoxylic acid-
methylester-O-
methyloxime, (EP-A-460,575); and
component i1 is a compound selected from the group
IlA) 5,7-dichloro-4-(4-fluorophenoxy)quinoline ("Quinoxyfen"), (EP-A-326,330);
IIB) 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine ("Cyprodinil") (The
Pesticide Manual,
10th. edition, 1994, 109);
IIC) benzo(1,2,3)thiadiazoie-7-carbothio-acid-S-methylester ("Acibenzolar-S-
methyl") (EP-A-
313,512);
IID) 3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione
("Famoxadone") (EP-
A-393,911 );
IIE) 8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-
methanamine
("Spiroxamin") (EP-A-281,842);
IIF) 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile
("Fludioxonil") (The Pesticide
Manual, 10th. edition, 1994, 326);
IIG) 4-(2,3-dichlorophenyl)pyrrole-3-carbonitrile ("Fenpiclonil") (The
Pesticide Manual, 10th.
edition, 1994, 302);
IIH) 1-methyl-cyclohexanecarboxylic acid-(2,3-dichloro-4-hydroxy-phenyl)-amide
("Fenhexamid") (EP-A-339,418);
I1J) 2-{2-[6-(2-cyano-phenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxy-acrylic
acid methyl
ester ("Azoxystrobin") (EP-A-382,375);
IIK) Methoximino-(2-o-tolyloxymethyl-phenyl)-acetic acid methyl ester
("Kresoxim-methyl")
(EP-A-398,692);
or repectively one of the salts or metal complexes of components I and II.
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Ii has now surprisingly been shown that the mixtures of components I and Ii
according to the
invention display not only additive action, but significant synergistically
increased action in the
prevention and control of plant diseases.
Favourable mixture ratios of the two active ingredients are !:II = 20:1 to
1:20, preferably I:I! _
10:1to1:10,6:1to1:6,2:1to1:10and10:1to1:2.
T he active ingredient mixtures I+II according to the invention have very
advantageous
properties in the protection of plants against the outbreaE; of disease.
In addition, mixtures with compound Ilc can activate the defence system, which
is latent in the
plant, against pathogenic microbial influences and can thus protect the plant
by immunisation.
With the present active ingredient mixtures, the microorganisms appearing on
plants ar plant
parts (fruits, flowers, foliage, stems, tubers, roots) of different useful
plants can be stooped or
destroyed, whereby plant parts growing later also remain free from such
microorganisms. They
may also be used as dressings for the treatment of plant propagation material,
especially
seeds (fruits, tubers, seed grain) and plant cuttings (e.g. rice) to provide
protection from fungal
infections, and against phytopathogenic fungi appearing in the soil. The
active ingredient
mixtures according to the invention are notable for their especially good
plant toleran;;e and
their environmental acceptability.
The active ingredient mixtures according to the invention are effective
against the following
classes of related phytopathogenic fungi: ascomycetes (e.g. Venfuria,
Podasphaera, Erysiphe,
Monilinia, Mycosphaerella, UncinulaJ; basidiomycetes (e.g. the genus Hemileia,
Rhi~octonia,
Puccinia); Fungi imperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporium,
Fusarium,
Septoria, Cercospora, Alternaria, Pyricularia and in particular
Pseudocercosporella
herpotrichoides); oomycetes (e.g. Phytophthora, Peronospora, Hremia, Pythium,
Plasmopara).
Target crops for the indicated fields disclosed herein are, within the context
of this invention,
e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice,
sorghum and the
like); beets: (sugar beet and fodder beet); pip, stone and berry fruit:
(apples, pears, plums,
peaches, almonds, cherries, strawberries, raspberries and blackberries);
leguminous plants:
(beans, lentils, peas, soybeans); oil plants: (rape, mustard, poppy, olives,
sunflowers, coconut,
castor oil plant, cacao, peanut); cucumber plants (gourds, cucumbers, melons);
fibre plants:
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(cotton, flax, hemp, jute); citrus fruits: (oranges, lemons, grapefruit,
mandarins); vegetable
varieties (spinach, lettuce, asparagus, cabbage varieties, carrots, onions,
tomatoes, potatoes,
peppers); Lauraceae: (avocado, cinnamon, camphor) or plants such as maize,
tobacco, nuts,
coffee, sugar cane, tea, grapevines, hops, banana and natural rubber plants,
as well as
ornamental plants (flowers, shrubs, deciduous trees and coniferous trees such
as conifers).
This is not intended to be a limiting list of plants.
The active ingredient mixtures according to the invention are especially
advantageous for the
following applications:
1+IIA: for cereals and vines;
I+IIB: for cereals, particularly wheat and barley, also for vines, vegetables
and fruit;
I+IIC: for cereals;
I+IID: for vines;
I+IIE: for cereals;
I+IIF: for cereals, particularly wheat and barley, also for vines and
vegetables;
I+IIG: for treatment of seeds;
I+IIH: for vegetables and vines;
I+IIJ: for cereals and vines;
I+IIK: for cereals, particularly for wheat and barley.
The active ingredient mixtures of formulae I and II are normally employed in
the form of
compositions. The active ingredients of formulae I and II may be applied to
the area or plants
to be treated either simultaneously or in succession on the same day, together
with further
optional fillers, surfactants or other application-enhancing additives which
are customary in
formulation techniques.
Appropriate fillers and additives may be solid or liquid, and correspond to
the substances
which are efficient in formulation techniques, e.g. natural or regenerated
mineral substances,
solvents, dispersants, wetting agents, adhesion agents, thickeners, binding
agents or
fertilisers.
A preferred method of applying an active ingredient mixture containing at
least one of each of
these active ingredients I and II is application to the parts of the plant
above ground, especially
the leaf system (leaf application). The number of applications and application
rate depend on
the biological and climatic living conditions of the instigator. However, the
active ingredients
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may also reach the plant through the root system (systemic action) via the
soil or the water,
whereby the plant site is drenched with a liquid formulation (e.g. in rice
cultivation) or the
substances are incorporated into the soil in solid form, e.g. in the form of
granules (soil
application). The compounds of formulae I and II may also be applied to seed
grain in a seed
treatment (coating), whereby the tubers or grains are either immersed in
succession with a
liquid formulation of each active ingredient, or are coated with an already
combined, wet or dry
formulation. In addition, in particular cases, further types of plant
application are possible, e.g.
the targeted treatment of buds or syncarpy. Here, the compounds of the
combination are used
in unchanged form or preferably together with excipients which are usual in
formulation
techniques, and they are processed in known manner e.g. into emulsion
concentrates,
coatable pastes, directly sprayable or diluable solutions, diluted emulsions,
wettable powders,
soluble powders, dusts, granules, or by encapsulation into, for example,
polymeric substances.
The application methods, such as spraying, misting, dusting, dispersing,
coating or drenching,
are selected according to the targeted aims and the given conditions, in the
same way as for
selection of the type of agent. Favourable application rates for the active
ingredient mixture are
in general 50 g to 2 kg active substance per ha, especially 100 g to 700 g
active substance per
ha, most preferably 75 g to 450 g active substance per ha. For the treatment
of seeds, the
application rates are 0.5 g - 600 g, preferably 5 g - 80 g active substance
per 100 kg seeds.
The formulations are produced in known manner, e.g. by intimately mixing
and/or grinding the
active ingredients with diluting agents, e.g. solvents, solid fillers, and
optionally surface-active
compounds (surfactants).
The solvents in question may be: aromatic hydrocarbons, preferably fractions C
8 to C,2, such
as xylene mixtures or substituted naphthalenes, phthalic acid esters such as
dibutyl or dioctyl
phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols
and glycols, as
well as the ethers and esters thereof, such as ethanol, ethylene glycol,
ethylene glycol
monomethyl ether or monoethyl ether, ketones such as cyclohexanone, strongly
polar solvents
such as N-methyl-2-pyrrolidone, dimethyl sulphoxide or dimethyl formamide, as
well as
optionally epoxidated vegetable oils such as epoxidated coconut oil or soybean
oil; or water.
The solid fillers, e.g. for dusting agents and dispersible powders, are
normally natural mineral
powder, such as calcitol, talcum, kaolin, montmorillonite or attapulgite. To
improve the physical
properties, highly disperse silicic acid or highly disperse, absorbent
polymerisates may also be
added. The granulated, adsorptive granulate fillers may be porous types such
as pumice
stone, brick fragments, sepiolite or bentonite, and non-sorptive fillers are
e.g. calcitol or sand.
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Furthermore, a number of pregranulated materials of inorganic or organic
nature may also be
used, especially dolomite or pulverised plant residues.
Depending on the type of active ingredients of formulae I and II to be
formulated, the surface-
active compounds may be non-ionic, cationic andlor anionic surtactants with
good emulsifying,
dispersing and wetting properties. By surfactants are also understood
surfactant mixtures.
Especially advantageous, application-enhancing admixtures are also natural or
synthetic
phospholipids from the series cephalins and lecithins, e.g.
phosphatidylethanolamine,
phosphatidylserine, phosphatidylglycerol, lysollecithin.
The agrochemical compositions normally contain 0.1 to 99%, especially 0.1 to
95% active
ingredients of formulae I and II, 99.9 to 1 %, especially 99.9 to 5% of a
solid or liquid additive
and 0 to 25%, especially 0.1 to 25% of a surfactant.
While concentrated formulations are preferred as commercial products, the
final user normally
uses diluted formulations.
The following examples serve to illustrate the invention, whereby "active
ingredient" indicates
a mixture of compound I and compound II in a certain mixture ratio.
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Formulation Examples
Wettablepowder a) b) c)
active ingredient [1:1I = 1:3(a),25 50 % 75
1:2(b), 1:1 (c)] %
Na ligninsulphonate 5 % 5 % -
Na laurylsulphate 3 % - 5
Na diisobutylnaphthalenesulphonate- 6 % 10
octylphenol-polyethylene-glycol-ether- 2 % -
(7-8 mots ethylene oxide)
highly disperse silicic acid 5 % 10 % 10
kaolin 62 27 % -
%
The active ingredient is mixed well with the additives and ground thoroughly
in an appropriate
mill. Spray powders are obtained, which can be diluted with water to form
suspensions of any
desired concentration.
Emulsifiable concentrate
active ingredient (1:1I = 1:6) 10
octylphenol polyethylene glycol ether 3
(4-5 mots ethylene oxide)
Ca dodecyl-benzene-sulphonate 3
castor oil polyglycol ether (35 cools 4
ethylene oxide)
cyclohexanone 30
xylene mixture 50
Emulsions of any desired dilution may be produced from this concentrate by
diluting it with
water, and they can be used in plant protection.
Coatedgranule
active ingredient (1:1I = 1:10) 8
polyethylene glycol (molecular weight 200) 3
kaolin 89
The finely ground active ingredient is applied evenly to the kaolin which is
moistened with
polyethylene glycol, in a mixer. In this way, dust-free coated granules are
obtained.
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Biological examples
A synergistic effect is present if the activity of the active ingredient
combination is greater than
the sum of activities of the individual components.
The activity E to be expected for a given active ingredient combination obeys
the so-called
COLBY formula and may be calculated as follows (COLBY, S.R. "Calculating
synergistic and
antagonistic responses of herbicide combination". Weeds, Vo1.15, pages 20-22;
1967):
ppm = milligrams active ingredient (= ai) per litre spray mixture
X = % activity from active ingredient I during application of p ppm of active
ingredient
Y = % activity from active ingredient II during application of q ppm of active
ingredient
The expected (additive) activity of active ingredients I+II during application
of p+p ppm active
ingredient is, according to Colby
E=X+Y-X~Y
100
If the activity actually observed (O) is greater than the expected activity
(E), then the
combination is super-additive in its activity, i.e. there is a synergistic
effect (SF = synergie
factor).
B-1: Activity against Puccinia recondita on wheat
a) Residual protective activity
Wheat plants are sprayed until dripping wet, 6 days after sowing, with an
aqueous spray
mixture prepared from wettable powder of the active ingredient mixture, and
are infected 24
hours later with a uredospore suspension of the fungus. After an incubation
period of 48 hours
(conditions: 95 to 100 % relative atmospheric humidity at 20 °C), the
plants are placed in a
greenhouse at 22 °C. 12 days after infection, the fungal attack is
evaluated.
b) Systemic activity
days after sowing, an aqueous spray mixture prepared from wettable powder of
the active
ingredient mixture is poured onto wheat plants. Care is taken that the spray
mixture does not
come into contact with the parts of the plants that are above ground. 48 hours
later, the plants
are infected with a uredospore suspension of the fungus. After an incubation
period of
48 hours (conditions: 95 to 100 % relative atmospheric humidity at 20
°C), the plants are placed
in a greenhouse at 22 °C. 12 days after infection, the fungal attack is
evaluated.
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Active ingredient mixtures comprising components IIB and IIC in particular
demonstrate good
synergistic activity.
Example B-2: Activity against Plasmopara viticola on vines
Vine seedlings at the 4 to 5 leaf stage are sprayed until dripping wet with an
aqueous spray
mixture prepared from wettable powder of the active ingredient mixture, and
are infected 24
hours later with a sporangia suspension of the fungus. The fungal attack is
evaluated 6 days
after infection, during which period the conditions of 95 to 100 % relative
atmospheric humidity
and a temperature of 20 °C are maintained.
Active ingredient mixtures comprising components IIB, IID and IIA in
particular demonstrate
good synergistic activity.
Example B-3: Activity against Er~ysiphe araminis on barley
a1 Residual protective activitK
Barley plants of approximately 8 cm height are sprayed until dripping wet with
an aqueous
spray mixture prepared from wettable powder of the active ingredient mixture,
and 3 to 4 hours
later are dusted with conidia of the fungus. The infected plants are placed in
a greenhouse at
22°C. 12 days after infection, the fungal attack is evaluated.
b) Systemic activity
An aqueous spray mixture prepared from wettable powder of the active
ingredient mixture is
poured onto barley plants of approximately 8 cm height. Care is taken that the
spray mixture
does not come into contact with the parts of the plants that are above ground.
48 hours Later,
the plants are dusted with conidia of the fungus. The infected plants are
placed in a
greenhouse at 22°C. 12 days after infection, the fungal attack is
evaluated.
Active ingredient mixtures comprising components IIA, IID and IIE in
particular demonstrate
good synergistic activity.
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Table 1: Active ingredient IIA = Quinox en
Test active active ratio % activity % activity SF
No. ingredient I ingredient IIA I:II found 0 calculated E O/E
mg/litre mg/litre
0 - - 0 (control)
1 0.1 - 6
2 1.0 - 30
3 - 0.1 4
4 - 0.5 6
- 1.0 8
6 - 10.0 2i
7 0.1 0.1 1:1 26 10 2.6
8 0.1 0.5 1:5 30 12 2.5
9 0.1 1.0 1:10 21 14 1.5
1.0 ~ 10.0 1:10 75 45 1.7
Example B-4: Activity against Phyto,~hthora iniestans on tomatoes
a~ Curative activi~
Tomato plants of the variety "red gnome" are sprayed with a zoospore
suspension of the
fungus after cultivating for three weeks, and incubated in a cabin at 18 to 20
°C and under
saturated atmospheric humidity. The humidity is stopped after 24 hours. After
drying off the
plants, they are sprayed with a mixture which contains the active substances
formulated as a
wettable powder. When the spray coating has dried on, the plants are again
placed in the
moist cabin for 4 days. The number and size of typical leaf spots which have
appeared after
this period are the criterion for evaluating the efficacy of the tested
substances.
b) Preventive systemic activity
The active substances formulated as wettable powders are applied to the
surface of the soil of
three week old tomato plants of the variety "red gnome" which have been potted
into single
pots. After leaving for three days, the undersides of the leaves of the plants
are sprayed with a
zoospore suspension of Phytophthora infestans. They are then kept for 5 days
in a sprayed
cabin at 18 to 20°C and under saturated atmospheric humidity. After
this period, typical leaf
CA 02564381 2006-11-07
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spots appear. The number and size thereof serve to evaluate the efficacy of
the tested
substances.
Active ingredient mixtures comprising components IIB and IIC in particular
demonstrate good
synergistic activity.
Example B-5: Activity against Botrytis cinerea on apple fruits. Residual
protective action
Artificially damaged apples are treated by applying a spray mixture to the
wound sites in drops.
The treated fruits are then inoculated with a spore suspension of the fungus
and incubated for
one week at high atmospheric humidity and ca. 20 °C. The fungicide
action of the test
substance is deduced from the number of wound sites that have started to rot.
Active ingredient mixtures comprising components IIB and IIC in particular
demonstrate good
synergistic activity.
Example B-6: Activity against Fusarium nivale on ye (seed treatment
Rye of the variety'Tetrahell" which is naturally infected with Fusarium nivale
is dressed with
the fungicide to be tested on a mixing roller, whereby the following
concentrations are used:
20 or 6 ppm AS (based on the weight of the seeds).
The infected and treated rye is sown in the open in October with a seed
drilling machine on
plots of 3 m length and 6 seed rows. 3 repeats per concentration. Up to
evaluation of the
attack, the test plantation is cultivated under normal field conditions
(preferably in a region with
a closed snow cover during the winter months).
To evaluate the phytotoxicity, an appraisal is made of the seed emergence in
the autumn and
an appraisal is made in spring of the crop density/number of plants.
To determine the active ingredient activity, the percentage of plants attacked
by Fusarium is
counted in spring, directly after the snow has thawed. The active ingredient
mixtures
demonstrate good synergistic activity.
