Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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PF/5-18421/A
Fun~icidal compositions
The present invention relates to novel active substance combinations for con~olling plant
diseases and to processes for ~pplying such mixtures for leaf, soil and seed clressing
application.
The combinations according to the invention comprise
a) 4 (4-chlorophenyl)-2-phenyl-2-[(lH-1,2,4-triazol-1-yl)methyllbutane nitlile of t:he
formula I
C~N N~) I
or acid addition salts and metal complexes thereof, and
b) cis-4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine of the formula II
~1"NJ~ 11
or acid acldition salts thereof and/or
1-[3-(4-tert-butylphenyl)-2-methylpropyl]piperidine of the formula III
~N~) Il[
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or acid addition salts thereof.
Component a) has become known under the code designation R~I-7592. Its synthesis and
fungicidal properties are described in EP 0 251 775.
Component b) has become known under the name fenpropimorph and component c) under
the name fenpropidin. Their syntheses and fimgicidal properties are described in Gerrnan
Offenlegungsschrift 2 752 135.
Surprisingly, it was found ~hat the fungicidal action of the active ingredient (a.i.)
combination according to the invention is significantly higher than the sum of the actions
of the individual active substances. This means that an unforeseeable synergistically
increased action is present and not only an additive action as could have been expected by
the combination of two active substances. I~e active substance combinations according to
the invention thus constitute an enlargement of the art.
When the active substances are present in the active substance combinations (hereaîter
called the mixtures)according to the invention in specified weight ratios, the synergistic
effect is p.~icularly apparent. However, ~e weight ratios of the active substances in the
active substance combinations can be v~ied wi~hin a relatively wide range, depending on
the type of application. In general, 0.2-20 parts by weight, preferably 0.5-10 parts by
weight of active substance(s) of the forrnula (II) and/or (III) are present per part by weight
of active substance of the formula (I). This corresponds to a weight ratio of component a)
to component b) of 5:1 to 1:20. Particularpreference is given to combinations in which 1
to 8 parts by weight of active substance(s) of the fo}mula (II) and/or (III) are present per
part by weight of the formala (I), in particular a~:b) = 2:1 to 1:10 and very par~icularly 1:1
to 1:4. Examples of mixing ratios of a):b) which are particularly suitable for practical
application are 2:3; 2:5; 1:2 and 1:3. The above weight ratios apply regardless of whether
the active components' acid addition salts or metal complexes are used.
Examples of acids which can be used for preparing salts of the forrnula I, II or III are:
hydrohalic acids such as hydrobronlic acid and hydrochloric acid, fi)rthermore phosphoric
acid, nitric acid and sulfuric acid, furthermore mono-, bi- or trifunctional carboxylic acids
and hydroxycarboxyl;c acids such as formic acid, succinic acid, acetic acid, glycolic acid,
fumaric acid, lactic acid, oxalic acid, propionic acid, sorbic acid, trichloroacetic acid,
trifluoroacetic acid, citric acid, furtherrnore sulfonic acids such as benzenesulfonic acid,
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1,5-naphthalenedisulfonic acid and p-toluenesulfonic acid and (thio)saccharin.
Metal complexes consist of the basic organic molecule and an inorganic or organic metal
salt, for example halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates,
trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates, and the like, of
the elements of main group III or IV, such as aluminium, tin or lead and of subgroup I to
VIlI, such as chromium, manganese, iron, cobalt, nickel, copper, zinc, and the like.
Preference is given to subgroup elements from the 4th period. In these metal complexes,
the metals can be present in the various valencies in which they usually occur.
The active substance mixtures according to the invention and acid addition salts thereof
have plant fungicidal action and can therefore be used for controlling ~ungi in agriculture
and horticulture. They are suitable in par~icular for inhibiting the growth of or for
destroying phytopathogenic fungi on parts of plants, for example leaves, s~alks, roots,
eubers, Eruits or flowers, and on seeds and of harmful fungi present in the soil.
The active substance mixtures according to the invention are suitable in particular for
controlling ascomycetes ~Erysiphe graminis, Uncinula necator, Venturia, Sphaerotheca
pannosa, Erysiphe betae) and basidiomycetes, which include rusts, for example those of
the genera Puccinia, Uromyces and Hemileia (in particular Puccinia recondita, Puccinia
striiformis, Puccinia graminis, Puccinia coronata, Uromyces fabae, Uromyces
appendiculatus, Hemileia vastatrix). Furthermore, the active substance combinations
according to the invention act against Fungi imperfecti of the genera Helminthospolium
(for example Helminthosporium olyzae, Helminthosporium teres, Helminthosporium
sativum, Helmin~hosporium tritici-repentis), Alternaria (for example Alternaria brassicola,
Alternaria brassicae), Septolia (for example Septoria avenae), Cercospora (for example
Cercospora beticola), Ceratocystis (for example Ceratocystis ulmi), Pyricularia (for
example Pyricularia oryzae and Mycospharella ~ljiensis).
I'he active substance combinations according to the invention are suitable in particuLIr
also for controlling mould strains which have developed a certain resistance towards
active substances from the class of triazoles.
In the ~ield, it is preferred to use dosages of 75 to 1000 g of active substance mixh~re per
hectare and treatment. For control}ing fungi in dressing treatments of seeds, dosages of
0.01 g to 1.0 g of active substance mixture are advantageously used per kg of seed.
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Analogously, these data also apply to plan~ propagation material in general, i.e. also for kg
amounts of cuttings, tubers, root material, and ~he like.
The fungicide combinations according to the invention are dis~inguished by systemic,
curative and preventive action.
The active substance mixtures according to the invention can be formulated to give a wide
range of agen~s, for example solutioas, suspensions, emulsions, emulsifiable concentrates
and pulverulent preparations. The present invention also relates to the fungicidal
compositions of this type. The fungicidal compositions according to the invention
comprise an effective amoun~ of RH-7592 and fenpropimorph and/or fenpropidin or acid
addition salts or metal complexes of these active substances and fo}mulation agents.
Advantageously, the compositions contain at least one of the following forrnulation
agents: solid carriers; solvents or dispersants; surFactants (wetting agents and emulsifiers);
dispersants (without surfactant action); asld additives OI other types~ such as s~abilisers.
Suitable solid ca~Tiers are in particular: natural minerals, such as kaolin, clays, kieselguhr,
talc, bentonite, challc, for example whiting, magnesium carbonate, limestone, quartz,
dolomite, attapulgite, montmorillonite and diatomaceous earth; synthetic minerals, such as
highly disperse silica, alumina and silicates; organic materials, such as cellulose, starch,
urea and synthetic resin; and fertilisers, such as phospha~es and nitrates, it being possible
for carriers of this type to be present, for example, as granules or powders.
Suitable solvents or dispersants are mainly: aromatics, such as toluene, xylenes,
polyallcylated benzenes and allcylnaphthalenes; chlorinated arornatics and chlorinated
aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes and methylene chloride;
(cyclo)aliphatic hydrocarbons, such as cyclohexane and paraffins, for example petroleum
fractions; alcollols, such as butanol and glycol, and ethers and esters thereof; ketones, such
as acetone, methyl ethyl Icetone, methyl isobutyl ketone, isophorone and cyclohexanone;
and strongly polar solvents and dispersants, such as dimethylforrnamide,
N-methylpyrrolidone and dimethyl sulfoxide, solvents and dispersants of this type
preferably having flash points of at least 30C and boiling points of at least 50C, and
water. Of the solvents and dispersants, so-called liquefied gaseous extenders or carriers
are also suitable. These are products which are gaseous at room temperature and under
atmospheric pressure. In the case where water is used as the solvent, it is possible, for
example, also to use organic solvents as solvent aids.
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The surfactants (wetting agents and emulsifiers) can be nonionic compounds, such as
condensation products of fatty acids, fatty alcohols or fat-substituted phenols with
ethylene oxide; fatty acid esters and ethers of sugars or polyhydric alcohols; products
obtained from sugars or polyhydric alcohols by condensation with ethylene oxide; bloclc
polymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.
The surfactants can also be anionic compounds, such as soaps; fatty sulfate esters, for
example dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate;
alkylsulfonates, arylsulfonates and fatty-aromatic sulfonates, such as
alkylbenzenesulfonates, for example calcium dodecylbenzenesulfonate, and
butylnaphthalenesulfonates; and more complex ~atty sulfonates~ ~or example the amide
condensation products of oleic acid and N-methyltaurine and sodium dioctyl
sulfosuccinate.
Finally, the surfactants can be cationic compounds, such as
alkyldimethylbenzylammonium chlorides, dialkyldimethylarnmonium chlorides,
alkyltrimethylammonium chlorides and ethoxylated quaternary amrnonium chlorides.
Suitable dispersants (without sur~actant action) are mainly: sodium salts and arnmonium
salts of lignosu}~onic acid7 sodium salts of maleic anhydride~diisobutylene copolymers,
sodium salts and ammonium salts of sulfonated polycondensation products of naphthalene
with formaldehyde, sodium salts of polymeric carboxylic acids and sulfite waste liquors.
Examples of dispersants which can be used and are suitable in particular as thickeners or
antisettling agents are methylcellulose, carboxymethylcellulose, hydroxyethylcelluloset
polyvinyl alcohol, alginates, caseinates and blood alburnin.
Examples of suitable stabilisers are acid-binding agents, for example epichlorohydrin,
phenyl glycidyl ether and soya epoxides; antioxidants, for exarnple gallic esters and
butylhydroxytoluene; UV absorbers, for example substituted benzophenones,
o~-cyano-,B"B-diphenylacrylic estters and cinnamic esters; and deactivators, for example
salts of ethylenediaminetetraacetic acid and polyglycols.
Apart from the combinations according to the invention, the fungicidal compositions
according to the invention can also contain other active substances, for example other
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fungicidal compositions [active substance components c) or d,~]; insecticides and
acaricides, bactericides, plant-growth regulators and fertilisers. These combination agents
are suitable for widening the activity spectrum or for other favourable effects on the plant
growtll.
Depending on their type, the fungicides according to the invention in general conta;n
between 0.0001 and 95 per cent by weight of the active substance combination according
to the invention. In concentrates, the active substance concentration is usually in the upper
region of the upper concentration interval. These forms can then be diluted with identical
or different formulation agents to give active substance concentrations suitable for
practical use, and these concentrations are usually in the lower region of the upper
concentration interval. Emulsi~lable concentrates in general contain ~ to 95 per cent by
weight, preferably 25 to 85 per cent by weight, vf the active substance combination
accorcling tO the invention. Suitable application forms are, inter alia, ready-to-use
solutions, emulsions and suspensions which are suitable, for example, as spray mixtures.
In spray mixtures of this type, ~or example, concentrations between 0.0001 and 20 per cent
by weight can be present. In the ultra-low volume process, it is possible to formulate spray
mixtures in which the active substance concentration is preferably 0.5 to 20 per cent by
weight, while the spray mixtures ~ormulated in the low-volume process and the
high-volume process preferably have an active substance concentration of 0.02 to 1.0 or
O.Q02 to 0.1 per cent by weight.
The fungicidal compositions according to the invention can be prepared by mixing an
active ingredient combination according to the invention with formuladon agents.
The compositions can be prepared in a known manner, for example by intimate rnixing of
the active substances with solid carriers, by dissolution or suspension in suitable solvents
or dispersants, if appropriate with the use of surfactants as wetting agents or emulsi~lers or
of dispers.lllts, by dilution of alrea~ly prep,ured emulsifiable concentrates using solve nts
an(l dispersants, and the like.
In the case of pulverulent compositions, the active substances can be mixed with a solid
carrier, for example by joint grinding; or t}ie solid carrier can be impregnated with a
solution or suspension of the active substances and the solvent or dispersant can then be
removed by slow evaporation, heating or by suction under reduced pressure. By adding
sur~actants or dispersants, pulver~llent compositions of this type can be made easily
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water-wettable, enabling them to be converted into aqueous suspensions, which are
suitable, for example, as sprays.
The active substance mixtures according to the invention can also be mixed with a
surfactant and a solid carrier in order to form a wettable powder, which is dispersible in
water, or they can be mixed with a solid pregranulated carrier in order to forrn a
granulated product.
If desired, the active substance mixtures according to the invention can be dissolved in a
water-imrniscible solvent, for example an alicyclic ketone, which advantageously contains
a dissolved emulsifier, so that the solwtion has a self-emulsifying effect when added to
water. Otherwise, the active substance combinations can be mixed with an emulsifier and
the mixture can be ~hen diluted with water tO ~he desired concentration. Moreover, the
active substance combinations can be dissolved in a solvent and then mixed with an
emulsifier. Such a mixture can likewise be diluted with water to the desired concentration.
This gives emulsifiable concentrates or ready-to-use emulsions.
The compositions according to the invention can be used by the application methods
customary in plant protection or agriculture. The process according to the invention for
controlling hannful fungi comprises treating the location of plant growth to be protected
or the plant material to be protected, for example plants, parts of plants or plant
propagation material ~e.g. seed), with an active arnount of an active substance combination
according to the invention or a composition according to the invention.
Formulation examples
Example 1: Emulsif~lable concentr~lte ~2
Fenpropimorph 375 g/L
RE-1-7592 50 g/L
N-Methylpyrrolidone (auxiliary solvent) 100 g/L
Nonylphenol polyethoxylate tnonionic emulsifier) 50 glL
Calcium dodecylbenzenesulfonate (anionic
emulsifier) 25 g/L
Alkylbenzenemixture(solvent) balance to1000 ml
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Such a concentrate can be diluted with water to give application mixtures for the treatment
of leaves, ~he treatrnent of soil or the treatment of parts of plants.
Example 2: Emulsifiable concentrate (EC)
Fenpropidin 240 g/L
RH-7592 40 g/L
N-Me~ylpyrrolidone ~auxiliarysolvent) 40 g/L
Isotridecanol polyethoxyla~e (nonionic
emulsifier) 50 g/L
Calcium dodecylbenzenesulfonate (anionic
emulsifier) 25 g/L
Isohexyl acetate (solvent~ balance to1000 ml
All components are dissolved with stirring, the dissolution process being accelerated by
gentle heating.
E~xamp e 3: Emulsi~lable concentrate (EC)
Fenpropimorph 50 g/L
Fenpropidin 50 gfL
~I-759~ 50- g/L
N-me;hylpyrrolidone (auxiliary solvent) 50 g/L
Nonylphenol polyethoxylate (nonionic emulsi~ler) 50
Calcium dodecylbenzenesulfonate (anionic
emulsifier) 25 g/L
Alkylnaphthalenemixture(solvent) balance to1ûO0 ml
All components are dissolved with stining, the dissolution process being accelerated by
gentle heating.
The resulting solutions ~ue emulsified in water according to Example 1 to Exarnple 3 and
thus produce a ready-to use spray mixture in a desired dilution. Such solutions are used for
protecting plants or parts of plants (seeds, cuttings, tubers, and the like) against infection
with fungi.
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Example 4: Wettable powder (WP)
Fenpropimorph 25 %w/w
RH-759~ 25 %w/w
Hydrated silica (silica carrier) 25 %w/w
Nonylphenol polyethoxylate (wetting agent) 4 %w/w
Sodium polycarboxylate (dispersant) 4 %w/w
Calcium carbonate (inert material, carrier) 17 %w/w
To prepare this wettable powder, fenpropimorph and nonylphenol polyethoxylate are
mixed in a first working procedurz and sprayed onto the initially introduced silica in a
powder mixer.
The further components are then admixed and milled, for example, in a pinned disc mill to
a fine powder.
The resulting wettable powder, when stirred into water, gives a fine suspension in ~he
des~red dilution, which is suitable as ready-to-use spray mixture, ~or example for dressing
plant p~opagation material, such as plant tubers, root material and leaf material of
seedlings or of plant seeds.
Example 5: Wettable powder (WP)
Fenpropimorph lS %w/w
Fenpropidin 25 %wlw
RH-7592 10 %w/w
Sodium lignosulfona.e 5 %w/w
Sodium diisobutylnaphthalenesulfonate 6 %wlw
Octylphenol polyethylelle glycol ether 2 %w/w
(7-8 mol of ethylene oxide)
Highly disperse silica 10 %w/w
Kaolin 27 %w/w
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Example 6: Wettable powder (WP)
Fenpropimorph 50 %w/w
Fenpropidin 20 %w/w
RH-7592 5 %w/w
Sodium lauryl sulfate 5 %w/w
Sodium diisobutylnaphthalenesulfonate 10 %w/w
Highly disperse silica 10 %w/w
The active ingredients from Examples S and 6 are thoroughly mixed with ~e additives and
thoroughly ground in a suitable mill. Th;s gives wettable powders which can be diluted
with water to give suspensions of any desired dilution.
F,xample 7: Dusts
Fenpropimorph 6 %w/w
RH-7592 2 %w/w
Kaolin 87 %w/w
Hignly disperse silica 5 %w/w
Dusts ready for application are obtained by mixing the active substances with the carrier
and grinding the mixture in a suitable mill.
Biolo~ical e~'amE~
Mycelium ~owth test using Helminthosporium epentis-tritici
a) Method:
The fungal strain is cultured at 18C and 16 hours/day of simulated sunlight irradiation for
7 days on potato-dexhose-agar (PDA), which contains one or both active substances or is
free of active substance (control). To this end, active substances I and Il are each dissolved
in pure etllanol and mixed in the desired relative amounts and diluted. A specified amount
is then added to the liquid PDA medium at 50C and intimately mixed therewith. Agar
media having active substance concentlations of 30; 10; 3; 1; 0.3; 0.1; 0.03 and 0.01 mg of
a.i./litre are preyared. The ethanol concentration in the medium is uniformly 0.1 %.
,
The liquid culture medium is then poured into Petri dishes (9 cm diameter) and inoculated
in the centre using an agar disc (5 mm diameter), which was stamped out from a 7 day old
fungal culture. The inoculated dishes are incubated at 18C in an air-conditioned chamber
in the dark for 5 days. Each test is repeated 3 or 4 times.
b) Evaluation:
After the incubation period, the diarneter of the colony is dete~r~ined. The fungicidal
actions according to Abbott are converted into C.I. Bliss, probit values (1935)* plotted
against the logarithms of the fungicide concentrations to give a dose-action relationship.
This probit-log graph converts the dose/action curve into a straight line (DL. Finney 1971
"Probit analysis", 3rd edition, Cambridge, UK: Cambridge Universi~y Press). The linear
regression and the ED-50 values (effective dosage) are deterrnined from this straight line.
c) Calculation of the svnergistic factors (SF) of fungicides in a mixture
The theoretical effect (ED,h) of a m~xture can be calculated using the formula of Wadley
(**) if the ED values of the individual components of the mixture are known:
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* Bliss, C.I. Ann. Appl. Biol. 2~" 134-167 (1935)
** Wadley, F.M. (1945)
The evidence required to show synergistic action of insecticides and a short cutin analysis. ET-223, U.S. I:)epartment of Agriculture, 8 pp.
Wadley, F.M. (1967)
Experimental Statistics in Entomology
Washington, U.S.A.: Graduate School Press, U.S.D.A.
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ED-50 (th) = a + b a, b = ratios of the fungicides
a _ ~ b in themixture
ED-SVa ED-SOb
The ratio of the calculated theoretical effect (ED,I,~ and the actually observed effect (FDob)
of the mixture gives Ihe synergic factor (SF).
SF l~D-50 (th)
ED-50 (ob)
SF > 1.2 synergistic interaction
SF > 0.5 < 1.2 additive interaction
SF < 0.5 antagonistic interaction
According to V. Gisi et al. (1987) and Y. Levy et al. (1986), a synergistic interaction is
already observed with SF values of greater than 1Ø(***)
The limits of the synergistic factor of a certain mixture are determined using the standard
deviation of the ED values observed. SF values of greater than 1.2 give a stadstically
significant synergism.
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*'~'~ Gisi, U., Binder, H., Rimbach, E. (1985)
Synergistic interactions of fungicides with different modes of action.
Trans~ Br. mycol. Soc. 85 (2), 299-306
Levy7 Y. et al (1986)
The joint action of fungicides in mixture:
comparison of two methods of synergy calculation.
Bulletin OEPP 16, 651-657 (1986)
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d) Results usin~ active substance I and active substance II
Activities of the individual components and of the mixture (ED-50)
Table 1
A~' 1 2 3
substance \ .
2.7 3.5 2.2
ll 2.3 1.7 0.9
I:II = 1:1 1.6 1.5 0.6
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SF of the 1.6 1.5 2.1
ED-50 values _ _~
e~ Results using active substance I and active substance III
Activities of the individual components and of ~he mixture (ED-50)
Table 2
A~. 1 2 3 4
substance \ _ . __ .
2.7 3.5 2.9 2.2
III 2.5 1.8 1.4 2.2
_ _
I:III = 1:1 1.9 1.7 0.9 0.'7
= _ __
SF of the 1.4 1.4 2.1 3.1
ED-50 values _
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f~ Comment
The values ~rom Tables 1 and 2 show for each of the three and four independently run
tests that the fungicidal action of a mixture comprising active substance I and active
substance II and of a mixture comprising active substance I and active substance III
undergoes a signi~lcant increase, i.e. a synergistically increased action is present. As can
be seen, these actions are each time reproducible.
Similar results are obtained with Alternaria brassicae, Helminthosporium oryzae,Rhizoctonia solani and Fusarium culmorum.
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