CA2054666A1

CA2054666A1 - Fungicidal compositions

Info

Publication number: CA2054666A1
Application number: CA002054666A
Authority: CA
Inventors: Ruth Kung; Dominique Guy Georges Driant
Original assignee: Individual
Current assignee: Novartis AG; Rohm and Haas Co
Priority date: 1990-11-02
Filing date: 1991-10-31
Publication date: 1992-05-03
Also published as: IE913841A1; IL99911A; RU2041627C1; BG51334A3; CH680895A5; DE59109148D1; HU209742B; LV10830B; AU8696591A; LT3875B; PL292229A1; ES2097200T3; LTIP1644A; DK0485330T3; FI915118A0; EP0485330A2; IE80838B1; JP3168472B2; MX9101870A; LV10830A

Abstract

Fungicidal compositions Abstract of the disclosure:

Plant fungicidal compositions based on two active ingredients a) and b) show a synergisti-cally increased effect in the case where component a) is 4-(4-chlorophenyl)-2-phenyl-2-[(1H-1,2,4-triazol-1-yl)methyl]butane nitrile and component b) is either fenpropimorph or fenpropidin or a mixture of the two.

Description

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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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s 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 2 0 ~ 4 ~

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 2 ~ 3 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 ------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 _ 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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Claims

1. A fungicidal composition based on at least two active ingredients, wherein a) one active ingredient is 4-(4-chlorophenyl)-2-phenyl-2-[(1H-1,2,4-triazol-1-yl)methyl]butane nitrile of the formula I

I

or an acid addition salt or metal complex thereof and b) the other active ingredient is fenpropimorph =
cis-4-[3-(4-tert-bulylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine of the formula II

II

or an acid addition salt thereof and/or fenpropidin = 1-[3-(4-tert-butylphenyl)-2-methylpropyl]piperidine of the formula III

III

or all acid addition salt thereof, together with a suitable carrier material therefor.

2. A composition according to claim 1, wherein the weight ratio of the active ingredients a):b) is 5:1 to 1:20.

3. A composition according to claim 1, wherein the weight ratio of the active ingredients a):b) is 2:1 to 1:10.

4. A composition according to claim 1, wherein the weight ratio of the active ingredients a):b) is 1:1 to 1:4.

5. A composition according to claim 1, wherein the active ingredient b) is a mixture of active swbstances II and III.

6. A composition according to claim 1, wherein the active ingredient b) is active substance II.

7. A composition according to claim 1, wherein the active ingredient b) is active substance III.

8. Use of an active substance combination according to claim 1 for controlling fungi or for preventing fungal infection.

9. A process for controlling fungi, which comprises treating a location infected or liable to be infected with fungi in any desired order or simultaneously with a) the active substance of the formula I, 4-(4-chlorophenyl)-2-phenyl-2-[(1H-1,2,4-triazol-1-yl)methyl]butane nitrile, or an acid addition salt or metal complex thereof and with b) the active substance fenpropimorph of the formula II or an acid addition salt thereof and/or the active substance fenpropidin of the formula III or an acid addition salt thereof.

10. A process according to claim 9, wherein plant propagation material is treated.

FD 4.5/PK/md