LT3875B - Fungicidal preparations and fungi control method - Google Patents

Abstract

Fungicidal compsns. contg. (a) RH-7592 or its acid-addn. salts or metal complexes and (b) fenpropidine or its acid-addn. salts are new. RH-7592 is 4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-traixol-1- ylmethyl)-butyronitrile (I) and is described in EP251775. Fenpropidine is 1-(3-(4-t-butylphenyl)-2-methylpropyl)-piperidine (II) and is described in DE2752135.

Description

The present invention relates to novel combinations of biologically active substances for combating plant diseases and methods of using such mixtures for leaf, soil treatment and seed treatment.

The combinations proposed in the invention differ

a) 4- (4-Chlorophenyl) -2-phenyl-2 - [(1H-1,2,4-triazol-1-yl) methyl] butyl nitrile of formula I

aroa The amount of its salts obtained by the addition of acids and its metal complexes, and

b) cis -4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine of formula II

(II) or its salts obtained by addition of acids and / or 1- (3- (4-tert-butylphenyl) -2-raethylpropyl) -piperidine of formula III

(III) and its salts obtained by addition of an acid.

Component a) is known by the code rh-7592:. Its synthesis and fungicidal properties are described in European patent no. 0251775Component b) is known as fenpropimorph and component c) is known as phenpropidin'a. Their synthesis and fungicidal properties are described in German patent application no. 2752135.

Unexpectedly, it has been found that the fungicidal effect of the combinations of the biologically active agents of the invention is significantly greater than the sum of the effects of the individual active substances. In this way, there is an unintended synergistic increase in effect, rather than a simple increase that could have been expected by mixing the two components.

The combinations of biologically active substances of the present invention enrich the prior art.

Where the biologically active agents in the combinations of the invention have certain weight ratios, the synergistic effect is particularly pronounced. However, the weight ratios of biologically active substances in mixtures may vary within a relatively wide range. Approximately one part by weight of the active ingredient of the formula (I) contains from 0.2 to 20 parts by weight, but preferably from 0.5 to 10 parts by weight of the active ingredient (s) of the formula (II) and / or III). This corresponds to a weight ratio of components a) and b) of from 5: 1 to 1: 20. Combinations in which one part by weight of the compound of formula I contains from 1 to 8 parts by weight of the active ingredient (s) of formula (II) and / or (III), preferably when a): b) = 2: 1 to 1: 10, and the best results are when the ratio is 1: 1 to 1: 4. Suitable components in mixtures may be exemplified in practical applications, namely: (a): (b) = 2: 3, 2: 5, 2: 2 and 1: 3. The following salts are used to form acid addition salts or metal complexes of biologically active compounds: as well as quantitative relationships.

The acids which may be used to form the salts of the compounds of formulas I, II and III are the following: halogenated acids such as hydrobromic or hydrochloric acids, in addition to phosphorous, nitric and sulfuric acids, in addition to mono-, bi- and tri-carbonic acids acids and hydroxycarboxylic acids such as formic, succinic, propionic, acetic, glycolic, fumaric, trifluoroacetic, lactic, oxalic, sorbic, trichloroacetic / citric acids, and in addition acids such as benzene sulfuric acid, 1,5-naphthalene disulphuric acid and p-toluene sulfuric acid as well as (thio) saccharine

The metal complexes are composed of an organic molecule forming a backbone and an inorganic or organic metal salt such as, for example, a second basic group of elements, such as aluminum, tin or lead, as well as the secondary groups I to VIII, such as chromium. , manganese, iron, cobalt, nickel, copper, zinc, etc., halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates, etc. Preference is given to the minor elements of period 4 groups. Metals can be of various valencies.

Mixtures of biologically active substances and their salts obtained after the addition of acids according to the invention have a fungicidal effect on plants and can therefore be used to control fungi in agriculture and horticulture. They are suitable, in particular, for inhibiting growth or for destroying phytopathic fungi on individual parts of plants, such as leaves, stems, roots, tubers, fruits or flowers, grains, and also for destroying harmful fungi occurring in the soil.

Mixtures of biologically active substances according to the invention are most suitable for combating ascomycetes (Erysiphe graminis, Uncinula neca tor, Venturia, Sphaerotheca pannosa, Erysiphe be tae) and basidiomycetes causing rust diseases, such as Puccinia, Uromyces and Hemileia recondita, Puccinia striiformis, Puccinia graminis, Puccinia coronata, Uromyces faboe, Uromyces appendiculatus, Hemileid vastratix). Further, the invention provides biologically active substances

- 5 combinations against Rungi imperfecta of the genera Helminthos porium (e.g. Helminthosporium oryzal, Helminthosporium teres, Helminthosporium sativum, Helminthosporium tretici - repentis), Alternaria (e.g. Alternaria Brassicola, Alternaria brassical), Septoria (e.g. Septoria avenac) for example, Cercospora beticola), Cera tocystis (e.g. Cera tocystis ulmi), Pyricularia (e.g. Pyricularia orizal and Mycosphaerella fijensis).

The combinations of biologically active substances of the present invention are suitable, in particular, for combating fungal strains ₍ which have acquired some resistance to biologically active substances of the triazole class).

In the open area, 75 to 1000 g of active compound per application is applied per application. For combating fungi, seed treatment is preferable to use a dose of 0.01 to 1.0 g of active ingredient per kg of seed. It seems logical to use the same amounts of processing for the materials used for plant propagation, namely; is, counting 1 kg of cuttings, tubers, sprouts, etc.

The fungicidal compositions of the invention have systemic, therapeutic and protective effects.

Mixtures of the biologically active substances of the invention may be processed into various forms, for example solutions, suspensions, emulsions, emulsifiable concentrates and powder formulations. Such fungicidal agents are the subject of the present invention. The fungicidal compositions of the present invention are characterized in that they contain RH-7592 and fenpropimorph and / or fenpropidin or. salts obtained by the addition of acids or metal complexes of these active substances. , active ingredient, and also excipients. The compositions usually contain at least one of the following excipients: solid fillers, solvents, and dispersants, surfactants (wetting and emulsifying agents), dispersants (non-surfactant), and other types of additives, such as stabilizers.

Natural minerals such as kaolin, clay, diatomite, talc, bentonite, chalk such as flaked chalk, magnesium carbonate, limestone, quartz, dolomite, atapulgite, montmorillonite and infuser earth, synthetic minerals such as kaolin, clay are mainly used as solid aggregates. highly dispersible silicas, alumina and silicates, organic materials such as cellulose, starch, urea and synthetic resins, and fertilizers such as phosphates and nitrates, and fillers can be used in the form of granular products or powders.

Suitable solvents and dispersants include aromatic compounds such as toluene, xylene, high alkylation benzenes and alkylnaphthalenes, chlorinated aromatic compounds and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes and methylene chloride, cyclohexane and paraffins such as petroleum fractions, alcohols such as butanol and glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone and cyclohexanone, and highly polar solvents and dispersants such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, more preferably such solvents or dispersants have a flash point of at least 90 ° C and a boiling point of at least 50 ° C, and water. gas thinners, or fillers These are products that are in gaseous state at room temperature under normal pressure. When using water as a solvent, organic solvents may also be used as an additional solvent.

Surfactants (wetting and emulsifying agents) may be non-ionic compounds such as ethylene oxide condensation products of fatty acids, fatty alcohols or phenols, ethers and esters of fatty acids and sugars or polyhydric alcohols, and products derived from sugars. or block polymers of ethylene oxide and propylene oxide or alkyl dimethylamine oxides by condensation of polyhydric alcohols with ethylene oxide.

The surfactants may also be ionic compounds such as soaps, esters of fatty sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate and sodium cetyl sulfate, alkyl sulfonates, aryl sulfonates, and fatty aromatic sulfonates such as alkylbenzenesulfonates, e.g. , calcium dodecylbenzenesulfonate, and butylnaphthalenesulfonates, and complex fatty sulfonates, such as amidocondensed products of butyric acid and N-methylturin and dioctylsuccinate sodium sulfonate.

Surfactants may also include cationic compounds such as alkyldimethylbenzylammonium chloride, dialkyldimethylammonium chloride, alkyltrimethylammonium chloride and ethoxylated quaternary ammonium chloride.

As the dispersants (non-surfactant) are mainly used the sodium and ammonium salts of polysaccharides of polycondensation of sodium and ammonium salts of lignin sulphuric acid, maleic anhydride and diisoblylene, polycondensation products of polycondensation, sodium carboxylic acids and polymeric carboxylic acids.

Dispersants which are also used as a thickener or antineoder can be used, for example, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.

Examples of suitable stabilizers include acid binding agents such as epichlorohydrin, phenylglycidic ether and soy epoxides, antioxidants such as terminal acid esters _and butylhydroxytoluene, UV absorbers such as substituted benzophenones, diphenylacrylonitrile esters and cinnamic acid, salts and polyglycols of ethylenediaminotetraacetic acid.

The fungicidal compositions of the invention may contain, in addition to the combinations proposed, other active ingredients such as other fungicidal agents (c) and (d) /, insecticidal and acaricidal agents, bactericides, plant growth regulators and fertilizers. Such combined measures make it possible to broaden the spectrum of action and have other positive effects on plant growth.

In general, the fungicidal compositions of the invention contain from 0.0001 to 95% by weight of the active compound combination proposed. Concentrates of active substances are usually in the upper range of the concentrations mentioned. Such forms may subsequently be diluted with the same or different excipients in order to obtain concentrations of the active substances which are suitable for practical use and are usually in the lower part of this range. The emulsifiable concentrates generally contain from 5 to 95% by weight, preferably 25 to 85% by weight, of the proposed combination of active ingredients. In practice, they may be used, among other forms, in the form of solutions, emulsions and suspensions, which may be used, for example, as spray solutions. Such solutions may contain, for example, from 0.0001 to 20% by weight. Using the Utra-Low-Volume method, solutions for spray application are prepared in a concentration ranging from 0.5 to 20% by weight of the active ingredient, while at the same time as Low-Volume and High-Volume. (high _volume)} prepared by spraying the active material solution concentration is usually from 0.02 to 1.0 or 0.002 to 0.1% by weight.

The fungicidal compositions of the invention may be prepared by combining the active ingredient combinations of the invention with excipients.

Preparation of the preparations may be accomplished by known techniques, for example, after thoroughly mixing the active ingredient with solid excipients, dissolving or suspending it in suitable solvents or dispersants, and, where appropriate, using surfactants as wetting or emulsifying agents or dispersants, diluting pre-formulated emulsifiers: or dispersants and so on

In the case of powder formulations, the active substances may be mixed with solid excipients, for example by co - grinding, or may be a solid excipient; impregnated with a solution or suspension of the active ingredients, followed by removal of the solvent or dispersant by evaporation, heating or suction under reduced pressure. After the addition of surfactants or dispersants, such powdered compositions can be made readily wettable with water so that they can readily obtain aqueous suspensions used, for example, as sprays.

Mixtures of the active compounds of the invention may also be mixed with surfactants and solid excipients to form a wettable powder dispersible in water, or they may mix with a solid granular excipient to form a granular product.

If desired, the active ingredient mixtures of the invention may be dissolved in a water immiscible solvent, such as an alicyclic ketone containing a dissolved emulsifier, so that the solution ·, if added to water, has the ability to emulsify. .

On the other hand, the active ingredient combination may mix with the emulsifier and then dilute with water to the desired concentration. In addition, mixtures of the active ingredients may be soluble in the solvent and subsequently mixed with the emulsifier. Such a mixture may also be diluted with water to the desired concentration. In this way, emulsifiable concentrates or ready-to-use emulsions are obtained.

The means of the invention can be used in practice in conventional ways used in plant protection or agricultural technology. The method of controlling the harmful fungi according to the invention is characterized in that the crop plot or the protected seed material, such as the plants themselves, parts thereof or seeds, are treated with an active amount of the combination of the active compounds or the inventive means.

If necessary, the affected or injured site of the fungus shall be treated in any sequence or at the same time with the active ingredient I, its salt or complex and the active substance II, its salt or complex and / or the active substance III or its salt.

Examples of mixtures.

Example: Emulsifiable Concentrate (EC)

Penpropimorph 375 g / l

RH-7592

0 g / 1

N-methylpyrrolidone (co-solvent) 100 g / l

Nonylphenol Polyethoxylate (Area Emulsifier) 50 g / 1 Calcium dodecylbenzenesulfonate (Anionic Emulsifier) 25 g / 1

Alkylbenzene mixture (solvent) up to 1000 ml.

This type of concentrate can be diluted with water to obtain solutions for treating leaves, soil or other parts of plants.

Example: Emulsifiable Concentrate (EG)

Fenpropidin s

240 g / 1 4 0 g / 1

RH-7592

Fenpropimorph's Fenpropidin's RH-7592

All components dissolve when mixed, and mild heating speeds up the dissolution process.

Example: Emulsifiable Concentrate (EG) g / 1 5 0 g / 1 5 0 g / 1

N-methylpyrrolidone (co-solvent) 50 g / l Nonylphenol polyethoxylate (nonionic emulsifier) 50 g / l Calcium dodecylbenzenesulfonate (anionic emulsifier) 25 g / l Alkylnaphthalene mixture (solvent) up to 1000 ml.

All components dissolve with stirring, and mild heating speeds up the dissolution process.

The solutions obtained in Examples 1-3 emulsify in water, thereby obtaining ready-to-use solutions with the desired degree of dilution for spray application. Such solutions are used to protect plants or parts thereof (seeds, cuttings, tubers, etc.) against fungal damage.

Example Fenpropimorph

Moisturizing Powder (WP) 25%

RH-7592 25%

Silicic Acid Hydrate (Silica Filler) 25%

Nonylphenol Polyethoxylate (Humidifier) 4%

Polycarboxylate sodium (dispersant) 4%

Calcium carbonate (inert, filler) 17%.

In order to obtain this wetting powder, in the first step of the process, phenpropidin and nonylphenol polyethoxylate are mixed and the mixture is pulverized on the silicon present therein.

- 13 Then another component is added and thoroughly ground, for example; impact disk mill.

The resulting wetting powder, when mixed with water, forms a fine dispersion suspension of the desired dilution, which can be prepared for use in a solution, for example, for seed propagation, for example, treatment of plant tubers, roots, seedlings, and seed dressing.

Example: Wetting Powder (WP)

Fenpropimorph 15%

Penpropidin 25%

RH-7592

10%

Lignin sulphonate sodium 5%

Sodium diisobutylnaphthalenesulfonate 6%

Octylphenolpolyethylene ether (7-8 moles ethylene oxide) 2%

highly dispersive silicic acid 10% Kaolin 27%. Example 6: Moisturizing Powder (WP) Fenpropimorph a 5 0% Fenpropidin 20% RH-7592 5%

Sodium laurilsulfate 5%

Sodium diisobutylnaphthalenesulphonate 10%

Highly dispersed silica 10%.

In Examples 6 and 6, the active ingredients are mixed well with the additives and thoroughly ground in a suitable mill. A wetting powder is obtained which can be diluted with water to obtain any desired concentration of suspension.

Example 7: In the form of dust measure Penpropimor f'a s 6% BH-7592 2% Kaolin 87% very disperse silicic acid 5%.

The ready-to-use dusting agent is prepared by mixing the active ingredient with a filler and grinding in a suitable mill.

Examples of biological tests.

B-l. Helminthosporium repentc - tritici growth test (a) method:

The fungal strain is cultivated for 7 days at 18 ° C under artificial sunlight for 16 hours per day in potato-dextrose-agar (PDA) medium containing one or both of the active substances or in an agar containing no active substance (control). For these reasons, each of the active substances I and II is dissolved in pure ethanol and the solutions are mixed in the desired quantitative ratios and diluted. A certain amount of the mixture is then added at 50 ° G to the liquid PDA medium and mixed thoroughly. Agar medium containing 3, 1, 0.3, 0.1, 0.03 and 0.01 mg / l of active substance is obtained. The concentration of ethanol in the medium is always 0.1%.

The liquid medium is then added to Petri dishes (^ 9 cm) and infected by placing an agar cylinder (<f> 5 mm) in the center of the plate, cut from a 7-day-old fungal culture. The infected plates are incubated for 5 days at 18 ° C in a climatic chamber in the dark. Repeat each test 3-4 times.

- 15 (b) Rating:

After the incubation period, the fungal colony diameter is measured. According to Abbott, the fungicidal effect is estimated by Probit values (C.I. Bliss, 1935), and they are put into the dose-effect equation by the logarithm of the fungicidal concentration. Probit - log transforms dose / effect curve into a straight line (D.Z. Pinney 1971, Probit analysis, 3rd ed., Cambridge University Press). Linear regression and ED - 50 (effective dosing) are derived from this line.

(c) Calculation of synergistic factors (SP) in a mixture of fungicides

The theoretical effect of the mixture (ED ^) can be calculated using the Wadley formula if the ED-values of the individual components of the mixture are known:

a -f- b

ED - 50 _(t) = ab

- + ED - 5 0a ED - 5 0b a, b = ratio of fungicides in the mixture.

Relationship between theoretically subtracted effect (ED ^.) And fak ^x CI Bliss, Ann. Appl. Biol., 22, ^134-167 (1935) ^Χ5ί ρ.Μ. Wadley, (1945), The evidence re-examined to show synergistic action on insecticides and a short cut in analysis, ET-223, US Department of Agriculture, Θ pp.

p.M. Wadley (1967), Experimental Statistics in Entomology, Washington, U.S.A. Graudual school Press V.S.D.A.

Closely observable carving effect (ED) gives synergistic factor S (SF):

ED - 50 _(t)

SF = ED - 50 z x {s J

SF> 1.2. synergistic interaction

0.5 z SF <1.2 additive interaction

SF> 0.5 antagonistic interaction.

According to U. Gisi et al. (1987) and J. Levy et al. (1986), SF-values greater than 1.0 already indicate synergistic interactions *. The limits of the synergistic factor for a given mixture are determined by the standard deviations of the observed ED - values. SF values greater than 1.2 give statistically characteristic synergism.

(d) Results of tests on active substances I and IX

Activity of the individual components and mixture (ED - 50) Table 1

Test no. 1 2 3 Active material I 2.7 3.5 2, 2 II 2.3 1.7 0.9 I; II = 1: 1 1.6 1.5 0, 6 SF - of values 1.6 1.5 2.1 ED - 50 ^K U. Gisi, H. Binder, E. Rimbąch (1985), Synergistics interactions

of fungicides with different modas of actions, —Trans.Br. mycol. Soc.j 85 (2), 299 - 306.

J. Levy et al. (1986). The joint action of fungicides in a mixture comparison of two methods of synergy calculation, Bulletin 0EPP, 6, 651-657 (1986) ^to

(e) Results of tests on active substances I and III. Table 1 Activity of individual components and mixture (ED - 50)

Test no. 1 2 3 4 Active material I 2.7 3.5 2.9 2.2 III 2.5 1.8 1.4 2.2 I: 111 = 1: 1 1.9 1.7 0.9 0.7 SF values ED - 50 1.4 1.4 2.1 3.1

f) Comment:

and Table 2 show that in each of the three or four independent trials, the fungicidal activity of both the active substance mixture I and II and the active substance mixture I and III is significantly increased, which is the synergistic effect observed.

We see that the effects of this effect are repeated at any time.

Similar results are obtained with Alteruaria brassical, Helminthosporium oryzal, Phizoctonia solani and Fusarium culmorum.

Claims (6)

DEFINITION OF INVENTION A fungicide based on at least two components and, if necessary, targeted additives, characterized in that one active component is 4- (4-chlorophenyl) -2-phenyl-2 / (1H-1,2,4-triazole). l-yl) -methyl t-butyl nitrile of the formula I or one of its salts obtained by the addition of an acid or metal complexes, and that b) the other active component is fenpropimorph s - cis -4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine of formula II, II or a salt thereof obtained by the addition of an acid and / or phenpropidin 1- [3- (4-tert-butylphenyl) -2-methylpropyl] -piperidine of formula III, III or a salt thereof, obtained by the addition of acids. 2. The measure according to claim 1, Come on s k i r i a n t i that that the weight of the active ingredients relative s is a) : b) =  from 5: 1 to 1: 20. 3. The measure according to claim 1, Come on s k i r i a n t i that that weights of active components: ratio is a) : b) =  from 2: ' 1 to 1: 10. 4. The measure according to claim 1, Come on s k i ι- i a n t i that that the weights of the active components ratios: έ is a) : b) = from 1: 1 to 1: 4. 5. The measure according to claim 1, Come on s k i r i a n t i that that the active ingredient b) is a mixture of the active ingredients II and III. 6. A method according to claim 1, wherein the active ingredient b) is active ingredient II. 7. A method according to claim 1, wherein the active ingredient b) is active ingredient III. Use of active ingredient combinations according to claim 1 for combating fungi and protecting against fungal damage. 9. A method for controlling fungi, wherein the fungicidal agent according to claims 1-7 is treated with a fungicidal agent according to claims 1-7 in a mixture of 75-1000 g / ha. 10. The method of claim 9, wherein the seed plant material is treated with a fungicide according to claims 1-7, containing from 0.01 to 1.0 g of a mixture of active ingredients per kg of seed.