Fungicidal agents.

0001The present invention relates to new combinations of active ingredients for combating plant diseases and processes for using such mixtures for leaf, soil and pickling application.

0002The combinations according to the invention are characterized by a content of<ul id="ul0001" list-style="none"><li>a) 2- (4-Chlorophenyl) -3-cyclopropyl-1 - [(1<u>H</u>- 1,2,4-triazol-1-yl) butan-2-ol of the formula I.<chemistry id="chem0001" num="0001"><img file="EP0484279A2_D0001.tif" /></chemistry> or its acid addition salts and metal complexes, and</li><li>b) cis-4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine of the formula II</li></ul><chemistry id="chem0002" num="0002"><img file="EP0484279A2_D0002.tif" /></chemistry> or its acid addition salts and / or

00031- [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine of the formula III<chemistry id="chem0003" num="0003"><img file="EP0484279A2_D0003.tif" /></chemistry> or, whose acid addition salts.

0004Component a) has become known under the name cyproconazole. Their synthesis and fungicidal properties are described in DE-OS 34 06 993.

0005Component b) has become known under the name Fenpropimorph and component c) under the name Fenpropidin. Their syntheses and fungicidal properties are described in DE-OS 2 752 135.

0006It has surprisingly been found that the fungicidal activity of the active compound combination according to the invention is significantly higher than the sum of the effects of the individual active compounds. There is therefore an unforeseeable, synergistically increased effect, and not just an addition to the effect that could have been expected by combining two active substances. The active substance combinations according to the invention thus represent an enrichment of the technology.

0007If the active substances are present in the active substance combinations according to the invention in certain weight ratios, the synergistic effect is particularly evident. However, the weight ratios of the active ingredients in the active ingredient combinations can be varied within a relatively wide range depending on the application. In general, 0.2-20 parts by weight, preferably 0.5-10 parts by weight of active compound (s) of the formula (II) and / or (III) are present per part by weight of active compound of the formula (I). This corresponds to a weight ratio of component a) to component b) of 5: 1 to 1:20. Combinations are particularly preferred in which 1 to 8 parts by weight of active compound (s) of the formula (II) and / or III are present per part by weight of the formula (I), particularly a): b) = 2: 1 to 1:10 and in full especially 1: 1 to 1: 4. Mixing ratios of a): b) = 2: 3; 2: 5; Called 1: 2 and 1: 3. The corresponding quantitative ratios are suitable for acid addition salts or metal complexes of the active ingredients.

0008Among the acids that can be used to prepare salts of the formula I, II or III are: Hydrohalic acids such as hydrobromic acid and hydrochloric acid, furthermore phosphoric acid, nitric acid and sulfuric acid, and also mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic 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, further Sulfonic acids such as benzenesulfonic acid, 1,5-naphthalenedisulfonic acid and p-toluenesulfonic acid and (thio) saccharin.

0009Metal complexes consist of the underlying organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates etc. of the elements of the second main group such as aluminum, tin or lead and the first to eighth subgroups such as chrome, manganese, iron, cobalt, nickel, copper, zinc etc. The subgroup elements of the 4th period are preferred. The metals can be present in the various valences that come with them.

0010The active ingredient mixtures according to the invention and their acid addition salts have plant fungicidal activity and can accordingly be used to combat fungi in agriculture and horticulture. They are particularly suitable for inhibiting growth or for destroying phytopathogenic fungi on parts of plants, for example leaves, stems, roots, bulbs, fruits or flowers, and on seeds and harmful fungi occurring in the soil.

0011The active substance mixtures according to the invention are particularly suitable for combating ascomycetes (Erysiphe graminis, Uncinula necator, Venturia, Sphaerotheca pannosa, Erysiphe betae) and Basidiomycetes, which include rust diseases, such as those of the genera Puccinia, Uromyces and Hemileia (especially Puccinia recondita, especially Puccinia recondita striiformis, Puccinia graminis, Puccinia coronata, Uromyces fabae, Uromyces appendiculatus, Hemileia vastatrix). Furthermore, the active compound combinations according to the invention act against fungi imperfecti of the genera Helminthosporium (e.g. Helminthosporium oryzae, Helminthosporium teres, Helminthosporium sativum, Helminthosporium tritici-repentis), Alternaria (e.g. Alternaria brassicola, Alternaria brassicae), Septoria (e.g. Septoria (e.g. Septoria ), Ceratocystis (e.g. Ceratocystis ulmi), Pyricularia (e.g. Pyricularia oryzae and Mycosphaerella fijiensis).

0012The active compound combinations according to the invention are also particularly suitable for combating fungal strains which have developed a certain resistance to active compounds from the triazole class.

0013In the field, doses of 75 to 1000 g of active compound mixture per hectare and treatment are preferably used. To control fungi in the seed dressing process, doses of 0.01 g to 1.0 g of active compound mixture per kg of seed are advantageously used. Analogously, this information applies to plant propagation material in general also for kg quantities of cuttings, tubers, roots, etc.

0014The fungicide combinations according to the invention are notable for systemic, curative and preventive action.

0015The active substance mixtures according to the invention can be formulated into various types of agents, for example solutions, suspensions, emulsions, emulsifiable concentrates and powdered preparations. Such fungicidal compositions form an object of the present invention. The fungicidal compositions according to the invention are characterized in that they contain an effective amount of cyproconazole and fenpropimorph and / or fenpropidine or Acid addition salts or metal complexes of these active ingredients and formulation auxiliaries. The compositions expediently contain at least one of the following formulation auxiliaries: Solid carriers; Solvents or dispersants; Surfactants (wetting agents and emulsifiers); Dispersant (without surfactant); and other additives, such as stabilizers.

0016The following are essentially suitable as solid carriers: natural minerals, such as kaolin, clays, kieselguhr, talc, bentonite, chalk, eg sludge chalk, magnesium carbonate, limestone, quartz, dolomite, attapulgite, montmorillonite and diatomaceous earth; synthetic minerals, such as finely divided silica, aluminum oxide and silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers, such as phosphates and nitrates, such carriers, for example can be present as granules or powder.

0017The following are essentially suitable as solvents or dispersing agents: aromatics, such as toluene, xylenes, higher alkylated benzenes and alkylnaphthalenes; chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene and methylene chloride; (Cyclo) aliphatic hydrocarbons, such as cyclohexane and paraffins, for example Petroleum fractions; Alcohols, such as butanol and glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone and cyclo-hexanone; and strongly polar solvents or dispersing agents, such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, such solvents or dispersing agents preferably having flame points of at least 30 ° C. and boiling points of at least 50 ° C., and water. Among the solution or Dispersants are also known as liquefied gaseous extenders or carriers. These are products that are gaseous at room temperature and under normal pressure. If water is used as the solvent, organic solvents can, for example, also be used as auxiliary solvents.

0018The surfactants (wetting agents and emulsifiers) can be non-ionic 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; the products obtained from sugars or polyhydric alcohols by condensation with ethylene oxide; Block polymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.

0019The surfactants can also be anionic compounds, such as soaps; Fatty sulfate esters, for example dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate; Alkyl sulfonates, aryl sulfonates and fatty aromatic sulfonates, such as alkylbenzenesulfonates, for example calcium dodecylbenzenesulfonate, and butylnaphthalenesulfonates; and more complex fatty sulfonates, such as the amide condensation products of oleic acid and N-methyl taurine and the sodium sulfonate of dioctyl succinate.

0020Finally, the surfactants can be cationic compounds, such as alkyldimethylbenzylammonium chlorides, dialkyldimethylammonium chlorides, alkyltrimethylammonium chlorides and ethoxylated quaternary ammonium chlorides.

0021The following are essentially suitable as dispersants (without surfactant action): sodium and ammonium salts of lignin sulfonic acid, sodium salts of maleic anhydride-diisobutylene copolymers, sodium and ammonium salts of sulfonated polycondensation products from naphthalene and formaldehyde, sodium salts of polymeric carboxylic acids and sulfite waste liquors.

0022Dispersants which are particularly suitable as thickening or anti-settling agents can be, for example, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.

0023Examples of suitable stabilizers are acid-binding agents, for example epichlorohydrin, phenylglycidyl ether and soya epoxides; Antioxidants, for example gallic acid esters and butylated hydroxytoluene; UV absorbers, for example substituted benzophenones, diphenylacrylonitrile esters and cinnamic esters, and deactivators, for example salts of ethylenediaminetetraacetic acid and polyglycols.

0024In addition to the combinations according to the invention, the fungicidal compositions according to the invention can also comprise other active compounds, for example other fungicidal compositions [active component c) or d)], insecticidal and acaricidal compositions, bactericides, plant growth regulators and fertilizers. Combination agents of this type are suitable for broadening the spectrum of action or otherwise having a beneficial effect on plant growth.

0025In general, the fungicidal compositions according to the invention contain, depending on their type, between 0.0001 and 95 percent by weight of the active compound combination according to the invention. In concentrates, the drug concentration is usually in the higher range of the above concentration interval. These forms can then be diluted with the same or different formulation adjuvants to active ingredient concentrations that are suitable for practical use, and such concentrations are normally in the lower range of the above concentrate interval. Emulsifiable concentrates generally contain 5 to 95 percent by weight, preferably 25 to 85 percent by weight, of the active ingredient combination according to the invention. As application forms come among others ready-to-use solutions, emulsions and suspensions, which are suitable, for example, as spray liquors. In such spray liquors, for example, concentrations between 0.00 1 and 20 percent by weight can be present. In the ultra-low-volume process, spray liquors can be formulated in which the active compound concentration is preferably from 0.5 to 20 percent by weight, while the spray liquors formulated in the low-volume process and in the high-volume process preferably have an active compound concentration of 0. 02 to 1.0 or 0.002 to 0.1 percent by weight.

0026The fungicidal compositions according to the invention can be prepared by mixing an active ingredient combination according to the invention with formulation auxiliaries.

0027The preparation of the compositions can be carried out in a known manner, for example by intimately mixing the active ingredients with solid carriers, by dissolving or suspending them in suitable solvents or dispersing agents, possibly using surfactants as wetting agents or emulsifiers or dispersing agents, by diluting those already prepared emulsifiable concentrates with solvents or dispersing agents, etc.

0028In the case of powdered agents, the active ingredients can be mixed with a solid carrier, for example by grinding together; or you can impregnate the solid carrier with a solution or suspension of the active ingredients and then the solution or. Remove dispersant by evaporation, heating or by suction under reduced pressure. By adding surfactants or Dispersants can be used to make such powdery compositions readily wettable with water, so that they can be converted into aqueous suspensions which are suitable, for example, as spray compositions.

0029The active compound mixtures according to the invention can also be mixed with a surfactant and a solid carrier to form a wettable powder which is dispersible in water, or they can be mixed with a solid pregranulated carrier to form a granular product.

0030If desired, the active compound mixtures according to the invention can be dissolved in a water-immiscible solvent, such as, for example, an alicyclic ketone, which advantageously contains dissolved emulsifier, so that the solution has a self-emulsifying effect when added to water. Otherwise, the active ingredient combinations can be mixed with an emulsifier and the mixture can then be diluted with water to the desired concentration. In addition, the active ingredient combinations can be dissolved in a solvent and then mixed with an emulsifier. Such a mixture can also be diluted with water to the desired concentration. In this way, emulsifiable concentrates or ready-to-use emulsions are obtained.

0031The agents according to the invention can be used according to the application methods customary in crop protection or in agriculture. The method according to the invention for combating harmful fungi is characterized in that the place of plant growth to be protected or the crop to be protected, for example plants, parts of plants or propagation material (for example seeds), with an effective amount of an active compound combination according to the invention or treated an agent according to the invention.

Formulation examples

Example 1: Emulsifiable concentrate (EC)

0032<tables id="tabl0001" num="0001"><img file="EP0484279A2_D0004.tif" /></tables>

0033Such a concentrate can be diluted with water to make application broths for leaf treatment, soil treatment or the treatment of parts of plants.

Example 2: Emulsifiable concentrate (EC)

0034<tables id="tabl0002" num="0002"><img file="EP0484279A2_D0005.tif" /></tables>

0035All components are dissolved with stirring, with slight heating accelerating the dissolution process. In diluted form, such solutions are used to protect plants or parts of plants (seeds, cuttings, tubers, etc.) from fungal attack.

Example 3: Emulsifiable concentrate (EC)

0036<tables id="tabl0003" num="0003"><img file="EP0484279A2_D0006.tif" /></tables>

0037The resulting solutions according to Example 1-3 can be emulsified in water and thus result in a ready-to-use spray liquor in a desired dilution. Such a spray liquor can be used, for example, to seed grain seeds.

Example 4: wettable powder (WP)

0038<tables id="tabl0004" num="0004"><img file="EP0484279A2_D0007.tif" /></tables>

0039To produce this wettable powder, fenpropidine and nonylphenol polyethoxylate are mixed in a first working process and sprayed onto the submitted silica in a powder mixer.

0040The other components are then mixed in and finely ground, for example using a pencil mill.

0041The resulting wettable powder, when stirred into water, results in a fine suspension in the desired dilution, which is suitable as a ready-to-use spray liquor, for example for dressing propagation material, such as plant tubers, roots and foliage from seedlings or plant seeds.

Example 5: wettable powder (WP)

0042<tables id="tabl0005" num="0005"><img file="EP0484279A2_D0008.tif" /></tables>

Example 6: wettable powder (WP)

0043<tables id="tabl0006" num="0006"><img file="EP0484279A2_D0009.tif" /></tables>

0044The active ingredients of Examples 5 and 6 are mixed well with the additives and ground well in a suitable mill. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

Example 7: Dusts

0045<dl id="dl0001"><dt>Fenpropimorph</dt><dd>6 % w / w</dd><dt>Cyproconazole</dt><dd>2nd % w / w</dd><dt>kaolin</dt><dd>87 % w / w</dd><dt>Fumed silica</dt><dd>5 % w / w</dd></dl>

0046Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.

Biological examples

B-1. Mycelial growth test with Helminthosporium repentis-tritici

a)

Method:

0047The fungus strain is cultivated for 7 days at 18 ° C. and 16 hours / day of simulated sunlight irradiation on potato dextrose agar (PDA) which contains one or both of the active ingredients or is free of active ingredients (control). For this purpose, the active ingredients I and II are each dissolved in pure ethanol and mixed and diluted according to the desired proportions. Then a certain amount is added to the liquid PDA medium at 50 ° C and mixed intimately. Agar media with active ingredient concentrations of 30; 10; 3; 1; 0.3; 0.1; 0.03 and 0.01 mg AS / liter. The ethanol concentration in the medium is a uniform 0.1%.

0048The liquid culture medium is then poured into petri dishes (9 cm ∅) and inoculated in the center with an agarrondelle (5 mm ∅) which has been punched out from a 7-day-old mushroom culture. The inoculated dishes are incubated for 5 days at 18 ° C in a climate chamber in the dark. Each attempt runs in 3 or 4 repetitions.

b)

Evaluation:

0049After the incubation period, the colony diameter is determined. Abbott's fungicide effects are transformed into probit values ​​(Bliss, CI 1935) * and put into a dose-response relationship against the logarithms of the fungicide concentrations. With the help of the probit-log display, the dose / effect curve is converted into a straight line (DL Finney 1971 "Probit analysis", 3rd ed., Cambridge, UK: Cambridge University Press. The linear regression and the ED-50 values ​​(effective dosage) are determined from this straight line. * Bliss, CI Ann. Appl. Biol.<u>22</u>, 134-167 (1935)

Calculation of the synergy factors (SF) of fungicides in a mixture

0050The theoretical effect (ED_th) of a mixture can be calculated using the formula from Wadley (**) if the ED values ​​of the individual components of the mixture are known:<maths id="math0001"><math display="block"><mrow><mtext>ED-50 (th) </mtext><mfrac><mrow><mtext>a + b</mtext></mrow><mrow><mfrac><mrow><mtext>a</mtext></mrow><mrow><msub><mrow><mtext>ED-50</mtext></mrow><mrow><mtext>a</mtext></mrow></msub></mrow></mfrac><mtext> + </mtext><mfrac><mrow><mtext>b</mtext></mrow><mrow><msub><mrow><mtext>ED-50</mtext></mrow><mrow><mtext>b</mtext></mrow></msub></mrow></mfrac></mrow></mfrac><mtext> a, b = ratios of the fungicides in the mixture</mtext></mrow></math><img file="EP0484279A2_D0010.tif" /></maths>(**) Wadley, FM (1945) The evidence required to show synergistic action of insecticides and a short cut in analysis. ET-223-, US Department of Agriculture, 8 pp. Wadley, FM (1967) Experimental Statistics in Entomology. Washington, USA: Graduae School Press, USDA

0051The ratio of the theoretically calculated effect (ED_th) and the effect actually observed (ED_if) of the mixture gives the synergy factor (SF).<maths id="math0002"><math display="block"><mrow><mtext>SF =</mtext><mfrac><mrow><mtext>ED-50 (th)</mtext></mrow><mrow><mtext>ED-50 (whether)</mtext></mrow></mfrac></mrow></math><img file="EP0484279A2_D0011.tif" /></maths> SF> 1.2 synergistic interaction SF> 0.5 <1.2 additive interaction SF <0.5 antagonistic interaction

0052According to U. Gisi et al. (1987) and Y. Levy et al. (1986), SF values ​​greater than 1.0 already indicate a synergistic interaction. *** *** Gisi, U., Binder, H., Rimbach, E. (1985) Synergistic interactions of fungicides with different modes of action. Trans. Br. Mycol. Soc. 85 (2), 299-306 Levy, Y. et al. (1986) The joint action of fungicides in mixture: comparaison of two methods of synergy calculation. Belletin OEPP 16, 651-657 (1986)

0053The limits of the synergy factor of a particular mixture are determined using the standard deviation of the observed ED values. SF values ​​greater than 1.2 give statistically significant synergism.

d)

Results of the tests with active ingredient I and active ingredient II

0054Activities of the individual components and the mixture (ED-50)<tables id="tabl0007" num="0007"><img file="EP0484279A2_D0012.tif" /></tables>

e)

Results of the tests with active ingredient I and active ingredient III

0055Activities of the individual components and the mixture (ED-50)<tables id="tabl0008" num="0008"><img file="EP0484279A2_D0013.tif" /></tables>

B-2.

Mycelial growth test with Septoria nodorum

0056The test method and its evaluation are the same as that of biological example B-1.<tables id="tabl0009" num="0009"><img file="EP0484279A2_D0014.tif" /></tables>

f)

Comment:

0057The values ​​in Tables 1 to 4 show for each of the two or four independent tests that the fungicidal activity of both a mixture of active compound I and active compound II and of a mixture of active compound I and active compound III experienced a significant increase, ie it was a synergistically enhanced effect. As can be seen, these effects can be reproduced at any time.

0058Similar results are also achieved against Helminthosporium teres.