IL108653A

IL108653A - Synergistic fungicidal composition

Info

Publication number: IL108653A
Application number: IL10865394A
Authority: IL
Original assignee: Basf Ag
Priority date: 1993-03-23
Filing date: 1994-02-15
Publication date: 1998-12-06
Also published as: WO1994021123A1; ATE144371T1; PL310805A1; GR3021492T3; NZ263170A; EP0690672B1; RU2129371C1; JP3611572B2; KR100316043B1; CZ288340B6; ES2092903T3; AU6376094A; AU676031B2; IL108653A0; DE59400914D1; DE4309272A1; EP0690672A1; PL173281B1; JPH08508019A; HU216718B

Abstract

The invention concerns a fungicidal mixture comprising (a) alpha -methoximino-2-[(2-methylphenoxy)methyl]-phenylacetic acid methyl ester represented by formula (I) and (b) 4-(2-methyl-3-[4-tert.-butylphenyl]-propyl)-2,6-dimethylmorpholine (fenpropimorph) represented by formula (II) or the active substance tridemorph or the active substance fenpropidin and (c) the active substance prochloraz or another azol active substance. The invention also concerns a method of controlling fungi using this mixture.

Description

108653/1 Synergistic fungicidal composition BASF Aktiengesellschaft C: 92570 Fungicidal composition The present invention relates to fungicidal compositions having a synergistic fungicidal action and methods of combating fungi with these compositions.

It is known (EP 253 213) to use methyl a-methoximino-2- [ (2-me-thylphenoxy) -methyl] -phenylacetate as a fungicide. It is also known (DE 26 56 747) to use the active ingredient 4- (2-methyl-3- [4-tert .-butylphenyl] -propyl) -2 , 6-dime-thylmorpholine or the active ingredient tridemorph or the active ingredient fen-propidin or salts thereof as fungicides.

It is further known (EP 72 156) to use N-propyl-N- [2 , 4 , 6-trichlo-rophenoxy) -ethyl] imidazole-l-carboxamide as a fungicide.

Furthermore, numerous azole active ingredients are known which have a fungicidal action, namely (Z) -2- (1,2 , 4-triazol-l-ylmethyl) -2- (4-fluorophenyl ) -3- (2-chloro-phenyl) -oxirane of the formula 1-buty1-1- (2 , 4-dichlorophenyl) -2- ( 1 , 2 , 4-triazol-l-yl ) -ethanol (common name hexaconazole) , 1- [ (2-chlorophenyl) methyl] -1- (1, 1-di-methyl ) -2- (1,2, 4-triazol-l-yl-ethanol , 1- (4-fluorophenyl ) -1- (2-fluorophenyl) -2- (1,2, 4-triazol-l-yl) -ethanol (common name flu-triafol) , (RS) -4- (4-chlorophenyl) -2-pheny1-2- (lH-1, 2, -triazol-l-ylmethyl ) -butyronitrile, l-[(2 RS, 4 RS; 2 RS, 4 SR) -4-bromo-2- (2 , 4-dichlorophenyl) -tetrahydrofurfuryl] -1H-1,2, 4-triazole, 3- (2 , 4-dichlorophenyl ) -2- (lH-1 , 2 , 4-triazol-l-yl) -quinazolin-4 (3H) -one, (RS) -2 ,2-dimethyl-3- (2-chloroben-zyl) -4- (lH-1, 2 , 4-triazol-l-yl) -butan-3-ol, bitertanol, triadime-fon, triadimenol, cyproconazole, dichlobutrazol, difenoconazole, diniconazole, etaconazole, propiconazole, flusilazole, tebucona-zole, imazalil, penconazole, tetraconazole or a salt of such an azole active ingredient.

We have now found that a composition of a) methyl a-methoximino-2- [ (2-methylphenoxy) -methyl] -phenylace- tate and b) 4- (2-methyl-3- [4-tert . -butylphenyl] -propyl ) -2 , 6-dimethylmor- pho1ine ( fenpropimorph) or the active ingredient tridemorph or the active ingredient fenpropidin and an azole active ingredient selected from the group consisting of N-propyl-N- [2,4, 6-trichlorophenoxy) ethyl] imidazole- 1-carboxamide (Z ) -2- (1 , 2 , 4-triazol-l-ylmethyl ) -2- (4-fluorophenyl ) -3- (2-chlorophenyl) -oxirane of the formula 1-butyl-l- (2 , -dichloropheny1 ) -2- ( 1 , 2 , 4-triazol-l-yl ) -ethanol (common name hexaconazole) , l-[ (2-chlorophenyl) methyl] -1- ( 1 , 1-dimethy1) -2- ( 1 , 2 , -triazol-l-yl-ethanol , 1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2, 4-triazol-l-yl) -ethanol (common name flutriafol) , (RS)-4- (4-chlo- rophenyl ) -2-phenyl-2- ( lH-1 , 2 , 4-triazol-l-ylmethyl) -butyroni- trile, l-[(2 RS, 4 RS; 2 RS, 4 SR) -4-bromo-2- (2 , -dichloropheny1 ) -tetrahydrofurfuryl ] -lH-1 , 2 , 4-triazole, 3- (2 , 4-dichloropheny1) -2- (lH-1, 2 , 4-triazol-l-yl) -quinazolin-4 (3H) -one, (RS) -2 , 2-dimethyl-3- (2-chlorobenzyl) -4- (lH-1 , 2 , -triazol-l-yl) -butan-3-ol, bitertanol, triadimefon, triadimenol, cyproconazole, dichlobutrazol, difenoconazole, diniconazole, etaconazole, propiconazole, flusilazole, tebuconazole, imaza- lil, penconazole, tetraconazole or a salt of such an azole active ingredient, has a synergistic fungicidal action. The weight ratio of compounds a) , b) and c) is selected in such a way as to give a synergistic fungicidal action, for example a) :b) :c) of from 10 to 1:10 to 1:10 to 1, for instance 5 to 1:5 to 1:5 to 1, especially 3 to 1:3 to 1:3 to 1, and preferably 2 to 1:2 to 1:2 to 1. The ratio of a) :b) :c) may for example be 10:1:1 to 1:10:1 to 1:1:10. The synergistic action of the composition is apparent from the fact that the fungicidal action of the composition of a) + b) + c) is greater than the sum of the fungicidal actions of a) , of b) and of c) .

With regardd to the -C=N double bond, component a) may be present in two stereoisomeric forms. The (E) isomer is preferred.

The invention embraces compositions containing the pure isomers of compound a) , especially the (E) isomer, and compositions containing mixtures of the isomers.

The component fenpropimorph may be present in two stereoisomeric forms (morpholine ring) , the cis isomer being preferred.

The invention embraces compositions containing the pure isomers of the compound fenpropimorph, especially the cis isomer, and compositions containing mixtures of the isomers.

Compositions containing component a) predominantly as (E) isomer and at the same time component b) predominantly as cis isomer are preferred. a, (E) isomer CH3 b, cis isomer The active ingredient fenpropimorph b) may also be present in the form of its salts. These compositions too are embraced by the invention.

Salts are produced by reaction with acids, e.g., hydrohalo acids such as hydrofluoric acid, hydrochloric acid, hydro- bromic acid and hydroiodic acid, or sulfuric acid, phosphoric acid, nitric acid, or organic acids such as acetic acid, tri- fluoracetic acid, trichloroacetic acid, propionic acid, gly- colic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesul- fonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid or 1 , 2-naphthalenedi- sulfonic acid.

In practice, the pure active ingredients a) , b) and c) are advantageously used, to which further active ingredients such as insecticides, acaricides, nematicides, herbicides, other fungicides, growth regulatores and/or fertilizers may be added.

The fungicidal compositions according to the invention may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

Normally, the plants are sprayed or dusted with the compositions or the seeds of the plants are treated with the compositions.

The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes) , paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol) , ketones (e.g., cyclohexanone) , amines (e.g., ethanolamine, dimethylforma-mide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dis-persants such as lignin-sulfite waste liquors and methylcellu- lose.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsul-fonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alk laryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols , and octadecanols , salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naph-thalenesulfonic acids with phenol and formaldehyde, polyoxyethy-lene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The compositions are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a systemic action and may be used as foliar and soil fungicides.

The fungicidal compositions are of particular interest for con-trolling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The compounds are applied by treating the seeds, plants, materials or soil to be protected against fungus attack with a fungi-cidally effective amount of the active ingredients.

The compounds may be applied before or after infection of the materials, plants or seeds by the fungi.

The compositions are particularly useful for controlling the following plant diseases: Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Rhynchosporium in cereals, Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.

, . The novel compositions may also be used for protecting materials (timber), for example against Paecilomyces variotii.

The fungicidal agents generally contain from 0.1 to 95, and pre- ferably from 0.5 to 90, wt% of active ingredient.

The application rates depend on the type of effect desired, but are generally from 0.01 to 3 kg of active ingredient composition per hectare.

When the compositions are used for treating seed, application rates of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are generally required.

Biological experiments Example 1 Eradicative action on wheat mildew Wheat plants of the "Kanzler" variety were inoculated at the 3-leaf stage with triazole-resistant wheat mildew (Erysiphe gra-minis var. tritici) and treated at a degree of fungus attack of about 30% with aqueous active ingredient formulations in the concentrations given. The amount of water corresponded to 200 1/h. The plants were cultivated in the greenhouse for 20 days at 10 to 22°C. The experiment was then evaluated by determining the leaf area under attack in percent. These figures were converted into degrees of action. The expected degrees of action of the active ingredient composition were determined by the Colby formula (Colby, S.R., "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, S. 20-22, 1967) and compared with the degrees of action observed.

The values for the fungicidal action varied between the various experiments because the plants exhibited varying degrees of attack, which meant that the figures for the fungicidal action vary too. For this reason, only the results within the same experiment can be compared with one another.

Colby formula E = x + y - x-y/100 E = expected degree of action, expressed in % of the untreated control, when active ingredients A and B are used in concentrations of m and n x = degree of action, expressed in % of the untreated control, when active ingredient A is used in a concentration of m y = degree of action, expressed in % of the untreated control, when active ingredient B is used in a concentration of n Active ingredient I . methyl a -methoximino-2- [ (2-methylphenoxy) -methyl] -pheny- lacetate (+) -cis-4-[3- (4-tert-butylphenyl) -2-methylpropyl] methylmorpholine (fenpropimorph) III . 2- ( 1 , 2 , 4-triazol-l-ylmethyl ) -2- (4-fluorophenyl) -3- (2-chlorophenyl) -oxirane (epoxiconazol) IV. 1- (N-propyl-N-2- (2,4, 6-trichlorophenoxy) ethylcarba- moyl) imidazole (prochloraz) V. Active ingredient combination Active ingredient I + fenpropimorph 105 : 210 I. Active ingredient combination Active ingredient I + epoxiconazol 1 : 1 Active ingredient combination Active ingredient I + prochloraz 1 : 1 Active ingredient combination fenpropimorph + prochloraz 281 : 200 Active ingredient combination fenpro imorph + epoxiconazol 3 : 1 Table 1 Erysiphe graminis test (wheat) eradicative Triazole-resistant Erysiphe graminis Active ingredient (a.i.) Active ingredient conDegree of action centration in the spray in % of the unliquor in % treated control Control (untreated) - 0 I. prior art a.i. 0.05 50 EP 253 213 II. prior art a.i. 0.05 47 fenpro imorph, DE 2 656 747 III. prior art a.i. 0.05 26 epoxiconazol IV. prior art a.i. 0.05 24 prochloraz, EP 72 156 V. prior art a.i. combina0.05 65 tion a.i. I + fenpropimorph EP 524 496 VI. prior art a.i. combina0.05 52 tion a.i. I + epoxiconazol EP 531 837 VII. prior art a.i. combina0.05 52 tion a.i. I + prochloraz EP 531 837 Compositions according to the invention The results show that 0.04% (0.01 + 0.03) of the compositions containing three active ingredients has a better fungicidal ac-tion than 0.05% of the individual active ingredients and the two-component active ingredient composition.

The same experiment, carried out with triazole-sensitive Erysiphe graminis, confirmed the results given in Table 1.

Table 2 Erysiphe graminis test (wheat) eradicative Triazole-resistant Erysiphe graminis Active ingredient (a.i.) Active ingredient conDegree of action centration in the spray in % of the unliquor in % treated control Control (untreated) - 0 I. prior art a.i. 0.1 55 0.01 29 II. prior art a.i. 0.1 52 fenpropimorph 0.01 25 III. prior art a.i. 0.1 36 epoxiconazol 0.01 10 IV. prior art a.i. 0.1 29 prochloraz 0.01 5 V. prior art a.i. 0.1 83 a.i. I + fenpropimorph 0.01 55 Compositions according to the invention *) calculated by the Colby formula In these results for various three-component active ingredient compositions, the observed degrees of action were always greater than the degrees of action calculated by the Colby formula.

The same experiment, carried out with triazole-resistant Erysiphe graminis, confirmed the results given in Table 2 .

Claims

108653/2 - 14 - C L A I M S:

1. A synergistic fungicidal agent containing a fungicidally effective amount of a composition of a) methyl a -methoximino-2- [( 2-methylphenoxy) -methyl ] -pheny- lacetate 4- (2-methyl-3- [4-tert-butylphenyl] -propyl) -2 , 6-dimethyl- morpholine ( fenpropimorph) or the active ingredient tridemorph or the active ingredient fenpropidin and c) an azole active ingredient selected from the following group N-propyl-N- [2 , 4 , 6-trichlorophenoxy) ethyl] imidazole- 1-carboxamid /43931 15 ( Z) -2- ( 1 , 2 , 4-triazol-l-ylmethyl ) -2- ( 4-fluoropheny1 ) -3- (2-chlorophenyl) -oxirane of the formula 1-butyl-l- (2 , 4-dichlorophenyl ) -2- (1 , 2 , 4-triazol-l-yl) - ethanol (common name hexaconazole) , 1- [ (2-chlorophe- nyl ) methyl] -1- ( 1 , 1-dimethyl ) -2- (1,2, 4-triazol-l-yl-etha- nol, 1- (4-fluorophenyl)-l- (2-fluoropheny1) -2- (1,2, 4-triazol-l-yl ) -ethanol (common name flutriafol) , (RS)-4- ( -chlorophenyl ) -2-phenyl-2- ( lH-1 , 2 , 4-triazol-l-ylme- thyl)-butyronitrile, l-[(2 RS, 4 RS; 2 RS, 4 SR) -4-bromo-2- ( 2 , 4-dichlorophenyl ) -tetrahydrofurfu- ryl] -lH-1 , 2 , 4-triazole, 3- (2 , 4-dichlorophenyl ) -2- ( lH-1 , 2 , 4-triazol-l-yl ) -quinazolin-4 (3H) -one , (RS) -2 , 2-dimethyl-3- (2-chlorobenzyl ) -4- ( lH-1 , 2 , 4-triazol-l-yl) -butan-3-ol, bitertanol, triadimefon, triadime- nol, cyproconazole, dichlobutrazol, difenoconazole, dini- conazole, etaconazole, propiconazole, flusilazole, tebu- conazole, imazalil, penconazole, tetraconazole or a salt of such an azole active ingredient.

2. A method of combating fungi, wherein a fungicidally effective amount of a composition of a ) methyl a -methoximino-2- [ (2-methylphenoxy) -methyl] -pheny- lacetate and b) 4- (2-methyl-3- [4-tert-butylphenyl] -propyl) -2, 6-dimethyl- morpholine (fenpropimorph) CH3— /43931 16 or the active ingredient tridemorph or the active ingredient fenpropidin and c) an azole active ingredient selected from the following group N-propyl-N- [2,4, 6-trichlorophenoxy) ethyl] imidazole- 1-carboxamid (Z) -2- (1, 2, 4-triazol-l-ylmethyl)-2- (4-fluorophenyl) -3- (2-chlorophenyl) -oxirane of the formula 1-buty1-1- ( 2 , 4-dichlorophenyl ) -2- (1,2, -triazol-l-y1 ) - ethanol (common name hexaconazole) , 1- [ (2-chlorophe- nyl ) methyl] -1- ( 1 , 1-dimethyl ) -2- (1,2, 4-triazol-l-yl-etha- nol, 1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2 , 4-tri- azol-l-yl) -ethanol (common name flutriafol) , (RS)-4- ( 4-chlorophenyl ) -2-phenyl-2- ( lH-1 , 2 , 4-triazol-l-yIme- thyl) -butyronitrile, l-[(2 RS, 4 RS; 2 RS, 4 SR) -4-bromo-2- (2 , 4-dichlorophenyl) -tetrahydrofurfu- ryl ] -lH-1 , 2 , 4-triazole, 3- (2 , 4-dichlorophenyl ) -2- (lH-1 , 2 , 4-triazol-l-yl ) -quinazolin-4 (3H) -one, (RS ) -2 , 2-dimethyl-3- (2-chlorobenzyl ) -4- ( lH-1 , 2 , 4-triazol-l-yl) -butan-3-ol , bitertanol, triadimefon, triadime- nol, cyproconazole, dichlobutrazol, difenoconazole, dini- conazole, etaconazole, propiconazole, flusilazole, tebu- 108653/2 - 17 - conazole, imazalil, penconaxole, tetraconazole or a salt of such an azole active ingredient. is allowed to act on the fungi or the materials, areas, plants or seed threatened by fungus attack.

3. A fungicidal composition as claimed in claim 1, containing compounds a), b) and c) in an amount creating a synergistic fungicidal effect.

4. A fungicidal composition as claimed in claim 1, containing compounds a), b) and c) in a weight ratio of a:b:c of from 10 to 1:10 to 1:10 to 1. For the Applicants, REINHOLD COHN AND PARTNERS BY: