PL202640B1 - Fungicidal combinations comprising a glyoxalic acid methylester methyloxime derivative - Google Patents

Abstract

A method of combating phytopathogenic diseases on crop plants which comprises applying to the crop plants or the locus thereof being infested with said phytopathogenic disease an effective amount of a combination of a) 2-[ alpha -{[( alpha -methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxalic acid methyl ester-O-methyloxime (I) in association with b) a broad variety of other plant fungicides is particularly effective in combating or preventing diseases of crop plants. These combinations exhibit synergistic fungicidal activity.

Description

Description of the invention

The invention relates to a fungicide composition for the control of phytopathogenic diseases on crops, in particular for the control of phytopathogenic fungi.

It is known that certain strobilurin derivatives exhibit biological activity against phytopathogenic fungi. The properties of these derivatives and the methods for their preparation are disclosed e.g. in EP-A-460575. On the other hand, fungicides containing anilides, carbamates and amino acid amides are generally known as plant fungicides for a wide variety of crops. However, plant tolerance and activity against phytopathogenic fungi mean that in many cases and aspects these substances do not always meet the agrotechnical requirements.

According to the invention, a fungicide composition for controlling phytopathogenic diseases on crops is characterized in that it comprises a fungicidally effective combination

a) 2- [α - {[(α-methyl-3-trifluoromethylbenzyl) imino] oxy} -o-tolyl] glyoxylic acid methyl ester O-methyl oxime - Compound I in combination with

b) the second component is compound IIL

N- (3 '- (1'-chloro-3-methyl-2, -oxopentyl)) - 3,5-dichloro-4-methylbenzamide.

Preferably, in the composition according to the invention, the weight ratio of component a) to component b) is between 10: 1 and 1:20.

The composition is particularly effective in controlling or preventing fungal diseases of crops and exhibits synergistic antifungal activity.

The active ingredient combination used in the composition is effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia); imperfect fungi (e.g., Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia, and Pseudocercosporella herpotrichoides (Tapesia spp.)); Oomycetes (e.g. Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).

Target crops affected by the indications disclosed herein include, within the scope of the present invention, for example the following plant species: cereals (wheat, barley, rye, oats, rice, sorghum and related crops); beet (sugar beet and fodder beet); stone fruit, hard fruit and soft fruit (apples, pears, plums, peaches, nuts, cherries, strawberries, raspberries and blackberries); legumes (beans, lentils, peas or soybeans); oil plants (rape, mustard, poppy, olive, sunflower, coconut, castor, cocoa, peanut); cucumber plants (pumpkin, cucumbers, melons); fiber plants (cotton, linen, hemp, jute); citrus fruits (oranges, lemons, grapefruits, mandarins); vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); laurel plants (avocado, cinnamon, camphor); or plants such as corn, tobacco, nuts, coffee, sugarcane, tea, grapevines, hops, banana trees and natural rubber trees, as well as ornamental plants (flowers, shrubs, broadleaf and evergreen trees such as conifers). The list is not intended to limit the scope in any way.

The composition according to the invention is particularly effective against Phytophthora, Peronospora, Bremia, Pythium and Plasmopara, and especially against monocotyledonous plant pathogens such as cereals including wheat and barley.

The amount of the composition according to the invention to be used depends on various factors such as the compound used, the subject of the treatment (plant, soil, seed), the type of treatment (e.g. application.

It has been found that the use of compound I in combination with a compound of formula IIB unexpectedly and significantly increases the fungus control efficiency compared to the fungus control efficiency of these compounds when used individually. The composition is also effective against a wider spectrum of fungi.

The weight ratio a): b) is selected so as to ensure a synergistic fungicidal action and is in the range between 10: 1 and 1:20, preferably between 5: 1 and 1:20, in particular 2: 1 and 1 : 20, and even more preferably 1: 1 to 1:10. The synergistic effect of the compositions is evident from the fact that the fungicidal action of the compositions a) + b) is stronger than the sum of the fungicidal actions a) and b).

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The composition according to the invention is applied by applying to the treated plants, or a fragment thereof, a mixed or individual combination of a fungicidally effective amount of compound I and compound component b).

The term "plant fragment used" is intended to include the fields where the treated plants are grown or where the seeds of the crops have been sown or the place in the soil where the seeds will be placed. The term seed is intended to include plant propagation material such as cuttings, seedlings, sprouted or soaked seeds.

The new composition is extremely effective against a wide spectrum of phytopathogenic fungi, especially the classes of imperfect fungi and Oomycetes. Some of them are systemic and can be used as foliar and soil fungicides.

Fungicide combinations are of particular interest for combating a large number of fungi in a variety of crops or seeds, especially wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, coffee, sugarcane, fruit and ornamental plants, in horticulture. and viticulture, and vegetables such as cucumbers, beans and squashes.

The composition is applied with a fungicidally effective amount of the active ingredients by direct treatment of the fungus, or seeds, plants or materials infested with the fungus, or soil.

The agents can be applied before or after infecting materials, plants or seeds with the fungus.

The new composition is particularly effective against the following plant diseases:

Erysiphe graminis on cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Podosphaera leucotricha on apples,

Uncinula necator on grapevines, Puccinia species on cereals, Rhizoctonia species on cotton, rice and lawns, Ustilago species on cereals and sugar cane,

Venturia inaequalis (scabs) on apples, Helminthosporium species on cereals,

Septoria nodorum on wheat,

Septoria tritici on wheat,

Rhynchosporium secalis on barley,

Botrytis cinerea (gray mold) on strawberries, tomatoes and grapes

Cercospora arachidicola on peanuts,

Peronospora tobacco on tobacco,

Bremia lactucae on lettuce,

Pythium debaryanum on sugar beet,

Pseudocercosporella herpotrichoides (Tapesia spp.) On wheat and barley,

Pyrenophera teres on barley,

Pyricularia oryzae on rice, Phytophthora parasites on potatoes and tomatoes, Fusarium and Verticillium species on various plants,

Plasmopara viticola on grapes, Alternaria species on fruit and vegetables.

In the case of plant application, compound I is applied at 50 to 200 g / ha, in particular 75 to 150 g / ha, e.g. 75, 100 or 125 g / ha, in combination with 50 to 1500 g / ha. especially 60 to 1000 g / ha, e.g. 75 g / ha, 80 g / ha, 100 g / ha, 125 g / ha, 150 g / ha, 175 g / ha, 200 g / ha, 300 g / ha, 500 g / ha, or 1000 g / ha of compound - component b).

Preference is given to applying 50 to 1500 g a.i./ha in combination with compound I. In agricultural practice, the application rates depend on the type of effect desired and are in the range of 0.02 to 3 kg of active ingredient per hectare.

If the active ingredient is used for seed treatment, amounts of from 0.001 to 50, preferably from 0.01 to 10 g per kg of seed are usually sufficient.

The composition according to the invention may be used in any conventional form, for example in the form of a twin pack, ready-to-use granules, pseudo-flowable or wettable powder in combination with agrotechnically acceptable adjuvants. Such compositions may be prepared in conventional manner, e.g. by mixing the active ingredients with appropriate adjuvants.

(Diluents or solvents and optionally other formulatory ingredients such as surfactants). Suitable carriers and adjuvants can be solid or liquid and are substances usually used in formulation technology, such as, for example, natural or regenerated minerals, solvents, dispersants, wetting agents, binders, thickeners, binders or fertilizers. Such carriers are for example disclosed in WO 96/22690.

Especially those formulations to be applied by spraying, such as water-dispersible concentrates or wettable powders, may contain surfactants such as wetting and dispersing agents, e.g. fatty alcohol.

The seed dressing formulation is applied in a manner known per se to the seeds using a combination of the invention and a diluent having a suitable seed dressing formulation form, e.g. in the form of an aqueous suspension or a dry powder with good adherence to the seed. Such seed dressing formulations are known in the art and may contain the individual active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.

In general, the formulations contain from 0.01 to 90% by weight of active ingredient, from 0 to 20% of agrotechnically acceptable surfactant and 10 to 99.99% of solid or liquid adjuvant (s), the active ingredient being at least a compound of formula I together with the compound - component b) and optionally other active ingredients, especially guazatin and fenpiclonil. Concentrate compositions generally contain between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of preparations may contain, for example, from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight, of active ingredient.

Examples of specific preparation-combinations are disclosed e.g. in WO 96/22690, e.g. wettable powders, emulsifiable concentrates, dusts, extruded granules, coated granules, suspension concentrate.

The slow release of part of the combination of compound I and compound-component b) or each of them individually from the capsule suspension was mixed with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate / polymethylene polyphenylisocyanate mixture (8: 1). This mixture was emulsified into a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoam and 51.6 parts of water until the desired particle size was obtained. To this emulsion was added a mixture of 2.8 parts 1,6-diaminohexane and 5.3 parts water. The mixture was agitated until the polymerization reaction was completed.

The obtained capsule suspension was stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The preparation-capsule suspension contains 28% of active ingredients. The capsule has an average diameter of 8-15 microns.

The obtained preparation was applied to seeds as an aqueous suspension in a suitable apparatus.

While commercial products are preferably formulated as concentrates, the end user typically employs dilute formulations.

Biological examples

A synergistic effect exists when the action of an active ingredient combination is greater than the sum of the actions of the individual components.

The expected effect of E for a given active ingredient follows the so-called COLBY formula and can be calculated as follows (COLBY, S.R. Calculating synergistic and antagonistic responses of herbicide combination, Weeds, vol. 15, pp. 20-22; 1967):

ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture,

X =% of the action of active ingredient I using p ppm of active ingredient,

Y =% of the activity of active ingredient II with q ppm of active ingredient.

According to Colby, the expected (additive) effect of active ingredients l = ll with the use of p + q ppm of active ingredients is

E = X + YX Y 100

If the observed effect (O) is stronger than the expected effect (E), then the action of the combination is superadditive, ie there is a synergistic effect.

Alternatively, the synergistic effect can also be determined from dose / response curves according to the so-called WADLEY method. With this method it is determined

The effectiveness of a.i. by comparing the degree of invasion of the treated plants with those of untreated, similarly inoculated and incubated controls. Each a.i. is tested at 4 to 5 concentrations. Dose / response curves are used to determine the EC90 (i.e. the concentration of a.i. providing 90% disease control) for the individual compounds as well as for the combination (EC 90 observed). The experimentally found values for mixtures of a given weight ratio are compared with the values that would be found if only a complementary effect of the components were present (EC 90 (A + B) expected). EC90 (A + B) expected from Wadley (Levi, et al., EPPO-Bulletin, 16, 1986, 651-657):

^{EC 90 (A + B)} expected a + bab

--1- ^{EC 90 (A)} observed ^{EC 90 (B)} observed where a and b are weight fractions of compounds A and B in the mixture, and indices (A), (B) (A + B) refer to observed EC 90 values of compounds A, B or a given combination of A + B. The proportion EC 90 (A + B) expected / EC 90 (A + B) observed expresses the interaction factor (F). In the case of synergism, F is> 1.

Example B-1: Residual protective effect against Venturia inaequalis on apples.

The seedlings of apple trees with fresh shoots 10-20 cm long were sprinkled with an aqueous spray mixture prepared from a wettable powder formulation of a mixture of active ingredients until dripping, and 24 hours later they were infected with a conidium suspension of the fungus. The plants were incubated for 5 days at 90-100% relative humidity and placed in a greenhouse for a further 10 days at 20-24 ° C. The fungus invasion was assessed 12 days after infection.

Example B-2 (a): Action against Botrytis cinerea on apples.

The artificially damaged apples were treated by spraying the spray mixture of the active ingredient mixture onto the damaged areas. The treated fruits were then inoculated with a spore suspension of the fungus and incubated for one week under high humidity at about 20 ° C. The fungicidal activity of the test compound depended on the number of damaged spots that started to rot.

Example B-2 (b): Action against Botrytis cinerea on tomatoes.

4 week old Roter Gnom tomato plants were treated with the formulated test compound in a spray booth. Two days after application, tomato plants were inoculated by spraying the spore suspension onto the test plants. After an incubation period of 4 days at 20 ° C and 95% relative humidity in a growth chamber, disease incidence was assessed.

Example B-2 (c): Action against Botrytis cinerea on grapes.

The 5-week-old Gutedel grapevine seedlings were treated with the prepared compound tested in the spray chamber. Two days after application, the grapevines are inoculated by spraying the spore suspension onto the test plants. After an incubation period of 4 days at 21 ° C and 95% relative humidity in a greenhouse, disease incidence was assessed.

Example B-3: Action against Podosphaera leucotricha on apple shoots.

Apple seedlings with a length of about 15 cm with fresh shoots were sprayed with the spray mixture of the active ingredient mixture. The treated plants at 24 were later infected with a conidium suspension of the fungus and placed in an air-conditioned chamber at 70% relative humidity and 20 ° C. The fungus invasion was assessed 12 days after infection.

Example B-4: Action against Drechslera teres on barley.

10-day-old barley plants of the "Golden Promise" genus were sprayed with the spray mixture of the active ingredient mixture. The treated plants at 24 were later infected with a conidium suspension of the fungus and incubated in an air-conditioned chamber at 70% relative humidity and 20-22 ° C. The fungus invasion was assessed 5 days after infection.

Example B-5: Efficacy against Erysiphe graminis f.sp. tritici on wheat.

Five to ten seeds of 'Arina were sown in 7 cm diameter plastic pots and cultivated for 7 to 12 days at 20 ° C, 50-70% RH. resp. After the first leaf had completely unfolded, the plants were treated with an aqueous spray containing individual compounds or mixtures thereof (a.i. herein). All compounds were used as experimental or commercial preparations; the combinations were applied as tank mixtures. Applications were foliar spraying until almost run-off (three tanks at a time). 24 hours after application or 24 hours before application, plants were inoculated in a sedimentation tower with fresh spores

PL 202 640 B1

Erysiphe graminis f.sp. tritici. Plants were then incubated in a growth chamber at 20 ° C, 60% hum. resp. Seven days after inoculation, the percent infection of primary leaves was estimated. The effectiveness of a.i. was determined by comparing the degree of fungal attack on the treated plants with that on untreated, similarly inoculated and incubated control plants. Each a.i. tested at 4 to 5 concentrations. The synergism factor was calculated according to the COLBY method.

Example B-7: Action against Uncinula necator.

4-week-old grapevines (4-5 leaves) were sprayed to almost run-off with a suspension containing 250 mg / l of active ingredient, then the deposit was allowed to dry. The next day, the treated plants were inoculated by spraying freshly harvested conidia over the test plants; the plants were then incubated in a growth chamber for 10-14 days at + 22 ° C and 70% hum. resp. The efficacy of the test compounds was determined by comparing the degree of fungal attack with that of untreated, similarly inoculated control plants.

Example B-8: Action against Plasmopara viticola on grapevines.

The 4- to 5-leaf stage vine seedlings were dripped with an aqueous spray mixture prepared from a wettable powder of the active ingredient mixture (0.02% active ingredient) and 24 hours later infected with a sporangia suspension of the fungus. Fungus invasion was assessed 6 days after infection; meanwhile, 95 to 100% relative atmospheric humidity and a temperature of 20 ° C were maintained.

Example B-9: Action against Phytophthora infestation on tomatoes. a) Healing effect.

After growing for three weeks, tomato plants, cv. "Roter Gnom," were sprinkled with a zoospore suspension of the fungus and incubated in a chamber at 18 to 20 ° C under a moisture-saturated atmosphere. Hydration was discontinued after 24 hours. After the plants had dried, they were sprinkled with a mixture which contained the active ingredient formulated as a wettable powder at a concentration of 200 ppm. After the spray layer has dried, the plants are placed back in the humidity chamber for 4 days. The number and size of the typical leaf spots that appeared after this period provided the scale for evaluating the efficacy of the test substances.

b) Protective systemic action.

The active ingredient, prepared as a wettable powder, was applied in a concentration of 60 ppm (based on the soil volume) to the soil surface of three-week-old tomato plants, cv. "Roter Gnom." After a three-day period, the underside of the leaves was sprayed with a zoospore suspension of Phytophthora parasites. The plants were then kept for 5 days in a spray chamber at 18 to 20 ° C in a moisture-saturated atmosphere. After this period, typical leaf spots developed, the number and size of which were used to evaluate the efficacy of the test substances.

Example B-10: Action against Phytophthora on potato plants. a) Residual-protective action.

2-3 week old potato plants (Bintje variety) were grown for 3 weeks and then sprinkled with a spray mixture (0.02% active ingredient) prepared from a wettable powder of the active ingredient. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation was assessed after 5 days of incubating the infected plants at 90-100% relative atmospheric humidity at 20 ° C.

b) Systemic Action.

A spray mixture (0.002% active ingredient by volume of soil) prepared from a wettable powder of the active ingredient was poured alongside 2-3 week old potato plants (cv. Bintje) which were grown for 3 weeks. Care was taken that the spray mixture did not come into contact with above-ground plant fragments. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation was assessed after 5 days of incubating the infected plants at 90-100% relative atmospheric humidity at 20 ° C.

The effectiveness of the tested combinations and the individual components in the above tests was determined by comparing the degree of attack of the fungus with that of untreated, similarly inoculated control plants.

The fungicide composition according to the invention showed good activity in all the above examples.

Claims (2)

1. A fungicide composition for controlling phytopathogenic diseases in crops, characterized in that it contains a fungicide-effective combination a) 2- [α - {[(α-methyl-3-trifluoromethylbenzyl) imino] oxy} -o-tolyl] glyoxylic acid methyl ester O-methyl oxime - Compound I in combination with b) the second component is the compound IIL N- (3 '- (1'-chloro-3-methyl-2'-oxopentyl)) - 3,5-dichloro-4-methylbenzamide. 2. A composition according to claim 1 A method according to claim 1, characterized in that the weight ratio of component a) to component b) is between 10: 1 and 1:20.