MXPA96006305A - Culti protection products - Google Patents

Abstract

Plant protecting active ingredient mixtures having a synergistically improved action, wherein component I is a compound having an immunizing action of the plant of formula I (See Formula) wherein: Z is CN, COOH or a salt of the same, CO-0-alkyl of 1 to 4 carbon atoms, or CO-S-alkyl of 1 to 4 carbon atoms, and wherein component II is a compound selected from the group: A) 4- [3- ( 4-cycrophenyl) -3- (3,4-dimethoxyphenyl) -acyloyl] morpholine ("dimethomorph"), B) 5-methyl-1,2,4-triazole [3,4-b] [1,3] benzothiazole ("triciclazole") and C) 3-allyloxy-1,2-benzothiazole 1,1-dioxide ("probenazole")

Description

CROP PROTECTION PRODUCTS The present invention relates to mixtures of novel protective active ingredients, which have a synergistically improved action, which comprise at least two active ingredient components, together with a suitable vehicle, wherein component I is a compound having a immunizing action of plant of the formula I: wherein: Z is CN, COOH or a salt thereof, CO-O-alkyl of 1 a. 4 carbon atoms, c O-S-alkyl of 1 to 4 carbon atoms; and wherein component II is a commercial product selected from the group: A) 4 - [3 - (4-chloro-phenyl) -3- (3,4-dimethoxyphenyl) acryloylmorpholine ("dimethomorph"), (Reference: C. Tomlin (Editor): The F "Esticide Manual, 10th edition, Farnham, United Kingdom, 1994, pages 351-352); B) 5-methyl-1,2,4-triazolo [3,4-b] [1,3] benzothiazole ("tricyclazole"), (Reference: C. tomlin (Editor): The Pesticide Manual, 10th edition, Faxnham, United Kingdom, 1994, pages 1017-101 =); and C) 3-allyloxy-1,2-benzothiazole 1,1-dioxide ("probenazole"), (Reference: C. Tomlin (Editor): The Pesticide Manual, 10th edition, Farnham, United Kingdom, 1994, pages 831 The invention also relates to metal salts and complexes of compounds I and II of the compounds of formula I, preference is given to those wherein: Z is COOH (compound IA) or a salt thereof, CN (compounds IB), COOCH3 (compound IC) or COSCH3 (compound ID). Preferred salts are alkali metal and alkaline earth metal salts, especially lithium, sodium, potassium, magnesium, or calcium salts, and also organic salts, especially salts of salt-forming amines, for example, trimethyl amine, triethyl amine, aniline N , N-dimethyl, pyridine, trietanolic amine, morpholine. A very special preference is given to the compound of formula I wherein: Z is COSCH3 (compound ID). It is known that the compounds of the formula I activate the plant's own latent defense system against pathogenic microbial influences, and according to the above, are able to protect the plant against pathogens (European Patent Number EP-A- 313, 512).

At low application rates, these compounds do not have a direct action on the harmful organisms, but they immunize the healthy plant against the diseases. The disadvantage of using compounds of formula I to control plant diseases is that the action is often inadequate at low application rates. Surprisingly, it has now been discovered that the compounds of the formula I, mixed with one of the conventional microbicides IIA to IIC have a synergistically enhanced action. By using these mixtures, it is possible to control plant diseases on the one hand by reinforcing the plant by activating its own defense system, and on the other hand, controlling the pathogens directly. Compared with the usual methods for controlling plant diseases, unexpectedly, small amounts of active ingredients are required. A particular advantage of the mixtures according to the invention is further that, because the modes of action of components I and II are completely different, the threat of the development of resistance in the control of the diseases of the plants . The synergistically improved action of the mixtures of components I and II manifests itself, for example, at lower rates of application, a longer duration of action, and together with higher crop yields. These improvements were not expected from the sum of the actions of the individual compounds. The present invention also relates to a method for protecting plants against plant diseases, especially against fungal infestation, by treating plants, parts of plants, or their surroundings, with a component I and a component II, in any desired sequence or in a simultaneous manner. Suitable mixing ratios of the two active ingredients are: I: IIA = from 1:30 to 1: 1, preferably I: II = from 1:30 to 1: 3 and from 1:10 to 1: 3. 1: 1IB = from 1:20 to 1: 1, preferably I: II = from 1: 5 to 1: 1 and from 1: 2.5 to 1: 1. I: IIC = from 1:50 to 2: 1, preferably I: II = from 1:25 a 1: 1 and from 1:10 to 1: 2. Mixtures of active ingredient I + II according to the invention have very convenient properties to protect plants against infestation of diseases. The active ingredient mixtures of the invention can be used to inhibit or destroy microorganisms that occur in plants or parts of plants (fruit, cocoon, leaves, stems, tubers, or roots) of different cultures of plants. useful plants, while at the same time, the parts of the plants that grow later are also protected against said microorganisms. They can also be used as coatings in the treatment of plant propagation material, especially seeds (fruit, tubers, grains), and plant cuts (eg, rice), to provide protection against fungal infections, as well as against fungi phytopathogenic that occur in the earth. The mixtures of active ingredient according to the invention are distinguished by the fact that they are especially well tolerated by plants, and are friendly to the environment. Mixtures of active ingredient are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (for example, Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula), - Basidiomycetes (for example, the genus Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (for example, Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and especially, Pseudocercosporella herpotrichoides); Oomycetes (for example, Phytophthora, Peronospora, Bremia, Pythium, Plasmopara). Objective crops for the indication areas described herein, comprise, within the scope of the present invention, for example, the following plant species: cereals (wheat, barley, rye, oats, rice, sorghum, and related crops); Beets (sweet beets and fodder beets); grapefruit, hard fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rapeseed, mustard, amapolat, olive, sunflower, coconut, castor oil plants, cocoa beans, peanuts); cucumber plants (courgettes, cucumbers, melons); fiber plants (cotton, linen, hemp, jute), • citrus fruit (oranges, lemons, grapefruits, tangerines); vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camfor); or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas, and natural rubber plants, as well as ornamentals (flowers, shrubs, broadleaf trees, and evergreen trees, such as conifers) . This list does not represent a limitation. The active ingredient mixtures according to the invention are especially suitable for use in vegetables, rice, and tobacco; also in potatoes, vines, meadows, and hops. The mixtures are especially suitable as follows: a) I + IIA for the treatment of vegetables and tobacco against Oomycetes, especially against Phytophthora, Peronospora, Bremia, - b) I + IIB for the treatment of rice against Fungi imperfecti, especially Pyricularia, - c) I + IIC for the treatment of rice against Fungi imperfecti, especially Pyricularia, and against bacterial diseases. The mixtures of active ingredients of the formulas I and II are generally used in the form of compositions. The active ingredients of the formulas I and II can be applied to the area or plant to be treated, either simultaneously or in succession on the same day, if desired, together with other vehicles, surfactants, or other auxiliary promoters of I read application that is used by custom in the technology of lei formulation. Suitable vehicles and auxiliaries can be solid or liquid, and are the substances ordinarily employed in the formulation technology, for example, natural or regenerated mineral substances, solvents, dispersants, wetting agents, viscosifiers, thickeners, binders, or fertilizers. A preferred method for applying a mixture of active ingredient comprising at least one of each of the active ingredients I and II, is the application to the parts of the plants that are above the ground, especially the leaves (foliar application) . The frequency and the rate of application depend on the biological and climatic living conditions of the pathogen. However, the active ingredients can also penetrate the plant through the roots through the soil or through water (systemic action), if the plant site is impregnated with a liquid formulation (for example, in the rice cultivation), or if the substances are introduced in solid form in the soil, for example, in the form of granules (application to the soil). In order to treat the seeds, the compounds of the formulas I and II can also be applied to the seeds (coating), either by impregnating the tubers or grains with a liquid formulation of each of the active ingredients in succession. , or by coating them with a wet or dry formulation already combined. In addition, in special cases, other methods of application to the plants are possible, for example, the treatment directed to the shoots or to the bunches of fruit. The compounds of the combination are used in an unmodified form, or preferably, together with auxiliaries conventionally employed in the technology of the formulation, and are therefore formulated in a known manner, for example, in emulsifiable concentrates, coatable pastes , directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dry powders, granules, or by encapsulation in, for example, polymeric substances. As with the nature of the compositions, the methods of application, such as spraying, atomizing, dusting, dispersing, coating, or pouring, are selected in accordance with the intended objectives and the prevailing circumstances. Suitable application rates of the active ingredient mixture are usually from 50 grams to 2 kilograms of active ingredient per hectare, preferably from 100 to 1000 grams of active ingredient per hectare, especially from 250 grams to 700 grams of active ingredient per hectare. . In the case of seed treatment, the application rates are from 0.5 grams to 1000 grams, preferably from 5 grams to 100 grams of active ingredient per 100 kilograms of seeds. The formulations are prepared in a known manner, for example, by homogenously mixing and / or grinding the active ingredients with extenders, for example, solvents, solid carriers, and where appropriate, surface-active compounds (surfactants). Suitable solvents are: aromatic hydrocarbons, preferably fractions containing from 8 to 12 carbon atoms, for example, mixtures of xylene or substituted naphthalenes, phthalates, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethylene glycol ethylene, monomethyl or monoethyl ether, ethylene glycol, ketones, such as cyclohexanone, strongly polar solvents, such as 2-pyrrolidone N-methyl, eulfoxid dimethyl, or dimethyl formamide, as well as vegetable oils or epoxidized vegetable oils, such as coconut oil or epoxidized soybean oil or water.

The solid carriers used, for example, for dry powders and dispersible powders, are normally natural mineral fillers, such as calcite, carbon, kaolin, montmorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly dispersed silicic acid, or highly dispersed absorbent polymers. Suitable granular absorbent carriers are porous types, for example, pumice, broken septum, sepiolite, or bentonite, and suitable non-sorptive carriers are, for example, calcite or sand. In addition, a large number of previously granulated materials of an inorganic or organic nature can be used, for example, especially dolomite or pulverized plant residues. Depending on the nature of the active ingredients of the formulas I and II to be formulated, suitable surface active compounds are nonionic, cationic, and / or anionic surfactants having good emulsifying, dispersing, and wetting properties. The term "surfactants" will also be understood to comprise mixtures of surfactants. Particularly convenient promoters of the application are also natural or synthetic phospholipids from the series of cephalin and lecithin, for example, phosphatidylethanolic amine, phosphatidyl serine, phosphatidyl glycerol, and lysolecithin.

The agrochemical compositions generally comprise from 0.1 to 99 percent, preferably from 0.1 to 95 percent of active ingredients of the formulas I and II, from 99.9 to 1 percent, preferably from 99.9 to 5 percent of a solid auxiliary or liquid, and from 0 to 25 percent, preferably from 0.1 to 25 percent of a surfactant. Although the commercial products of preference will be formulated as concentrates, the end user will usually employ diluted formulations. The following examples serve to illustrate the invention; in these Examples "active ingredient" denotes a mixture of compound I and compound II in a specific mixing ratio.

Formulation Examples Wettable powders a) b) c) active ingredient [1: 11 = 1: 3 (a), l: 2 (b), l: l (c)] 25% 50% 75% sodium lignosulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutyl naphthalene sulfonate _ 6% 10% octylphenol polyethylene glycol ether (7 to 8 moles of ethylene oxide) - 2% - highly dispersed silicic acid 5% 10% 10% kaolin 62 % 27% The active ingredient is mixed thoroughly with the auxiliaries, and the mixture is completely milled in a suitable mill, providing wettable powders that can be diluted with water to give suspensions of the desired concentration.

Concentrate emulsifiable active ingredient (1: 11 = 1: 6) 10% octylphenol polyethylene glycol ether (4 to 5 moles of ethylene oxide) 3% calcium dodecylbenzenesulfonate 3% polyglycol ether castor oil 35 moles of oxide of ethylene) 4% cyclohexanone 30% 50% xylene mixture Emulsions of any required dilution can be obtained, which can be used in plant protection, from this concentrate, by dilution with water.

Dry powders a) b) c) active ingredient [I: 11 = 1: 6 (a), 1: 2 (b), l: 10 (c)] 5% 6% 4% talc 95% kaolin - 94% filler mineral - - 96% Ready-to-use dry powders are obtained by mixing the active ingredient with the vehicle, and grinding the mixture in a suitable mill. These powders can also be used for dry coatings for seeds.

Granules of extruder active ingredient (1: 11 = 2: 1) 15% sodium lignosulfonate 2% carboxymethyl cellulose 1% kaolin 82% The active ingredient is mixed and ground: cn the auxiliaries, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated granules active ingredient (1: 11 = 1: 10 8% polyethylene glycol (molecular weight: 200) 3% kaolin 89% The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. In this way, certain non-dusty rec granules are obtained.

Concentrate in suspension active ingredient (1: 11 = 1: 8) 40% propylene glycol 10% nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% sodium lignosulfonate 10% carboxymethyl cellulose 1% silicone oil (in the form of a 75% emulsion in water) 1% water 32% The finely ground active ingredient is intimately mixed with the auxiliaries, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using these dilutions, live plants, as well as plant propagation material, can be treated and protected against infestation by microorganisms, by spraying, pouring, or immersion.

Biological Examples There is a synergistic effect provided that the action of a combination of active ingredients is greater than the sum of the actions of the individual components. The action to be expected E for a given combination of active ingredients, obeys the so-called COLBY formula and can be calculated as follows (COLBY, SR "Calculating synergistic and antagonistic responses of herbicide combinations." Weeds, volume 15, pages 20-22; 1967): ppm = milligrams of active ingredient (= ia) per liter of spray mixture. X =% action by the active ingredient I using p ppm active ingredient. Y =% action by active ingredient II using qppm of active ingredient. According to Colby, the expected action (additive) of the active ingredients I + II, using p + q ppm of active ingredient, is: XY E = X + Y 100 If the action actually observed (O) is greater than the action expected (E), then the action of the combination is superadditive, that is, there is a synergistic effect. O / E = synergy factor (FS). In the following examples, it is assumed that the infestation of the untreated plants is 100 percent, which corresponds to an action of 0 percent. g-j «» tn io B-1: Action against Phvtophthora infestans on tomatoes a) Curative action After a 3-week culture period, tomato plants of the "Gnome Red" variety are sprayed with a suspension of zoospores of the fungus, and incubated in a cabinet of 18 ° C to 20 ° C and with 100 percent humidity. Humidification stops after 24 hours. When the plants have dried, they are sprayed with a mixture comprising the test compound formulated as a wettable powder in a concentration of 200 ppm. After the spray coating has dried, the plants are again placed in the humidity cabinet for 4 days. The activity of the test compounds is evaluated based on the number and size of the typical leaf spots that have occurred after that time. b) Preventive systemic action The test compound formulated as a numectable powder, is applied in a concentration of 60 ppm (based on the volume of the soil) to the soil surface of tomato plants of 3 weeks of age of the variety "Gnome P.ojo", planted in pots. After a waiting period of 3 days, the lower sides of the leaves of the plants will be. sprayed with a zoospore suspension of Phytophthora infestans.

Then the plants are kept in a spray cabinet for 5 days from 18 ° C to 20 ° C and with 100 percent humidity. After that time, the typical leaf mottles are formed, whose number and size are used to evaluate the activity of the test compounds. In particular, mixtures of component IA or ID with IIA produce good results. gj ^ mpTn B-2: Action against Peronospora tabacina on tobacco plants Tobacco plants (6 weeks old) are sprayed with a formulated solution of the test compound. Four days after the treatment, the plants are inoculated with a sporangia suspension of the fungus, kept at high humidity for 4 to 5 days, and then incubated further under a normal day / night sequence. The evaluation of the symptoms in the tests is based on the surface of the leaves infested with fungi. The infestation of the untreated plants corresponds to an action of 0 percent. Component I: compound ID (thiomethyl ester of benzothiadiazole-7-carboxylic acid). Component II: compound IIA (dimethomorph) Example B-3: Action against Colletotrichum l q * »" »t-i? Wn on Cucumis sativus L. a) After a culture period of 10 to 14 days, the cucumber plants are sprayed with a spray mixture prepared from a wettable powder formulation of the test compound. After 3 to 4 days, the plants are infected with a spore suspension (1.0 10: milliliter spores) of the fungus, and incubated for 30 hours in a high humidity and at a temperature of 23 ° C. Then the incubation is continued at a normal humidity and from 22 ° C to 23 ° C. The evaluation of the protective action is made 7 to 10 days after the infection, and is based on the infestation of the fungus. b) After a culture period of 10 to 14 days, the cucumber plants are treated by applying to the soil a spray mixture prepared from a wettable powder formulation of the test compound. After 3 to 4 days, the plants are infected with a spore suspension (1.5 x 105 spores / milliliter) of the fungus, and incubated for 30 hours in a high humidity and at a temperature of 23 ° C. Then the incubation is continued at a normal humidity and at 22 ° C. The evaluation of the protective action is made 7 to 10 days after the infection, and is based on the infestation of the fungus. In particular, mixtures of component IA or ID with HA produce good results.

Example B-4: Action against Pyricularia oryzae on rice plants. Rice plants of about 2 weeks old are placed together with the soil around the roots in a container filled with the spray mixture. The fungus infestation is evaluated 36 days later. The infestation of the untreated plants corresponds to an action of 0 percent. Component I: compound ID (thiomethyl ester of benzothiadiazole-7-carboxylic acid). Component II: compound IIB (tricyclazole).

Claims (15)

NOVELTY OF INTENT Having described the above invention, it is considered as a novelty, and therefore, the content of the following is claimed as property: REVINDICACIC EN

1. A plant protection composition having a synergistic action against the disease infestation, which comprises at least two competent of active ingredient together with a suitable vehicle, wherein the component I is a compound having an immunizing action on the plant of the Formula I: wherein: Z is CN, COOH or a salt thereof, C0-0-alkyl of 1 to 4 carbon atoms, or CO-S-alkyl of 1 to 4 carbon atoms; and wherein component II is a compound selected from the group: A) 4- [3 - (4-chlorophenyl) -3- (3, 4-dimethoxyphenyl) -acyloyl] morpholine ("dimethomorph"); B) 5-methyl-1,2,4-triazolo [3,4-b] [1,3] enzotiazole ("tricyclazole"); and C) 3-allyloxy-1,2-benzothiazole 1,1-dioxide ("probenazole").

2. A composition according to the claim 1, wherein the weight ratio of I: II is from 1:30 to 1: 1.

3. A composition according to the claim 2, wherein the weight ratio of 1:11 is from 1:20 to 1: 1.

4. A composition according to the claim 3, wherein the weight ratio of I: II is from 1:10 to 1: 3.

5. A composition according to claim 1, wherein, in the compound of the formula I Z is COOH (compound IA) or a salt thereof, CN (compound IB), OOCH3 (compound IC) or COSCH? (compound ID).

6. A composition according to claim 5, wherein, in the compound of the formula I, Z is C0SCH3 (compound ID).

7. A composition according to claim 1, wherein component II is the compound HA ("dimethomorph").

8. A composition according to claim 1, wherein component II is compound IIB ("tricyclazole").

9. A composition according to claim 1, wherein component II is compound HC ("probenazole").

10. A method for protecting plants against plant diseases, by treating plants, parts of plants, or their surroundings, with a component I and a component II according to claim 1, in any desired sequence or in a simultaneous manner.

11. A method according to claim 10, wherein, in the compound of formula I: Z is COOH (compound IA) or a salt thereof, CN (compound IB), COOCH3 (compound IC) or COSCH3 (compound ID). C

12. A method according to claim 11, wherein, in the compound of the formula I, Z is COSCH3 (compound ID).

13. A method according to claim 10, for the treatment of vegetables and tobacco, wherein the component 5 II is the compound HA.

14. A method according to claim 10, for the treatment of rice, wherein component II is compound IIB.

15. A method according to claim 10, for the treatment of rice, wherein component II is compound IIC.