RU2141203C1 - Fungicide-insecticide mixture for protection of plants against sicknesses and insects, composition containing thereof, method of seed treatment, product of plant multiplication - Google Patents

Abstract

FIELD: agriculture. SUBSTANCE: invention describes a novel fungicide-insecticide mixture for protection of plants against sicknesses and insects containing fungicide 2-(4-chloro-benzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazole-1-yl-methyl)-1-cyclopentanol and an insecticide. The mixture has an effective amount of fungicide and insecticide and has (±)-5-amino-1-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)-4-trifluoro-methylsulfinylpyrazole-3-carbonitrile as an insecticide at the ratio of fungicide and an insecticide providing a synergetic effect. Invention describes also a method of seed treatment, product of plants multiplication and the composition containing the above indicated mixture where fungicide acts as a synergist of an insecticide. EFFECT: enhanced effectiveness of the composition. 11 cl, 8 tbl, 10 ex

Description

 The present invention relates to new agrochemical mixtures for plant protection, including both fungicidal active principle and insecticidal active principle, as well as to a method for treating plants using these mixtures.

 In the context of the present invention, a plant is understood to mean a whole plant, part of a plant, or plant propagation material, in particular a seed.

 More specifically, the subject of the invention is an agrochemical mixture for protecting plants from diseases and insects, which consists in that it contains at least an effective amount of a benzylidene-azolylmethylcycloalkane-type fungicide and at least an effective amount of an insecticide with a pyrazole, pyrrole or phenylimidazole group, in ratios causing a synergistic effect.

 As the benzylidene-azolylmethylcycloalkane fungicide, mention may in particular be made of those described in European patent application EP 0378953, and preferably 2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazole- 1-yl-methyl) -1-cyclopentanol, or triticonazole, and 2- (4-chlorobenzylidene) -1- (1H-1,2,4-triazol-1-yl-methyl) -1-cyclohexanol. Triticonazole is also known as a seed treatment fungicide according to European Patent Application EP 0467791.

 As insecticides with a pyrazole, pyrrole or phenylimidazole group, mention may be made of those described in European patent applications EP 0295117, EP 0460940 or EP 0484165, respectively. Preferably, the insecticide according to the present invention is selected from the group of insecticides with a pyrazole group. Preferably, a compound is chosen whose common name is fipronil, corresponding to the chemical formula (±) -5-amino-1- (2,6-dichloro-α, α, α-trifluoro-p-tolyl) -4-trifluoromethylsulfinylpyrazole-3-carbonyl. It is described in European patent application EP 0295117, and the properties of this compound are described in published reports of the Brighton Crop Protection Conference, 1992 (Pest and Diseases, pp. 29-34).

 From European patent applications EP 018943 and EP 019581, mixed synergistic agrochemical compositions are known in which the fungicide is a triazole or imidazole derivative and the organochlorine derivative is an insecticide. However, it is desirable to have new associations to eliminate, for example, resistance phenomena and for reasons related to environmental protection.

 It was unexpectedly found that the associations according to the invention are better than could be expected from them, since in addition to the simple complementarity of the two compounds, the fungicide, in addition to its own action, acts as a synergist of the insecticide. This is completely different from the information in European patent application EP 0545834, which describes the association of triticonazole with imidacloprid of the formula 1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylidene-amine. This application does not say anything about synergism. Each compound exhibits its own specific effectiveness without adversely affecting each other.

 Associations according to the invention show the phenomenon of antagonism no more than the above association, but they have the advantage over this latter, consisting in the fact that they are synergistic when it comes to insecticidal activity.

 Moreover, the associations according to the invention also have a completely surprising feature in that the insecticide acts as a synergist of the fungicide.

 In this regard, the associations according to the invention are of particular interest for protecting plants from diseases from insects.

 Preferably, the associations of the invention are suitable for seed protection or for tillage.

 The invention also relates to compositions comprising the above association according to the invention.

 The invention also relates to a method for protecting plants, in particular seeds, from diseases and insects, which consists in applying an association of two active principles. You can also apply one composition containing two active principles, or, either simultaneously or sequentially apply two compositions, each of which contains one of two active principles.

Preferably, the fungicide is used in a dose reaching 1 to 1000 g per centner [= 10 ³ kg] (g / c), and the insecticide is used in a dose of 5 to 2000 g per centner of seeds, the fungicide / insecticide ratio then being 0.0005 - 200, and the ratio of insecticide / fungicide is 0.005 - 2000. The doses of the mixture of compounds according to the invention used can vary widely and depend, in particular, on the virulence of the fungus and climatic conditions, and depending on the nature and degree of insect damage.

 Another subject of the invention is a seed treatment method in which the seeds to be processed are selected from the group consisting of crops (wheat, rye, barley), corn, sorghum, sunflower, cotton, rice, peas, rape, potatoes, and garden crops.

According to a variant, the subject of the invention is also a method of cultivating the soil by applying, in particular, to the seed furrow:
- either granules containing two active principles, in the form of an association or in the form of a composition;
- or mixtures of two types of granules, each of which contains one of two active principles, if necessary together with one or more solid or liquid acceptable in agriculture, carriers and / or, if necessary, together with one or more surface-active Agents Acceptable in Agriculture.

 This method is preferably carried out in the case of crops of grain crops, corn, cotton, sunflower. For cereals and maize, the doses of fungicide are 1–200 g / ha (grams per hectare), and those of the insecticide are 10–1000 g / ha. In the case of treating cereal seeds, the doses used for fungicide are 1-200 g / c, preferably 5-120 g / c, and for an insecticide 5-150 g / c, preferably 50-100 g / c.

 In the case of treating corn or sorghum seeds, the doses used for the fungicide are 5 to 150 g / c, preferably 10 to 100 g / c, and for the insecticide they are 25 to 1000 g / c, preferably 100 to 500 g / c.

 In the case of treating sunflower seeds, the doses used for the fungicide are 10-1000 g / c, preferably 50-200 g / c, and for the insecticide they are 50-2000 g / c, preferably 200-1000 g / c.

 In the case of treating cotton seeds, the doses used for the fungicide are 1 to 500 g / c, preferably 5 to 100 g / c, and for the insecticide they are 25 to 1000 g / c, preferably 100 to 500 g / c.

 The method according to the invention is particularly suitable for the destruction of pathogenic fungi and the extermination of harmful insects.

 Among the insects, there are such species of flies as gray fly (Hylemia coarctata, Phorbia coarctata, Delia coarctata, or sprout fly (Hylemia platura, Phorbia platura, Delia platura), also nutcrackers (Agriotes Sp., Athous Halmorrhoidalis), and especially the larvae of beetles nutcrackers, which are very well destroyed by the association, composition and processing method according to the invention.

Among pathogenic fungi, it is worth mentioning in particular: - for wheat: Microdochium nivale, Fusarium rozeum, Septoria nodorum, Ustilago sp., Tilleta sp., Puccinia sp., Erysiphe graminis, Septoria Tritici, Pseudocercosporella Rerpotrichoides;
- for barley: Pyrenophora sp., Fusarium roseum, Microdochium nivale, Ustilado sp., Phynchosporium secalis, Puccinia hordei, Erysiphe graminis;
- for rice: Pyricularia oryzae, Rhizoctonia solani, Helminthosporium oryzae, Jibberella fujikuroi;
- for corn: Pythium sp., Fusarium sp., Sphacelotheca reiliana, Colletotrichum sp., Diplodia sp.,;
- for sorghum: Fusarium sp. , Diplodia natalensis, Colletotrichum sp., Pyshium sp .;
- for sunflower: Botrytis cinerea, Sclerotinia sp., Alternaria sp., Phomopsis sp .;
- for cotton: Rhizoctonia solani, Fusarium sp., Pythium sp .;
- for peas: Ascochyta sp., Rhizoctonia sp., Fusarium sp .;
- for rapeseed: Phoma sp., Alternaria sp., Cylindrosporium sp.

 Finally, the invention also relates to a plant propagation product, in particular to a seed coated and / or containing an association as defined above, or a composition comprising a mixture of two active principles, or a mixture of two compositions, each comprising one of the active principles. It is readily understood that the seed, in particular, can be treated either with a composition containing a fungicide, preferably triticonazole, then with a composition containing an insecticide, preferably fipronil, or vice versa, or with a composition containing both active principles.

 The term "coated and / or containing" means that the active principle in a predominant amount is on the surface of the propagation product when applied, and more or less a significant part of it can penetrate, depending on the method of application. When the above propagation product is again planted, it adsorbs the active principle. From the point of view of a commercial product, we can say that most of the active principle most of the time is on the surface of the seed.

 The following examples are given to illustrate the mixtures, compositions and processing method according to the invention. Of course, these examples do not limit the scope of protection of the invention, and with the mixtures and compositions according to the invention it is possible to combat other types of lesions spread by insects or phytopathogenic fungi.

Example 1
Wheat grains are processed according to the classical seed treatment scheme by coating them:
- on the one hand, a concentrated suspension (CS) of Fipronil with a concentration of 600 g / l (0,083 l / c);
- on the other hand, with a mixture of 0.4 l of a concentrated suspension (COP) with a concentration of 300 g / l of triticonazole and 0,083 l of a concentrated suspension (COP) of Fipronil with a concentration of 600 g / l per centner of seeds;
- finally, using a 0.4 l / c concentrated suspension for seed treatment (COP) containing 250 g / l Endosulfan and 100 g / l Lindane (Complement SMGFLO ^® = standard).

 The untreated portion of the seeds serves as a control sample.

After sowing, wheat plants are attacked by sulfur flies (Hylemia coarctata) and the effectiveness of various treatments is evaluated several days after this attack. Then get the results shown in table. 1
Example 2
Wheat grains are processed according to the classical seed treatment scheme by coating them:
- on the one hand, a concentrated suspension (CS) of Fipronil with a concentration of 600 g / l (0,083 l / c);
- on the other hand, with a mixture of 0.4 l of a concentrated suspension of KS with a concentration of 300 g / l of triticonazole and 0.083 l of a concentrated suspension of KS Fipronil with a concentration of 600 g / l per centner of seeds;
- finally, using a 0.4 l / c concentrated suspension for seed treatment (COP) containing 250 g / l Endosulfan and 100 g / l Lindane (Complement SMGFLO ^® ) = standard.

 The untreated portion of the seeds serves as a control sample.

After sowing, wheat plants are attacked by sulfur flies (Hylemia coarctata) and the effectiveness of various treatments is evaluated several days after the attack. Then get the results shown in table. 2
Example 3
Wheat grains are processed according to the classical seed treatment scheme by coating them:
- on the one hand, a concentrated suspension of CS Fipronil with a concentration of 600 g / l (0,083 l / c);
- on the other hand, with a mixture of 0.4 l of a concentrated suspension of KS with a concentration of triticonazole of 300 g / l and 0.083 l of a concentrated suspension of KS Fipronil with a concentration of 600 g / l per centner of seeds;
- finally, using a 0.4 l / c concentrated suspension for seed treatment (COP) containing 250 g / l Endosulfan and 100 g / l Lindane (Complement SMGFLO ^® ) = standard.

 The untreated portion of the seeds serves as a control sample.

 After sowing, wheat plants are attacked by a germ fly (Hylemia platura) and the effectiveness of various treatments is evaluated several days after this attack. Then get the results shown in table. 3.

Example 4
Wheat grains are processed according to the classical seed treatment scheme by coating them:
- on the one hand, a concentrated suspension of Kipron Fipronil with a concentration of 250 g / l (0.2 l / c);
- on the other hand, with a mixture of 0.4 l of a concentrated suspension of KS with a concentration of triticonazole of 300 g / l and 0.2 l of a concentrated suspension of KS Fipronil with a concentration of 250 g / l per centner of grains (seeds);
- finally, using a 0.4 l / c concentrated suspension for seed treatment containing 250 g / l Endosulfan and 100 g / l Lindane (Complement SMGFLO ^® ) = standard.

 The untreated portion of the seeds serves as a control sample.

 After sowing, wheat plants are attacked by a sprout fly (Hylemia platura), then attacked by a nutcracker (Athous haemorrhoidalis), and the effectiveness of various treatments is evaluated several days after these attacks. Then get the results shown in table. 4.

 In addition, in examples 1-4 there is no phenomenon of phytotoxicity.

 These examples also illustrate the superiority of the mixture, compositions and methods according to the invention both with respect to a single insecticide and to a commercial standard product.

Example 5
In vivo testing of a mixture of fipronil with triticonazole against Microdochium nivale (causing Fusarium in wheat) by seed treatment.

 Prepare aqueous suspensions of individual products or in the form of a mixture with ratios of triticonazole / fipronil equal to 1; 0.5; 0.2; 0.1; 0.05.

 Durum wheat grains naturally infected are treated with these suspensions according to the classic seed treatment by applying a protective coating.

Seeds are dried at 20 ^o C for 24 hours.

After sowing, the seeds are kept in a humid atmosphere at 5 ^o C for 15 days, then at a temperature of 10 ^o C for a week.

 The measurement is carried out by counting the number of healthy plants, and the percentage of efficiency is calculated in comparison with the control (wheat originating from infected and untreated seeds).

 The results are presented in table 5.

Example 6
In vivo test of a mixture of fipronil with triticonazole against Pyrenophora graminea (causing helminthosporiasis in barley) by seed treatment: helminthosporiosis in barley) by seed treatment:
Prepare aqueous suspensions of individual products or as a mixture at a ratio of triticonazole / fipronil equal to 0.5; 0.2; 0.1.

 Naturally infected barley grains are treated with these suspensions according to the classic seed treatment by applying a protective coating.

Seeds are dried at 20 ^o C for 24 hours.

After sowing, the seeds are kept in a humid atmosphere at 5 ^o C for 15 days, then at 10 ^o C for a week, and then at 20 ^o C for 3 weeks.

 The measurement is carried out by counting the number of healthy plants, and the percent efficiency is calculated by comparison with the control (barley originating from infected and untreated seeds).

 The results are presented in table 7.

Example 7
In vivo test of mixtures of fipronil with triticonazole against Puccinia recondita forme speciale tritici (smut causing wheat) by seed treatment:
Prepare aqueous suspensions of individual products or in the form of a mixture with ratios of triticonazole / fipronil equal to 1; 0.5; 0.2; 0.1; 0.05.

 Soft wheat grains are treated with these suspensions according to the classical seed treatment by applying a protective coating.

Seeds are dried at 20 ^o C for 24 hours.

After sowing, the seeds are kept in a humid atmosphere at 10 ^° C. until the two-leaf stage, also called stage 12 according to the Zadoks scale. This scale is presented in the journal Phytiatrie phytopharmacie, N 26, p. 129-140, 1977

 The plants are then infected with an aqueous suspension containing 100,000 spores of Puccinia recondita per ml.

After this, the plants are placed for 24 hours at 20 ^o C in an atmosphere with a relative humidity of 100%, then at 20 ^o C in an atmosphere with a relative humidity of 70% for 10 days.

 The determination is carried out by assessing the percentage of infected leaf surface for every 2 leaves, and calculate the percentage of efficiency compared to the control (infected and untreated wheat plants): F 1 for the first leaf, and F 2 for the second leaf (see table. 7).

Example 8
In vivo test of a mixture of fipronil with triticonazole against Fusarium culmorum (causing fusarium in corn) by seed treatment:
Aqueous suspensions of individual products are prepared or in the form of a mixture with a triticonazole / fipronil ratio of 0.01.

 Sweet corn kernels are treated with this suspension according to the classical seed treatment by applying a protective coating.

Seeds are dried at 20 ^o C for 24 hours.

After sowing, the seeds are infected with an aqueous suspension containing 500,000 spores of Fusarium culmorum per ml, then kept in a humid atmosphere at 10 ^o C for 21 days, then at 15 ^o C for 2 weeks.

 The measurement is carried out by counting the number of healthy plants, and the percentage of efficiency is calculated by comparison with the control (corn originating from infected and untreated seeds).

 The results are presented in table 8.

 Examples 5 to 8 illustrate the superiority of the mixtures, compositions and methods according to the invention compared to one fungicide.

 In addition, no phytotoxicity phenomenon was observed in these examples.

 For their practical application, the mixtures according to the invention are rarely used individually, and they can be used in compositions containing one or the other of the active principles or both together. In each composition, the active principles are usually combined with a solid or liquid carrier used in agriculture and, if necessary, with at least one surface-active agent.

 These compositions used to protect plants against fungal diseases and / or against insects, as an active principle, contain at least one of the components of the mixture according to the invention, in combination with solid or liquid agriculturally acceptable carriers and / or surfactants Agents also acceptable in agriculture. In particular, inert and conventional carriers and conventional surface-active agents are used.

 These compositions typically contain 0.5 to 95% of a compound of the invention, i.e. either a mixture, or one of two active principles.

 By the term “carrier”, as used herein, is meant an organic or mineral, natural or synthetic substance with which an active principle is combined to facilitate its application to a plant, grain or soil. This carrier, therefore, is usually inert and should be acceptable in agriculture, especially for the treated plant. The carrier can be solid (clays, natural or synthetic silicates, silicon dioxide, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases , etc.).

 The surfactant may be an emulsifier, dispersant or wetting agent of the ionic or non-ionic type. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic acids or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (especially alkyl phenols or aryl phenols), salts of sulfonate succinic acid esters, taurine especially alkyl taurates, polyoxyethylated esters of phosphoric acid and alcohols or phenols. The presence of at least one surfactant is usually necessary when the active principle and / or inert carrier is insoluble in water and the transporting agent for application is water.

 These compositions may also contain any kind of other ingredients, such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, complexing compounds, etc., as well as other known active principles with pesticidal properties ( in particular insecticides or fungicides), or with properties conducive to plant growth (in particular fertilizers), or with the properties of regulating plant growth. Advantageously, the compounds of the invention can be combined with any solid or liquid additives corresponding to conventional formulation methods.

 Therefore, the components of the mixture are often in the form of compositions, which themselves are in quite different, solid or liquid forms.

 As solid forms of the compositions, dusting or spraying powders (with a content of the mixture according to the invention that can reach 100%) and granules obtained, for example, by extrusion, compaction, impregnation of a granular carrier, granulation from a powder (content of a mixture according to the invention) can be mentioned in these granules in these cases is 0.5 - 80%).

As an example of a composition in the form of granules, the following components can be used:
Example G.

Association or one of two active principles - 50 g
Epichlorohydrin - 2.5 g
Cetyl polyglycol ether - 2.5 g
Polyethylene glycol - 35 g
Kaolin (granulometry: 0.3-0.8 mm) - 910 g
In this particular case, the active principles are mixed with epichlorohydrin and dissolved in 60 g of acetone, then polyethylene glycol and cetyl-polyglycol ether are added. The resulting solution was poured into kaolin and then the acetone was evaporated in vacuo. Such micro granulate is preferably used to control soil fungi.

 Compounds or mixtures of these compounds may be used in the form of dusting powder. You can also use a composition comprising 50 g of active principle (active principles) and 950 g of talc, or you can also use a composition containing 20 g of active principle (active principles), 10 g of finely divided silica and 970 g of talc. These components are mixed, crushed and the mixture is applied by dusting.

 As liquid forms of compositions, or forms intended to formulate liquid compositions before application, mention may be made of solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or powder for spraying), pastes.

 Emulsifiable or soluble concentrates most often contain 10 - 80% of the active principle; moreover, in ready-to-use emulsions or solutions contains 0.01 to 20% of the active principle.

 For example, in addition to the solvent, emulsifiable concentrates may contain, if necessary, 2 to 20% of appropriate additives, such as stabilizers, surfactants, penetration agents, corrosion inhibitors, dyes or the above adhesives.

 Concentrated suspensions, also applied by spraying, are prepared so as to obtain a stable liquid product that does not precipitate. Usually they contain 2 - 75% of the active principle, 0.5 - 15% of surface-active agents, 0.1 - 10% of thixotropic agents, 0 - 10% of the corresponding additives, such as antifoams, corrosion inhibitors, stabilizers, penetration agents and adhesives, and, as a carrier, water or an organic liquid in which the active principle is poorly soluble or insoluble. Some solid organic substances or inorganic salts can be dissolved in a carrier in order to inhibit sedimentation, or as antigels for water.

The following is an example of such a wording:
COP example
Active principle - 600 g
Polyethoxylated Tristyryl Phenol Phosphate - 50 g
Polyethoxylated Alkyl Phenol - 50 g
Sodium Polycarboxylate - 20 g
Ethylene glycol - 50 g
Polyorganosiloxane oil (antifoam) - 1 g
Polysaccharide - 1.5 g
Water - Sufficient up to 1 L
Wettable powders (or spray powder) are usually prepared in such a way that they contain 20 to 95% of the active principle.

 Usually they contain, in addition to a solid carrier, 0-5% wetting agent, 3-10% dispersant, and, if necessary, 0-10% one or more stabilizers and / or other additives, such as penetration agents, adhesives, or anti-clumping agents agents, dyes, etc.

 To obtain these pulverizable or wettable powders, the active principles are thoroughly mixed in the respective mixers with additives and crushed using mills or other appropriate crushers. In this way, pulverizable powders with high wettability and suspendibility are obtained. They can be suspended with water at any desired concentration.

 Instead of wettable powders, pastes can be prepared. The conditions for the preparation and use of these pastes are similar to the conditions for the preparation of wettable powders or pulverization powders.

 As already mentioned, aqueous dispersions and emulsions, for example, compositions obtained by dilution with water of a wettable powder or emulsifiable concentrate according to the invention, are included in the general framework of the present invention. Emulsions can be of the type water-in-oil or oil-in-water and they can have a thick consistency, such as mayonnaise.

Claims (11)

 1. Fungicidal-insecticidal mixture for protecting plants from diseases and insects, including fungicide-2- (4-chlorobenzylidene-5,5-dimethyl-1- (1H-1,2,4-triazol-1-yl-methyl) - 1-cyclopentanol and an insecticide, characterized in that it contains an effective amount of a fungicide and an effective amount of an insecticide, and as an insecticide contains (±) -5-amino-1- (2,6-dichloro-α, α, α-trifluoro- n-tolyl) -4-trifluoromethylsulfinylpyrazole-3-carbonitrile at ratios of fungicide and insecticide, creating a synergistic effect.  2. The mixture according to claim 1, characterized in that the fungicide is an insecticide synergist.  3. The mixture according to claim 1, characterized in that the insecticide is a synergist fungicide.  4. The mixture according to any one of claims 1 to 3 for the protection of seeds.  5. The composition used to protect plants against insects and / or against fungal diseases, comprising a mixture of fungicide and insecticide, one or more solid or liquid agriculturally acceptable, carriers and / or, if necessary, one or more surface-active agents used in agriculture, characterized in that as the specified mixture contains a mixture according to any one of claims 1 to 3 in an amount of 0.5-95 wt. %  6. A method of treating seeds to combat diseases and insects, characterized in that the mixture according to claim 1 is applied, or two compositions at the same time, each containing one of two active principles, moreover, of these mixtures or compositions applied to a centner of seeds, the dose of fungicide is 1-200 g, and the dose of insecticide is 5-150 g.  7. The seed treatment method according to claim 6, characterized in that the seeds are selected from the group consisting of grain crops (wheat, barley), corn.  8. The method according to claim 7, characterized in that for cereals, the doses used are 4-120 g / c for fungicide and 50-100 g / c for insecticide.  9. The method according to any one of claims 6 to 8, especially suitable for the destruction of pathogenic fungi and the extermination of harmful insects.  10. The method according to claim 9, characterized in that the insects belong to the group consisting of gray flies, sprout flies, nutcrackers, in particular larvae of nutcracker beetles.  11. The product of plant propagation, in particular, seeds coated with a mixture and / or containing a mixture according to claim 1, or a composition according to claim 5, or a mixture of two compositions, each of which contains one of two active principles.  The priority of 09/14/94 was rejected because all the signs are reflected in the application 9313400 with a priority of 11/04/93.

Images