MXPA97005721A - Insecticides combinations that include an insecticide of the class of clinical scientific einsecticida that has a pirazol group, pirrol ofenilimida - Google Patents

Abstract

The present invention relates to agrochemical combinations that include an effective amount of an insecticide which includes an insecticide of the chloronicotinyl family A such as imidaclopride, acetamipride or nitenpyram, and an insecticide B having a pyrazole group, or phenyl imidazole; they contain one or both of such active substances, and a method for treating and protecting plants and seeds, in particular of insects or arthropods, by applying a combination of both substances. A composition containing both active substances can also be applied, alternatively, two compositions can be applied, each containing one or both active substances, simultaneously or in sequence, to ensure a combined effect

Description

* CLASS OF CLO8miaC? OMJO AND INSBgpCIEA 00B TIEMB tM awTn PTPASOT .. PTPBOT. O tnottt, t tn 7 ^ Tr Description of the invention The present invention relates to novel agrochemical combinations, for the protection of plants, comprising at least an effective amount of an insecticide A of the class of chloronicotinyl, such as imidaclopride, acetamipride or nitenpyram, and therefore Less an effective amount of an insecticide B than an organophosphorus, pyrethroid or carbamate insecticide, and a method of treating plants using these combinations. In the context of the present invention, the The term "plants" refers to a complete plant, a part of the plant or the propagation material of the plant, especially the seeds. More advantageously, the objective of the invention is an agrochemical combination for the protection of plants against insects or arthropods, characterized by REF: 25326 that an effective amount of an insecticide comprising an insecticide A of the class of chloronocotiniles such as imidaclopride, acetamipride or nitenpidam, and an insecticide B with a pyrazole, pyrrole or phenylimidazole group is used. Insecticides B with a pyrazole, pyrrole or phenylimidazole group include those described in European Patent Applications EP 0295117, EP 0460940 or EP 0484165, respectively. Preferably, the insecticide chosen in the present invention is of the class of insecticides with a pyrazole group. Advantageously, the compound chosen is that whose common name is fipronil, of chemical formula (±) -5-amino-1- (2,6-dichloro-a, a, o-trifluoro-p-tolyl) -4- trifluoromethylsulfinylpyrazole-3-carbonitrile, the compound 5-amino-1- (2,6-dichloro-a, o, a-trifluoro-p-tolyl) -4-ethylsulfinylpyrazole-3-carbonitrile or the compound 5-methylamino-l- (2,6-dichloro-a, o, α-trifluoro-p-tolyl) -4-ethylsulfinylpyrazole-3-carbonitrile. In addition to its description in the application EP 0295117, the properties of the fipronil compound have been published in the report of the 1992 Brighton Crop Protection Conference (Pests and Diseases, pages 29-34). Imidaclopride is the common name for l- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylidenamine, the insecticidal properties of which have been described, in particular in the "Pests and deseases" reports of the 1990 Brighton Crop Protection Conference, p. 21. Acetamipride is the common name for (E) -N1- ((6-chloro-3-pyridyl) methyl) -N2-cyano-N1-methylacetamidine. This product is listed in the Pesticide Manual (tenth edition) under the code number NI-25. It was first described in International application PCT / JP90 / 01282 published under the number WO 91/04965. Since then, other properties of this compound have been described in International application PCT / EP93 / 01286 published under WO 93/24004. Nitenpyram is the common name for (E) -N- ((6-chloro-3-pyridyl) methyl) -N-ethyl-N '-methyl-2-nitrovinylidene diamine. This product is listed in the Pesticide Manual (tenth edition) published by Clive TOMLIN and published by the British Crop Protection Council, 1994. Preferably, the combinations according to the invention can be used for the protection of seeds or for treating the floor. A further object of the invention are compositions comprising a combination mentioned above, according to the invention. The invention additionally comprises a method for the treatment against insects or against plant arthropods, characterized in that the combination of the two active ingredients is applied. It is also possible to apply a composition containing the two active ingredients or, either simultaneously or in succession so as to have a combined effect, the two compositions, each containing one of the two active ingredients. A further object of the invention is a method for treating seeds, characterized in that the seed is selected from the group consisting of cereals (e.g., wheat, barley, rye), corn, sorghum and sunflower, cotton, rice, peas, rapeseed, potatoes and market-garden crops. The rates of application of the compositions of the compounds according to the invention can vary within wide limits, in particular according to the group of seeds and according to the virulence, nature and degree of attack of the insects or arthropods and of the weather conditions. The insecticide (B), preferably fipronil, is used at a rate ranging from 10 to 500 g, preferably from 40 to 300 g per quintal (g / q), and the insecticide A, preferably imidaclopride, acetamipride or nitenpyram, is used at a rate ranging from 10 to 800 g, preferably from 20 to 500 g per quintal of seed, the ratio of B / A is then between 0.0125 and 50, preferably between 0.08 and 15, and the A / B ratio is between 0.02 and 80, preferably between 0.067 and 12.5.

In the case of treatment of maize or sorghum seeds, the rates used will be between 20 and 500 g / q for insecticide A, preferably imidaclopride, acetamipride or nitenpyram, and from 40 to 300 g / q for insecticide B (preferably fipronil). Another object of the present invention is a method for treating beet seeds with the compositions or combinations mentioned above. In the case of treatment of beet seeds, the rates used will be between 20 to 100 g / unit for the insecticide A, preferably imidaclopride, acetamipride or nitenpyram, and from 25 to 50 g / unit for the insecticide B (so preferable fipronil). The unit is the amount of seed required to plant one hectare. According to a variant, a further objective of the invention is a method for treating in soil by application, in particular in seed rows: - any of the granular formulations containing two active ingredients in combination or as a composition, - or as a mixture of two granular formulations, each containing one of the two active ingredients, optionally with a solid or liquid carrier acceptable agriculturally and / or optionally with one or more agriculturally acceptable surfactants.

This method is advantageously used in seed beds of cereal, corn, cotton, and sunflower. For cereals and maize, the rates of an insecticide of the class of chloronicotinyl, such as imidaclopride, acetamipride or nitenpyram are between 50 and 500 g / ha (grams per hectare), and for insecticide B (preferably fipronil) is between 50 and 200 g / ha. The methods according to the invention are particularly useful for the destruction of insects or arthropod pests. Among these insects various varieties of flies such as the wheat bulb fly (Phorbia coarctata) are destroyed. or the moth of the corn seed (Phorbia platura). Atomaria, millipedes, centipedes, Cicadellidae, aphids and also spring beetles and larvae of the spring beetle (Agriotes sp .. Athous haemorrhoidalis). by the use of a combination, composition and / or treatment according to the invention. The invention also relates to the propagation product of plants, and especially seeds, coated with and / or containing a combination as defined above, or a combination containing the mixture of two active ingredients or a mixture of two compositions, each providing one of the two active ingredients. It will be readily understood that the particular seeds can be planted with either a composition comprising insecticide B, preferably fipronil, and then with a composition comprising insecticide A, preferably imidaclopride, acetomipride or nitenpyram, or vice versa, or with a composition containing the two active ingredients. The term "coated with and / or containing" generally means that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the product. , according to the application method. When the propagation product is sown, it absorbs the active ingredient. Indeed, it can be established for commercial purposes that most of the active ingredient is on the surface most of the time. The invention also relates to a product comprising an insecticide A of the class of chloronicotinyl, such as imidaclopride, acetamipride or nitenpridam A, and an insecticide B with a pyrazole, pyrrole or phenylimidazole group, preferably fipronil, for simultaneous application , successive or in sequence, in the protection of plants against insects or arthropods. The following examples are provided to illustrate the combinations, compositions and treatment according to the invention. These examples are, of course, non-limiting, and many other kinds of insects or arthropods controlled by combinations and compositions according to the invention can be treated.

KjffiplQ-1 Corn seeds are treated according to a conventional treatment for seeds: - on the one hand, with a concentrated suspension of FS or fipronil at a concentration of 500 g ai / 1 (0.125 1 / q) • - on the other hand, with a wettable powder for WS seed treatment of imidaclopride (Gaucho WS) a a concentration of 700 g ai / kg (0.35 or 0.7 kg of this formulation are used per quintal of seed). - finally, a portion with 0.125 1 / q of fipronil and 0.35 kg / q of imidaclopride is treated.

An untreated portion of seeds serve as a control sample. In addition, a comparison is also made with carbofuran, which is applied in the form of microgranules in the seed of the row of seeds. Corn seeds treated in this way, or control seeds are planted in virgin soil, while an untreated portion is planted in a soil in which carbofuran granules are present. 49 days after sowing, an evaluation is made of the percentage of plants which have been attacked by the larva of the spring beetle (Agriotes sp.). The results are as follows: Treatment% (Plants attacked) Untreated control 90 Fipronil 62.5 g ai / q 18.3 Fipronil 62.5 + imidaclopride 245 g / q 3.1 Imidaclopride 245 g ma / q 20 Imidaclopride 490 g ai / q 5 Carbofuran 600 g ai / ha 10 This example illustrates well the superiority of the combinations, compositions and methods according to the invention in relation to both the insecticides alone and commercial reference products. In addition, in this example the phenomenon of phytotoxicity is not observed.

EjfiaTylo 2 Test in barley (Rhopalosiphus padi). Imidaclopride + fipronil.

Barley seeds are treated as follows: a) a part with 50 g / q of fipronil, b) a part with 35 g / q of imidaclopride, c) a part with 50 g / q of fipronil + 35 g / q of imidaclopride , d) finally, a last quantity of seeds is not treated and serves as control.

At 160 days after having sown the barley seeds, an analysis of the percentage of color change associated with yellow barley dwarf virus infection transmitted by Rhqpalosiphu padi shows that there is a 6.3% change in color in the case of c ) against 67.8 and 19.5%, respectively, in cases a) and b). Control plants d) change color by more than 80% (81.3%). It is noted that the two insecticides individually make it possible to reduce the color change, but that this reduction is more pronounced in a remarkable manner when both products are combined.

BjaM lo 3 Essay in Plutella xylostella. Acetamipride + fipronil The test is carried out on a diamond back moth (Plutella xylostella) that shows the addition of an ineffective amount of NI25 (acetamipride) to fipronil, which makes it possible to reduce the dose of the latter by a factor of 2.5 (proportion of synergism). to get the same activity. The test is carried out as follows: larvae of Plutella xylostella are placed in an intermediate stage in their development (third larval stage) in cabbage leaves which serve as biological support. Then different leaves are treated with varying concentrations of active ingredient and, 48 hours after treatment, dead larvae are counted. From the mortality curve as a function of the concentration of the active ingredient, the CLS0 is determined (concentration which destroys 50% of the population). The LC50 is obtained with 0.4 ppm of fipronil by itself. The LC50 of NI25 is 40 ppm. When a mixture of fipronil (two doses) + NI25 (1 dose) is used, the LC50 becomes 0.16 ppm (dose expressed as the concentration of fipronil).

Test in eggplant (Myzus persicae) Acetamipride + fipronil.

A certain number of eggplant plants are infested with green peach acid (Myzus persicae). An amount of the untreated plants serve as control and it becomes possible to calculate the percentage of activity obtained in plants treated beforehand either with fipronil by itself, at various doses, or with acetamipride itself, or, finally, with the mix in volume. The percentage of mortality of the insects is calculated three days after the foliar treatment of the eggplant plants, and this reading leads to the results established in the following table: * Control untreated ** Calculated by Colby's formula, which is well known to those skilled in the art: E - X + Y - X.Y / 100 in which - E is the expected percentage of insect mortality for a mixture of two insecticides A and B defined as doses, equal to a and b, respectively, X is the percentage of mortality observed for insecticide A at dose a, and Y is the percentage of mortality observed for insecticide B at dose b.

When the percentage of mortality obtained by the mixture is greater than E, then there is synergism. For use in practice, the combinations according to the invention are rarely used alone and can be used in compositions containing one or other of the active ingredients or can also contain both together. In each composition, the active ingredients are usually combined with a liquid or solid carrier, usable agriculturally, and optionally, with at least one surfactant. These compositions, which can be used for the protection of plants against insects, contain as an active ingredient at least one of the constituents of the combination according to the invention, as described above, in combination with liquid or solid carriers , agriculturally acceptable, and / or with agriculturally acceptable surfactants. It is possible in particular to use customary inert carriers and the usual surfactants. Typically, these compositions contain between 0.5 and 95% of the compound according to the invention, i.e., any combination of one or both of the active ingredients. Unless stated otherwise, in this description the percentages are expressed by weight.

The term "carrier" in the present description indicates a natural or synthetic, inorganic or organic substance with which the active ingredient is combined to facilitate its application to the plant, to the seeds or to the soil. Therefore, this carrier will generally be inert and must be agriculturally acceptable, especially in treated plants. The carrier can be solid (clays, natural or synthetic silicates, silica, 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 emulsifying, dispersing or wetting agent of the ionic or non-ionic type. Examples which may be mentioned are salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenylsulphonic or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids or with fatty amines, substituted phenols (especially alkylphenols or arylphenols), salts of sulfosuccinic ester, taurine derivatives (especially alkyl taurates), or phosphoric esters of phenols or polyethoxylated alcohols. The presence of at least one surfactant is generally essential when the active ingredient and / or the inert carrier are insoluble in water, and the vehicle for application is water. These compositions may also contain any kind of other additional ingredients such as, for example, protective colloids, adhesives, thickeners, exotropic agents, penetrating agents, stabilizers, sequestering agents, etc., and also other active ingredients known for their pesticidal properties (especially insecticides or fungicides) or their properties to promote the growth of plants (especially fertilizers) or their properties to regulate the growth of plants. More generally, the compounds according to the invention can be combined with all the solid or liquid additives corresponding to the usual formulation techniques. For its application, the constituents of the combination in this way are presented in the form of compositions which in themselves are relatively diverse, in solid or liquid forms. The compositions in solid form which can be mentioned are powders for dusting or dispersion (with a content according to the invention, which can vary up to 100%) and granules, especially those obtained by extrusion, by compaction, by impregnation of a granular support or by granulation from a powder (the content of combination of according to the invention in these granules is between 0.5% and 80% in the latter cases). In an example of the composition of granules, the following constituents are used: Eifia ?? L £ Q - combination, or one of the two active ingredients 50 g - epichlorohydrin 2.5 g - cetyl polyglycol ether 2.5 g - polyethylene glycol 35 g - kaolin (particle size 0.3 to 0.8 mm) 910 g In this particular case, the active ingredients are mixed with epichlorohydrin and the mixture is dissolved in 60 g of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The kaolin is moistened with the obtained solution and then the acetone is evaporated off under vacuum. The compounds or combinations of the compounds can also be used in the form of dispersion powders. It is also possible to use a composition containing 50 g of the active ingredient or ingredients and 950 g of talc or further to use a composition containing 20 g of active ingredient or ingredients, 10 g of finely divided silica and 970 g of talc. These constituents are mixed and ground, and the mixture is applied by dispersion. The compositions which may be mentioned and which are in liquid form or which are proposed to constitute liquid compositions at the time of application include solutions, especially water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders. and pasta. Emulsifiable or soluble concentrates usually constitute 10 to 80% active ingredient, while ready-to-apply solutions or emulsions contain from 0.01 to 20% active ingredient. For example, in addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20% of the appropriate additives, such as the stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes to adhesives mentioned above. Concentrates in suspension which can also be applied by spray are prepared so as to obtain a stable fluid product which does not form deposits, and which usually contains from 2 to 75% of active ingredient, from 0.5 to 15% of surfactants , from 0.1 to 10% of thixotropic agents, from 0 to 10% of the appropriate additives, such as defoamers, corrosion inhibitors, stabilizers, penetration agents and adhesives, and as a carrier, water or an organic liquid, in which The active ingredient is of little or no solubility. Certain organic substances or inorganic salts can be dissolved in the carrier to help prevent sedimentation, or as antifreeze agents for water. An example of such a formulation is provided below: E £ Bclfi_S £ - active ingredient 600 g - tristyrylphenol-polyethoxylated phosphate 50 g - polyethoxylated alkylphenol 50 g - sodium polycarboxylate 20 g - polyethylene glycol 50 g - organopolysiloxane oil (antifoam) 1 g - polysaccharide 1.5 g - water qs 11 Wettable powders are usually prepared so that they contain 20 to 95% of the active ingredient, usually containing, in addition to the solid carrier, 0 to 5% of a wetting agent, 3 to 10% of a dispersant and, when necessary, 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, substances to prevent the formation of cakes, dyes, etc. In order to obtain wettable powders, the active ingredients are intimately mixed in suitable mixers with the additional substances, and the mixtures are milled with appropriate mills or other grinders. In this way, wettable powders are obtained whose wetting and suspension characteristics are advantageous. They can be suspended with water at any desired concentration. Instead of wettable powders, it is possible to form pastes. The conditions and methods for the production and use of these pastes are similar to those for use for wettable powders. As already mentioned, aqueous emulsions and dispersions, for example, compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention, with water, are included within the general scope of the present invention. The emulsions may be of the water-in-oil or oil-in-water type and may have a sticky consistency such as that of mayonnaise sauce. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates. Having described the invention as above, property is claimed as contained in the following:

Claims (20)

REIVPOICACIQMES

1. An agrochemical combination for the protection of plants against insects or arthropods, characterized in that it has an effective amount of an insecticide comprising an insecticide A of the class of chloronicotinyl, such as imidaclopride, acetamipride or nitenpyram, and an insecticide B with an pyrazole, pyrrole or phenylimidazole group.

2. - The combination according to claim 1, characterized in that the insecticide B is an insecticide with a pyrazole group.

3. - The combination according to claim 2, characterized in that the insecticide B is fipronil, of chemical formula (±) -5-amino-l- (2,6-dichloro-a, a, a-trifluoro-p-tolyl) ) -4-trifluoromethylsulfinylpyrazole-3-carbonitrile, the compound 5-amino-1- (2,6-dichloro-o, a, α-trifluoro-p-tolyl) -4- (ethylsulfinylpyrazole-3-carbonitrile or compound 5) -methylamino-1- (2,6-dichloro-o, a, α-trifluoro-p-tolyl) -4-ethylsulfinylpyrazole-3-carbonitrile.

4. - The combination according to any of claims 1 to 3, characterized in that it is used for seed protection.

5. - The combination according to any of claims 1 to 3, characterized in that it is used for the treatment of the soil.

6. Compositions, characterized in that they are constituted between 0.5% and 95% of a combination according to any of claims 1 to 3, one or more agriculturally acceptable solid or liquid carriers and / or one or more agriculturally acceptable surfactants.

1 . - The compositions, characterized in that they comprise between 0.5% and 95% of a combination according to claim 4, and one or more agriculturally acceptable solid or liquid carriers and / or one or more agriculturally acceptable surfactants.

8. - The compositions characterized in that they comprise between 0.5% and 95% of a combination according to claim 5, one or more agriculturally acceptable solid or liquid carriers and / or one or more agriculturally acceptable surfactants.

9. - A method for the treatment against insects or against plant arthropods, characterized in that a combination according to any one of claims 1 to 4 is applied, a composition according to any of claims 6 or 7, or, either simultaneously or in succession, so that they have a combined effect, two composicones, each one has one of the active ingredients.

10. - The method of treatment of seeds, according to claim 9, characterized in that the seeds are selected from the group consisting of cereals (for example wheat, barley, rye), corn, sorghum, sunflower, cotton, rice, peas, rapeseed, potato and market-garden crops.

11. - The method according to claim 10, characterized in that the insecticide (B) preferably fipronil, is used at a rate ranging from 10 to 500 g per quintal of seed (g / q) and insecticide A, of Preferably imidaclopride, acetamipride or nitenpyram, is used at a rate of varies from 10 to 800 g / q.

12. - The method according to claim 11, characterized in that for corn and sorghum, the regimes used vary from 20 to 500 g / q for the insecticide A, preferably imidaclopride, acetamipride or nitenpyram, and from 40 to 300 g / q for insecticide B, preferably fipronil.

13. - A method for treating beet seeds, according to claim 9.

14. - The method according to claim 13, characterized in that the regimes used vary from 20 to 100 g / unit for the insecticide A, preferably imidaclopride, acetamipride or nitenpyram, and from 25 to 50 g / unit for the insecticide B , preferably fipronil.

15. A method for treating the soil by application, in particular to the rows for seeding seeds, of a granular formulation containing a combination according to claim 5, or a composition according to claim 8, or a mixture of two granular formulations, each containing one of the two active ingredients, optionally with one or more agriculturally acceptable solid or liquid carriers and / or one or more agriculturally acceptable surfactants.

16. - The method according to claim 15, characterized in that the regime of an insecticide of the class of chloronicotinyl, such as imidaclopride, acetamipride or nitenpyram, is between 50 and 500 g / ha, and that of insecticide B, so preferable fipronil, is between 50 and 200 g / ha in the case of soil treatment to be used for corn or cereals.

17. - The method according to any of claims 9 to 16, characterized in that it is particularly useful for the destruction of insect pests or arthropods that are chosen from the group consisting of the wheat bulb fly, the worm of the seed of corn, Atomaria, centipede, millipede, Cicadellidae, aphids, spring beetle and larvae of the spring beetle.

18. - A product for propagation in plants, especially the seed, coated with and / or containing a combination, according to any of claims 1 to 4, or a composition according to one of claims 6 and 7, or a mixture of two compositions, each provides one of the two active ingredients.

19. - A product characterized in that it comprises an insecticide A of the class of chloronicotinyl, such as imidaclopride, acetamipride or nitenpyram, and an insecticide B with a pyrazole, pyrrole or phenylimidazole group, for simultaneous, sequential or sequential application in the protection of plants against insects or arthropods.

20. - The product according to claim 19, characterized in that the insecticide B is fipronil.