KR100952092B1 - Insecticide Composition - Google Patents

Abstract

The subject matter of the present invention relates to pesticide compositions useful for controlling arthropods, particularly insects, and more particularly insects attacking crops, which are devastating or pests. The composition is a combination of at least one pesticidal compound of the general formula (I) in the description of the invention with a vegetable oil having a high drying power.

Insecticides, Insecticide Compositions, Fipronil, Ethiprolol, Vegetable Oils

Description

Insecticide Composition

FIELD OF THE INVENTION The present invention relates to pesticide compositions useful for controlling arthropods that are devastating or pests, and more particularly to pesticide compositions containing a phenyl pyrazole compound as an active ingredient together with an oil adjuvant.

Pesticide compositions containing phenyl pyrazole compounds are known and specifically in EP 029511, 5-amino-3-cyano-1- (2,6-dichloro-4, commonly known as fipronil). A pesticide composition containing -trifluoromethylphenyl) -4-trifluoromethylsulfinylpyrazole is disclosed. The more recently known phenyl pyrazole compounds which are also used as active ingredients of the pesticide composition are 5-amino-3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-ethyl Sulfinylpyrazole. This compound is commonly known as ethiprole and is disclosed in US Pat. No. 5,814,652.

In order to control pests damaging crops, it is desirable to reduce the dose of chemical products spread to the environment, and in particular, to reduce the dose used in application. To this end, certain auxiliaries, for example named biologically active agents such as mineral oils, humectants, penetrants, are combined with commercially available products and presently, for example, mineral oil forms of auxiliaries may be combined with pesticide compounds. It is possible to combine, which has the advantage of reducing the one-time use of the compound to be applied. This thus broadens the options available to farmers, so that they can find the best solution for their particular problem. On the other hand, when phytotoxicity is observed in certain crops, the use of some of these proprietary products is limited.

The present invention, when combined with certain phenyl pyrazole compounds, maintains equal biological activity against the targeted pests, whereas the resulting pesticides do not harm so-called sensitive crops and selectively Works.

Accordingly, the present invention provides a pesticide composition comprising a compound of formula (I) and an oil having a high drying power of vegetable origin.

In which R ₁ represents a halogen atom, a —CN radical or a methyl radical or a radical —C (S) NH ₂ , a radical —C (═NY) Z or a radical C (O) CH ₃ ;

R ₂ represents an —S (O) _n R ₃ or 4,5-dicyanoimidazol-2-yl radical or a halo alkyl group;

R ₃ represents an alkyl or halo alkyl radical;

R ₄ is a hydrogen atom, a halogen atom, a hydroxyl or alkoxy group, and -NR ₅ R ₆ , C (O) R ⁷ -C (O) OR ₇ , -S (O) _m R ₇ , alkyl, haloalkyl, Selected from the group containing radicals which may be -OR ₈ or -N = C (R ₉ ) (R ₁₀ );

R ₅ and R ₆ are independently selected from a hydrogen atom, alkyl, haloalkyl, -C (O) alkyl, alkoxycarbonyl, alkoxyalkyl-C (O)-or -S (O) _r CF ₃ radicals; Or R ₅ and R ₆ together form a divalent radical into which one or more heteroatoms such as oxygen or sulfur may be inserted;

R ₇ is selected from alkyl radicals and haloalkyl radicals;

R ₈ is selected from alkyl radicals, haloalkylradicals and hydrogen atoms;

R ₉ is selected from a hydrogen atom and an alkyl radical;

R ₁₀ is selected from heteroaryl radicals and phenyl radicals which may be substituted with one or more hydroxy radicals, halogen atoms, —O-alkyl, —S-alkyl, cyano or alkyl or combinations thereof;

X is selected from a nitrogen atom and a CR ₁₂ radical;

Y is selected from the group of hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl, alkylcarbamoyl and pyrazole, which may be substituted or substituted May not be;

Z is selected from the group of hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl and alkylcarbamoyl;

R ₁₁ and R ₁₂ are independently selected from halogen atoms or hydrogen atoms or alternatively -CN or -NO ₂ ;

R ₁₃ is selected from halogen atoms, haloalkyl, haloalkoxy, —S (O) _q CF ₃ and —SF ₅ radicals;

m, n, q, r are independently selected from 0, 1 and 2;

Provided that when R ₁ represents a methyl radical, R ₃ represents a haloalkyl radical, R ₄ represents -NH ₂ , R ₁₁ represents C1, R ₁₃ represents -CF ₃ , and X represents N Indicates.

The present invention is a pesticide composition useful for protecting crops, which is based on phenyl pyrazole compounds and supplements of vegetable oil type with high drying power. Many examples of the use of vegetable oils in the formulation of pesticides, and in particular in the preparation of pesticide compounds, are known for example in US Pat. No. 6,149,913. However, the use of vegetable oils with high drying power has not been reported in pesticide compositions. Thus and very surprisingly, it has become possible to obtain very advantageous results due to the use of the above in the pesticide compositions according to the invention.

Furthermore, the compositions of the present formulations make it possible to obtain excellent physical qualities of the plant-protective mixtures in application and thus allow them to be used in combination with various other commercially available products without the risk of physicochemical incompatibility. This safety of the plant-protective mixture in the application of the pesticide composition according to the invention also makes it possible to formulate certain active ingredients which would otherwise be difficult or impossible to apply.

Pesticides of the present invention contain a compound of the general formula (1) and a vegetable oil. With respect to the compounds of general formula 1, the alkyl and alkoxy radicals of formula (I) are preferably lower alkyl and alkoxy radicals, ie radicals having from 1 to 4 carbon atoms; Haloalkyl and haloalkoxy radicals likewise preferably comprise 1 to 4 carbon atoms; Haloalkyl and haloalkoxy radicals may have one or more halogen atoms; Preferred radicals of this type contain -CF ₃ and -OCF ₃ .

A preferred compound of the general formula (1) is when R ₁ represents -CN; R ₂ represents —S (O) _n R ₃ ; R ₃ is alkyl or haloalkyl; R ₄ represents -NR ₅ R ₆ ; R ₅ and R ₆ are independently selected from hydrogen atoms, alkyl, haloalkyl, —C (O) alkyl and C (O) OR ₇ radicals; R ₇ is an alkyl or haloalkyl radical; X represents -CR ₁₂ ; R ₁₃ is haloalkyl; R ₁₁ and R ₁₂ are independently selected from halogen or hydrogen atoms or alternatively -CN or -NO ₂ .

The first particularly preferred compound according to general formula (1) of the present invention is (1) when R ₁ represents -CN; R ₂ represents -S (O) ₂ CF ₃ ; R _{4 represents} -NH ₂ ; X represents -C-Cl; R ₁₁ is chlorine and R ₁₃ is methyl chloride. This compound is the chemical name 5-amino-3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinylpyrazole and is known as fipronil.

A second particularly preferred compound is when R ₁ represents -CN; R ₂ represents -S (O) ₂ C ₂ H ₅ ; R ₄ represents -NH ₂ ; X represents -C-Cl; R ₁₁ is chlorine and R ₁₃ is methyl chloride. This compound is the chemical name 5-amino-3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-ethylsulfinylpyrazole and is known as etiprolol.

The second component of the composition is vegetable oil. The advantage of using vegetable oils according to the invention is that they are non-toxic or have minimal phytotoxicity, high biodegradability compared to the least minimally toxic, mineral oils. The oils are suitably unsaturated vegetable oils, isomerized oils, vegetable oil esters of plant polymers or mixtures of various organic phases thereof.

The oils may be of various origins, but are preferably derived from linseed, sunflower, soybean, corn, cottonseed, safflower and rapeseed.

The oils are available in other grades, ie Crude, purified or isomerized grades. Preferably, the oil is a polyunsaturated vegetable oil that naturally contains a large number of unsaturated bonds. The above polyunsaturated oils are to be understood as meaning triglycerides wherein the majority of linear fatty chains are C18: 2 or C18: 3, ie 2 or 3 double bonds, having two or three double bonds per chain. It is a chain of 18 carbon atoms. As an example of a polyunsaturated oil, triglycerides mainly containing so-called linolenic fatty acid chains (C18: 3) such as flaxseed may be mentioned. As a guide, the weight composition of the oil, characterized by fatty acids, can be in the following ranges: 50 to 60% C18: 3-10 to 17% C18: 2-15 to 25% C18: 1-2 To 4% of C18: 0-5 to 8% of C16: 0. As examples of polyunsaturated oils, mention may be made of triglycerides comprising mainly fatty acid chains (C18: 2) of the linolenic type, such as sunflower, corn, soybean, safflower, cottonseed and rapeseed oils, for example. As a guide, the composition of the oil, characterized by fatty acids, can be in the following ranges: 45 to 70% C18: 2-0.1 to 10% C18: 3-10 to 40% C18: 1-0.1 to 10% of C18: 0-1 to 26% of C16: 0. In other words, oils falling within the scope of the present invention are called dry oils.

Drying power is obtained by chemical treatment of natural (dry or semi-dry oils) or low or no drying power (so-called semi-dry or non-dry oils); The oil is then said to be isomerized. Isomerization reactions yield conjugated dienes such as -CH = CH-CH = CH-CH _2- , thus increasing their drying power (reactivity with air), and the fatty acid chains -C = Conjugation of a double bond of CH—CH ₂ —CH═CH—. Therefore, as isomerization oil, isomerized sunflower oil having a percentage of conjugated diene of 16 to 18% may be mentioned, but isomerized flaxseed oil containing 11 to 13% of conjugated diene may also be mentioned. Can be.

In the compositions according to the invention, vegetable oils having an iodine value associated with a drying force of more than 70, preferably more than 90, more preferably more than 130, and most preferably more than 150 It is preferable to use.

The oil is preferably refined and / or isomerized sunflower oil.

The weight ratio of the oil to the compound of the general formula (1) in the composition according to the invention is suitably 0.15 to 1.6, preferably 0.2 to 1.35, more preferably 0.25 to 1.

The composition according to the invention may be in the form of a liquid and concentrated composition, ie it may be a commercially available product in which both materials are mixed. It may also be a diluted composition which can be sprayed directly onto the crop to be treated. In the latter case, dilution with water is carried out using a commercially available concentrated composition comprising a both material (this mixture is called a ready mix) or commercially available, containing one substance each. This may be done by a tank mix method of concentrated both compositions.

Liquid compositions according to the invention may be in the form of solutions, suspensions or emulsions or emulsifiable concentrates. Oil-aqueous liquid compositions are preferred due to their ease of use and simplicity in their preparation. Preferably, an aqueous suspension thickener using vegetable oil in the form of an oil-in-water emulsion can also be used.

The composition according to the invention may further contain solid or liquid additives corresponding to customary techniques for the formulation of plant-protective products. The composition may also contain all conventional additives or auxiliaries for the plant-protective composition, specifically carriers, surfactants, adhesion promoters and flow-enhancing agents, cryoprotectants.

Such compositions may contain additional ingredients such as protective colloids, tackifiers, thickeners, thixotropic agents, permeability-enhancers, stabilizers, sequestrants, pigments, colorings, polymers, antifoams. It may also include The term "carrier" in the context of the present invention refers to an organic or inorganic material, natural or synthesized, in which the active ingredient is combined to facilitate its application to their plants. The carrier should therefore be normally inert and acceptable to agriculturally, specifically processed plants. The carrier may be solid (clay, natural or synthesized silicate, silica, resin, wax, solid fertilizer, etc.) or liquid (water, alcohol, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.). have.                 

The surfactant may be an emulsifier, dispersant or wetting agent in ionic or nonionic form. For example polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic acid or naphthalenesulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (specifically alkylphenols or arylphenols) Mention may be made of sulfosuccinic ester salts, taurine derivatives (specifically alkyl taurate), polyoxyethylenated phenols or phospho esters of alcohols. The presence of at least one surfactant is preferred for promoting the dispersion of the active ingredient in water and for good application to plants. The expression oil-aqueous suspension thickener means an aqueous suspension in which the solid active ingredient is in the form of a crystal of suspension in water and the organic phase of the oil in the form of an oil-in-water emulsion, here the vegetable oil plus It is understood to mean an emulsive substance.

Suspension thickeners can also be applied by spraying, so that a stable fluid product is obtained such that no viscosity is increased or no sediment is formed after storage or no phase separation occurs, and they are produced in a range of 10 to 75% As an active ingredient, 0.5 to 15% surfactant, 0.1 to 10% thixotropic agent, 0 to 10% suitable additives, such as pigments, colorants, antifoams, corrosion inhibitors, stabilizers, permeability-enhancing agents, tackifiers and carriers, It includes organic liquids in which water or active ingredients are almost insoluble or insoluble. Any organic solid material or inorganic salt may be dispersed or dissolved in the carrier to prevent precipitation or as a cryoprotectant in water.

The pesticide compositions of the present invention may be applied to the crop by a variety of known methods, such as by spraying, sprinkling, injecting or applying a liquid containing the composition to the aerial part of the crop to be treated. Can be applied. Spraying at the tip of the crop to be treated is a preferred treatment method.

According to a further aspect of the present invention, the present invention also provides an arthroscopic damaging crop, characterized in that the pesticidal composition as defined herein above is applied to the plant tip in a single dose, which is effective and non-phytotoxic. It relates to a treatment method for controlling animals.

The term "effective and one-time use without phytotoxicity" refers to the amount of the composition according to the invention sufficient for controlling or eradicating arthropods present or likely to occur in crops, and not causing symptoms of phytotoxicity to the crops. It is understood to mean that. The amount is likely to vary within wide limits depending on the pests to be controlled, the variety of the crop, the climatic conditions and the compounds contained in the composition according to the invention; This amount can be determined by systematic field tests, for example, within the ability of those skilled in the art.

The pesticide composition according to the present invention can be advantageously used and the one-time use amount of the pesticide compound applied is 5 to 1000 g / ha, preferably 10 to 250 g / ha in the general formula (1). In the case of the oil component, an amount of 0.25 to 0.45 times the amount of single use of the compound of the general formula (1) is appropriately required. The actual single use will of course depend on various factors such as the plant to be treated, the extent of damage caused by pests, the weather conditions and the like.                 

Among the crops suitable for the treatment method according to the invention are cereal grains, in particular barley, protein-rich and oil-rich plants such as peas, rapeseeds, sunflowers, corn, vines, potatoes, tomatoes, vegetable crops [ Lettuce, curcurbitaceous plants, etc.], rice, cultivated trees (apples, pears, cherry trees, etc.), citrus fruits, grasses.

In the treatment method according to the invention, two components of the pesticide composition according to the invention can be applied simultaneously by means of the composition according to the invention, prepared from a ready-mix concentrate or from a tank mix.

Another aspect of the invention relates to a product for the simultaneous, continuous or alternating application of an oil of the pesticidal composition according to the invention and a compound of the general formula (1).

The following examples do not limit the advantageous properties of the compositions according to the invention.

Example 1 Preparation of Insecticide Composition

Insecticide compositions according to the invention containing the following components:-Insecticidal active ingredient of formula (I) 375-Ethoxylated polyararylphenol potassium phosphate salt 60-Dioctyl sulfosuccinate sodium salt 10-Ethoxylated oleic acid 8.5- Polyunsaturated Vegetable Oil 170-Monopropylene Glycol 50-Polysaccharide 1.4-1,2-Benzisothiazolin-3-one 0.7-Isotridecanol 10-Citric Acid Monohydrate 1-Water (qs 1 liter)

The composition is prepared according to known methods and as described in detail below: monopropylene glycol, isotridecanol, ethoxylated polyararylphenol potassium phosphate salt, dioctyl sulfosuccinate sodium salt, and mono citrate The hydrate is added to water at the same time while stirring. Stirring is continued to allow the components to disperse and dissolve. The active ingredient is then added with stirring. The suspension is precrushed using a colloid mill and then ground to a final particle size using a ball mill. A solution containing 2% polysaccharide and 1% 1,2-benzisothiazolin-3-one is added to the ground suspension while stirring. An oil phase consisting of a homogeneous mixture of vegetable oil and ethoxylated oleic acid is added with stirring to form an oil-in-water emulsion.

Example 2

Two compositions according to the present invention comprising rapeseed oil and soybean oil were prepared as described in Example 1. Table 1 below describes the components present in each formulation.

Composition 1 Composition 2 g / kg g / kg 5-Amino-3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-ethyl-sulfinylpyrazole Insecticide compound 105.26 103.63 Selected Rapeseed Oil Vegetable oil with high drying power 200 Selected soybean oil Vegetable oil with high drying power 100 Sopropor FLK Dispersant 50 50 Gerophone SDS Wetting agent 10 10 AlkaMule A Emulsifier 15 15 Propylene glycol Cryoprotectants 55 20 Rodorsil 454 Antifoam 5.0 5.0 Rhodopol G Thickener 2.0 1.2 Proxel GXL Biocides 1.0 0.2 water 586.74 586.74

Example 3 Treatment of Rice Crops

Compositions 1 and 2 according to the present invention are treated by foliar application at a concentration of 50 g / ha in rice crops about 16-17 cm tall and with small Laodelphax striatellus. The pesticide composition is applied with a spray gun.

Mortality of insects is observed over a two day period. The results are in Table 2 below:

Insecticide composition Insecticide efficacy (6 hours) Insecticide efficacy (24 hours) Insecticide efficacy (48 hours) Composition 1 31 100 100 Composition 2 27.6 100 100

Example 4 Treatment of Rice Crop

Compositions 1 and 2 according to the present invention are treated by foliar application at two single use ratios of 25 and 50 g / ha for rice crops approximately 16 to 17 cm tall and having small Nilaoarvara lugens. . The pesticide composition is applied with a spray gun.

In a comparative experiment, similar suspension compositions containing the same active ingredient but no oil component were also applied to the crop.

The number of insects per square meter of plant is observed over a period of 14 days. The results are in Table 3 below:

Insecticide composition 3 hours 1 day 3 days 7 days 10 days 14 days Composition 1 (25 g / ha) 1166 495 204 319 259 154 Composition 1 (50 g / ha) 1194 495 165 358 215 110 Composition 2 (25 g / ha) 1249 363 182 281 297 77 Composition 2 (50 g / ha) 1089 336 160 176 110 55 Comparative Composition (25 g / ha) 1056 605 248 462 325 172 Comparative Composition (50 g / ha) 930 517 154 341 204 121

From the above results it can be seen that the composition containing the oil of the present invention provides better eradication activity than the corresponding composition without the oil.

Claims (11)

Ethiprole and plant origin with high drying power as a pesticidal compound with the compound name 5-amino-3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-ethylsulfinylpyrazole Insecticide composition characterized in that it contains an oil having. delete delete delete The insecticide composition of claim 1, wherein the vegetable oil has an iodine value greater than 70. The insecticide composition of claim 1, wherein the vegetable oil has an iodine value of greater than 150. 7. The pesticide composition according to any one of claims 1, 5 or 6, wherein the vegetable oil is selected from flaxseed, sunflower, soybean, corn, cottonseed, safflower and rapeseed oils. 7. The pesticide composition according to any one of claims 1, 5 or 6, wherein the weight ratio of oil / ethiffrol is 0.15 to 1.6. An arthropod that damages crops is characterized by applying an effective and non-phytotoxic dose of the insecticide composition according to any one of claims 1, 5 or 6 to the tip of the plant. Treatment method to control. 10. The method according to claim 9, wherein the one-time use amount of the pesticidal compound applied is 5 to 1000 g / ha for etiprolol and the oil component is 0.25 to 0.45 times the one-time use amount of etiprolol. A product for the simultaneous, continuous, or alternation of oils and etiprols of the pesticidal composition according to claim 1, 5 or 6.