TWI568352B - Insecticidal composition - Google Patents

Description

Insecticidal composition

The present invention encompasses novel agrochemical formulations and uses thereof, particularly an agrochemical dosage form containing insecticidal active compounds and fertilizers.

In particular, the invention includes a composition comprising one or more N-arylpyrazole insecticides, and one or more nitrogen based fertilizers. The invention also includes a method of improving the insecticidal efficacy and crop yield of such compositions.

N-arylpyrazoles are well known in the art and are widely used as insecticides. Such compounds are disclosed and described in U.S. Patent 5,232,940. Due to their wide range of uses, these compounds can effectively control pests such as ants, beetles, fleas, ticks, thrips, rootworms, weevils and mites, especially termites and mites. N-arylpyrazoles block the passage of chloride ions, thus destroying the central nervous system of target insects.

Patent EP 0 822 746 discloses a plant treatment method for promoting growth regulation by applying a phytotoxic N-arylpyrazole to the plant.

Studies have found that dosage forms containing one or more N-arylpyrazoles and nitrogen-based fertilizers have significantly improved insecticidal efficacy while also increasing crop yields in plants. Fertilizer can be used as a "safener" to reduce crops to N- Adverse reactions of arylpyrazole insecticides. Thus, the present dosage form can substantially reduce or eliminate side effects or phytotoxicity caused by the application of an insecticidally effective amount of an N-arylpyrazole insecticide. In other words, fertilizers can increase the resistance of crops to N-arylpyrazole pesticides. In addition, studies have found that simultaneous application of N-arylpyrazole insecticides and nitrogen-based fertilizers in the treatment of plants can greatly improve insect control and increase plant yield.

Accordingly, in a first aspect, the present invention provides a pesticidal composition comprising: a) a pesticidally effective amount of one or more compounds of formula (I):

Wherein: R ¹ is alkyl, halogen, or CN; R ² is 4,5-dicyanoimidazol-2-yl, haloalkyl, or S(O) _m R ⁷ ; R ³ is hydrogen, halogen, NR ⁸ R ⁹ , S(O) _n R ¹⁰ , C(O)R ¹¹ , alkyl, haloalkyl, OR ¹² , or N=CR ¹³ R ¹⁴ ; R ⁴ and R ⁶ independently of each other represent hydrogen, halogen, halogen Alkyl, CN, or NO ₂ ; R ⁵ is hydrogen, halogen, haloalkyl, haloalkoxy, or S(O) _p R ¹⁵ ; R ⁷ , R ¹⁰ , R ¹² and R ¹⁵ independently of each other represent an alkyl group Or haloalkyl; R ⁸ and R ⁹ independently of each other represent hydrogen, alkyl, alkenyl, haloalkyl, alkoxycarbonyl, or S(O) _q CF ₃ ; R ¹¹ and R ¹⁴ independently of each other represent hydrogen or alkyl R ¹³ is a phenyl group optionally substituted by one or more halogen atoms or OH, an alkyl group, an alkoxy group and a cyano group; and m, n, p and q independently represent 0, 1 or 2; and b) At least one nitrogen based fertilizer.

The present invention employs a nitrogen based fertilizer to enhance the insecticidal efficacy of the N-arylpyrazole active ingredient. Nitrogen is a basic element of fertilizers and is described in detail in Farm Chemicals Handbook, 1992, page B23. Commercial nitrogen-based fertilizers include ammonium salts (e.g., phosphates, sulfates, and chlorides), nitrates, anhydrous ammonia, urea, nitrogen solutions (including urea ammonium nitrate), and combinations of the foregoing. Such fertilizers can be prepared according to procedures well known in the art.

Insecticides and fertilizer mixtures are well known in the art in the form of granules, tablets, sticks and tablets. However, the performance of these products is not as good as it is, especially for large-scale agricultural applications. For example, patent US 5,783,203 describes a mixture of fertilizers and insect nicotinic acetylcholine receptor agonists or antagonists. The mixture is prepared as a stick and is suitable for use in protecting ornamental indoor plants, but is not suitable for agricultural use.

Patent application US 2006/0166939 describes an insecticidal fertilizer dosage form in the form of a spray. However, when a dosage form is applied, the presence of a salt of a strong acid can damage the plant.

Studies have found that the use of the compositions of the present invention greatly reduces the environmental impact The impact of the planter's workload is also reduced. More importantly, the compositions of the present invention significantly enhance insecticidal efficacy compared to known dosage forms of N-arylpyrazoles, thereby substantially increasing crop yield. In particular, studies have found that the presence of nitrogen-based fertilizers reduces the phytotoxicity of the active compounds of formula (I), thereby reducing damage to the target plants and increasing yield.

As set forth above, the compositions of the present invention comprise one or more pesticidally active compounds of formula (I). In the compounds of the formula (I), the alkyl, haloalkyl and haloalkoxy moieties may contain any suitable number of carbon atoms, preferably more than 1 to 12 carbon atoms. Preferably, it contains from 1 to 8 carbon atoms, and particularly preferably from 1 to 4 carbon atoms. Desirable groups are methyl, halomethyl, halomethoxy, ethyl, haloethyl, haloethoxy, propyl, halopropyl and halopropoxy.

Similarly, in the compounds of formula (I), the alkenyl moiety may contain any suitable number of carbon atoms, preferably more than 1 to 12 carbon atoms, more preferably from 1 to 8 The carbon atom, particularly preferably contains 1 to 4 carbon atoms. Desirable groups are vinyl and propenyl.

In the compound of the formula (I), the alkyl group, the alkenyl group, the haloalkyl group and the haloalkoxy group may be straight-chain or branched.

In the compounds of formula (I), the halogen- bearing group may comprise one or more suitable halogen atoms, preferably a fluorine or chlorine atom.

In the compounds of the formula (I), R ^{1 is} preferably methyl, halogen (especially fluorine or chlorine) or CN. Particularly preferred compounds of the general formula (I) are compounds of the R ¹ -based CN.

Further, in the compound of the formula (I), R ^{2 is} preferably 4,5-dicyanoimidazol-2-yl, halomethyl (especially a methyl group substituted by one or more fluorine or chlorine atoms) or S(O) _m R ⁷ . In the formula of S(O) _m R ⁷ , m may be an integer between 0 and 2, preferably 1. R ⁷ may be an alkyl group or a haloalkyl group, preferably a haloalkyl group, especially a haloalkyl group having one or more fluorine atoms. Particularly preferred compounds of the general formula (I) are those in which R ⁷ is a methyl group (especially CF ₃ ) which contains one or more fluorine substituents.

In the compound of the formula (I), R ^{3 is} selected from hydrogen, halogen, NR ⁸ R ⁹ , S(O) _n R ¹⁰ , C(O)R ¹¹ , alkyl, haloalkyl, OR ¹² or N=CR ¹³ R ¹⁴ . If R ³ is halogen, it is preferably chlorine or fluorine. In the compound wherein R ³ is S(O) _n R ¹⁰ , n is preferably 1, and R ^{10 is} preferably a methyl group or a methyl group containing one or more halogens (especially fluorine or chlorine). In the compound wherein R ³ is C(O)R ¹¹ , R ^{11 is} preferably hydrogen or methyl. In addition to this, R ³ may also be an alkyl group which may optionally contain one or more halogen substituents, ideally a methyl group or a one or more halogens (especially fluorine or chlorine) base. In the compound of the formula (I) wherein R ³ is OR ¹² , R ¹² is an alkyl group which may optionally contain one or more halogen substituents, and the desired group is a methyl group or contains one or more halogens (especially A methyl group of fluorine or chlorine). Further, R ³ may also be N=CR ¹³ R ¹⁴ , wherein R ¹³ is optionally one or more halogens (preferably chlorine or fluorine), OH, an alkyl group (preferably a methyl group), an alkoxy group. (preferably methoxy) or cyano substituted phenyl.

Particularly preferred compounds of the formula (I) are compounds of the R ³ system NR ⁸ R ⁹ . In such compounds, R ⁸ and R ⁹ independently of each other represent hydrogen, alkyl (preferably methyl), alkenyl (preferably vinyl or propenyl, optionally having one or more methyl branches) And a haloalkyl group (preferably a methyl group containing one or more fluorine or chlorine atoms), an alkoxycarbonyl group (preferably a methoxycarbonyl group) or S(O) _q CF ₃ (q is preferably 1). It is especially preferred that R ³ is NR ⁸ R ⁹ , wherein R ⁸ and R ⁹ are both hydrogen (-NH ₂ ). In an alternative embodiment, R ³ is NR ⁸ R ⁹ , wherein R ⁸ is a hydrogen atom and R ⁹ may be an alkenyl group (especially a propylene group bearing a methyl branch).

In the compound of the formula (I), R ⁴ and R ⁶ may be hydrogen, halogen, haloalkyl (preferably a methyl group having one or more fluorine or chlorine atoms), a cyano group or a nitro group. The compositions of the invention in particular comprise compounds in which both R ⁴ and R ⁶ are halogen atoms, the two of which are especially preferably the same halogen, in particular chlorine.

In the compound of the formula (I), R ⁵ may be hydrogen, halogen (preferably chlorine or fluorine), haloalkyl (preferably a methyl group containing one or more fluorine or chlorine atoms), haloalkoxy group. (preferably a methoxy group containing one or more fluorine or chlorine atoms) or S(O) _p R ¹⁵ . More preferably, R ⁵ is S(O) _p R ¹⁵ , wherein p is preferably 1, and R ¹⁵ is preferably a methyl group or a methyl group having one or more fluorine or chlorine atoms. It is especially desirable that R ⁵ is a methyl group with three halo substituents, especially CF ₃ .

Preferred compounds of the formula (I) of the present invention include the following compounds: 5-amino-1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-4-[(trifluoro Methyl) sulfinyl]-pyrazole-3-carbonitrile (Fipronil Fipronil); 1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-5-[2- Methylallyl-amino]-4-[(trifluoromethyl)sulfinyl]-pyrazole-3-carbonitrile (butenfluramide Flufiprole); 5-amino-1-[2 ,6-dichloro-α,α,α-trifluoro-p-toluene]-4-(ethylsulfinyl)-pyrazole-3-carbonitrile (Ethiprole); 1-[5-amino group -1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-4-(methylsulfinyl)-pyrazol-3-yl]-ethanone (acetazinonitrile Acetoprole) (RS)-O-[1-(4-chlorophenyl)-pyrazol-4-yl-O-ethyl-S-propyl-phosphorothioate] (pyrazolofos); -[2,6-dichloro-α,α,α-trifluoro-p-toluene]-4-[(fluoromethyl)thio]-5-[(pyridyl) Methyl)amino]-pyrazole-3-carbonitrile (pyridyl) Flurazine (Pyrafluprole); 1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-4-[(difluoromethyl)thio]-5-[(2-pyridylmethyl) Amino]-pyrazole-3-carbonitrile (pyridylpyridylpyryl); 3-methyl-1-phenyl-pyrazol-5-yldimethylcarbamate (pyrazole) And E-1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-5-[4-hydroxy-3-methoxybenzylideneamino]-4-[( Trifluoromethyl)thio]-pyrazole-3-carbonitrile (Methiliprole).

It was found that the composition of the present invention is a 5-amino-1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-4-[(trifluoromethyl) compound having the generic name fipronil. A particularly effective method for the sulfinyl]-pyrazole-3-carbonitrile.

The amount of the compound of formula (I) present in the composition may vary widely depending on factors such as the form and application ultimately employed in the application of the composition. Desirably, the compound of the formula (I) is present in an amount of from 0.5 to 80% by weight of the composition, particularly preferably from 1 to 50% by weight.

The compositions of the present invention may also comprise one or more nitrogen based fertilizers. "nitrogen The term "basic fertilizer" refers to a major nutrient containing nitrogen, and all plants require a certain amount of such nutrients for growth. Any suitable nitrogen based fertilizer is also included in the composition. The preferred nitrogen-based fertilizer is selected from the group consisting of ammonium salts (such as ammonium sulfate, ammonium nitrate, ammonium phosphate), anhydrous ammonia, ammonia water, fluid nitrogen fertilizer, urea, urea-formaldehyde condensate, urea ammonium nitrate, amino acid and metal nitrate ( Such as sodium nitrate, potassium nitrate, calcium nitrate and magnesium nitrate). In addition, salts of micronutrients (preferably manganese, magnesium, iron, boron, copper, zinc, molybdenum and/or cobalt) and phytohormones (such as vitamin B1 or indole acetic acid) may also be added.

The amount of nitrogen-based fertilizer in the composition can be any suitable portion. It is generally present in an amount of from 0.5 to 50% by weight; more desirably from 2 to 40% by weight; more desirably from 5 to 20% by weight.

The compound of formula (I) and the nitrogen-based fertilizer can be included in the composition at the same time or in any corresponding ratio. The weight ratio of the two components to each other in the composition is preferably from 100:1 to 1:100, more preferably from 1:20 to 20:1.

The compound of formula (I) and the nitrogen-based fertilizer can be applied in a single dosage form or separately in different dosage forms. In the latter case, the insecticidally active compound of the formula (I) and the nitrogen-based fertilizer can be applied continuously, separately or simultaneously.

The compositions of the present invention may contain one or more adjuvants. The auxiliaries selected for the compositions and their amounts will depend on the type of dosage form and/or the form in which the end user will administer the dosage form. Suitable auxiliaries are all customary auxiliaries or components, including solvents, surfactants, stabilizers, anti-foaming agents, antifreeze agents, preservatives, antioxidants, colorants, thickeners and inerts. filler. Such auxiliaries are well known in the art and are commercially available. It will be apparent to those skilled in the art that it is used in formulating the compositions of the present invention.

The composition may contain one or more solvents, and the solvent may be organic or inorganic. Suitable solvents are selected from all customary solvents which are effective in completely dissolving agrochemical actives. Such solvents are well known in the art and are commercially available. Examples include water; aromatic hydrocarbon solvents such as xylene, such as solvent products sold by SolvessoTM; mineral oils; animal oils; vegetable oils; alcohols such as methanol, butanol, pentanol, benzyl alcohol; ketones such as cyclohexanone and gamma-butyl Lactone; pyrrolidone, such as N-methyl-2-pyrrolidone (NMP), N-octyl-2-pyrrolidone (NOP); acetate, such as ethylene glycol diacetate; glycol; fatty acid dimethyl Indoleamine; fatty acid; and fatty acid ester.

The composition may additionally contain one or more surfactants. Suitable surfactants include, but are not limited to, alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid; alkylarylsulfonates; alkyl sulfates ; alkyl sulfonate; aryl sulfonate; fatty alcohol sulphate; fatty acid and sulfated fatty alcohol glycol ether; sulfonated naphthalene and naphthalene derivatives and formaldehyde condensate; naphthalene or naphthalene sulfonic acid and phenol, a condensate of octylphenol and nonylphenol; an alkylphenyl polyglycol ether; a tributylphenyl polyglycol ether, a tristearyl phenyl polyglycol ether, an alkyl aryl group Ether alcohol; condensate of alcohol and aliphatic alcohol with ethylene oxide; ethoxylated castor oil; polyoxyethylene alkyl ether; ethoxylated polyoxypropylene; lauryl polyethylene glycol ether acetal; Alcohol ester; lignin-sulfite Waste liquid; methyl cellulose; and block copolymer of ethylene oxide/propylene oxide.

The composition may additionally contain one or more polymeric stabilizers. Polymer stabilizers suitable for use in the present invention include, but are not limited to, polypropylene, polyisobutylene, polyisoprene, copolymers of monoolefins and diolefins, polyacrylates, polystyrene, polyvinyl acetate, polyaminos Formate and polyamine. Suitable stabilizers are well known in the art and are commercially available.

The composition may contain an anti-foaming agent. Suitable anti-foaming agents include those which are generally useful in agrochemical compositions and will be apparent to those skilled in the art. Suitable anti-foaming agents are well known in the art and are commercially available. A particularly desirable antifoaming agent is a mixture of polydimethyl siloxane and perfluoroalkylphosphonic acid (e.g., a decane anti-foaming agent sold by GE or Compton).

The composition may also contain one or more preservatives. Suitable preservatives include all of the preservative materials which are generally useful in this type of agrochemical composition, and such antiseptic materials are also well known in the art. Suitable examples worth mentioning include Preventol® (sold by Bayer AG) and Proxel® (sold by Bayer AG).

Additionally, the compositions may contain one or more antioxidants. Suitable antioxidants are all antioxidants which are generally useful in agrochemical compositions, and such antioxidants are well known in the art. A preferred example is butylated hydroxytoluene (BHT).

The composition may additionally contain one or more solid binders. Such adhesives are well known in the art and are commercially available. Which includes Machine binders (including tackifiers such as cellulose, powdered, granulated or layered natural or synthetic polymers in place of cellulose), and inorganic binders (such as gypsum, alumina or cement).

The composition may additionally contain one or more inert fillers. Such inert fillers are well known in the art and are commercially available. These include natural ground minerals such as kaolin, bauxite, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth; and synthetically ground minerals such as highly dispersed tannins, alumina, and tannic acid. Salt; calcium phosphate; and calcium hydrogen phosphate. Inert fillers suitable for granules include: pulverized and classified natural minerals such as calcite, marble, pumice, sepiolite and dolomite; synthetic granules of inorganic and ground organic materials; and granules of organic materials such as sawdust and coconut Shell, corn cob and stem.

The composition may additionally contain one or more thickeners. Suitable thickeners are all thickening materials which are generally useful in agrochemical compositions. Suitable thickeners include gums such as xanthan gum, polyvinyl alcohol (PVOH), cellulose and its derivatives, clay hydrated silicates, aluminosilicates or mixtures of the foregoing. Likewise, such thickeners are well known in the art and are commercially available.

The insecticidal active compound of the formula (I) and the nitrogen-based fertilizer, as well as any other optional pesticide, can be applied and used in the form of a solid active ingredient in a pure state (for example, at a specified particle size or preferably with at least one The additive components are used together. This method is commonly used in dosage form technology and has also been described in detail in the previous paragraph.

The pesticidal composition can be used in any suitable dosage form as described above. Ideal The dosage form is a granule, a suspension concentrate, a water-dispersible granule, a water-soluble granule, a water-dispersible powder, a water-soluble powder or a flowable suspension.

The compositions of the invention may be applied to the target plant or related plant, one or more parts thereof (such as leaves or seeds) or its surroundings.

In one embodiment, the combination of the compound of formula (I) and the nitrogen-based fertilizer is applied as a composition of the foregoing.

Examples of the types of preparations of the premixed composition embodiments of the present invention are as follows:

A) Water Soluble Concentrate (SL)

One or more insecticidally effective compounds of the general formula (I) and nitrogen-based fertilizers are dissolved in a water-soluble solvent, and one or more wetting agents and/or other auxiliaries may also be added. The active compound can be dissolved when diluted in water.

B) emulsifiable concentrate (EC)

One or more insecticidally effective compounds of formula (I) and nitrogen-based fertilizers may be dissolved in a solvent in which one or more nonionic emulsifiers and cationic emulsifiers are added. The mixture is agitated (e.g., stirred) to obtain a uniform dosage form. It can be a stable emulsion after dilution with water.

C) Emulsion (EW)

One or more insecticidally effective compounds of formula (I) and nitrogen-based fertilizers may be dissolved in a suitable solvent in which one or more nonionic emulsifiers and cationic emulsifiers are added. The resulting mixture can be added to water by a suitable method (e.g., an emulsifier) to form a uniform water-based emulsion. It can be a stable emulsion after dilution with water.

D) Suspending agent (SC, OD, FS)

In a stirred bead mill, one or more insecticidally effective compounds of the general formula (I) and nitrogen-based fertilizers are added to one or more dispersing agents and wetting agents, water or solvent to form a fine active compound suspension. It can be a stable active compound suspension after dilution with water.

E) Water-dispersible granules and water-soluble granules (WG, SG)

One or more insecticidally effective compounds of formula (I) and nitrogen-based fertilizers are added to one or more dispersing agents and wetting agents and ground into microparticles, by suitable techniques (eg by extrusion, drying in a spray tower or Treatment in a fluidized bed) is made into a water-dispersible or water-soluble granule. After dilution with water, it can be a stable active compound dispersion or solution.

F) water-dispersible powder and water-soluble powder (WP, SP)

In one or more insecticidal effective compounds of formula (I) and nitrogen-based fertilizers, one or more dispersing agents, wetting agents and hydrazine gels are added and ground in a suitable apparatus (e.g., a rotor sub-mill). After dilution with water, it can be a stable active compound dispersion or solution.

G) Granules (GR, FG, GG, MG)

In one or more insecticidal effective compounds of the general formula (I) and nitrogen-based fertilizers, up to 99.5 parts by weight of the carrier are added and ground into fine particles by a suitable means, by suitable techniques (eg by extrusion, spray tower drying) Dry or use a fluidized bed) to make granules.

In another aspect, the present invention provides a method of protecting plants from insects thereby increasing crop yield. The method comprises applying an insecticidal active compound of the formula (I) as described above and a nitrogen-based fertilizer to one or a portion of the plant, the plant or the periphery thereof.

The composition of the present invention can prevent or eliminate insect infestation to plants and promote plant growth.

The compositions of the invention are more useful to increase crop yield. Target crops include particularly suitable cereals such as wheat, barley, rye, oats, rice, corn, sorghum, millet and cassava; beets (such as sugar beet and beet); fruits such as pears and drupes And non-nuclear fruits, including apples, pears, plums, peaches, almonds, cherries or berries (such as strawberries, raspberries and blackberries); legumes (such as beans, lentils, peas and soybeans); oil plants ( Such as rapeseed, mustard, poppy, olive, sunflower, coconut, ramie, cocoa and groundnut); Cucurbitaceae (such as zucchini, cucumber and melon); fiber plants (such as cotton, flax, hemp and jute); citrus fruits (eg orange, lemon, grapefruit and orange); vegetables (eg spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes and red peppers); medlars (eg avocados, cinnamon and eucalyptus); and tobacco , nuts, coffee, eggplant, sugar cane, tea tree, pepper, vines, hops, bananas, natural rubber plants, eucalyptus and ornamental plants. Particularly desirable use ranges are groundnut, cocoa, sugar cane, coconut, rice, cotton, millet, corn, cassava, sorghum and amaranth crops.

In general, the compositions may be formulated and administered according to the needs of the treatment site such that the pesticidal active ingredient of formula (I) can be administered in any suitable ratio. In particular, the compositions may be formulated as appropriate such that the compound of formula (I) can be applied at a rate of from 10 grams to 1000 grams per hectare, more preferably from 10 grams to 500 grams, and more desirably from 10 per hectare. G to 200 Gram.

As described above, the insecticidally active compound of the formula (I) and the nitrogen-based fertilizer can be applied in any suitable form, and can be applied simultaneously or at intervals in a short period of time (e.g., within one day) in a locus to be treated. In a preferred embodiment, the pesticidally active compound of formula (I) and the nitrogen-based fertilizer are applied simultaneously, more particularly preferably with the compositions of the present invention. The pesticidally active compound of the formula (I) and the nitrogen-based fertilizer can be applied to the plant or locus in any order. Each compound can be administered once or several times. It is desirable to apply each compound several times (two to five times), with three being especially desirable.

The insecticidally active compound of the formula (I) and the nitrogen-based fertilizer can be applied in any corresponding component. In particular, the relative amounts of the compound applied to the plant or locus are the same as described above, and the ratio of the compound of the formula (I) to the nitrogen-based fertilizer is preferably from 1:100 to 100:1.

In the case where the insecticidal active compound of the formula (I) and the nitrogen-based fertilizer are simultaneously applied, the two can be obtained from a separate dosage form source and mixed (referred to as a spray mixing ingredient, ie, a soup or a spray soup or slurry). (Optional), optionally mixed with other pesticides; or obtained as a single dosage form mixture source (referred to as premix, concentrate, formulated compound (or product)) and optionally remixed with other pesticides.

In a further aspect, the invention provides for the treatment of plants in a locus using an insecticidal active compound of the general formula (I) as described above and a nitrogen based fertilizer application. As described above, the insecticidal active compound of the formula (I) and the nitrogen-based fertilizer can be used separately or in combination in a single dosage form.

As described above, the production of the target plant to be treated can be improved by using one or more insecticidally effective compounds of the formula (I) and a nitrogen-based fertilizer as described above. The term "yield" as used herein refers to any plant product of economic value made by plants, such as cereals, fruits, vegetables, nuts, seeds, wood or flowers. These plant products can be further used and/or processed after harvest. By comparing the following plant characteristics with plants grown in the same environment but without the application of the insecticidal fertilizer of the present invention, the increase in "yield" can be understood:

- plant weight and / or height rise;

- increased biomass (eg fresh weight and/or dry weight increase)

- the number of tillers increases and/or becomes stronger

- leaves become larger and / or greener

- the number of basal leaf deaths has decreased

- increased shoot growth

- Early sprouting

- early flowering

- Early grain ripening

- Increase in cereal production

- The number of fruits and the increase in yield (weight)

- increased protein content

- increased oil content

- increased starch content

- increase in pigment content

In yet another aspect, the present invention provides a reduction of the aforementioned general formula (I) A method of phytotoxicity of a compound to a plant in a locus comprising applying a compound of the above formula (I) and a nitrogen-based fertilizer in the locus.

In yet another aspect, the present invention provides a method of reducing the phytotoxicity of a compound of the above formula (I) using a nitrogen-based fertilizer.

The invention will be further described in terms of the following examples (described only by way of illustration):

Example Composition Example 1 Water Soluble Concentrate (SL)

A water-soluble concentrate containing a compound of the formula (I) and a nitrogen-based fertilizer is prepared by the following components:

Composition Example 2 Emulsifying concentrate (EC)

Emulsifying concentrates containing a compound of formula (I) and a nitrogen-based fertilizer are prepared by the following ingredients:

Composition Example 3 Water Dispersible Powder (WP)

A water-dispersible powder containing a compound of the formula (I) and a nitrogen-based fertilizer is prepared by the following components:

Composition Example 4 Water Dispersible Granules (WG)

Water-dispersible granules containing a compound of the general formula (I) and a nitrogen-based fertilizer are prepared by the following components:

Composition Example 5 Suspending Agent

Suspensions containing a compound of formula (I) and a nitrogen-based fertilizer have been prepared and the ingredients are summarized in the table below:

Composition Example 6 Water Soluble Concentrate (SL)

A water-soluble concentrate containing a compound of the formula (I) and a nitrogen-based fertilizer has been prepared, and the ingredients are summarized in the following table:

Composition Example 7 Water Dispersible Granules (WG)

Water-dispersible granules containing a compound of the general formula (I) and a nitrogen-based fertilizer have been prepared, and the ingredients are summarized in the following table:

Composition Example 8 Suspension Seed Coating (FS)

The suspension seed coating composition is prepared by the ingredients listed in the following table:

Composition Example 9 Water Soluble Concentrate (SL)

A water-soluble concentrate containing a compound of the formula (I) and a nitrogen-based fertilizer has been prepared, and the ingredients are summarized in the following table:

Composition Example 10 Granules (GR) for food baits

A granular composition comprising a compound of the general formula (I) and a nitrogen-based fertilizer has been prepared, and the ingredients are summarized in the following table:

Test Example 1 - Crop yield test of soybean plants

Soybean seeds are planted in the greenhouse. Soybean plants were treated with fipronil (Regent® from BASF) and each of the above Examples 1 to 10 during development and early flowering. The application rates are shown in the table below. When the crop is ripe, harvest and measure the grain yield in tons per hectare.

*Application rate is based on (fipronil + nitrogen based fertilizer) g / ha

According to the above data, the addition of nitrogen-based fertilizers when processing soybean plants can effectively improve grain yield. Treatment with a composition containing the active ingredient but no nitrogen-based fertilizer compared to the untreated plant reduced grain yield due to the phytotoxicity of fipronil. The addition of a nitrogen-based fertilizer to the treatment of plants reduces the phytotoxicity of the active ingredients. The high concentration of fertilizer components can effectively remove the phytotoxicity of fipronil, thereby increasing grain yield.

Test Example 2 - Crop yield test of rice plants

Rice seeds were germinated in water at 30 ° C for 48 hours and then sown in pots. After emergence, fipronil (Regent® from BASF) and each of the above formulations of Examples 1 to 10 were applied to the soil. The application rates are shown in the table below. Allow the plants to mature to the harvesting stage, at which point the grain yield is measured in tonnes per hectare.

Test Example 3 - Test for insecticidal properties against fire ants ( Solenopsis invicta )

In the early summer, about 5,000 square feet per piece (about 465 square meters) On the land, an average of nine fire ant nests are arranged and processed. Count the number of living ants that live on each land before processing. Each treatment was repeated three times, and fipronil (Regent® from BASF) and each of the above dosage forms of Examples 1 to 10 were applied. On the 30th, 60th and 90th day of the "DAT" (until early autumn), the live ant nest is counted and the percentage of ant nest reduction is calculated based on the number of points before treatment to evaluate the utility. The test results are as follows:

Test Example 4 - Test for insecticidal properties against Ixodes scapularis

The turnip leaf discs were placed in agar in a petri dish and infected with 20 larvae (second-instar ticks). Each treatment was repeated four times, fipronil (Regent® from BASF) and the various dosage forms of Examples 1 to 10 above were applied. Mortality of the larvae was determined on the fourth to fifth days after the treatment. The test results are as follows:

Claims (21)

A pesticidal composition comprising: a) a pesticidally effective amount of one or more compounds of formula (I): Wherein: R ¹ is alkyl, halogen, or CN; R ² is 4,5-dicyanoimidazol-2-yl, haloalkyl, or S(O) _m R ⁷ ; R ³ is hydrogen, halogen, NR ⁸ R ⁹ , S(O) _n R ¹⁰ , C(O)R ¹¹ , alkyl, haloalkyl, OR ¹² , or N=CR ¹³ R ¹⁴ ; R ⁴ and R ⁶ independently of each other represent hydrogen, halogen, halogen Alkyl, CN, or NO ₂ ; R ⁵ is hydrogen, halogen, haloalkyl, haloalkoxy, or S(O) _p R ¹⁵ ; R ⁷ , R ¹⁰ , R ¹² and R ¹⁵ independently of each other represent an alkyl group Or haloalkyl; R ⁸ and R ⁹ independently of each other represent hydrogen, alkyl, alkenyl, haloalkyl, alkoxycarbonyl, or S(O) _q CF ₃ ; R ¹¹ and R ¹⁴ independently of each other represent hydrogen or alkyl R ¹³ is a phenyl group optionally substituted by one or more halogen atoms or OH, an alkyl group, an alkoxy group and a cyano group; and m, n, p and q independently represent 0, 1 or 2; and b) At least one nitrogen-based fertilizer selected from the group consisting of ammonium salts, fluid nitrogen fertilizers, urea, urea-formaldehyde condensates, urea ammonium nitrate, amino acids, metal nitrates, and mixtures thereof; and wherein the compound of formula (I) and nitrogen-based fertilizer The weight ratio is from 1:100 to 100:1, and the nitrogen-based fertilizer is present in an amount of from 0.5 to 50% by weight of the composition. The pesticidal composition according to claim 1, wherein R ¹ is fluorine, chlorine or CN. The pesticidal composition according to claim 2, wherein R ¹ is CN. The pesticidal composition according to claim 1, wherein R ² is S(O) _m R ⁷ . The pesticidal composition according to claim 4, wherein R ⁷ is a haloalkyl group. The pesticidal composition according to claim 5, wherein R ⁷ is CF ₃ . The pesticidal composition according to any one of claims 1 to 6, wherein m is 1. The pesticidal composition according to any one of claims 1 to 6, wherein R ³ is NR ⁸ R ⁹ . The pesticidal composition according to claim 8 wherein both R ⁸ and R ⁹ are hydrogen. The pesticidal composition according to any one of claims 1 to 6, wherein R ⁴ and R ⁶ are each a halogen. The pesticidal composition according to claim 10, wherein R ⁴ and R ⁶ are both chlorine. The pesticidal composition according to any one of claims 1 to 6, wherein R ⁵ is a haloalkyl group. The pesticidal composition according to claim 12, wherein R ⁵ is CF ₃ . The pesticidal composition according to any one of claims 1 to 6, wherein the compound of the formula (I) is selected from the group consisting of 5-amino-1-[2,6-dichloro-α,α,α -trifluoro-p-toluene]-4-[(trifluoromethyl)sulfinyl]-pyrazole-3-carbonitrile (Fipronil Fipronil); 1-[2,6-dichloro-α,α, --trifluoro-p-toluene]-5-[2-methylallylamino]-4-[(trifluoromethyl)sulfinyl]-pyrazole-3-carbonitrile (butene fipronil Flufiprole); 5-amino-1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-4-(ethylsulfinyl)-pyrazole-3-carbonitrile (B Nitrile Ethiprole); 1-[5-Amino-1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-4-(methylsulfinyl)-pyrazole-3 -yl]-ethanone (acetamidazole Acetoprole); (RS)-O-[1-(4-chlorophenyl)-pyrazol-4-yl-O-ethyl-S-propyl-thio Phosphate](pyrazolofos); 1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-4-[(fluoromethyl)thio]-5-[(pyridyl) Methyl)amino]-pyrazole-3-carbonitrile (pyridyl) Flurazine (Pyrafluprole); 1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-4-[(difluoromethyl)thio]-5-[(2-pyridylmethyl) Amino]-pyrazole-3-carbonitrile (pyridylpyridylpyryl); 3-methyl-1-phenyl-pyrazol-5-yldimethylcarbamate (pyrazole) ; and (E)-1-[2,6-dichloro-α,α,α-trifluoro-p-toluene]-5-[4-hydroxy-3-methoxybenzylideneamino]-4- [(Trifluoromethyl)thio]-pyrazole-3-carbonitrile (Methiliprole). The insecticidal composition according to claim 14, wherein the compound of the formula (I) is fipronil. The pesticidal composition according to any one of claims 1 to 6, wherein the compound of the formula (I) is present in an amount of from 1 to 50% by weight. The pesticidal composition according to any one of claims 1 to 6, which further comprises a salt of one or more micronutrients. The pesticidal composition according to any one of claims 1 to 6, wherein the weight ratio of the compound of the formula (I) to the nitrogen-based fertilizer is from 1:20 to 20:1. The pesticidal composition according to any one of claims 1 to 6, which further comprises one or more selected from the group consisting of a solvent, a surfactant, a stabilizer, an anti-foaming agent, an antifreeze, a preservative, and an antioxidant. Additives for agents, colorants, thickeners, inert fillers and mixtures thereof. The pesticidal composition according to any one of claims 1 to 6, wherein the composition is a granule, a suspension concentrate, a water-dispersible granule, a water-soluble granule, a water-dispersible powder, and a water-soluble powder. Or a flowable suspension. Use of a composition according to any one of claims 1 to 20 for the treatment of plants in a locus.