HU177610B - Process for preparing ring-substituted n-/2,2-difluoro-alkanoyl/-o-phenylene diamine derivatives and pesticides containing such materials as active substances - Google Patents

Description

FIELD OF THE INVENTION The present invention relates to a novel process for the preparation of ring-substituted N- (2,2-difluoroalkanoyl) -o-phenylene diamine compounds and to pesticides containing them as active ingredients.

These compounds may be active ingredients in herbicidal, insecticidal, parasiticidal, anthelmitic and nematocidal agents.

The eradication of animal parasites is one of the oldest and most serious problems of animal husbandry, especially industrial animal husbandry. Certain parasite breeds attack virtually all animal species. Most animals are free-living parasites such as flies, animal parasites such as lice and mites, self-drilling parasites such as mole fly larvae and meat fly larvae, as well as microscopic internal parasites such as coccidia. as well as long internal parasites such as worms. From this point of view, it can be seen that the control of parasites is already a very complex and multifaceted task for a single breed of host animal.

Particularly harmful are insect pests and acarine parasites that destroy the living tissues of a host animal. This group includes pests of farm animals, including ruminants and single-digested mammals and poultry, as well as domestic animals such as dogs and cats.

Numerous methods have already been developed to eradicate such parasites. In some areas, such as Florida, virulence has been practically eradicated by the release of large numbers of sterile female flies. However, this method can only be successfully applied in an easily distinguishable area. Freedom to fly insects is usually controlled by conventional methods, such as air dispersed and contact insecticides and fly traps. The control of parasitic parasitic parasites is done by bathing, spraying and spraying the animals with the appropriate parasiticide.

There has been some progress in eradicating certain parasites by systemic methods, particularly those that drill into the host animal or migrate into the host animal. Systemic eradication of parasitic parasites in animals is accomplished by introducing the pesticide into the bloodstream or other tissue of the host animal. Parasites that consume or come into contact with these pesticidal 3-containing tissues are poisoned via the digestive tract or by contact. To date, only a small amount of phosphate, phosphoramidate and phosphorothioate insecticidal agents have been found to be suitable non-toxic agents for topical use in animals.

U.S. Patent No. 3,557,211 to Rumanowski describes N, N-bis (acetyl) -ophenylene diamines useful for controlling plants, insects and fungi.

The process of the present invention provides compounds useful as systemic antiparasitic agents.

The present invention therefore relates to a process for the preparation of new ring-substituted N- (2,2-difluoroalkanoyl) -o-phenylene diamine compounds of formulas (1), (11) and (111).

In these formulas:

Ο

II

R 0 is a 2,2-difluoroalkanoyl radical of formula -C-CF ₂ -Y wherein Y is hydrogen, chlorine, fluoro, difluoromethyl, C 1 -C ₈ perfluoroalkyl or a radical of formula (a) , wherein each Z is independently hydrogen or halogen and n is a number 0 or 1,

SHE

R ^{1 is} hydrogen, a group -C-O-Y ¹ , wherein Y ^{1 is} a C ¹ -C ₄ -alkyl or phenyl, benzoyl, furoyl, naphthoyl or a substituted benzoyl of formula (b) wherein each Z 'is independently halo or nitro, Z is C 1 -C ₄ alkyl or C 1 -C ₄ alkoxy, p is 0,1 or 2, q is 0 or 1, while the sum of p and q is 1-3,

R ² is the same as R 0 or R ¹ , moreover it represents C ₁ -C ₈ alkanoyl, C ₃ -C ₄ alkenoyl, C ₃ -C ₄ alkoyl or C ₂ -C ₄ halogenated alkanoyl; means a group having one or more halogen atoms in any position or position, with the proviso that the alpha carbon atom contains at least one hydrogen atom or a halogen atom of 35 to 127 atoms,

Each R ³ substituent may be independently halo;

R ^{4 is} nitro,

R ^{5 is} trifluoromethyl, difluoromethyl or dichlorofluoromethyl, and in the compounds of formula II, R ⁴ and R ⁵ are in a meta position relative to each other,

R ^{6 is} C 1 -C ₄ alkylsulfonyl and 4-cs or

Attached to the 5-position and R ⁴ group is in the meta position relative to R ^6, m is a number from 0 to 4, n is 0 or 1, and (1) compounds of formula m + n is 1 to 4, wherein the with the further proviso that when R ¹ or R ^{2 is a} hydrogen atom, one of the given R ³ , R ⁴ , R ⁵ or R ⁶ groups is located on the ring at the ortho position to the -NH-R ¹ or -NH- R ² group.

The process is characterized by reacting a compound of formula (VII), (VIII) or (IX), wherein the substituents are as defined above, with an acylating agent (IV), wherein Y is as defined above, or a reactive derivative thereof. reaction.

Compounds of formula (I), (II) and (III) are prepared by introducing the typical 2,2-difluoroalkanoyl group into the corresponding diamine starting materials. The introduction of this group is accomplished by a number of suitable acylation reactions using various acylating agents of formula IV wherein Y is as defined above. The identity of the acylating agents is not critical and suitable acylating agents are 2,2-difluoroalkanoyl halides of formula V and 2,2-difluoroalkanoic anhydrides of formula VI wherein Y is as defined above. The diamine starting materials with which the acylation reaction is carried out may vary.

For example, for compounds of formula (I), (H) and (III), wherein R ^{1 is} hydrogen or wherein R ² or hydrogen or R 0, the starting diamine is one of general formula (X), (XI) and (XII). or a single acyl group (R ¹ or R ² hydrogen) or two identical acyl groups (R 0 and R ² each)

O-C-CF ₂ -Y).

On the other hand, when R ^{1 is} other than hydrogen and R ² is other than hydrogen or R ² represents R ² , the corresponding diamine starting material already contains the desired R ¹ or R ² group as in (XIII). ), Compounds of Formulas XIV and XV, wherein the other substituents have the same meanings as defined above, the representative R 0 group is introduced by acylation in the same manner as above. It is mentioned that the R ² group may be a 2,2-difluoroalkanoyl group other than the group represented by R 0, in which case the groups are introduced sequentially into the molecule.

The synthetic methods described above are suitable; and are preferred, but other methods may be used. For example, in the case where R ¹ a-2,2-difluoralkanoil radical scavenger other than acyl group, the R ¹ group is introduced into the molecule in such a case, if the group R ° has been introduced. Because of the activating activity of the alpha-fluoro atom, it is generally preferred that groups other than the 2,2-difluoroalkanoyl moiety are already present in the molecule prior to the introduction of this moiety. In the case where R ^{2 is a} formyl group, the acylation is carried out with mixed acetic and formic anhydrides. However, other acylating agents for introducing formyl groups may also be used.

Acylation of amines with various acylating agents to produce the appropriate amides is a known synthetic method. The methods of the invention are carried out in accordance with known methods. Thus, in the case where the acylating agent is an anhydride, the reaction is usually carried out at room temperature. Except anhydride with an excess of solvent can be used those amides in which R ¹ or R ² is hydrogen. In the case where the acid halide is used as the acylating agent, the reaction is carried out, if necessary, in the presence of a hydrogen halide-binding agent, preferably in an inert solvent, while cooling the reaction mixture, such as θ-10 ° C. When any acylating agent is used, the product is isolated by conventional means and purified by conventional methods, if necessary.

For the sake of uniformity, starting materials and products are referred to hereinafter as o-phenylenediamines, where possible. In accordance with standard nomenclature practice, to identify the various substituent positions, formula (XVI), wherein each nitrogen atom contains an alkanoyl or other (R 0, R ¹ , R ² ) substituent, is given by its ring position numbers as its number. in order to distinguish it from the number of sites on R 0, R ¹ or R ² .

In the foregoing definitions of the compounds of Formulas I, II and III, as well as in the specification and claims, the term halogen, alone or in the halogenated alkanoyl term, refers to bromine, chlorine, fluorine or iodine.

An important and distinguishing structural feature of the compounds of formulas I, II, and III is the 2,2-difluoroalkanoyl radical represented by R 0, some of which are listed below:

difluoroacetyl, trifluoroacetyl, difluoro chloroacetyl, pentafluoropropionyl, heptafluorobutyryl, nonafluorvaleryl,

2.2.3.3- tetrafluoropropionyl, undecafluorohexanoyl, tridecafluoroheptanoyl, pentadecafluorooctanoyl,

2.2- difluoropropionyl,

2.2- difluorobutyryl,

2.2-difluoro-3-bromopropionyl,

2,2-difluoro-3-chloropropionyl, 2,2-difluoro-3,4-dichlorobutyryl,

2.2-difluoro-4-bromobutyryl,

2.2.3 - trifluoropropionyl,

2.2.3 - trifluorobutyryl,

2,2,3,4-tetrafluorbutiril-,

2.2-Difluoro-3-bromo-4-chlorobutyryl.

Preferred R 0 groups are trifluoroacetyl, difluoroacetyl, difluoro chloroacetyl and 2,2,3,3-tetrafluoropropionyl.

The starting materials used in the process of the invention may be prepared by known methods and some of them are commercially available. Said starting materials of formulas (VI), (VIII) and (VIII) are prepared in a number of synthetic steps for the introduction of the desired moieties and substituents. Most preferably, one or two NH ₂ groups may be introduced into the molecule by conversion of a halogen group. The amino group or amino groups can also be introduced into the molecule by nitration and subsequent reduction. These various synthesis steps are generally and most suitably carried out with starting materials that already contain the desired R ³ , R ⁴ , R ⁵ and R ⁶ groups. In some cases, it is preferable to introduce these substituents, such as a nitro group or a halogen, at the same time as the synthesis step for introducing the amino group.

For example, where the diamine is tetrasubstituted, the corresponding tetrasubstituted benzene is nitrated at each of the remaining ortho positions and the nitro groups are subsequently reduced. 3-Nitro-5-substituted diamine wherein the substituent is cyano or alkylsulfonyl can be readily prepared by nitration of a 5-substituted-2-hydroxynitrobenzene to introduce the 3-nitro group, followed by conversion of the hydroxyl group to chlorine, and subsequent amination and selective reduction.

Compounds of formula (I) or (II) wherein R ¹ is an acyl radical other than hydrogen or represented by R 0 are generally prepared from diamine starting materials that already contain the desired R ¹ . These starting materials are prepared from the appropriate diamine starting materials described above with a suitable acyl halide or when both R ¹ and R ²

SHE

II-C-Y 'by reaction with a suitable lower alkyl or phenyl haloformate. Alternatively, these starting materials may also be prepared from the corresponding o-nitroanilines of Formula (XVII), (XVI11) or (XIX) by acylation followed by reduction. However, these methods are known in the art.

Each of the compounds of formulas I, II and III can be used as herbicidal active ingredient. These formulations containing the ring-substituted (2,2-difluoroalkanoyl) -o-phenylene diamine compounds of formulas I, II and III have a broad herbicidal action and therefore the invention is broadly understood to include plant parts such as stems, leaves. such as flowers, fruits, roots, seeds or similar growth organs of plants, wherein the compositions may be used in an amount that inhibits growth. These compounds are also useful as active ingredients in selective herbicidal compositions. It is known in the art that the herbicidal effect can be increased by mixing several active ingredients. When using a mixture, the amount of each compound can be reduced and the desired herbicidal effect is achieved.

It is not a critical requirement for the utility of the compounds that the composition completely destroy the undesired plants. It is sufficient if they inhibit the growth of undesirable plants properly. Where, for example, a selective effect is required, the time of destruction should be short, especially when combined with natural phenomena such as limited moisture, which hinder the growth of selectively inhibited vegetation rather than crop plants.

The compounds of formulas I, II and III are suitable for a wide range of herbicidal applications. For example, these compounds can be used as active ingredients of selective herbicides in various crop plants such as cotton, corn, sorghum and soybeans. In such cases, the compositions may be applied before emergence to both crop plants and weeds, or, preferably, to post-emergence crop plants by direct spraying, but may be applied to both weeds before and after emergence.

In other applications, formulations containing the compounds of formulas I, II, and III exhibit broad herbicidal activity in non-crop areas, including temporarily not planted edges surrounding arable land. When applied on set-aside land, so-called fallow land, in the spring, vegetation can be retained until it is weakened or spring sown, or vegetative development can be delayed until hatching or seedling. In other applications, compositions containing the compounds of the present invention may be used to control weeds in tree plantations, such as those of various citrus trees. A great advantage of the various applications mentioned is that these formulations do not have to be incorporated into the treated soil, since the same good results are obtained when the formulations are applied only to the soil surface. If desired or necessary, it can be incorporated into the soil or otherwise mechanically mixed with it.

In addition to the above-mentioned terrestrial applications, the compositions of the invention may also be used as aqueous herbicides.

However, in order to obtain good results in the use of the compounds of the formulas I, II and III as herbicides, it is necessary to use the compounds as a component of the composition in order to increase the plant growth inhibitory effect. For example, the active ingredient may be mixed with water, or mixed with other liquids or liquids, preferably with the aid of a surfactant. The active ingredient may be incorporated into a finely divided solid which may also be a surfactant, as in the case of wettable powders which may then be dispersed in water or other liquid or embedded in a powder formulation for direct use. In addition to these, there are other methods of preparing compositions known in the art.

The amount of active ingredient used is not critical and depends on the type of growth inhibitory effect desired, the species of plants in question, the active ingredient used and the weather conditions. Generally, a broad growth inhibitory effect can be achieved with 0.5 to 20 kg / ha of active compound application and such amounts are suitable and effective for reducing the growth of arable land crops. In cases where weeds need to be selectively inhibited in areas planted with crop plants such as corn, soybeans and cotton, application of 0.5 to 10 kg / ha of active ingredient will generally provide good results. Concentration of the active ingredient in the composition is not critical unless the concentration and the total amount of formulation used are equivalent to the corresponding amount calculated on a hectare basis. Generally, good results can be obtained using formulations containing the active ingredient in a concentration of 0.5 to 10% or greater, such as a liquid formulation and 1.0 to 5.0% or more of a powder, powder, granules or other dry preparations. More concentrated compositions can also be prepared and often preferred, depending on the particular application and the particular concentration, these compositions are suitable for shipping and storage on board, further concentrated compositions are compositions for final treatment. The compositions preferably contain, for example, a surfactant and an active ingredient which may be in the range of 0.5 to 95% by weight or a finely divided inert solid and active ingredient in this case may be 1.0 to 95% by weight. Such formulations, as mentioned above, may in some cases be directly used, but may be diluted and then used.

Liquid compositions containing a desired amount of the active ingredient are prepared by dissolving the material in an organic liquid or dispersing the material in water with or without a surfactant, such as an ionic or nonionic emulsifier. Such compositions may also contain modifying agents to aid spread or adhesion of the active ingredient to the foliage of plants. Suitable organic liquid carriers are agricultural distillation oils and petroleum distillation products, such as diesel oil, kerosene, fuel oil and the so-called Stqodart solvent. Petroleum distillation products are generally preferred. Aqueous formulations may contain one or more water immiscible solvents to dissolve the active ingredient. In such compositions, the carrier is a mixture of an aqueous emulsion such as water, an emulsifier, and a water immiscible solvent. The choice and amount of dispersant and emulsifier will be determined by the nature of the composition and will determine the ease with which the active ingredient is dispersed in the vehicle in order to obtain the desired composition. Dispersing and emulsifying agents for use in the composition may include condensation products of alkylene oxides with phenols and organic acids, alkylarylsulfonates, polyoxyalkylene derivatives or sorbitan esters, and complex lexether alcohols. Surfactants useful in the preparation of the compositions of this invention are disclosed in U.S. Patent No. 3,095,299.

Column 2, columns 25 to 36 , U.S. Patent No. 2,655,447, column 5, and

Columns 4 and 5 of U.S. Pat. No. 2,412,510.

In preparing the powder formulations, the active ingredient of Formula I, II or III is finely dispersed in a finely divided solid or material which may be chalk, talc, limestone, gypsum, clay, fine vermiculite or perlite. Alternatively, such a dispersion is prepared by mechanically mixing or grinding the finely divided carrier with the active ingredient.

Similarly, powder formulations containing the active compounds may be prepared with various solid surfactant dispersants such as bentonite, fuller earth, attapulgite or other chalk. Depending on the active ingredient ratios, these powder formulations may be formulated as concentrates and subsequently diluted with additional solid surfactant dispersants or chalk, talc, gypsum to provide the active ingredient in an amount necessary to inhibit plant growth. Such powder formulations may also be dispersed in water with or without a dispersant to form spray compositions.

The formulations containing the active compounds of the formulas I, II or III can advantageously be further modified by the addition of a surfactant, which facilitates the dispersion and spraying of the compositions on the leaf surfaces and their penetration into the plants.

The active ingredient may also be dispersed in soil or other media by any conventional method. Application can be by simple mixing with media, application to the soil surface and then harrowing or dialing to the desired depth, or a liquid carrier 55 may be used to aid delivery or impregnation into the soil. Application of the spray or powder compositions to the soil surface, parts of plants or the underside of the leaves may be effected by conventional means such as dusters, field or hand sprayers and sprayers. The great advantage of the compounds of formulas (1), (U) and (III) is that they are effective herbicides in formulations even when applied only to the soil surface without further application to the soil. Thus, these compounds are essentially effective in formulations, even when applied only to the soil and when applied to the soil after application.

Alternatively, the composition may be dispersed in soil by mixing it with water. In such methods, the amount of water, the porosity of the soil and its water uptake are adjusted and vary according to the depth of distribution of the active ingredient in the soil.

The toxicity of the compounds of formulas I, II and III to mammals is much lower than that of the corresponding benzimidazoles. In addition, the compounds of formula (I), (II) or (III) may also be formulated as an aerosol formulation. Such compositions are prepared by conventional means by dispersing the active ingredient in a solvent and mixing the resulting dispersion with a liquid propellant. The solvent and drug concentration in the solvent will depend on the drug used and the vegetation to be treated. Suitable solvents include water, acetone, isopropanol and 2-ethoxyethanol.

In particular, satisfactory results are obtained when the active ingredient of formula (I), (II) or (III) or a composition containing such active ingredient is combined with other agricultural ingredients used in plants, parts of plants or in their natural environment. Such materials include fertilizers, fungicides, insecticides, other herbicides and soil conditioners.

Specifically, various compounds of formula I, II or III have been investigated as herbicidal agents and evaluated for their effects on pre-emergence application in different plant species. In the experiment, a part of the sand and a part of the upper soil layer were mixed in a cement mixer. 4.5 liters of this soil was placed in a 25 x 35 cm galvanized bowl and smoothed evenly. Using a three-furrow row guide, 2.5 cm deep furrows were made in about two-fifths of the soil in the pot. Four grains of cereal seed, five grains of cotton and five grains of soybean seeds were sown in these furrows. Subsequently, with a four-furrow row guide, furrows were pulled over the remainder of the soil and approximately the same number of seeds of the following plants were sown into the furrows: Brush lawn (millet) 80-100 seeds; silkworm (40-50 cores); coarse porcine parsnip (150-250 seeds) and broad finger (100-150 seeds).

Then we put another earth in the pot and covered the seeds with it. In this way the weed seeds were about 6 mm deep, while the weed seeds were 3 cm deep.

During the pre-emergence testing of the composition, on the day of seeding or the following day, a vessel similar to the above vessel was prepared and placed in a room equipped with a turntable and a vent. The herbicidal composition was applied as a spray-type emulsion or wettable powder with a DeVilbiss modified nebulizer attached to an air source and applied to the ground. An amount of 12.5 ml of the test composition was applied to the soil in each pot on the day of sowing or the day after. At eleven-twelve days after treatment, the extent of damage was determined. Evaluation was based on the following damage rating scale:

no damage, slight damage, moderate damage, severe damage, death.

When more than one assay is performed on a given amount, the degree of damage is averaged. Each compound was prepared as a spray by one of the following methods.

In one experiment, the compound was ground with a portion of a polyoxyethylene sorbitan monolaurate and moistened. Five hundred parts of water were then added slowly to the resulting creamy paste to obtain an aqueous dispersion with 0.2% surfactant content. This dispersion was perfectly suitable for use as a spray. Alternatively, the compound was dissolved in one volume of acetone and the acetone solution was diluted with nineteen parts of water containing 0.1% polyoxyethylene sorbitan monourate.

The following Table I shows the results of the evaluation. Column 1 shows the test compound, column 2 shows the application rate in kg / ha, and the other columns show the degree of damage to each crop, as measured by the previous scale.

Table I

Degree of damage during pre-emergence treatment

agent kg'ba maize cotton soy-bean ujjas- mallow pig- paríj brush- lawn silk- ryegrass N, N-trifluoroacetyl-tetrachloro-o- S'Á'.S'.ó' phenylenediamine N-trifluoroacetyl-S 'S'-chloro-nitro-o-phenylene 8 1 0 0 4 4 2 1 diamine 8 1 0 1 4 4 2 3 N ¹ , N ² -bis [trifluoroethyl (-5 '-) methylsulfonyl] -phenylenediamine N'-trifluoroacetyl-S'-nitro-S'-trifluoro-methyl-o- 8 1 1 2 3 4 3 3 phenylenediamine 8 0 0 2 4 4 3 3 N * - (2,2,3,3-tetra- 8 1 - - 3 4 3 4 fluorpropionil) -3 ' 4 0 1 1 2 4 3 4 , nitro-5'-trifluoromethyl-o-, 2 0 0 0 3 4 3 4 phenylenediamine, _z t _<t 1 0 1 0 2 3 2 3

S

The post-emergence effects of some formulations containing the compounds of formulas I, II and III as active ingredients were also investigated in crop plants and weeds. Experiment and evaluation were carried out according to the previous experimental methods except that solutions containing the test compounds were applied 9-12 days after preparation of the soil and seeding of the seeds into the soil. The results are shown in the following II. table.

II. spreadsheet

Degree of damage during post-emergence treatment

agent kg / ha maize crabgrass pigweed foxtail velvetleaf N-trifluoroacetyl-J'-nitro-O'-trifluoromethyl-o- phenylenediamine 8 1 4 4 4 4 N-trifluoroacetyl-3'-nitro-5'-chloro-o-feniIéndiamin 8 1 3 4 4 4 4 2 4 4 4 4 2 1 4 4 4 4 1 1 4 4 3 4 N ¹ , N ² -bis (trifluoroacetyl) - 8 2 4 4 3 4 5 '- (methylsulfonyl) -o- 4 1 4 4 4 3 phenylenediamine 2 1 4 4 4 2 N ¹ - (2,2,3,3-tetrafluoropropionyl) - 8 2 4 4 4 4 3'-nitro-5'-trifluoro- 4 3 4 4 4 4 methyl-p-phenylene 2 3 4 4 4 3 diamine 1 1 4 4 4. 4

AN ^2- (2,2,3,3-tetrafluoropropionyl) -N'-methoxycarbonyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine was tested as a post-emergence herbicide. The experiment was carried out according to the experimental methods described above, but with a single and large application rate (15 kg / ha) and with different plant species (tomato, finger fly, pork leg). The compound exterminated all said species.

The compounds of formula (I) and (II) also have insecticidal and acaricidal activity. This effect is more pronounced for the compounds of formula II. These compounds are useful for controlling insect and mite pests when selected in appropriate amounts to avoid phytotoxic effects. These compounds are useful for the control of insects and mites that attack the roots and above-ground parts of plants. For example, said compounds are active against the following mites: red spider mite, fruit spider mite, two-spotted mite, Pacific mite, clover mite, fowl mite, various tick species and various mite species. The compounds of the invention are also active against insects of various orders. Examples of such insects are: Mexican bean beetle, cotton bug beetle, cereal beetle, ground flea, boring insect, potato beetle, corn beetle, lucerne bug beetle, museum beetle, , white aphids, melon aphid, rose aphid, white fly, green aphid, corn aphid, pea aphid, aphid, aphid, citrus aphid, spotted aphid, green apricot aphid, beans wheat germ, house fly, yellow fever mosquito, stallion fly, beef stallion, carrot fly, American silkworm, apple moth, cotton worm, moth, indian wheatgrass, rolling moth, cornflower, European cornflower, European cornflower barrel butterfly, grasshopper insect, root-chewing worm, German cockroach and American cockroach.

In addition to controlling plant-parasitic pests, these latter compounds may also be incorporated in paints, adhesives, polymeric materials, diluents or oils, and latex materials. These compounds can be dispersed in textiles, cellulosic materials or cereals, but can be used to impregnate wood and lumber. They can also be used for pickling seeds. Alternatively, these products may be vaporized and dispersed in the form of an aerosol or spray in the air or applied to surfaces in contact with the air. For such applications, the compositions exhibit the above-mentioned advantageous properties.

By using these compounds as insecticidal or acaricidal agents, an insect or arachnid is treated with an effective amount of the aforementioned formulations, which may be achieved by delivering one or more products to the site of the insect or arachnid. Pests can be found in soil, air, water, food, vegetation, inert materials, stored products such as grain and animal organisms. The treatment can be such that the pests die immediately or later, that is, receive a lethal dose, or kill insects or arachnids in smaller doses, thereby paralyzing a vital function of these pests. In the case of known insects, the latter method is most often used, in which some function of the body, often the nervous system, is severely impaired. The exact mechanism of action of the compounds of the present invention is not yet known, and insecticidal or arachnicidal activity is not related to the mode of administration.

The concentration of the compounds may vary with the one or more excipients in the composition, but care should be taken to ensure that the active ingredients are present in amounts sufficient to kill insects or arachnids. In some cases, a composition containing 0.000 001% of the active ingredient is already suitable for controlling insects and arachnids. Of course, compositions having a higher concentration of active ingredient, such as 0.000001-0.5% active ingredient, can also be prepared. In other cases, compositions containing 0.5 to 95% by weight of a single compound or 0.5 to 95% by weight of more than one active ingredient may also be used. Such compositions may be used as treatment compositions or applied to or to control insects and arachnids, and stored as concentrates and diluted with suitable excipients when used.

Compositions containing such compounds are used for the direct control of said pests or otherwise delivered to their sites, for example by hand-spraying or spraying, but may also be mixed with a nutrient which the pests digest. Formulations are applied to the foliage of plants by means of dusters, field sprayers or mist generators. When applied to foliage plants, the formulations used should not contain significant amounts of phytotoxic diluents. For large-scale operations, when using powders or small volume sprays, aerial spraying can also be performed. Compositions containing one or more of the compounds of the invention may also be used.

The compounds used for the control of insects and arachnids and presented in the following experiments were formulated as described below.

First, 55 g of a mixture of two non-ionic sulfonate emulsifiers were mixed with 1 liter of cyclohexanone. 0.9 ml of the resulting mixture was then mixed with 0.9 mg of the test compound and diluted to 90 ml with distilled water to give a formulation containing 1000 ppm of the test compound. To obtain lower concentrations, the mixture thus prepared was diluted with 1.8 ml of the aforementioned nonionic sulfonate emulsifier in 4 liters of distilled water.

The insecticidal and acaricidal activity of the compounds of formulas I and II is also demonstrated in the following experiments.

Mexican bean drill beetle

Epilachna varivestis (Coleoptera)

Four biennial green bean plants with ^two leaves and nearly 33 cm ² leaf area were placed in water. The leaves were sprayed with a composition containing about 5 to 10 ml of a predetermined amount of the test compound for wetting. One half of the formulation was sprayed onto the leaf surface and the other half onto the back using a DeVilbiss nebulizer 0.6 atm. overpressure from a distance of about 45 cm. After the spray had dried, the leaves were removed from the stem and placed separately in Petri dishes. Thirteen larvae, Mexican bean beetle larvae, which were developed on high-yielding green bean plants, were then placed on each leaf and, for comparison, two leaves were sprayed with 5 ml of 500-ppm S-(1,2-dicarbethoxyethyl) -0,0-dimethylphosphorothioate and two leaves were left untreated as a control. 48 hours after treatment, the number of dead larvae was determined and the amount consumed was noted. The larvae in extinction were considered dead. The following toxicity rating scale was used for the evaluation:

Death Rate Rating

0-10 0

11-20 1

21-30 2

31-40 3

41-50 4

51-60 5

61-70 6

71-80 7

81-90 8

91-100 9

The test compound, the amounts used and the results of the evaluation are shown in the following IV. table. For more than one rating, mean values were calculated.

ARC. spreadsheet

agent Quantity (Ppm) Toxicity value against Mexican bean drill beetle NktrifluoracetilG'-nitro-S'- 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 9.0 50 9.0 NkdifluorklóracetilG'-nitro-o'- 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 8.0 - 50 9.0 N ^, -trifluoroacetyl-N ² -benzoyl-3 '- 1000 7.0 nitro-5-trifluoromethyl-p-phenylene 500 9.0 diamine 250 7.5

Gabonahernyó

Prodenia eridania (Leptinotarsa)

Ten identical beans of Henderson-type lime beans were cut into petri dishes on cut leaves of the same Henderson species. The bean leaves were sprayed with the insecticide in the same way as the green bean leaves for the Mexican bean drill beetle. In this case, the reference was sprayed with 5 ml of 100 ppm DDT solution. 48 hours after spraying, dead larvae were counted, and dead larvae were again considered dead. The missing larvae, which the others probably ate, were counted as alive. We used the scale used for the Mexican bean drill fly as the rating scale.

The test compounds, the amounts of active compound used and the results of the evaluation are as follows

This is given in Table V. For more than one value, an average value was calculated.

Table V.

agent Quantity (Ppm) Toxicitósi value grain- caterpillar Elten N ¹ -difluorochloroacetyl-3'-nitro-5'- trifluoromethyl-o-phenylenediamine 1000 8.5

Dinnyelevéltetű

Aphis gossypii (Hemiptera)

Four blue pumpkin seeds were placed in a vermiculite-filled pot and the soil was moistened from the bottom of the pot. After six days, the two weakest plants were cut and one cotyledon and the first leaves were removed from both plants. The remaining cotyledon was infected with 100 pieces of melon aphid from one strain by attaching the cotyledon to a lice infected with lice and allowing the lice to pass through. After transferring the stakes, the strains were removed. After 48 hours, infected leaves were sprayed with formulations containing increasing amounts of insecticidal active ingredient. Spraying was performed with DeVilbiss at a pressure of 0.7 atm from a distance of 30-38 cm. For comparison, two infected but not sprayed leaves and 100 ppm leaves sprayed with herbicide containing S- (1,2-dicarbethoxyethyl) -0,0-dimethylphosphorothioate served as reference. Death was determined 24 hours after spraying with a 10x magnification microscope. For the evaluation we used the rating scale given above.

The test compounds, the amounts of active compound used and the results of the evaluation are as follows

VI. table. For more than one value, an average value was calculated.

Two-spotted mite

Tetranychus urticae (Acarina)

Two-spotted weaving mites were grown on green bean plants and then planted on a pumpkin plant. The pumpkin plants were kept for two days during which time the infection was complete. Infected pumpkin plants were then sprayed with a composition containing the test compound according to the methods described above. Death was determined 48 hours after spraying. The evaluation was performed according to the rating scale provided previously.

The test compounds, the amounts of active compound used and the results of the evaluation are as follows

VII. table.

VII. spreadsheet

agent Quantity (Ppm) Toxicitósi value spotted spider mites against N ¹ -tr ifluoroacetyl-3 '-nitro-5' - 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 9.0 50 8.5 N'-pentafluoropropionyl-S '-nitro- 1000 9.0 -5 '-trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 9.0 50 8.5 N ¹ -pentafluorochloroacetyl-3 '-nitro- 1000 9.0 -5 '-trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 8.0 50 9.0 NMrifluoracetil-S 'trifluoromethyl- 1000 9.0 -5'-nitro-o-phenylenediamine 500 9.0 250 9.0 100 9.0 50 8.0

VI. spreadsheet

agent Quantity (Ppm) Toxidtísi value melon- blackfly against N ^, -trifluoroacetyl-3 '-nitro-5'- 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 8.0 50 7.0 N '-difluorochloroacetyl-3'-nitro-5'- 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 250 8.5 100 8.0 N '-trifluoroacetyl-J' -trifluoromethyl- 1000 9.0 -5'-nitro-o-phenylenediamine 500 9.0 250 9.0

Bíborpoloska

Oncopelitis fasciatus (Hemiptera)

Ten adult pimple bugs were cooled and placed in a test pot. Poles containing pouches were sprayed with a formulation of the insecticide to be tested with a DeVilbies nebulizer at a pressure of 0.7 atm at a distance of about 80 cm from the top of the box. While the cassava was dried, the bugs were fed with food and drinking water for 48 hours, using 2- (1,2-dicarbethoxyethyl) -0,0-dimethylphosphorothioate (500 ppm) as a reference and leaving two untreated controls They served. 48 hours after spraying, dead individuals were counted. Specimens in death were considered dead. Evaluation was performed according to the rating scale given above.

The compounds tested in this way, the amounts of active compound used and the results of the evaluation are set forth in the following section VIII. table.

VIII. spreadsheet

Quantity (Ppm) Toxicitági value purple- bug against agent N-trifluoroacetyl-3'-nitro-5'- 1000 9.0 -trifluoromethyl-o-phenylene diamine 500 9.0 250 9.0 100 9.0 50 8.0 N '-difluorochloroacetyl-3' -nitro-5'- 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 N * -difluoro-chloroacetyl-3 '-nitro-5'- 250 9.0 trifluoromethyl-o-phenylenediamine 100 9.0 N '-trifluoroacetM' -trifluoromethyl- 1000 9.0 -5'-nitro-o-phenylenediamine 500 9.0 250 9.0 N ¹ -heptafluorobutyryl-3 '-nitro-5'- 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 9.0 50 9.0

house fly

Musca domestica (Diptera)

The culture box containing four-day adult pet flies was cooled to 2-4 ° C for about 1 hour. 100 flies from the breeding cage were transferred to the test cages with a small spoon, where the flies were kept at 21-27 ° C for 1-2 hours. The cassettes were sprayed with 5 ml of the active compound to be tested, as described for the pepper bug. Two un sprayed boxes were kept as controls and two were sprayed with 50 ppm DDT as a reference. Twenty-four hours after spraying, mortality was determined by counting dead individuals. All flies that could not fly or could not climb from the bottom of the cass were considered dead. For the evaluation we used the rating scale used previously.

The compounds tested in this way, the amounts of the active compounds and the results of the evaluation are shown in the following section IX. is shown in Table.

IX. spreadsheet

agent Quantity (Ppm) Toxicitági value house fly against NMrifluoracetil ^ '- nitro-S 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 8.5 50 8.5

agent Quantity (Ppm) Toxicitáli értéit hizilégy against N ¹ -difluorochloroacetyl-3 '-nitro-5'- 500 9.0 trifluoromethyl-o-phenylenediamine 250 9.0 100 9.5 50 9.0

Cotton seed drill beetle

Anthonomus grandis (Coleoptera)

The method used in this study was the same as that used for the Mexican bean drill beetle and cereal beans. The difference was that 10 seedlings of cotton seed drill were planted as leaves on immersed leaves in a solution containing the active ingredient. For the evaluation we used the rating scale given above.

The compounds tested in this way, the amounts of active compound used and the results of the evaluation are summarized in Table X below.

Table X.

agent Quantity (Ppm) toxicity value cotton seed drill against beetle N Lheptafluorobutyryl-3 '-nitro-5 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 9.0 50 9.0 25 9.0 N * -pentafluoropropionyl-3 '-nitro- 1000 9.0 -5 '-tetrafluoromethyl-o-phenylene- 500 9.0 diamine 250 9.0 100 9.0 50 9.0 25 8.5 10 8.5 N '-perfluorooctanoyl-3' -nitro-5'- 1000 9.0 trifluoromethyl-o-phenylenediamine 500 9.0 250 9.0 100 9.0 50 9.0 25 9.0

Substantially similar results were obtained as given in the preceding tables, with the following compounds:

N ¹ - (2,2-difluoro-3-bromopropionyl) -N ² - (2-chloro-4-tert-butylbenzoyl) -3'-nitro-5'-trifluoromethyl-o-phenylenediamine,

N'-difluorochloroacetyl-N ² - (phenoxycarbonyl) -3'-nitro-5

difluoromethyl-p-phenylenediamine,

N ¹ -trifluoroacetyl-N ² -naphthaloyl-3'-nitro-5'-trifluoromethyl-O-phenylenediamine,

N'-trifluoroacetyl-N ² - (pn-butoxybenzoyl) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine,

N'-trifluoroacetyl-N ² - (p-nitrobenzoyl) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine,

N '-heptafluorobutyryl-3'-nitro-5' -trifluoromethyl-o-phenylenediamine,

Pentafluorpropionil-N'-nitro-S 'S'-trifluoromethyl-o-phenylenediamine,

N ^, -trifluoroacetyl-N ² -methoxycarbonyl-4'-trifluoromethyl-6'-nitro-o-phenylenediamine,

Pentadekafluoroktanoil-N'-nitro-3'-5'-trifluoromethyl-o-phenylenediamine.

In addition to their use, the compounds of formula II are useful as systemic agents for controlling parasites and acarines which feed on animal tissues. These compounds protect the living tissues of the host animal when administered to them in formulations. Insect and acarina parasites, which consume blood or other living tissues of the host animal, also devour tissue-impregnating preparations and are consequently killed. Blood is likely to be the vehicle through which the product is distributed to the host animal, but parasites such as wire worms are killed by these compounds, which do not absorb blood. These compounds are absorbed into the tissues where these worms parasitize.

Some parasites, like most ticks, eat the living tissue of the host animal throughout their lives. Other parasites, such as wireworms, only destroy the larval tissues of the host animal. A third group of parasites, e.g. the blood-sucking flies parasite on the host animal in their adult state. When administered to a host animal, the formulations containing the compounds of formula (II) will kill the parasites that devour the host animal tissues at any stage of their development.

Any species of insect and acarina consuming animal tissue is destroyed by formulations containing compounds of formula II. All parasites that absorb the blood of the host fetus are drilled into the tissues of the animal, as well as the larvae of the hoverfly, which enter the animal orally and attack the mucous membrane, are destroyed by formulations containing the compounds of the invention. For the sake of clarity, specific parasites of various host animals which may be killed by formulations containing the compounds of the present invention are listed below. The developmental state of the parasite and the manner in which it infects the host animal are also given.

Equine parasites equine eagle, adult specimen, blood suck, stallion, adult specimen, blood suck, black fly, adult specimen, blood suck, equine lice, underdeveloped, adult specimen, blood suck, typhus, nymph, adult specimen, skin piercing, varicose vein , biting skin, common goblin, larva, gastrointestinal immigration, barking, larva, migrating into the gastrointestinal tract, sucking horse eagle, larva, migrating into the gastrointestinal tract.

Cattle parasites cattle owl, adult individual, blood sucker, bovine parasitic drill, adult individual, dermal, bovine blood sucker lice, nymph, adult individual, blood sucker, chick, adult individual, blood sucker, stallion, adult lymphatic, adult , bloodsucker, follicle mite, adult specimen, penetrating skin, beef tick, larvae, nymph, adult specimen, bloodsucking, catching tick, nymph, bloodsucker, coastal tick, adult specimen, bloodsucker,

Rocky Mountains Spotted Fever-tick, adult specimen, bloodsucker, texas tick, adult specimen, bloodsucker, buckwheat, larva, wanders through the body, acne fly, larvae, wanders through the body, dead, larvae, infects wounds, bloodsucker,

Swine parasites are porcine, nymph, adult, sucker, sand flea, adult, sucker.

Sheep and goat parasites blood sucking litter, adult individual, blood sucking, blood sucking hoof, adult individual, blood sucking, sheep tick, adult individual, blood sucking, sheepskin, nymph, adult individual, ingrown, sucking mug, larvae, immigration , larvae, infects wounds, black grouse, larvae, infects wounds, secondary wire worm, larvae, infects wounds.

Poultry parasites domestic bug, nymph, adult individual, blood sucking, chicken flea, adult individual, blood sucking, poultry tick, nymph, adult individual, blood sucking, chicken mite, nymph, adult individual, blood sucking, scaly mite, adult individual, puncture mite an individual penetrating the skin. Dog Parasites Horse Mole, adult specimen, blood sucker, stallion, adult specimen, blood sucker, rabbit, nymph, adult specimen, skin piercing, follicle mite, adult specimen, hair follicle, flea, adult specimen, blood aspirator.

The parasites listed here are not only parasitic on the aforementioned single host animal. Most parasites attack different animals, but there are preferred host animals. For example, the thistle attacks horses, pigs, mules, dogs, cats, foxes, rabbits, sheep, and cattle. Horse eagles attack horses, mules, cattle, pigs, dogs and most animals. Formulations containing compounds of Formula II kill parasites parasitic in the above-mentioned host animals as well as parasiticides in other animals, such as those effective against cats, goats, camels, and zoos.

The host animals in which these compositions can be used to control ticks, fleas, flies, or wire worms, dogs, cattle, sheep, or horses.

The time, mode and amount of effective application of these formulations can vary widely. Details of these are given below.

These formulations are administered to the animals in an amount of 1 to 100 mg of active ingredient / kg. The best amount to eradicate a parasite infecting a particular host animal should be determined individually for each animal, but in most cases the most suitable amount will range from 2.5 mg to 50 mg per kilogram body weight. In a particular case, the most appropriate amount will depend on various factors, such as the health of the animal to be treated, the sensitivity of the parasite, the damage that occurs at birth and the effect to be achieved. Smaller amounts are less harmful to the host animal, less harmful and often easier to administer, but are likely to result in only minor parasite killing and thus further infection. On the other hand, the administration of larger amounts results in complete destruction of the parasite, but amounts are much more harmful and cause stress in the host animals.

Formulations containing compounds of Formula II are effective in animals of any age when administered at any time of the year. These formulations can be continuously administered to the animals along with the diet containing these compounds to ensure that all parasites that come into contact with the host animals are killed. However, such routes of administration are not economical and are generally found to be superior to administration at times when the best parasiticidal effect is achieved. Certain parasites, such as larvae, which are larvae of meat flies and dead flies, attack animals during well-known active periods. In the event that the eradication of such a parasite is of paramount importance, the compositions are administered during this period and provide protection throughout the year. Other parasites, such as ticks, infect animals and suck their blood throughout the year. However, the control of such parasites can occur over a relatively short period of time, during which the active ingredient is administered to all animals on a farm or area for a short period, such as several weeks. In this way, all parasites of a generation are killed and the animals remain parasitic for a relatively long period of time, that is, until they are re-infected by parasites introduced by an animal from outside.

Formulations containing the compounds of Formula II may be administered by conventional oral or percutaneous routes. Some compounds undergo chemical transformation as they pass through the rumen of ruminants. Oral administration of these compounds to ruminants is only appropriate if the compounds are specifically formulated in the rumen. Such embodiments are described below.

Methods of formulating and administering biologically active compounds to animals are already well-established and have been developed. Various forms and routes of administration of the compounds of the present invention are described below.

Percutaneous administration of formulations containing the compounds of formula (II) may be effected by any route suitable for veterinary use. The water soluble salt of the compounds of formula II is very suitable. When a water-insoluble compound is to be administered, the compound is dissolved in a substantially physiologically acceptable solvent, such as polyethylene glycol. Similarly, injectable suspensions of the compounds are prepared by suspending the active ingredient as a fine powder in a mixture of a physiologically acceptable non-solvent, a surfactant and a suspending agent.

The non-solvent, for example, may be a vegetable oil such as peanut oil, corn germ oil or sesame oil, a glycol such as polyethylene glycol, or water, depending on the compound chosen.

Suitable physiologically acceptable excipients are required to maintain the compounds of formula (II) in suspension. Excipients include emulsifiers such as dodecylbenzenesulfonate salts, toluenesulfonate salts and alkylphenols adducts with ethylene oxide, oleate and laurate esters, and dispersants such as naphthalene sulfonate salts, lignin sulfonate salts and fatty alcohol sulfates. Thickeners such as carboxyethylcellulose, polyvinylpyrrolidone, gelatin and alginates may also be used as excipients for injection suspensions. Some of the above-mentioned surfactants can also be used to suspend these compounds. For example, lecithin and polyoxyethylene sorbitan esters are useful surfactants.

For percutaneous administration, the compounds will usually be administered as injectable formulations by subcutaneous, intramuscular or intravenous injection. For this purpose, conventional needle injection devices and needle-less breathless injection devices may be used.

The uptake of the compounds of formula (II) by the living tissues of the animals can be delayed or sustained for a period of time with suitable formulations. For example, a poorly soluble compound may be used. The low solubility of the compounds provides a long-lasting effect, since the animal's body fluid dissolves only a small amount of the compound at a given time.

The sustained action of the compounds of formula (II) may also be achieved by incorporating the compounds in a substance which physically prevents dissolution. The substance embedded in the substance acts as a kit after delivery to the body, from which the active ingredient is slowly released. Such matrices are well known in the art and include semi-soluble waxes such as vegetable waxes and high molecular weight polyethylene glycols.

An even more potent and lasting effect is achieved by incorporation of a composition comprising a compound of formula II into the animal. Such materials are well known in the veterinary art and are generally made from silicone-containing gums. The active ingredient is uniformly distributed in the rubber carrier or is contained in a hollow carrier. Care should be taken to select a compound which is soluble in the rubber as it is first distributed by dissolution in the rubber and then leached by the treated animal's body fluid.

The release rate of the active ingredient from the matrix and consequently the length of time the matrix material remains effective can be precisely controlled by adjusting the concentration of the matrix compound in the matrix. The release rate is also influenced by the appearance of the embedded material and the appearance of the polymer.

Administration of the compounds of the present invention by means of a built-in material is a particularly preferred mode of administration. Such an intake is a very economical method since a well-defined incorporated substance provides the exact concentration of the active ingredient in the host animal tissues. An integrated material can provide the active ingredient for a few months and can be easily inserted into the animal. Once such an incorporated material is inserted, the animal does not require any other treatment and no compound administration is required after the material is inserted.

Oral administration of the compounds of formula (II) may be carried out by mixing the active ingredient in animal feed or drinking water, or in the form of a liquid preparation, tablet or capsule.

When the compounds of formula (II) are administered orally to ruminants, the compounds should be protected from the destruction of the ruminant process. Effective methods of coating or encapsulating active ingredients to counteract the effect are known in the veterinary art. For example, U.S. Patent No. 3,697,640 to Grant et al. coating materials and methods for this purpose are described. According to Grant's method, the active ingredients are protected from the process of rumination by coating them with a film of cellulose propionate-3-morpholinobutyrate. Tablets or capsules containing a compound of formula II are suitably film-coated in a coating device or fluidized bed sprayer. Pellet-shaped parasiticidal compositions are prepared by coating the pellets with film and filling them into capsules. Alternatively, a mixture of the compound and the film former can be prepared by breaking or grinding it into tiny particles, each containing the active ingredient embedded in the film former. The particles may be filled into capsules suitable for oral administration, or they may be formulated as an oral suspension.

Preparation of veterinary additives with animal feed is a well-known method. The compound is usually first prepared as a premix in which the compound of formula (II) is dispersed in a liquid or solid solid carrier. The premixture may contain from 2 to 800 g of active ingredient per kg, depending on the concentration desired in the diet. As is known in the art, some of the compounds of formula (II) are hydrolysable or degraded by animal food ingredients. Such compounds are usually embedded in a protective material, such as gelatin, before being added to the premix. This premix is then formulated together with the food by distributing it in the food using a conventional mixer. The amount of compound or premixture to be added to the diet can be readily calculated from the weight of the animal and the daily intake, and the concentration of compound in the premixture.

Similarly, the amount of active ingredient of the invention to be added to the drinking water of the animal may be calculated from the weight of the animal and the amount of water the animal consumes daily. In the case of administration by drinking water, the water-soluble salts of the compounds of the formula (II) are most suitable. In the absence of salt, a suspensible form of the active ingredient is prepared. The prepared molding material may be a concentrated suspension which is admixed to the drinking water or it may be a dry composition which is suspended in the drinking water while stirring. In all cases, the active ingredient of the present invention should be in the form of a finely divided powder and the formulation should be in accordance with the principles described for injectable suspensions.

The compounds of the present invention can be converted into tablets and capsules by conventional means, and are omitted from these methods. Liquid preparations contain the compounds dissolved or dispersed in an aqueous liquid mixture. Again, the water-soluble salts of the compounds of formula (II) are preferably used to prepare these water-soluble or liquid compositions. A dispersion of the compounds of the present invention, prepared as described in drinking water preparation, is nearly as suitable and equally effective.

The following examples illustrate agents containing compounds of Formula II by controlling a number of parasites that regularly attack farm animals. The compositions were tested for their activity against the black worm larvae, blackfly larvae, mosquitoes and adult American dog ticks. The dead fly and the stallion fly are insects, while the tick belongs to the acorns.

Stallion is a common, free-flowing, blood-sucking parasite, a tick that is a typical blood-sucking parasite that spends part of its lifetime on a host animal, mostly cattle. Dead-tailed larvae or wire-worms, hatching eggs that the free-flying fly-Tovar puts near a wounded part of the host animal. The larvae chew on healthy meat through the wound and spend their lives there, feeding on the meat and blood of the host animal.

Stall fly is a parasite that parasites on horses, mules, cattle, pigs, dogs, cats, sheep, goats, rabbits and humans. The tick is primarily a parasite of cattle, but it also attacks horses, mules and sheep. The larvae of the dead fly infest any wounded animal, but primarily parasitize cattle, pigs, horses, mules, sheep and goats.

The following experiments demonstrate the efficacy of formulations containing compounds of formula II in cattle. In most examples, experiments were performed on infected animals initiated with parasites.

A calf is treated with 15 mg / kg of N * - (2.2 _t 3,3-tetrafluoropropionyl) -3'-nitro-5'-tetrafluoromethyl-o-phenylenediamine! treated with a single subcutaneous injection. The compound was administered as a 10% dispersion of polyvinylpyrrolidone.

The mature sheds were kept in a room that was completely enclosed with wire mesh. From two or more such rooms, each containing 60-100 stallions, flies were allowed into the stall where the calf was housed. Flies were released 24 hours after drug administration. The flies fed on the calf blood for the period of time specified below. At that time, we counted the number of dead flies and allowed the flies to parasitize on the calf even further. Dead flies were counted again and live flies initially counted. Several experiments were performed separately.

The percent mortality is given below.

experiments Number of hours after treatment Stallion Destruction Sun. 1 72 95 2 77 70 96 100 3 77 88 96 100 4 24 85 24 95

In the case where we performed the above experiment with a mosquito instead of a stallion fly, the following result was obtained:

Experiment Number of hours after treatment Mosquito Destruction Ά 1 96 100

When the above experiment was repeated with 25 mg / kg of active ingredient in 10% polyvinylpyrrolidone, the following results were obtained:

Accompany- being Malware Number of hours after treatment Destruction · /. 1 mosquito 5 75 1 mosquito 24 100 2 mosquito 48 70 3 American dog ticks 168 86

N, N, N-tetrafluoropropioniOG'-nitro-5'-trifluoromethyl-o-phenylenediamine was tested against sturgeon in calves at 10 mg / kg in sesame oil. The above method was modified by placing the wire mesh cage on the calf's back 24 hours after drug administration. The results obtained are shown in Table XI. table.

XI. spreadsheet

Time Live perished Percentage One day 6 hours 20 20 50 24 hours 0 40 100 2 days 6 hours 3 37 92 24 hours 0 40 100 3 days 6 hours 16 24 60 24 hours 4 36 90 4 days 6 hours 10 30 75 24 hours 0 40 100 5 days 6 hours - - - 24 hours 0 40 100 6 days 6 hours - - - 24 hours 0 30 100 7 days 6 hours 3 37 93 24 hours 6 34 85 8 days 6 hours 35 5 12 24 hours 15 25 62 Day 9 6 hours 30 10 33 24 hours 0 40 100 10 days 6 hours 40 0 0 24 hours 40 0 0 Day 11 6 hours 40 0 0 24 hours 40 0 0

The above experiments show that agents containing compounds of formula II have a long-lasting insecticidal and acaricidal action. Even at low doses and for a few days after administration, these compounds killed parasites that parasitized on treated animals. The results show that the effect was complete, since all parasites on the animals were killed.

The following method describes a bioassay and its results.

Black dead larvae were used as experimental animals in the bio-experimental system. The experiments were performed by administering a composition containing the compound of the invention to a calf in a single subcutaneous injection. On the days following the administration of the preparation, blood was collected from the calf and fed to the fly larvae. The end point of the experiment was the day on which 90% or more of the larvae were killed. The results are presented in the following XII. table.

XII. spreadsheet

agent Solvent Dose (Mg / kg) Days to 90% or greater effect N * - (2,2,3,3-tetrafluoro- propionyl) -3'-nitro-5'- 10% polyvinylpyrrolidone 40 25 15 10 25 18 11 trifluoromethyl-p-phenylene 8 diamine 5 6 2.5 nothing sesame oil 15 20 2.5 nothing dimethyl sulfoxide 5 8 polyethylene glycol 15 9 N ¹ -difluorochloroacetyl- sesame oil 15 8 3'-nitro-5'-trifluoromethyl 10% polyvinyl 20 8 p-phenylenediamine pyrrolidone

A further in vitro experiment was conducted to determine the activity of the compounds containing the compounds of formula (II) against adult stallion parasites. Adult eighteen-hour-old starved flocks were placed in a petri dish or wire cage and given 25 blood-soaked baits. The bait-infused blood was collected from treated calves in defined periods of time following treatment. The mortality of the stallions after contact with blood was determined at specific intervals. The mortality rate obtained over a given period was compared with the mortality rate of flies in Petri dishes or wire cages receiving blood from untreated calves (control). N ¹ - (2,2,3,3-tetrafluoropropionyl) -3'-nitro-5'-trifluoromethyl-o-phenylenediamine was used as this test substance. The results are shown in the following XIII. Table.

XIII. spreadsheet

Dose (mg / kg) The number of hours after treatment until blood collection Number of hours after blood contact Death% 15 10% Polyvinyl 72 5 22 NMP 72 24 89 24 22 100 25 dimethylsulfoxide 2 18 100 24 24 100 25 10% Polyvinyl 168 24 92 NMP 284 24 84 40 10% Polyvinyl 312 24 100 NMP 360 24 88

In the above experiments, the parasites were indirectly supplied with animal blood instead of allowing them to parasitize directly on the animal. The devastating effect achieved was as characteristic as the parasites sucking blood directly from the animal. These experiments show the degree of protection of the animals against this very harmful parasitic amygdala, since they have provided anti-parasitic protection for several days even after a single administration of the compound of formula (II).

In addition to their herbicidal, insecticidal and parasiticidal activity, the compositions of the present invention also exhibit anthelmitic and nematocidal activity.

The anthelmintic activity in the formulations is most pronounced for the compounds of the formula II, while the nematocidal activity is for the compounds of the formulas I, II and III.

With regard to the anthelmintic activity, the formulations containing the compounds of formula II can be administered to warm-blooded animals to control internal parasites, in particular gastrointestinal parasites such as Nematospiroides dubius, Haemonchus contortus and Syphacia obvelata. The active ingredient will generally be administered orally in admixture with the nutrient and may be in the form of a tablet or bolus. Good results are obtained with single doses of 5 to 500 mg / kg and 0.001 to 0.05% of the active ingredient in food. In each assay, N'-trifluoroacetyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine was mixed with a modified mouse diet at a concentration of 0.01%. This modified diet was administered to a group of four mice, while the other four groups of four mice, which served as controls, were given unmodified food. The members of both groups were infected with Nematospiroides dubius parasites approximately two hours after the start of feeding. Feeding was continued for eight days, and on the ninth day 50 mice were autopsied and the number of Nematospiroides dubius parasites present. No larvae were found in the animals fed with modified diets, while the control animals had an average of 28 larvae per mouse. Similar results were obtained with 55 formulations containing other compounds of formula II as active ingredients.

The compositions containing the compounds of formulas I, II and III can also be used to control nematodes, such as root-tuber nematodes, numeroderms, root rot fusarium and rhizoctonia. Generally, 1 to 40 kg of active ingredient is used per hectare. For standard experimental methods, the following compounds are found to have total or near complete control of tuber nematode · 65 in these formulations when used in the amounts indicated:

N, 5'-trifluoroacetyl-5'-, 5''''-tetrachloro-o-phenylenediamine (5 kg / ha),

N * -trifluoroacetyl-N ² -naphthaloyl-4'-trifluoromethyl-6'-nitro-o-phenylenediamine (20 kg / ha),

N * -Trifluoroacetyl-N ² - (3,4-dichlorobenzoyl) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine (20 kg / ha).

The following examples illustrate the preparation of compounds of formulas I, II and III.

Example 1

A solution of 3,4,5,6-tetrachloro-o-phenylenediamine (2.0 g) in benzene (50 ml) and triethylamine (0.8 ml) was treated with trifluoroacetic anhydride (1.84 g). The resulting reaction mixture was then heated to reflux and maintained at this temperature for 16 hours, then concentrated to 20 ml and the resulting N ¹ -trifluoroacetyl-3 ', 4', 5 ', 6'-tetrachloro-o-phenylenediamine filtered. isolated and recrystallized from chloroform. Mp 245-247 ° C.

Example 2

2.2 g of finely ground 3-trifluoromethyl-5-nitro-o-phenylenediamine, 1.0 ml of triethylamine and 10 ml of chloroform are mixed and 2-3 ml of trifluoroacetic anhydride in 20 ml of chloroform are added with stirring. The addition was carried out in small portions over 20 minutes at room temperature. The resulting reaction mixture is filtered to isolate the product, which is the desired N'-trifluoroacetyl-3'-trifluoromethyl-5'-nitro-o-phenylenediamine. After recrystallization from benzene, this compound melts at 201-202 ° C.

Analysis for C ₉ H ₅ F ₆ N ₃ O ₃ :

Calculated: C, 34.08; H, 1.58; N, 13.24%. Found: C, 34.24; H, 1.60; N, 13.24%.

Example 3

5.0 g of 3-nitro-5-trifluoromethyl-o-phenylenediamine are mixed with 15 ml of pyridine and the mixture is cooled to 0 ° C. Chlorodifluoroacetifloride (3 mL) was then added to the reaction mixture with stirring over 20 minutes. The reaction mixture was allowed to stand for 1.5 hours at 20 ° C and then stirred with 150 g of ice and 20 ml of hydrochloric acid. The resulting precipitate, the desired N'-chlorodifluoroacetyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, was isolated by filtration and recrystallized from benzene. Mp 186-188 ° C.

Example 4

Mixed with trifluoroacetic anhydride in 3.2 g of N ² -benzoyl-6-nitro-4-trifluoromethyl-o-phenylenediamine in excess and the mixture is allowed to stand overnight. The excess trifluoroacetic anhydride and the resulting by-product acid are evaporated in vacuo to give the desired N'-trifluoroacetyl-N'-benzoyl-o '-nitro-4'-trifluoromethyl-o-phenylenediamine, which is recrystallized from benzene at 193-195 ° C. are.

Example 5

Other compounds of the invention may also be readily prepared from the appropriate starting materials by the methods described above. Such compounds include:

N '-trifluoroacetyl-3'-nitro-5' -trifluoromethyl-o-phenylenediamine, m.p. 194-195 ° C, was prepared by trifluoroacetic anhydride 3-nitro-5-trifluoromethyl-o-. with phenylenediamine.

N ¹ -propionyl-N ² - (2,2-difluoro-3-iodopropionyl) -5 '- (sec-butylsulfonyl) -o-phenylenediamine is prepared by

2,2-Difluoro-3-iodo-propionyl chloride is reacted with N * -propionyl-5- (sec-butylsulfonyl) -o-phenylenediamine.

N ¹ , N ² -bis (trifluoroacetyl) -5 '- (methylsulfonyl) o-phenylenediamine, m.p. 179-181 ° C, was prepared by reacting trifluoroacetic anhydride with 5- (methylsulfonyl) o-phenylenediamine.

N * -trifluoroacetyl-N ² -p-toluene-5 ', 6'-dichloro-o-phenylenediamine is prepared by reacting trifluoroacetic acid chloride with N ² -p-toluene-5,6-dichloro-o-phenylenediamine.

N ¹ -Trifluoroacetyl-N ² -acetyl-4 '- (methylsulfonyl) -o-phenylene diamine, m.p. 200-201 ° C, was prepared by trifluoroacetic anhydride with N ² -acetyl-4- (methylsulfonyl) -o-phenylenediamine. with.

N'-Difluoro-chloroacetyl-β-hexanoyl-S'-propylsulfonyl) -o-phenylene diamine is prepared by reacting difluoro-chloroacetic anhydride with N ² -hexanoyl-5- (n-propylsulfonyl) -o-phenylenediamine.

N'-trifluoroacetyl-N'-nitro-5'-chloro-o-phenylenediamine was prepared by melting at 184-186 ° C by reacting trifluoroacetic anhydride with 3-nitro-5-chloro-o-phenylenediamine.

N ¹ - (3-bromopropionyl) -N ² -trifluoroacetyl-5 '- (ethylsulfonyl) o-phenylenediamine is prepared by reacting trifluoroacetic anhydride with N' - (3-bromopropionyl) -5- (ethylsulfonyl) o-phenylenediamine.

N ¹ - (2,2-difluoro-3-bromopropionyl) -N ² - (2-chloro-4-tert-butylbenzoyl) -3'-nitro-5'-trifluoromethyl-o-phenylenediamine is prepared by 2-Difluoro-3-bromopropionyl chloride is reacted with N ² - (2-chloro-4-tert-butylbenzoyl) -3-nitro-5-trifluoromethyl-o-phenylenediamine.

N'-Trifluoroacetyl-N ² - (methoxycarbonyl) -5 ', 6'-difluoro-o-phenylenediamine is prepared by reacting trifluoroacetic anhydride with N ² - (methoxycarbonyl) -5,6-difluoro-o-phenylenediamine.

N * -difluorochloroacetyl-N ² - (phenoxycarbonyl) -3'-nitro-5'-difluoromethyl-o-phenylenediamine is prepared by reacting difluorochloroacetic anhydride with N ² - (phenoxycarbonyl) -3-nitro-5-difluoromethyl-o-phenylenediamine. .

N * -difluoroacetyl-N ² - (3,4-dichlorobenzoyl) -5'-chloro-o-phenylenediamine is prepared by reacting difluoroacetic anhydride with N ² - (3,4-dichlorobenzoyl) -5-chloro-o-phenylenediamine.

N'-pentafluoropropionyl-N ² - (5-bromo-m-toluoyl) -3 ', 4', 5 ', -6'-tetrachloro-o-phenylenediamine is prepared by treating pentafluoropropionic anhydride with N ² - (5-bromo- m-toluoyl) -3,4,5,6-tetrachloro-o-phenylenediamine.

N ^, -heptafluorobutyryl-N ² - (sec-butoxycarbonyl) -4'-bromo-o-phenylenediamine is prepared by reacting heptafluorobutyric anhydride with N ² - (sec-butoxycarbonyl) -4-bromo-o-phenylenediamine.

N * - (2,2-difluoropropionyl) -N ² - (3-nitro-5-iso-propoxybenzoyl) -5 ', 6'-dichloro-o-phenylenediamine is prepared by treating 2,2-difluoropropionyl bromide with N ² - (3) -nitro-5-iso177610-propoxybenzoyl) -5,6-dichloro-O-phenylenediamine.

^{N-trifluoroacetyl-N-2-naphthoyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine,} melting point ° C 200 204, is prepared by reacting trifluoroacetic ^{N2-naphthoyl-6-nitro-4-trifluoromethyl} reaction with -o-phenylenediamine.

N ¹ -iodoacetyl-N ² -trifluoroacetyl-5 '- (methylsulfonyl) -o-phenylenediamine is prepared by reacting trifluoroacetic anhydride with N'-iodoacetyl-S-C-methylsulfonyl-o-phenylenediamine.

Example 6

The compounds of formulas (1), (II) and (III) which can be prepared by the methods described in the previous examples are:

N * -trifluoroacetyl-N ² - (pn-butoxybenzoyl) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine, m.p. 172-174 ° C.

N ^, -Trifluoroacetyl-N ² - (p-nitrobenzoyl) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine, m.p. 210-212 ° C.

N * -trifluoroacetyl-N ² - (2,4-dichloro-6-methoxybenzoyl) -6'-nitro-o * phenylenediamine, m.p. 200-201 ° C.

N'-heptafluorobutyryl-S'-nitro-S'-trifluoromethyl-o-phenylenediamine, m.p. 118-120 ° C.

N'-pentafluoropropionyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, m.p. 161-163 ° C.

N'-trifluoroacetyl-NL-methoxycarbonyl-N'-trifluoromethyl-6'-nitro-o-phenylenediamine, m.p. 129-130 ° C.

N ¹ -pentadecafluorooctanoyl-3 '-nitro-5' -trifluoromethyl-to-phenylenediamine, m.p. 111-113 ° C.

N-trifluoroacetyl-HP-benzoyl-S'-trifluoromethyl-S'-nitro-o-feniféndiamin.

N ¹ -trifluoroacetyl-N ² -naphthaloyl-4'-trifluoromethyl-6'-nitro-o-phenylenediamine.

NLtrifluoroacetyl-N'-trichloroacetyl-S'-nitro-S'-methylsulfonyl) -o-phenylenediamine.

N * -pentadecafluorooctanol-N ² -acetyl-4 '- (methylsulfonyl) -o-phenylenediamine.

N ¹ , N ² -bis (heptafluorobutyryl) -4 '- (methylsulfonyl) o-phenylenediamine.

N ¹ -trifluoroacetyl-N ² -acryloyl-4 '- (methylsulfonyl) -o-phenylenediamine.

N ¹ -trifluoroacetyl-N ² -propioloyl-4 '- (methylsulfonyl) -o-phenylenediamine.

N-trifluoroacetyl-EN-benzoiM' letilszulfoniO-O'-nitro-o-phenylenediamine.

Pcntafluorpropionil ^{N'-2-naphthoyl-N-4} '- (methylsulfonyl) -o-phenylenediamine.

N'-Difluoroacetyl-N ² -methoxycarbonyl-4 '- (methoxysulfonyl) o-phenylenediamine.

N'-heptafluorobutyryl-N ² -p-toluoyl-4 '- (methylsulfonyl) -6'-nitro-o-phenylenediamine.

N'-trifluoroacetyl-N ² -benzol-4 ', 5'-dichloro-o-phenylenediamine.

N-trifluoroacetyl-N ^ naftoiM'-nitro-o-phenylenediamine.

N'-trifluoroacetyl-N ² -furoyl-5 '- (methylsulfonyl) -o-phenylenediamine, m.p. 185-187 ° C.

Difluoracetil-N'-nitro-NLfuroil-a'-S'-trifluoromethyl-o-phenylenediamine.

N '-chlorodifluoroacetyl-N ² -furoyl-4', 5'-dichloro-o-phenylenediamine.

N * - (2,2,3,3-tetrafluoropropionyl) -N ² -methoxycarbonyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine, m.p. 129-130 ° C.

N '- (2,2,3,3-tetrafluorpropionil) -3'-nitro-5-trifluoromethyl-o-phenylenediamine.

N ¹ - (2,2,3,3-tetrafluoropropionyl) -3'-nitro-5'-trifluoromethyl-o-phenylenediamine, m.p. 144-145 ° C. This compound was prepared by reacting 2,2,3,3-tetrafluoropropionyl bromide with 3-nitro-5-trifluoromethyl-o-phenylenediamine.

N'-pentafluoropropionyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, m.p. 161-163 ° C. This compound was prepared by reacting pentafluoropropionyl bromide with 3-nitro-5-trifluoromethyl-o-phenylenediamine.

Preparations (1) Wettable powder

N '- (2,2,3,3-tetrafluoropropionyl) -3'-nitro-5'-trifluoromethyl-o-phenylenediamine 70%

Kaolin 12%

Active silica 8%

Fatty alcohol sulphate 2 5%

Sodium lignosulphate 2 5% (2) Wettable powder

N ¹ - (2,2,3,3-tetrafluoropropionyl) -3'-nitro-5'-trifluoromethyl-o-phenylenediamine 5%

Kaolin 40%

Active silica 50%

Sodium oleylmethyl taurides 5% (3) Granules

N * - (2,2,3,3-tetrafluorpropionil) ^{-3'-nitro-5/20-trifluoromethyl-o-phenylenediamine%}

Attapulgite Clay 80% (4) Emulsion Concentrate

N * - (2,2,3,3-tetrafluoropropionyl) -3'-nitro-5 '· -trifluoromethyl-o-phenylenediamine 50%

Emulsogen 140 2%

Isophorone 48%

Claims (48)

Patent claims CLAIMS 1. A pesticidal agent, characterized in that the N- (2,2-difluoroalkanoyl) -o-phenylenediamine substituted in the ring of formula I, II or III is present in an amount of 0.01 to 20% by weight as an active ingredient. contains where SHE II R 0 is a 2,2-difluoroalkanoyl radical of formula -C-CF ₂ -Y wherein Y is hydrogen, chlorine, fluoro, difluoromethyl, C 1 -C ₈ perfluoroalkyl or a radical of formula (a) each Z is independently hydrogen or halogen and n is a number 0 or 1, SHE R ^{1 is a} hydrogen atom, a group of the formula -C-O-Y ¹ , wherein Y ^{1 is} a (% -C ₄ alkyl or phenyl group, benzoyl, furoyl, naphthoyl group or a group of the formula (b) substituted benzoyl wherein each Z 'is independently halo or nitro, Z is a C 1 -C ₄ alkoxy group, p is 0,1 or 2, q is 0 or 1, and p and q are 1 to 1; 3 ^R2 is the same as R c or R ¹ report, also represents a C-C _s alkanoyl group or a C ₂ -C ₄ represents -halogénezett alkanoyl group which carry one or more halogen atoms at any position or positions with the restriction that the α-carbon has at least one hydrogen atom or a 35 to 127 atom halogen atom, R ³ substituents each independently selected halogen, R ^{4 is} nitro, R ^{5 is} trifluoromethyl, and in the compounds of formula II, R ⁴ and R ⁵ are in the meta position with respect to each other, R ^{6 is} attached to a C 1 -C ₄ alkylsulfonyl group at the 4 or 5 position and R ^{4 is in} a meta position relative to R ⁶ , m is a number from 0 to 4, n is represents 0 or 1 and the compounds of formula (I), m and n are 1-4, with the further proviso that when ^R1 or ^R2 is hydrogen, -NH-R or -R-NH ² group on the ring in the ortho position, one or more of the indicated R ³ , R ⁴ , R ⁵ or R ⁶ groups together with one or more diluents, preferably aromatic hydrocarbons or particulate matter of mineral origin, preferably emulsifying or suspending agents. The pesticidal composition of claim 1, wherein the active ingredient is a compound of formula (I), wherein the substituents are as defined in claim 1. 3. The pesticidal composition according to claim 2, wherein the active ingredient is N'-trifluoroacetyl-3'-nitro-5'-chloro-o-phenylenediamine. 4. The pesticidal composition according to claim 2, wherein the active ingredient is N * -trifluoroacetyl-3 ', 4', 5 ', 6'-tetrachloro-o-phenylenediamine. 5. The pesticidal composition according to claim 2, wherein the active ingredient is N * -trifluoroacetyl-N ² - (2,4-dichloro-6-methoxybenzoyl) -6'-nitro-o-phenylenediamine. 6. The pesticidal composition according to claim 1, wherein the active ingredient is a compound of formula II, wherein the substituents have the same meaning as in claim 1. 7. The pesticidal composition according to claim 6, wherein the active ingredient is N'-trifluoroacetyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine. 8. The pesticidal composition according to claim 6, wherein the active ingredient is N '- (2,2,3,3-tetrafluoropropionyl) -3'-nitro-5'-trifluoroethyl-o-phenylenediamine. 9. The pesticidal composition according to claim 6, wherein the active ingredient is N'-trifluoroacetyl-3'-trifluoromethyl-5'-nitro-o-phenylenediamine. 10. The pesticidal composition according to claim 6, wherein the active ingredient is N'-chlorodifluoroacetyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine. 11. The pesticidal composition according to claim 6, wherein the active ingredient is N * -trifluoroacetyl-N ² -benzoyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine. 12. The pesticidal composition according to claim 6, wherein the active ingredient is N ¹ -trifluoroacetyl-N ² -naphthalyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine. 13 pest control agent according to claim 6 embodiment, wherein said compound is N-trifluoroacetyl-N ² - comprises (pn butoxibenzoil) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine. 14. The pesticidal agent according to claim 6 embodiment, wherein said compound is ^{N-trifluoracetii-N2} - contain (p-nitrobenzoyl) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine. 15. The pesticidal composition according to claim 6, wherein the active ingredient is N'-heptafluorobutyryl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine. 16. The pesticidal composition according to claim 6, wherein the active ingredient is N * pentafluoropropionyl-3'-nitro-5 '-trifluoromethyl-o-phenylenediamine. 17. The pesticidal composition according to claim 6, wherein the active ingredient is N'-trifluoroacetyl-N ² -methoxycarbonyl-4'-trifluoromethyl-6'-nitro-o-phenylenediamine. 18. The pesticidal composition according to claim 6, wherein the active ingredient is N * -pcntadecafluorooctanoyl-3'-nitro-5 '-trifluoromethyl-o-phenylenediamine. 19. The pesticidal composition according to claim 6, wherein the active ingredient is N * (2,2,3,3-tetrafluoropropionyl) -N ² -methoxycarbonyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine. 20. The pesticidal composition according to claim 6, wherein the active ingredient is N * -pentafluoropropionyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine. 21. The pesticidal composition of claim 1, wherein the active ingredient is a compound of formula (III), wherein the substituents are as defined in claim 1. 22. The pesticidal composition according to claim 21, wherein the active ingredient is N *, N ² -bis (trifluoroacetyl) -5 '- (methylsulfonyl) -o-phenylenediamine. 23. The pesticidal composition according to claim 21, wherein the active ingredient is N'-trifluoroacetyl-N ² -acetyl-4 '- (methylsulfonyl) -o-phenylenediamine. 24. The pesticidal composition according to claim 21, wherein the active ingredient is N'-trifluoroacetyl-N ² -furoyl-5 '- (methylsulfonyl) -o-phenylenediamine. A process for the preparation of N- (2,2-difluoroalkanoyl) -o-phenylenediamine derivatives substituted on a ring of formula (I), (II) or (III), wherein the various substituents have the same meaning as in claim 1, characterized in that: a compound of formula (VII), (VIII) or (IX) wherein the substituents are as defined in claim 1, with an acylating agent of formula (IV) wherein Y is as defined in claim 1 or a reactive derivative thereof with. A process for the preparation of a compound of formula (I) according to claim 25, wherein the substituents have the same meaning as in claim 1, characterized in that a compound of formula (VII) wherein each substituent has the meaning given in claim 1 with an acylating agent of formula (IV) wherein Y is as defined in claim 1 or a reactive derivative thereof. 27. A process according to claim 26 for the preparation of N'-trifluoroacetyl-S'-nitro-S'-chloro-o-phenylenediamine, which comprises reacting 3-nitro-5-chloro-o-phenylenediamine with trifluoroacetic anhydride. 28. The process of claim 26 for the preparation of N '-trifluoroacetyl-3', 4 ', 5', 6 '-tetrachloro-o-phenylenediamine, characterized in that 3,4,5,6-tetrachloro-o- phenylenediamine is reacted with trifluoroacetic anhydride. 29. The method of claim 26 embodiment N'-trifluoroacetyl-N ² - (2,4-dichloro-6-metoxibenzoiI) -ó'-nitro-o-phenylenediamine preparation, wherein N ² - (2, 4-Dichloro-6-methoxybenzoyl) -6'-nitro-o-phenylenediamine is reacted with trifluoroacetic anhydride. A process for the preparation of a compound of formula (II) according to claim 25, wherein the substituents have the same meaning as in claim 1, characterized in that a compound of formula (VIII) wherein each substituent has the meaning given in claim 1 with an acylating agent of formula (IV), wherein Y is as defined in claim 1, or a reactive derivative thereof. 31. A process according to claim 30 for the preparation of N'-trifluoroacetyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, which comprises reacting 3-nitro-5-trifluoromethyl-o-phenylenediamine with trifluoroacetic anhydride. 32. A process according to claim 30 for the preparation of N '- (2,2,3,3-tetrafluoropropionyl) -3'-nitro-5'-trifluoromethyl-o-phenylenediamine, characterized in that 3-nitro-5- trifluoromethyl-o-phenylenediamine is reacted with 2,2,3,3-tetrafluoropropionyl bromide. 33. The method of claim 30 embodiment _{N'-trifluoroacetyl-3'-trifluoromethyl-5'-nitro-o-phenylenediamine} thereof, which comprises the reaction of 3-trifluoromethyl-5-nitro-o-phenylenediamine trifluoroacetic anhydride. 34. A process according to claim 30 for the preparation of N'-chlorodifluoroacetyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, which comprises reacting 3-nitro-5-trifluoromethyl-o-phenylenediamine with chlorodifluoroacetic acid chloride. 35. A process according to claim 30 for the preparation of N'-trifluoroacetyl-N ^2- benzoyl-6'-nitro-4'-trifluoromethyl-o-dimethylenediamine, characterized in that N ² -benzoyl-6-nitro-4- trifluoromethyl-o-phenylenediamine is reacted with trifluoroacetic anhydride. 36. The method of claim 30 embodiment ^{N'-trifluoroacetyl-N-2-naphthoyl} 6'-niti-4'-trifluoromethyl-o-phenylenediamine preparation, characterized in that ^{N2-naphthoyl-6-nitro-4-} trifluoromethyl-o-phenylenediamine is reacted with trifluoroacetic anhydride. 37. A process according to claim 30 for the preparation of N ¹ -trifluoroacetyl-N ² - (pn-butoxybenzoyl) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine, characterized in that N ² - (pn-butoxybenzoyl) ) -4-Trifluoromethyl-6-nitro-o-phenylenediamine is reacted with trifluoroacetic anhydride. 38. The process of claim 30 for the preparation of N ¹ -trifluoroacetyl-N ² - (p-nitrobenzoyl) -4'-trifluoromethyl-6'-o-phenylenediamine, wherein N ² - (p-nitrobenzoyl) - 4-Trifluoromethyl-6-nitro-o-phenylenediamine is reacted with trifluoroacetic anhydride. 39. The process of claim 30 for the preparation of N ¹ -heptafluorobutyryl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, wherein the 3-nitro-5-trifluoromethyl-o-phenylenediamine is reacted with heptafluorobutyryl bromide. 40. The process of claim 30 for the preparation of N'-pentafluoropropionyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, wherein 3-Nitro-5-trifluoromethyl-o-phenylenediamine is reacted with pentafluoropropionyl bromide. 41. The process according to claim 30, for the preparation of N ¹ -trifluoroacetyl-N ² -methoxycarbonyl-4'-trifluoromethyl-6'-nitro-o-phenylenediamine, wherein N ² -methoxycarbonyl-4-trifluoromethyl-6- nitro-o-phenylenediamine is reacted with trifluoroacetic anhydride. 42. The process according to claim 30, for the preparation of N'-pentadecafluorooctanoyl-3'-nitro-5 '-trifluoromethyl-o-phenylenediamine, which comprises reacting 3-nitro-5-trifluoromethyl-o-phenylenediamine with pentadecafluorooctanoyl bromide. 43. A process according to claim 30 for the preparation of N * - (2,2,3,3-tetrafluoropropionyl) -N ² -methoxycarbonyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine, wherein ^2- Methoxycarbonyl-6-nitro-4-trifluoromethyl-o-phenylenediamine is reacted with 2,2,3,3-tetrafluoropropionyl bromide. 44. The process according to claim 30, for the preparation of N ¹ -pentafluoropropionyl-3'-nitro-5 '-trifluoromethyl-o-phenylenediamine, which comprises reacting 3-nitro-5-trifluoromethyl-o-phenylenediamine with pentafluoropropionyl bromide. 45. A process for the preparation of a compound of formula (III) according to claim 25, wherein the substituents have the same meaning as in claim 1, wherein a compound of formula (IX) wherein each substituent has the meaning given in claim 1 with an acylating agent of formula (IV) wherein Y is as defined in claim 1 or a reactive derivative thereof. 46. A process according to claim 45 for the preparation of N, N, N'-bis-trifluoracetoyl-methyl-sulfone-D-o-phenylenediamine, which comprises reacting 5- (methylsulfonyl) -phenylenediamine with trifluoroacetic anhydride. 47. The process of claim 45 for the preparation of N ¹ -tritluoroacetyl-N ² -acetyl-4 '- (methylsulfonyl) -o-phenylenediamine, characterized in that N ² -acetyl-4- (methylsulfonyl) -o-phenylenediamine with trifluoroacetic acid chloride. 48. A process according to claim 45 for the preparation of N'-trifluoroacetyl-NU-furoyl-S'-Cmethylsulfonyl-O-o-phenylenediamine, which comprises reacting N'-furoyl-5- (methylsulfonyl) -o-phenylenediamine with trifluoroacetic anhydride.