CS195698B2 - Herbicide,insecticide and arachnicide - Google Patents

Description

The invention relates to herbicidal, insecticidal and arachnicidal compositions comprising ring-substituted N- (2,2-difluoroalkanoyl) -o-phenylenediamines.

control of animal parasites is one of the oldest and most important problems of animal production. Many types of parasites affect all animal species. The vast majority of animals are affected by free-flying parasites such as flies, crawling ectoparasites such as lice and aphids, drilling parasites such as larvae and flyworms, and microscopic endoparasites such as coccidia as well as larger endoparasites such as worms. Thus, control of parasites even in a single host is a complex problem with many side problems. '

Parasitl from the group of insects and mites that consume living tissues of host animals is harmful to ya. This group includes parasites of all economic animals including ruminants and mammals with one stomach and poultry and companion animals such as dogs. Recently, many methods for controlling these parasites have been tested. Cochlimyia hominivorax worms were practically exterminated in Florida by the release of a large number of sterile males of these flies. The method is, of course, applicable only in an easy to train area. Free-flying insects are usually controlled by conventional methods such as freely dispersed air and contact insecticides and fly traps. Climbing parasites inhabiting the skin are usually controlled by dipping, soaking or spraying the animals with the appropriate parasiticidal agents. ; LíV

Some progress has been made in the systematic control of certain parasites, in particular those living in or migrating in the host species. Systemic control of animal parasites was performed by absorption of the parasiticide in the bloodstream or other tissue of the host animal. Parasites which eat or come into contact with tissue containing a parasiticidal substance are either killed by contacting or contacting the parasiticidal substance. Some phosphate, phosphoramidate and phosphorothioate insecticides and acaricides have been found to be sufficiently nontoxic and can be used systemically in animals.

Rumanowski, ^US: Patent 3,557,211, discloses N, N-bis (acetyl) -of phenylenediamine which -použitelné to control plants, insects and fungi. . - ';;'.'

It is an object of the present invention to provide a herbicidal, insecticidal and arachnidic composition comprising 1988898

The ring substituted N- (2,2-difluoroalkanoyl-o-phenylenediamines of formula ΙΪ),

where

R c is 2,2-difluoroaralkanoyl of the formula

O li.

-C-CF2-Y, wherein Y is a chlorine, fluorine, difluoromethyl or perluoroalkyl group having 1 to 6 carbon atoms,

R ¹ is hydrogen, methoxycarbonyl, 3,6-dichloro-2-methoxybenzoyl, benzyl, p-nitrobenzoyl, naphthyl, ph-butoxyhenzoyl or

3,4-dichlorobenzoyl,

R ⁴ is nitro,

R ⁵ is trifluoromethyl, wherein R ⁴ and R ⁵ are meta to each other, and when R ¹ is hydrogen, the ortho position relative to the -NH-R ¹ group contains one of the radicals listed for R ⁴ or R ⁵ . ·

All compounds of formula (II) may be formulated to be useful as herbicides. These compounds can be used in such a way that a broad herbicidal effect is obtained; therefore, in the broadest sense, the invention relates to a method of application which is characterized in that plant parts, such as scape, leaves, flowers, fruits, roots or seeds, or similarly reproductive units of plants, are applied with growth inhibiting amounts of one. z ring-substituted N- (2,2-difluoroalkanoyl) -o-phenylenediamines of formula II. However, these compounds may also be used by utilizing selective herbicidal activity. As is known to those skilled in the art, a mixture of polynucleotides may also be used to achieve a herbicidal effect. If a mixture is used, the amount of each individual compound can be reduced so that the mixture exhibits only the desired herbicidal effect.

It is not critical for the herbicidal utility of the compounds whether undesirable vegetation is controlled by the uptake; it is sufficient, if undesirable, that the vegetation is only inhibited. Particularly with regard to the selective effect, inhibition of underestimation is sufficient, especially when combined with natural conditions such as limited humidity, which has a more adverse effect on vegetation selectively inhibited than on useful plants.

The compounds of formula II are suitable for various variations of herbicidal applications.

For example, in amounts that produce a selective effect of the compounds - the amounts are more precisely defined below - the compounds can be used as selective herbicides in useful plants such as cotton, corn, sorghum and soybeans. In this application, the application can be carried out before emergence of both the crop plants and the weeds, or preferably by direct spraying after emergence of the crop plants, but both before emergence and after the emergence of weeds.

In another application, the compounds of formula II can be used to provide a broad herbicidal effect on non-sown soil including un-sown bands of contour from agricultural land. For such use on so-called fallow soils, the application is carried out in the spring so as to suppress vegetation growth until autumn or the following spring sowing. or in autumn to suppress vegetation growth until spring or the following autumn sowing. Further, in another application, the compounds may be used for the preparation of a compound. controlling weeds when planting utility trees, such as planting various citrus trees. In all of these various applications and others for which the compounds are suitable, the additional advantage is that the compounds need not be added to the soil or otherwise mechanically mixed with the soil. In addition to the previous soil treatment applications, the compounds of the invention may also be used as aqueous herbicides.

For example, the use of the compounds of formula II as herbicides can be carried out with unmodified compounds, but for good results it is generally necessary that the compounds be used in modified form, i.e., as one component of a composition adapted to achieve a plant growth inhibitory effect. For example, the active agent may be mixed with water or other liquid or liquids, preferably using surfactants. The active agent may also be combined with a finely divided solid, which may be a surfactant, to form a wettable bird which may be dispersed in a liquid or other liquid, or the active ingredient may form part of a dust that is applied directly. Other methods of preparation known from the literature can also be used to use these compounds.

The exact amount of active ingredient used in the formulation is not critical and varies depending on the type of growth inhibitory effect desired, the type of plant in question, the type of active ingredient and the weather conditions. In general, a broad growth inhibitory effect is obtained with amounts ranging from 0.6 to 22.20 kg of active ingredient per hectare and these amounts are suitable for effective control of vegetative growth on fallow soil. If a selective weed inhibitory effect is needed in a sown area such as maize, soybean and cotton, an amount of from 0.6 to 11.1 kg hectare generally yields good results. Where an active agent is used in the Jarme mixture containing the active agent, the precise concentration of the active agent in the composition containing the active agent is not critical, except that the concentration and total amount used must correspond to the appropriate amount of active agent per hectare. In general, good results are obtained when formulations containing the active ingredient are present at a concentration of 0.5 to 10% or higher for liquid preparations and a concentration of 1.0 to 5.0% or higher for dusts, powders, granules and other dry preparations. Concentrated preparations can also be prepared and often are advantageous since they can serve as concentrated preparations for shipping and storage purposes, as well as a masterbatch for treatment, depending on their intended application and appropriate concentration. For example, the preparations often preferably contain a surfactant and an active ingredient of the invention, the latter being present in an amount of from 0.5 to 99.5% by weight, or an inert finely divided solid and the active ingredient of the invention, the latter is present in an amount of from 1.0 to 99 wt. These preparations, as mentioned, can be used directly in certain applications, but can also be diluted and then used in many other applications.

Liquid compositions containing the required amount of active ingredient are prepared by dissolving the compound in an organic liquid or dispersing the ingredient in water with or without the aid of a suitable surfactant dispersant. These compositions may also contain modifying compounds that serve to "spread" and "stick" to the leaves of plants. Suitable organic liquid carriers are agricultural spray oils and petroleum distillates such as diesel oil, kerosene, fuel oil and Stoddard solvent. Of these liquids, petroleum distillates are generally preferred. The aqueous compositions may contain one or more water-immiscible solvents for the toxic compound. In these compositions, the carrier comprises an aqueous emulsion, for example, a mixture of water, an emulsifying agent and a water-immiscible solvent. The choice of the dispersing and emulsifying agent and the amount thereof is determined by the type of composition and the ability of the agent to disperse the active compound in the carrier to produce the desired composition. Dispersing and emulsifying agents that may be used in the compositions include the condensation products of alkylene oxides with phenols and organic acids, alkyl-arylsulfonates, polyoxyalkylene derivatives, sorbitan esters and complex ether alcohols. Examples of surfactants which are useful in the application of the invention are disclosed in U.S. Patent Nos. 3,095,299, in the second column of rows 25-36, No. 2,655,447, in columns 5 and 2, and No. 412,510, in columns 4 and 5.

In the preparation of dusts, the active compounds of formula II are intimately mixed with or applied to a finely divided solid, such as clay, talc, chalk, gypsum, limestone, vermiculite or perlite. According to a fine method of preparing this dispersion, the finely divided carrier is mechanically mixed or milled with the active compound.

Similarly, dusts containing toxic compounds can be prepared with various solid surfactants such as bentonite, fuller clay, attapulgite and other clays. Depending on the proportions of the ingredients, the dusts may be used as concentrates and then diluted with other solid surfactant dispersants or chalk, talc, gypsum to obtain the desired amount of active compound in a composition adapted for use in controlling plant growth. Also these dusts can be dispersed in water and with or without the use of dispersants to form spray mixtures.

Preparations containing the active compounds of the formula II are often advantageously modified such that. an effective amount of a surfactant is admixed therewith to allow dispersion and spreading of the preparation on the leaf surface of the plant and its incorporation into the plant.

The active agent may be dispersed in the soil or other growth medium in any manner desired. Applications can be carried out simply by mixing with the medium by application to the surface of the soil and then by plowing or pushing into the soil to the desired depth or by using liquid carriers to achieve penetration and impregnation. Application of sprays and dusts to the surface of soil or part. Plants or plant surfaces above the soil may be carried out by any conventional method, for example, dusters, sprinklers and hand-held sprinklers and spray dusters with both surface driven and driven air. While these conventional methods of application may be used, they are not required. The advantage of the compounds of formula II is that they are active and effective as herbicides once they are only placed on the soil surface without the use of an additional step to facilitate incorporation. Thus, the compounds are essentially equally effective whether applied to the surface only or applied to the surface. the surface, and then drag into the soil.

The spreading of the active substance in the soil can also be achieved by adding the composition to the water used for irrigation of the soil. In these procedures, the amount of water varies according to the porosity of the soil and the soil retention capacity of the soil so as to achieve the desired degree of agent distribution.

The compounds of formula II exhibit low mammalian toxicity, relative to benzimidazoles. In addition, the compounds of formula II may be dispersed as an aerosol mixture containing one or more active ingredients of the invention. This mixture is prepared according to conventional methods, wherein the active substance is dispersed in a solvent and the resulting dispersion is mixed with the propellant in a liquid state. These variations as to the use of a particular agent and the type of vegetation to be treated determine the solvent requirements and the concentration of the active ingredient therein. Examples of suitable solvents are water, acetone, isopropanol and 2-ethoxyethanol.

Appropriate results are obtained if:. the active substances of the formula II or a mixture containing them are mixed with other agricultural materials to be applied to the plants, plant parts and their surroundings. These materials include fertilizers, fungicides, insecticides, other herbicides and soil conditioners. '·

The various compounds of the formula II to be used as active herbicidal agents are evaluated after application on emergence in different plant species. In this evaluation, a soil containing one part of sand, and one part of a crushed top soil layer is prepared, blended perfectly in a cement mixer. 4.5 liters of this soil is placed in a 25 X 35 cm galvanized tin bowl and the cellar is below the rim. A 2.5 centimeter deep groove of ase is made in three rows in two fifths of the dish. The four corn kernels, five cotton seeds and five soybean seeds are planted in these grooves. In the remaining four grooves, the approximate number of each of the following seeds, each species in a row, is sown in the remaining soil: , cotton-grass 40a-50 seeds, insect 150-250 seeds and bloody tree-100 to 150 seeds.

A further sufficient amount is then added so that the area is sufficiently covered.

Thus the weed seeds are covered with a layer of about 6 mm and the seeds of the useful plants with a layer of about 3 cm.

In determining the effect of the composition as a herbicidal composition for pre-emergence use, the area is prepared as described above and placed in a turntable and air vent chamber on the day of sowing or the following day. The herbicidal mixture, either of the spray emulsion or of the wettable powder, is applied to the surface with a modified DeVllbls atomizer attached to an air source. Twelve and a half milliliters of the mixture that. It is to be tested, then applied to each area either on the day of sowing or the following day. The severity of the lesion and the observation of the lesion type are performed 11 to 12 days after treatment. Damage is assessed according to the following scale:

0, -. no damage, - slight damage, - moderate damage, - significant damage, death, / Where more than one determination was made at the indicated amount, the average of the damage was calculated. Each test compound is sprayed by one of the following procedures. In one test, the compound is wetted in a mortar with one part of polyoxyethylene sorbitan monolaurate. Fifty parts of water is slowly added to the resulting cream-colored paste to give an aqueous dispersion with a base concentration; 0.2%. The dispersion is suitable for spray application. In a second process, the compound is dissolved in one part of acetone and the acetone solution is diluted with nineteen parts of water containing 0.1% polyoxyethylene sorbitan monolaurate. i. ^! . Table 1 shows the test compound, column 2, the amount in kilograms per hectare in which the compound is applied to the test area, and the remaining columns show the degree of damage to certain plant seeds or plant seedlings according to evaluation above.

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Some of the compounds of Formula II were evaluated for post-emergence in plants including maize and some weed species. Evaluation is carried out according to the previous test, except that the test solution is applied 9 to 12 days after preparation and sowing into the soil. The results are shown in Table II below.

1958 ««

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Degree of damage during emergence treatment

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195898

N ² - (2,2,3,3-tetrafluoropropionyl thoxycarbonyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine is evaluated for use as emergent carbide after evaluation. Evaluation is carried out as above but with a single higher dose of administration (1Θ kg / haj and for different species such as tomatoes, bloody dew, gooseberry) Certain compounds provide complete death of each of the above species. The herbicidal compounds described above may be treated and used with known herbicides of any kind. however, in general, those compositions where a substantial proportion of each component is present, such as compositions wherein the ratio of the individual components is in the range of 1:10 to 10: 1, are particularly suitable, in particular from 1: 5 to 5: 1.

Known herbicides with which the compounds of formula Π are preferably mixed include

N, N-di-n-propyl-2,6-dinitro-4- (trifluoromethyl) aniline;

N, N-di-n-propyl-2,6-dinitro-4-methyl-aniline, N-ethyl-N-butyl-2,6-dlnitro-4- (trifluoromethyl) aniline,

N, N-di-n-propyl-2,6-dinitro-4- (methylsulfonyl) aniline,

N, N-dl-n-propyl-2,6-di-nitro-4-sulfampylaniline,

N, N-di-n-propyl-2,6-dinitro-4-isopropylaniline,

N, N-di-n-propyl-2,6-dinitro-4-tert-butylaniline,

Ν, Ν-bis (2-chloroethyl) -2,6-dinitro-4-methylaniline.

For example, these possible combinations are evaluated by the following procedures:

The combination of N ^1- (pentafluoropropionyl) -3'-nitro-5 * - (trifluoromethyl) phenylenedlamine and N, N-di-n-propyl-2,6-dlnitro-4- (trifluoromethyl) aniline is evaluated for application before emergence using different plant species.

The soil is made up of one part sand and one part crushed top soil and mixed in a cement mixer. 4.5 liters of this soil are then placed in

21.5 X 31.5 cm Galvanized Tin Bowl And Cellar Under The Edge. The rows are marked and the seeds are sown, one species per row, except in the case of a mixture, and the mixture is also sown in a row. Cotton seeds (two separate rows), Ipomea purpurea, Walnuts, Durmans, Downy-goosefoot and a mixture of foxtail, Ipomea quamoclit and Croťolaria are used as individual species.

The treated topsoil is then prepared. The compounds are separately treated by suspending each of them in a 1: 1 solution of acetone and ethanol containing a small amount of a mixture of two sulfonate nonionic surfactants. Each suspension is then further diluted sequentially with an aqueous solution of the same surfactant mixture to produce a series of aqueous solutions containing the corresponding compounds at various concentrations, and additionally a surfactant mixture uniformly at a total concentration of 0.55% and a uniform amount of acetone and ethanol at a concentration. 4.15 The solution containing the compounds is then sprayed onto soil of the same type as prepared above while rotating in the Cement Mixer. Rotation is continued for 5 to 7 minutes. Each batch of this treated soil is spread over an area of 0.9 mm.

Another surface is prepared and sown in the same manner, except that the surface layer is left untreated and serves as a control. All areas are then maintained in a greenhouse under normal conditions for thirteen days, after which time the type of damage is monitored and determined. Damage is assessed according to the following scale:

- no damage, up to 3 - slight damage, up to 6 - moderate damage, up to 9 - considerable damage, - death,

B - burns,

N - non-germination,

R - reduced germination, —- stopped development.

The results of the evaluation of the treated areas are given in Table III below. Control areas were healthy for all species tested.

195S98

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199898 13

The same results were obtained when N ¹ - (pentafluoropropolyl) -3'-nitro-5'- (trifluoromethyl) -phenylenediamine or another new compound of formula II was combined with another dinitroaniline listed above. they are obtained when the mixtures are used in an amount of from 0.55 to 8.8 kg of N- (2,2-difluoroalkanoyl) -o-phenylenediamine per hectare and from 0.28 to 2.77 kg of dinitroaniline per hectare.

Nearly the same results as those above for the previous tests are obtained when the following compounds of Formula II are used:

N ^{1 N-trifluoroacetyl-2-naphthoyl} 3 ^{<nitro-5-trifluoromethyl-o-phenylenediamine,} Rh-trifluoracetvl-N ² - (PN-j butoxybenzov 1 4'-trifluoromethyl-6'-nitro-o- phenylenediamine,.

N ¹ -trifluoroacetyl-N ² - (p-nitrobenzoyl) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine, N ¹ -heptafluorobutyryl-3'-nitro-5'-trifluoromethyl-phenylenediamine, N ¹ - pentafluoropropionyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, N ¹ -trifluoroacetyl-N ² -methoxycarbonyl-4'-trifluoromethyl-6'-nitro7O-phenylenediamine, N ¹ -pentadecafluorooctanoyl-3'-nitro-5 1'-trifluoromethyl-o-phenylenediamine, N ¹ -trifluoroacetyl-N ² -benzyl-3'-trifluoromethyl-5'-nitro-o-phenylenediamine, N ¹ -trifluoroacetyl-N ² -naphthyl-4'-trifluoromethyl-6'- nitro-o-phenylenediamine.

The compounds of formula (II) also exhibit an insecticidal and arachnicidal effect. These compounds are useful for the control of insects and arthropods of the Arachnidae class, wherein the amount can be selected to prevent phototoxicity and the compounds can be used to control those insects and arthropods of the Arachnidae class that occur on the roots or aerial parts of plants. These compounds are active, for example, against such arthropods of the Arachnidae class, such as the spider mite (Epitetranychus altheaej, the spider mite (Panonychus citri), the spider mite (Tetranychus télarius), the spider mite (Tetranychus pacificia), spider mite Dermanyssus gallinae), various ticks and various spider species The compounds of this subgroup are also active against insects of various orders including

Epilachna varivestis,

Anthonomus grandia,

Crambus caliginosellus,

Oulema melanopus, various beetles of the genus Altica and Epitrix, drilling insects,

Leptinotarsa decemlineate, grain beetles,

Hypera postica,

Anthrenus scrophulariae,

Tribolium confusum, the larvae of beetles attacking the roots,

Sitophilus oryzae,

Gonotrachelus ninuplar, white greetings,

Aphis gossypii,

Macroslphum rosae,

Rhopalosiphum maidls,

Acyrthosiphon onobrychis, insects of the genus Pseudococcidae, insects of the genus Coccidae, insects of the genus CícadeUidae ,. citrus aphids,.

Therlophis maculata,

Myzus persicae,

Aphis fobae,

Lygus lineolaris,

Leptocoris trivittatus,

Címex lectularus,

Anasa tristis,

Blissus leucopterus,

Musea domestica,

Aedes áegypti,

Stompxys ealtritrans,

Haomatobia Irritaris,

Hylemia braseteue,

Psila rosae, //

Prodenia eridania, caterpillars of the genus Noctuldae, moths,

Fruits of intérpunotella,

Heliothls zea,

Ostrinia nubilališ,

Trichoplusiaini,.

Alabamu argillacea,

Thyridoptéryx aphemeráeíomis,

Spodoptera frugiperda,

Blattella geřmánica a

Periplahéta americana.

In addition to the use of Iconteol undesirable pests on. in plants, the compounds of this subgroup may be added to inks, adhesives, soaps; polymeric materials, cutting oils or oil or latex paints. The products may also be distributed in textile or cellulosic materials or elsewhere or may be used for impregnating wood and lumber. In addition, they can also be applied to the seeds. According to another method, the products can be gasified or sprayed or spread in the form of aerosols into the air or onto the surface in admixture with air. In these applications, the compounds exhibit useful properties described above.

The use of these insecticidal and arachnidic compounds consists in contacting insects or arthropods of the Arachnidae class with the compounds of this subgroup. The contacting is carried out by applying one or more products to the environment in which the insects or arthropods occur. Examples of these are soil, air, water, food, vegetation, mineral objects, stored products such as cereals, and other animal organisms. The inactivation may be carried out tethally, immediately or with a delay, or over time, and the inactivated insects or arthropods of the Arachnidae class 15 are then unable to convert at one or more of their normal life stages. Among the known insecticides in which the latter situation prevails are those in which one of the body's systems, often the nervous system, is severely disrupted, but the exact mechanism by which the compounds act is unknown and the insecticidal and arachnicidal activity is not limited in any way .

The use of an inactivating amount of one of the compounds of this subgroup is not critical for insecticidal or arachnicidal activity. The inactivating amount can sometimes be applied by using the compounds in unmodified form. However, it is often desirable that the insecticidal and arachnicidal properties of the compounds of this subgroup can only be used as in the case of herbicidal properties when one or more compounds are formulated with one or more ingredients. Regarding mixtures and additives, reference is made to the discussion above. Where the insecticidal and arachnicidal compounds of formula (II) are used to control insects and arthropods of the Arachnidae class attacking plants, preferably those additives which are substantially non-phytotoxic in the prepared mixture are used.

Specifically, the amount of one or more of these Compounds of this subgroup in admixture with one or more ingredients may be varied, merely requiring that one or more of the products be present in an amount sufficient to permit inactivation doses of insects or Arachnidae. In many situations, a composition containing 0.000001% active compound is effective for administering an inactivating amount to harmful insects or arthropods. Mixtures containing a higher concentration of active ingredient such as. For example, concentrations from Q10f10OQ1 to Q1.5% may also be used, even in other processes, as appropriate. using mixtures containing from 0 * 5 to 9% by weight of one compound or from 0.5 to 98% by weight of more than one compound. These mixtures are. adapted to be used as a means for use on insects and arthropods of the Arachnidae class; and in their environment to be used as concentrates and then diluted with an additional ingredient to prepare a suitable treatment composition. One or more compounds of this sub-group, or a mixture containing one or more compounds, is directly applied to the insects or arthropods to be controlled or applied to part or all of their environment by any suitable means, such as a hand-held duster or sprayer or by simply mixing with the food to be ingested by the organism. The application to the leaves of the plants is preferably carried out by hand sprayers, boom sprayers and fog sprayers. For foliar application, the mixture used must not contain any amount of phytotoxic diluent. For large-scale procedures, small volume dusts or sprays can be applied from aircraft. It is also possible to use mixtures of one or more compounds of this subgroup, an additive and one or more biologically active substances such as other insecticides, fungicides, acaricides, bactericides and nematicides.

Compounds contemplated for the control of insects and arthropods of the Arachnidae class are evaluated by the following tests and modified according to the following procedure.

First, 55 grams of a mixture of two nonionic sulfonate emulsifiers is mixed with one liter of cyclohexanone. From the resulting mixture, 0.9 mL was sequentially mixed with 90 mg of the compound of the invention, diluted to 90 mL with distilled water to give a concentration of 1000 ppm. To prepare lower concentrations, the mixture is further diluted with a diluted mixture containing 4 liters of distilled water and a total of 1.8 mL of the same two nonionic sulfonate emulsifiers.

The insecticidal and arachnicidal effect of the compounds of formula II is illustrated by the following tests on representative insects and arthropods of the Arachnidae class.

Epilachna varivestis (Coteoptera) ·

The cuttings of four six-day Bountiful snap bean plants containing two leaves of approximately 12.5 cm ² are placed in water. The leaves are sprayed with about 5-10 ml of a preparation containing a predetermined amount of test compound. Half of the formulation is sprayed on the top surface and half on the bottom surface of the sheet using a De Vilbis atomizer and a pressure of 70 kPa from a distance of 45 cm from the sheet. After drying the leaves, the leaves are cut from the stem and placed separately in petri dishes. A third instar larvae of Epilachna varivestis, grown on Bountiful snap · bean leaves, is placed on each leaf. Controls consist of two leaves sprayed with 5 zeros of the preparation containing! 500 ppm of B- (1,2-dicarbethoxyethyl) -, 0-dimethylphosphardithioate (corresponding standard), two leaves sprayed with the preparation without active ingredient and two leaves maintained as an untreated control. After 48 hours, mortality is calculated and the amount of food eaten is measured. Dying larvae count as dead. The following toxicity scale was used, percentage of dead scores

0— 10 0 ll- 20 May 1 Žl— 30. 2 31— 40 3 41— 50 4 51— 60 5 61— 70 6 71— 80 7 81— 90 8 91— 100 ALIGN! 9

The compounds so used, the amounts used and the results are shown in Table IV below. If more than one experiment was performed for the indicated amount, the average of several results is given.

Table IV Compound

N-trifluoracephyl-S-nitro-trifluoromethyl-o-phenylenediamine

NMifluorochloroacetyl-S-nitro-S-trifluoromethyl-o-phenylenediamine

NMrifluoroacetyl-N ² -benzoyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine

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

NMrifluoroacetyl-N ² -ethoxycarbonyl-4'-trifluoromethyl-6'-nitro-o-phenylenediamine

N ^1- (2,2,3,3-Tetrafluoropropionyl) -N ² -methoxycarbonyl-6'-nitro-4'-trifluoromethyl-O-phenylenediamine

ppm toxicity for, Épilachna varivestis 1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 50 9.0 1000 9.0 500 9.0 250 ; 9.9 100 ALIGN! 8.0 50 9.0 ’ 1000 tirin 7.0 he 250 1 7.5. 1000 9.0 500 '.' 9.0 ' 1000 9.0 '·· 500 9,0- 250 9.0 100 ALIGN! 9.0, - ⁵⁰ 9i0.i> · 1000 g, 0. - 500 9.0. . 250 9.0 100 ALIGN! ' ^J ' 9.0

Prodenia eridania (Lepidoptera)

Ten uniform Prodenia eridania larvae, 1 - 1.5 cm long, grown on Henderson lima beans, are placed on torn leaves of beans in Petri mills. Bean leaves are obtained and sprayed with the insecticide in the same manner as the leaves listed in the Épilachna varivestis test. The corresponding standard for this case is the leaves sprayed with 5 ml of 100 ppm DDT solution. The number of dead is assessed 48 hours after spraying and the again dying larvae are counted as dead. Missing larvae likely to be eaten are considered to be alive. The same scale as the Épilachna varivestis test was used for the evaluation.

The compounds so used, the amount used and the evaluation results are shown in the following Table V. If more than one experiment was performed, the results are an average of several results.

Table V Compound ppm Toxicity. Prodenia eridania

NMifluorochloroacetyl-4-nitro-4-tri- 1000 8,5 fluoromethyl-o-phenylenediamine

N ¹ -trifluoroacetyl-N ² - (p-nitrobenzoyl) -4'-1000 9.0

-trifluoromethyl-6‘-nitro-o-phenylenedlamine

195898

Aphis gossypii (Hemiptera)

Four seeds of blue pumpkin seed are sown with the yermiculite container and the containers are green from below. After six days, two weaker plants are cut off and one uterus and primary strips are removed from each of the remaining plants. The remaining uterus is infected with 100 Aphis gossypii from the stock colony by advancing the uterus to the infected uterus from the stock colony and allowing the aphids to crawl. After climbing, the colony leaf was removed. After 48 hours, the infected leaves are sprayed with a preparation containing a graded amount of insecticide using a DeVilb atomizer > 28 per kPa at a distance of 30 to 37.5 cm from the plant. Controls consist of two infected unpainted pumpkin plants and two infected plants sprayed with a preparation containing 100 ppm of S - (1,2-dicarbethoxyethyl) -, O, O-dimethylphthisphosphodethanol as standard. Mortality was reduced 24 hours after spraying using a 10X magnification microscope. The same scale as before was used for the evaluation.

The compounds used, the amounts used and the results are shown in Table VI below. If multiple experiments were performed, the values are the average of several results.

Table VI Compound ppm Toxicity to

Aphis gossypii

N-Trifluoroacetyl-SLnitro-S-trifluoromethyl-o-phenylenediamine.

N-Difluoro-chloroacetyl-S-nitro-S-trifluoro;

methyl-o-phenylenediamine

NMilfluoroacetyl-S-trifluoromethyl-S-nitro-o-phenylenediamine

1000 9.0 500 9.0 250 9.0 100 ALIGN! 8.0. 50 7.0 1000 9.0 500 9.0 250 8.5 ^{100 ALIGN!} 8,0 ' 1000 9.0 .500 ... . 9.0 250 9.0

Tetranychusurticae (Acarina) «i. <. ».

Red spider mite, grown with green bean plants, se. pumpkins on plants. Pumpkin plants are maintained so that infection can go well. Infected pumpkin plants are then sprayed with the test composition containing the compound of the invention according to the previous test procedure. . Mortality was determined 48 hours after spraying. The same rating as for the other .tests is used.

The compounds used, the doses used and the evaluation are shown in Table VII below. ... '/

. Compound // Table VII • -ppm toxicity ma

Tetranychus urtlcae

N-Trifluoroacetyl-trifluoromethyl-trifluoromethylphenylenediamine.

N-pentafluoropropylpropylbenzyl-o-phenylenediamine

N-trifluoromethylphenyl-N-pitr-5‘-trifluoromethyl-C 1 -phenylene <31amines

N-Trifluoromethyl-S-trifluoromethyl-1H-trifluoro-o-phenylenediamine

N ¹ -trifluoroacetyl-N ² -methoxycarbonyl-4'-trifluoromethyl-6'-nitro-o-phenylenedtamine

N ^1- (2,2,3,3, -tetrafluoroproplonyl) -N ² -methoxycarbonyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine

, 1000. AQ 500 9.0 2SQ. 9.0 100 ALIGN! 9.0 50 8.5 1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 5Q. 8.5 1000 9 n 500 9; 0 250 9.0 1Q0. ' 8.0 50 8.0 1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 50 8.0 1000 9.0 500 9.0 250 7.5 1000 9.0 500 6.5

Qwpeltttsfaseiatus (Hemiptsral

Adult Oncopelitasasclatus is cooled and placed in test cages. The beetle-containing cages are sprayed with 5 ml of the test preparation containing a predetermined amount of Insecticide DeVllblss with an altoherizer at a pressure of 70 kPa from a distance of 80 cm from the top of the cage. Once the cage dries, the beetles are fed and watered for 48 hours. A preparation containing 500 ppro2 '(X, 2-dicarbethoxyethyl-O, O-diethyl ethyl thiosulfonyl thioate) was used as the corresponding standard and the two unprotected sprouts were kept as a control. Mortality was counted 48 hours after spraying. uses the same scale as previous tests.

The compounds used, the amounts used and the test results are shown in Table VIII below.

isssae compound

Table VIII

Oncopelitis fasciatus

N ¹ -trifluoroacetyl-3'-nitro-5'-trifluoromethyl · 1000 1000 9.0

-o-phenylenediamine. 500 9.0 '2o0. · 9.0

100 '9.0

NMifluorochloroacetyl-3‘-nitro-5‘-trifluoromethyl-o-phenylenediamine

NMrifluoroacetyl-3‘-trifluoromethyl-5‘-nitro-o-phenylenediamine

N-Heptafluorobutyryl-S-nitro-S-trifluoromethyl-Q-phenylenediamm

50 8.0 - 1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 1000 9.0 500 9.0 250 9.0 1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 50 9.0

Domestica (Diptera)

Breeding cages containing four days ₍ old adult house flies are cooled to 2 to 4 ° C for about one hour. One hundred flies are transferred from the breeding cage to each cage using a small blade. The flies in the cage are kept for about one to two hours at 21 to 27 ° C, after which they were sprayed in the same manner as described for Oncopelitis fasclatus, five milliliters of test preparation. Two unprotected cages were kept as controls and two cages were sprayed with 50 ppm DDT as a standard preparation. All flies that do not fly or crawl from the bottom of the cage are counted as dying, using the same scale as for the previous test.

The compounds used, the amounts used and the test results are shown in Table IX below. Where more than one test has been performed, averages of several results are given.

Table IX Compound ppm Toxicity to housefly

NMrifluoroethyl-3‘-nitro-5'-trifluoromethyl-o-phenylenediamine

Nt-difluorochloroacetyl-Shnitro-S-trifluoromethyl-o-phenylenediamine

NMrif trifluoro acetyl-N ² - (p-fluorine nltrobenzoyl * methyl 6-nitro-o-phenylene lendtamin

NMrifluoroacetyl-N ² -methoxycarbonyl-4'-trifluoromethyl-6'-nitro-O'-phenylenediamine

N ¹ - (2,2,3,3-tetrafluoropropionyl) N ³ -methoxycarbonyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine

1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 50 8.5 500 9.0 250 9.0 100 ALIGN! 9.0 50 9.0 1000 7.5 500 7.5 250 7.5 1000 9.0 ^: 500 9.0 250 9.0 100 ALIGN! 9.0 1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 50 7.5

195898 25

Anthonomus grandis (Coleoptera)

The procedure is similar to that used for Epilachna variestis and Prodenia eridania, except that 10 Anthonomus grandis are placed on sheets of cotton which have been soaked in the test compound preparation 28. For evaluation, the same scale as for the above tests is used.

The compounds used, the amounts used and the results obtained are shown in Table X. Where more than one test was performed, the results are an average of several results.

compound

N-Heptafluorobutyryl-S-nitro-SMrifluoromethyl-o-phenylenediamine

N1-pentafluoropropionyl-SLnitro-BMrifluoromethyl-o-phenylenediamine

N ¹ -perfluorooctanoyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine

N ¹ N ^{2 -trlfluoracetyl-methoxycarbonyl-4} -trlfluormethyl-6'-nitro-o-phenylenediamine

N ^1- (2,2,3,3-Tetrafluoro-propionyl) -N ² -methoxycarbonyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine

Almost the same results are obtained when the following compounds are used in the same way instead of the compounds listed in the table:

N ¹ -trifluoroacetyl-N ² -naphthyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine,

NMrifluoroacetyl-N ² - (p-butoxybenzoyl) -4'-trifluoromethyl-6'-nitro-o-phenylenediamine

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

N-heptafluorobutyryl-S-nitro-SMrifluoromethyl-o-phenylenedlamine,

N, N-pentafluoropropionyl-SMitro-SMrifluoromethyl-o-phenylenediamine,

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

N-pentadecafluorooctanoyl-S-nitro-SM-trifluoromethyl-o-phenylenediamine.

Table X ppm Anthonomus grandis toxicity to

1000 9.0

500 9.0. . ..

250 9.0

100 9.0

9.0

9.0

1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 50 . 9.0 25 8.5 10 8.5 1000 9.0 500 9.0 250 . 9.0 100 ALIGN! 9.0 50 9.0 25 9.0 1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 1000 8.0 500 7.0 250 7.0

In addition, the compounds of formula II are useful as parasiticidal agents for the systematic control of insects and mites that have been ingested by animals. These compounds have the ability to penetrate living tissues of the host animal to which one of the compounds has been administered. Insect parasites and parasites from the group of mites that consume blood or other living tissues of host animals will ingest the compounds that have passed through the tissue and are thus killed. It is likely that blood serves as a carrier through which the compounds are dispersed by the host animal, but parasites such as Cochliomyia hominivorax that carry blood are also killed by these compounds, which means that the compounds pass through other tissues as well as blood.

Some parasites, such as the vast majority of ticks, feed on living tissues of host animals during the vast majority of parasite life. Other parasites, such as Cochliomya hominivorax, feed on the host tissue only at the larval stage. The third group of parasites, such as blood-sucking flies, feed on the host animal only -ve

Π At the adult stage. Administration of the compounds of formula II kills the host animals by parasites that feed on the animal's feed tissue, regardless of the stage at which the parasites feed.

All species of insect and acarid parasites that feed on the nutrient tissues of animals are killed by the compounds of formula II. The parasites that suck the blood of animals, those who dig into and feed on animal tissue, who, like the larvae of Gasterophilus haemorrhoidalls, penetrate through the natural openings of the host, attack the mucous membranes and feed on them, are all equally effectively exterminated. For the sake of clarity, a number of specific parasites of various host animals are given; which can be controlled using these compounds. The life stage of the parasite to which the host animal is infected is indicated for each parasite.

Horse parasites

Gastrophilus intestinalis Stomoxys calcitrans Phormia regina Haemalupinus assini Cecidophyes ribis Psoropter equi Gasterophills intestinalis Blusus leucoptérus Gasterophilus haemorrhoidalis

Skate parasites

Haemátobis irritans.

Bovicola bovis

Haematopinus quadripertusus fly tsetse Stomoxys calcitrans Gasterophilus intestinalis Demodex bovis Boophilus annulatus Otobius magini Amblyomma mulatulatum Derrnacentor andersoni Amblyomma americanum flies of the genus Caliphoridae blood-borne adults adult blood-sucking adults blood-sucking adults larvae migrating the digestive tract larvae migrating the digestive tract larvae migrating the digestive tract adults sucking blood adults jerking the skin of a nymph, adults; sucking blood adults sucking blood and adults sucking blood adults sucking blood adults drilling into the skin of larvae, nymphs, adults sucking blood nymphs sucking blood 'adults sucking blood .., adults sucking blood adults sucking blood larvae infecting wounds sucking blood

Pig parasites

Haematopinus suis

Tungá penetrans

Sheep and goat parasites

Pediculus humanus

Pediculus capitis

Malophagus ovinus

Psoroptes ovis

Gasterophylus haemorrhoidalis Thialeurodes vaporariorum Phormia regina Cochliomyia macellaria adults sucking blood adults sucking blood adults sucking blood adults sucking blood nymphs, adults eating skin larvae migrating in cavities larvae infesting wounds larvae infesting wounds. wound-infesting larvae weIOKraJž

Cimex, lectularius Cnclotogaster heterographa Argus pervisus Knemldokoptes mutana Khemidokopíes galtnae

0.30 «adults sucking the adult's adult! sucking blood. nymphs, adults sucking blood adults drilling into the skin adults drilling into the skin

Dog parasites

Gasterophilus intestinalis adults sucking blood

Stomoxys calcitrans adults sucking blood

Cecidophyes ribis nymphs, adults drilling into the skin

Demodex canis adults drilling into the roots of fleas hairs sucking blood

It is understood that the parasites listed above are not dependent on one host animal. Most of the parasites are capable of utilizing different hosts, although each parasite has the most advantageous host. For example, Cecidophyes ribis attacks horses, pigs, mules, humans, dogs, cats, foxes, rabbits, sheep and cattle. Gaserophilus intertinalis attacks horses, mules, cattle, pigs dogs and many other animals. The use of the compounds of formula II kills the parasite of the type # described. above living in the host animal as above, as in other host animals. For example, these compounds are effective in cats, goats, camels and animals. kept in the zoo. :

The host animals in which the compounds are preferably used are canine, bovine, sheep or horse in which ticks, fleas, flies and worms are contaminated.

The time, method, and amount at which the compounds are effectively administered vary within wide limits. A detailed explanation of the way these compounds are used is given above.

The compounds are administered to the animals in an amount of about 1 to about 100 mg / kg. Preferably, the amount for controlling said parasites infesting said rirasf animals can be determined individually, but in many cases the optimum amount has been found to be in the preferred range of about 2, 5 to 50 mg / kg. The optimum amount for a given case depends on such factors as the health of the animal to be treated, the susceptibility of the parasite, the costs that the animal may incur, and the degree of control required. Lower doses are safer for the host animals, are less expensive and are often easier to administer, but provide incomplete or minimal control of the parasites so that new infections can occur. On the other hand, higher doses provide more complete control of the parasites, but they are more expensive and can cause discomfort in the treated animals.

The compounds of formula II are effective when administered at any time of the year and at any age of the animal. These compounds can be continuously administered to animals as a constant feed additive, ensuring that all parasites that come into contact with the treated animals are killed. This one. the method of administration is by no means economical and it is usually best to administer the compounds at a time when the best control of the parasites can be achieved using the compounds. Certain parasites, such as cattle worms, which are horse larvae, are active. · The period when cattle are attacked. Although the parasites are primarily important, the compounds can only be used at this time and this guarantees a one-year parasite control. Other parasites, such as ticks, infect and attack animals throughout the year. Control of these parasites can also be achieved by a relatively short application time by administering the compounds to all animals in a form, in the vicinity, for a relatively short time, such as several weeks. All parasites of one generation will be killed and the animals will remain free of parasites for a sufficient period of time until there is a new infection with the imported animals.

The compounds of formula II may be administered by any oral or dermal application. It should be emphasized that many compounds are chemically altered by passage through the stomach of the ruminant. Oral administration to ruminants It is therefore only dependent on whether the compounds are protected against the action of the stomach of the ruminant by special treatment. These modifications to suitable preparations are given below.

The treatment and administration of biologically active compounds to animals varies depending on age and mode. Some formulations of the preparations and methods of application are disclosed which illustrate the practical use of these compounds for controlling parasites.

Cutaneous application of the compounds of formula II can be carried out in a manner commonly used in veterinary practice. Preferably, water-soluble salts of the compounds of formula (II) are used so that no preparation is required. Alternatively, if it is desired to use water-insoluble compounds, it is preferable to dissolve the compounds in a physiologically acceptable solvent such as polyethylene glycols. It is also practical to use injectable suspensions of the compounds in the form

199699 fine powder suspended in the formulation. . a physiologically acceptable solvent, surfactant, and susceptible agent.

The non-solvent may be, for example, edible, whitening, such as peanut oil, corn oil or sesame oil, glycol, such as polyethylene glycol or water, depending on the winning action. -. ····.

Physiologically acceptable additives are necessary to keep the compounds of formula (II) in a suspended state. These additives are selected from emulsifiers such as dodecylbenzenesulfonate and toluenesulfonate salts, ethylene oxide and alkylphenol addition compounds oleate and laurate esters, and dispersing agents such as naphthalene sulfonate, lignin sulfonate, and fatty alcohol sulfates may be used as excipients for suspending agents. such as carboxymethylcellulose, polyvinylpyrrolidone, gelatin and alginates. For suspending. The compounds may be used in this class of surfactants, including. those that were. Suitable surfactants are, for example, lecithin and polyoxyethylene sorbitan esters.

Preferably, the cutaneous application is administered subcutaneously, totramiscularly, and even intravenously in the form of injectables. preparations. A suitable needle type injection device as well as a 1 non-rod type injection device is used.

It is also possible to use a preparation with delayed or prolonged permeation of the compounds of formula II through animal tissues. Thus, for example, very insoluble compounds may be used. In this case, the mild solubility of the compounds causes prolonged action by the body. animal fluids can dissolve only small amounts of the compound at a time.

The prolonged action of the compounds of formula II can be obtained by treating the compound to a form that physically inhibits dissolution. The thus prepared formulation is injected into the body, where it remains as a bed from which the compound slowly dissolves. Formulation forms of this type are known and consist of waxy semisolids such as vegetable waxes and high molecular weight polyethylene glycols.

An even more effective sustained action is obtained when an animal is administered an implant containing one of the compounds of formula II. Such implants are known in vetertesary practice and are usually prepared from silicone-containing rubber. The compounds are dispersed in the solid rubber implant or are contained in the implant opening. When selecting a compound, it is necessary to proceed to be soluble in the gum, since the compound is first dissolved in the gum and then released into the body liquid of the animal.

The amount of compound that is released from the implant, and hence the time during which the implant is effective, is controlled with good accuracy by appropriately adjusting the concentration of the compound in the implant, the external ptoehau of the polymer meroma from which the implant is prepared.

Application of the compounds by implants is a particularly preferred route of administration. This application is highly economical and effective since the time the implant is effective is known and a constant concentration of the compound in the tissue of the host animal is ensured. The implant can be modified to deliver the compound for several months and is easy to administer to the animals. in any way.

Oral administration of a compound of formula II is accomplished by mixing the compound with feed or drinking water or by administering an oral dosage form, such as. are infusions, tablets or capsules.

If the compound of formula H is to be administered orally to a ruminant animal, it is necessary to protect the compound from the undesirable decomposition effect of the ruminant process. In veterinary practice, effective methods are now known for coating and encapsulating drugs so that they would. protected in the stomach of the ruminant. For example, such coating agents and methods are disclosed by Grant et al., U.S. Patent No. 3 09,7 6401 Grant discloses a method of protecting compounds from the effect of a ruminant plaque consisting in coating a substance with a film of propionate 3-mercaptool cellulose propionate. protect compounds of formula. II. Preferably, the tablets or capsules containing the stopper of formula II are coated with a film in a coating pan or sprayed in a fluidized bed. The parasiticide pill may be prepared by film coating and then filled into capsules. Alternatively, a solid mixture of the compound and the film-forming agent can be prepared, comminuted and milled into small particles, each containing the compound ux encapsulated in the matrix of the film-forming agent. The particles may be filled into capsules for oral administration or may be used in oral snspensi.

Repair of veterinary ingredients in animal feed is well known. Typically, the compound is first formulated into a masterbatch in which the compound of formula II is dispersed in a liquid or solid particulate carrier. The masterbatch may conveniently contain from about 1 to 400 g of compound per 0.454 kg, depending on the desired concentration in the feed. However, it is known that many compounds of formula II can be hydrolysed or degraded by the action of feed components. These compounds are generally formulated by treating them with a protective matrix such as gelatin prior to preparing the masterbatch. The premix is then dispersed in the feed with a conventional mixer. The exact amount of compound and hence the premix to be added to the feed is then easily calculated from the amount the animal eats per day and the compound concentration in the premix.

I ./

Likewise, the amount of compound added to the drinking water of the animals is calculated taking into account the weight of the animal and the amount it consumes per day. Most preferred is the use of water-soluble salts of the compound of formula II. If such a salt is not desired, then a suspendable preparation of the desired compound must be prepared. The preparation may be a suspension in concentrated form and the suspension may be admixed into drinking water or may be a dry preparation which is then suspended in the drinking flavor. In any case, the compound must be in finely powdered form, and the preparations are then prepared on the same principles as injectable suspensions.

The compounds are readily formulated as tablets and capsules by conventional methods well known in the art and need not be mentioned herein. The infusions comprise a compound dissolved or dispersed in an aqueous liquid mixture. Here too, it is most preferred to prepare the infusion by dissolving the water-soluble salt of the compound of formula II. It is also almost as convenient and equally effective to use dispersion compounds as are prepared in the drinking water as mentioned above.

The examples presented immediately below demonstrate the effect of the compounds of formula II in controlling a number of parasites that normally attack economically important animals. The compounds were tested against Cochliomyia hominivorax, larvae of Phormia regina, against Stomoxys calcitrans, against mosquitoes and against Dermacentor varlabills. In the case of Phormia regina and Stomoxyš calcitrans, these are insects, Dermacentor variabilis is representative of mites.

Stomoxos calcitrans is a common free-flying, blood-sucking parasite; Amblyomma americanum is a typical blood sucking parasite that has .. nymphal a. part of the adult life cycle associated with the host animal, usually cattle. Phormia regina larvae develop from eggs laid near the wounds of the host animal by free-flying insects. The larvae dig into healthy flesh around the wounds and lose part of their life cycle in it, feeding on host meat and blood. ''

Stomoxys calcitrans is a parasite of horses, 'mules, cattle, pigs, dogs, cats, sheep, goats,' rabbits and humans; Amblyomma ameřlcanum attacks primarily cattle, but also horses, rotting and sheep. larvae of Phormia regina attack- any injured animal, but are particularly harmful to cattle, pigs, horses, mules; sheep sheep.

The following tests illustrate the effect (s) of the compounds of formula II applied to bovine animals. In the vast majority of cases, the tests listed below were carried out in animals infected with parasites.

The calf treated 15 mg / kg of N ^1- (2,2,3,3-tetrafluoropropionyl) -3'-nitro-5'-trifluoromethyl-1-o-phenylenediamine in a single subcutaneous injection. The compound is applied in the form of a dispersion in 10% polyvinylpyrrolidone.

Stomoxy calcitrans spawns are placed in a chamber completely enclosed with a wire mesh. Two or more chambers; containing from 60 to 100 adults Stomoxys calcitrans which are placed in contact with the clipped back of a calf 24 ^; hours after application. Stomoxy flies calcitrans are allowed to eat on the calf for a specified period of time, after which an evaluation is made and the flies are allowed to eat for another specified period of time. The mortality of flies is determined by counting the living and dead after a certain time. Each group was performed separately.

Results. ascertained mortality rates are as follows:

group hours after treatment. mortality Stomoxyš • calcitrans% _,. .....- ·. - ~ - - - _g5

77 70 • 96 100

77 88 ^: 100, 24 85

95

If this procedure is repeated using mosquitoes instead of Stomoxys calcitrans, the results are as follows:

group

195898 hours after treatment mosquito mortality%. ·>'···.'7<'^; 100 _;

If the above procedure is repeated using 25 mg / kg in 10% glycolicrolidone, the results are as follows:

group species

- mosquito mosquito mosquito

Dermacentor variabilis hours after treatment mortality%

........

100 ALIGN!

70

• N ^1- (2,2,3,3, -tetrafluoroproplonyl) -3'-nitro-5''-trifluoromethyl-O-phenylenediamine was tested at 10 mg / kg in sesame oil against Stomoxys calcitrans in calves . The procedure was modified from the above by placing the wire chambers on the back of the calf 24 hours after compound administration, the results are shown in Table XI below.

Table XI

time number of live number of dead % den 1 6 hours 20 May ^! 20 May 50 24 hours 0 40 100 ALIGN! den 2 ·· 6 hours 3 37 92 24 hours 0 ; 40 100 ALIGN! den 3 . '·· » 6 hours 16 24 60 24 hours '4 38 90 den 4 .of 6 hours 10 30 - ' . 75 ,24 hours . 0 40 100 ALIGN! den 5 6 hours - 24 hours 0 40, 100 ALIGN! den 6 6 hours __ _ __ 24 hours 0 30 . 100 ALIGN! den 7 6 hours 3 37 93 - 24 hours 6 34 85 den 8 6 hours 35 5 12 24 hours ^: '15. 25, ^: 62 den 9 6 hours 20 May 10. 33 24 hours 0 40 100 ALIGN! den 10; 6 hodift 40 0 0 24 hours 40 0 . · ··· 0 den 11 6 hours 40 0 0 24 hours 40 0 0

The tests immediately above demonstrate the control of insect and mite parasites using compounds of formula II. The application of these compounds, even at very low doses, kills the parasites that feed on the treated vomit even several µm after application of the compounds. It is also noteworthy that the control of these parasites is very complete, as a few or nearly total number of parasites have been killed.

The following procedures give representative bioassay results.

Table XII solvent compound

The larvae of Phormia regina are used as test organisms in a bioassay. The tests are carried out by administering a compound of the invention in the form of a single subcutaneous injection of calf. The calves are collected, blood samples the day after application and the larvae of Phormia regina are nourished with this blood. The end of the test is the last day when 90% or more of Phormia regina larvae still die. The results are shown in Table XII below.

dose charged days at figig kg ') 90% higher mortality

N ^1- (2,2,3,3-Tetrafluoropropio-10% polyvinylpyrrolidone) -3'-nitro-5'-trifluoromethyl-o-phenylenediamine sesame oil dimethylsulfoxide polyethylene glycol

NMifluorochloroacetyl-3‘-nitro-sesame oil -5‘-trifluoromethyl-o-phenylene- 10% polyvinylpyrrolidone diamine

40 25 25 48 15 Dec 11 10 8 5 6 2.5 -, 15 Dec 2Q 2.5 5 8 15 Dec 9 15 Dec 8 20 May 6

Another in vitro assay to determine the control of Stomoxys calcitrans adult parasites using compounds of Formula II is as follows. Stomoxys calcitrans adults are starved for 18 hours before being placed in petri dishes or in a flying cage and a blood bait is added. Blood used for the bait is collected from treated calves at indicated intervals after treatment. Stomoxys calcitrans mortality is determined after a certain interval after introduction of the bait. The percent mortality at this time is compared to normal mortality obtained in petri dishes or flying cages containing blood from untreated calves (control). Nt- (2,2,3,3-tetrafluoropropionyl) -3‘-nitro-5‘-trifluoromethyl-o-enlenediamine is used in this assay and the results are shown in Table XIII below.

Table xm

dose (mg / kg) hours of blood collection after treatment hours of determination. post mortality mortality in contact with blood pracant © mortality 15 in 10% polyvinylpyrrolidone: 72 5 (22 72 24 89 25 in dl-ethylsulfoxide 24 22nd $ 00 2 18 100 ALIGN! 24 24 100 ALIGN! 25 in 10% polyvinylpyrrolidone 168 24 92 40 in 10% polyvinylpyrrolidone 284 24 84 312 24 100 ALIGN! 380 24 88

195893

In the tests described above, parasites are exposed! blood of treated animals indirectly, instead of directly so that the parasites feed directly on the animal. However, using controls, this test is as significant as when parasites suck blood directly from the animal. The degree of protection of the animals against very harmful parasites of Phormia regina is clearly demonstrated by the test since several days after the administration of a single dose of the compound of formula II complete control of the parasites is complete.

In addition to the herbicidal, insecticidal and parasiticidal activity, the compounds of the formula Π exhibit anthelmitic activity.

In view of the anthelmitic effect of the compounds of formula II, the compounds of formula II can be administered to warm-blooded animals to control internal parasites, particularly intestinal tract parasites such as Haemonchus contortus, Syphacia obvelata and Nematospiroides dubium. Administration is preferably carried out orally and may be included in the side or the compound may be administered alone or formulated as tablets or livestock pills. A typical good result is obtained at doses of 5 to 500 mg / kg per dose and at doses of from 0.001 to 0.05% when used in the diet. In representative procedures, Ni-trifluoroacetyl-S-nitro-S-trifluoromethyl-o-phenylenediamine is added to the modified mouse food at a concentration of 0.01%. The modified food is administered to a group of four mice and the unmodified food to another group of four mice as control. Mice from both groups are infected with Nematospiroides dubius about seven hours after the start of feeding. Feeding is continued for eight days, on day 9 all mice are killed and the presence or number of Nema40 tospfhoiifes aatas in the intestine is determined. No larvae were observed in the group of modified food mice, group, with an average of 28 larvae per mouse. The same results were obtained using other compounds of formula II.

Comparative tests

For comparison, tests were performed with a compound of formula

Cl Q r-t il known from U.S. Patent No. 3,557,211, referred to herein as Compound A, while the compound of formula

referred to herein as Compound B is an active compound of the invention. Pre-emergence herbicide test

The assay was performed similarly to the assay described in Table 1.

Table Ia corn cotton soya alfalfa sugar beet rice. cucumbers bloody mustard gooseberry durman

1.1 kg / ha

and

AND

1.2 kg / ha

.1

4.4 kg / ha

1.1 kg / ha .1

(B)

2.2 kg / ha '

2 1 3

4.4 kg / ha

5 5 5

2

195898

42

Insecticidal test for Epilachna varivestis

The test was performed similarly to the fest described in Table IV.

Table IVa

compound amount in ppm toxicity for Epilachna varivestis AND inactive 0.0 (B) 1000 9.0 500 9.0 250 9.0 100 ALIGN! 9.0 50 9.0 '25 8.5 ¹⁰ 8.5 Insecticide test for Oncopelitls fasciatus The assay was performed similarly to the assay described in Table VIII. . 'Table Vlila compound amount in ppm toxicity for · - Oncopelitis fasciatus AND inactive 0.0 (B) 1000 9.0 500 ^; 9.0 250 9.0 100 · 9.0 50 8.0 25 8.5 10 7.0

Insecticide test for cockroach

Adult cockroach adults were chilled and placed in a test cage. In the cockroach cage, 5 ml of the test composition with a pre-calculated amount of insecticide was sprayed using a de Vilbls atomizer at a pressure of 70 kPa, which is held 82.5 cm from the top of the cage. The cage is then allowed to dry. A formulation containing 500 ppm 1,4,5,6,7,8,8-heptachlor-3a, 4,7,7a-tetrahydro-4,7-methanoindene was used as the reference standard, and two unsprayed cages were used as controls. Mortality calculations are made 72 hours after spraying. Dying cockroaches are considered dead. The same calculation scale is used as described above. The results are shown in Table IIIb.

compound. Table VlIIb.

amount in ppm toxicity to cockroach inactive

1000

500

250

100 ALIGN!

0.0

9.0

8.5

9.0

7.0

5.0

Insecticide test for housefly

Compounds A and B were tested on housefly fed serum taken from guinea pigs 24 hours after treatment with guinea pigs with the test compound. The serum is placed on a blood support so that flies can easily feed. The results were determined in a manner similar to that described above; when the flies were directly contacted with the compound. The results are shown in Table IXa.

195898

Table IXa compound amount in ppm Toxicity to housefly

AND (B) inactive 1000 500 250 100 ALIGN! 0.0 0.0 9.0 9.0 9.0 Insecticide test on Anthomonus grandis ; . . Compounds A and B were tested by method. The results are shown in the table described in the description of Anthomonus Xa. - Table Xá compound amount in ppm toxicity to Anthomonus grandis AND inactive 0.0 (B) 500 9.0 250 8.5 , 100 8.5 50 7.0 25 7.0

PRÉDMBT I will invent

Claims (3)

Herbicidal, anecticidal and arachnicidal agent, characterized by. comprising a carrier and, as active ingredient, a compound of formula (II) wherein: R ° is 2,2-difluoroalkanoyl radical of the formula -C-CF2-Y, II o. wherein Y is chlorine, fluorine, difluoromethyl or perfluoroalkyl of 1 to 6 carbon atoms, R ¹ is hydrogen, methoxycarbonyl, 3,6-dichloro-2-methoxybenzoyl, benzoyl, 2-nitrobenzoyl, naphthoyl, p-butoxybenzoyl or 3,4-dichlorobenzoyl, R ⁴ is nitro, R ⁵ is trifluoromethyl wherein R ⁴ and R ⁵ are in meta position with each other, and when R ¹ is hydrogen, one of the substituents R ⁴ or R ⁵ is ortho-to the -NH-R ¹ group.