JPS5910341B2 - Compounds useful as agricultural chemicals and veterinary drugs and their production methods - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel N-(2. The present invention relates to a method for producing a 2-difluoroalkanoyl)-0-phenylenediamine compound.

Control of animal parasites is one of the oldest and most important problems in animal husbandry.

Many types of parasites harm virtually all animals. Most animals have free-floating parasites such as flies, crawling ectoparasites such as lice and mites, burrowing parasites such as horsefly maggots and insect larvae, and coccyges. are attacked by microscopic internal parasites as well as larger internal parasites such as phlegmon. Control of such parasites is complex and multifaceted even in a single host animal. Particularly harmful are insect and mite parasites that deplete the living tissues of their host animals.

This group includes parasites of all commercial animals, including ruminants and monogastric mammals and poultry, as well as companion animals such as dogs. Many methods of controlling such parasites have been attempted.

American fly larvae have been virtually eradicated in Florida by releasing large numbers of sterile male adults. It is clear that this method can only be applied to areas that are easily isolated. Free-flying insects are commonly controlled by conventional methods such as aerial spray contact with insecticides or fly traps. Parasites that live and crawl on the skin are usually controlled by bathing, drinking, or spraying the animal with a suitable antiparasitic agent.
Some parasites, especially those that make holes in the host animal,
Some progress has been made in the systemic control of parasites that alter the parasitic habitat within the host animal.

Systemic control of animal parasites is achieved by absorbing antiparasitic agents into the bloodstream or other tissues of the host animal. Parasites that feed on or come into contact with tissue containing the antiparasitic agent are killed by ingestion or contact with the agent. It is known that certain phosphatate, phosfluoramidate and phosfluorothioate insecticides and acaricides are sufficiently non-toxic for systemic use in animals. RumanOwski
) discloses N-N-bis(acetyl)-0-phenylenediamines useful for plant, insect and fungal control (see US Pat. No. 3,557,211).

The object of the present invention is to provide herbicides, parasitic killers, insecticides, anthelmintic agents or spider killers containing novel N-(2,2-difluoroalkanoyl)-0-phenylenediamine derivatives as active ingredients, especially systemic The object of the present invention is to provide an antiparasitic agent and a method for producing the active ingredient.

According to the present invention, a compound of the formula: can be reacted with an acylating reagent of the formula or an active derivative thereof to produce a compound of the formula:
[In the formula, RO is 2.2 represented by the formula: 1C-CF, -Y
-difluoroalkanoyl group (where Y is chlorine, fluorine, difluoromethyl, or perfluoroalkyl having 1 to 6 carbon atoms);

R1 is hydrogen, a group represented by the formula: C-0-Y1 (where Y
1 is alkyl having 1 to 4 carbon atoms.

), benzoyl, naphthol or substituted benzoyl of the formula
-4 alkoxy, p is 011 or 2, q is O or 1, and the sum of p and q is 1-3.

). However, NO2 and CF3 in formula [] are in meta positions with respect to each other, and when R1 is hydrogen, cyclic,
NO2 or C in the position ortho to the -NH-R1 group
Either F3 is present. ]. Compound of the present invention []
are prepared by introducing a unique 2,2-difluoroalkanoyl group into the appropriate corresponding diamine starting material.

This reaction is expressed by the formula: [wherein, Y has the same meaning as above.

] or its active derivatives by a number of available acylation reactions.

Various acylating agents can be used,
Particularly suitable acylating agents include difluoroalkanoyl halides: [wherein 11a1 represents halogen]. Y has the same meaning as above. ] and 2,2-difluoroalkanoic anhydride: [wherein, Y has the same meaning as above.

], etc. are included.

Diamine starting materials for acylation reactions are diverse. When R1 is hydrogen in the object compound of the present invention [], a compound represented by the formula: is used as the starting diamine,
One acyl group is introduced into this to obtain a target compound in which R1 is hydrogen, or two identical acyl groups are introduced to obtain a target compound in which RO is C-CF2-Y.

On the other hand, when R1 is a group other than hydrogen, a compound having the desired R1 moiety of the formula: [wherein the symbols have the same meanings as above] is used as the diamine starting material, and a desired RO group is added to this compound. may be similarly introduced by acylation.

Although the synthetic method described above is easy and preferred, other methods can also be used.

For example, when R1 is an acyl group, R1 may be introduced after RO is introduced in advance. However, due to the activating effect on the acylation of α-fluorine atoms,
Generally, when introducing a 2,2-difluoroalkanoyl group, it is preferable that a group other than the 2,2-difluoroalkanoyl group already exists. Acylation of the amine starting materials with various acylating agents to obtain the corresponding target amide compounds can be carried out in a conventional manner.

That is, the compound of interest of the present invention can be produced by conventional operations to make such treatment effective. For example, when the acylating agent is anhydrous, the reaction is readily carried out at room temperature. A solvent may be used, and an excess of anhydride may be used as a solvent, especially except in the case of amides where R1 is hydrogen. If an acyl halide is used as the acylating agent, the reaction must be carried out in the presence of a hydrogen halide acceptor, preferably in the presence of an inert solvent, and the reaction mixture is cooled to e.g. It is preferable to do so. In the case of either acylating agent, the product can be separated by conventional methods and, if desired, purified by likewise conventional methods. Starting materials and products for unification
Name as o-phenylenediamine whenever possible.

The positions of the various substituents on the ring are defined by general nomenclature as follows:
When having one substituent, the position numbers on the phenylene ring are primed to distinguish them from the position numbers on the RO or R1 substituents.

In general, in this specification, with regard to the definition of the target compound represented by the formula [], unless otherwise specified, the term halogen is used alone or in a compound term such as halogenated alkanoyl, including bromine, chlorine, fluorine and Indicates iodine.

An essential and distinguishable structural feature of the compounds of the present invention [ ] is the presence of a 2,2-difluoroalkanoyl group (RO), and specific examples of such groups include the following.

Difluoroacetyl, trifluoroacetyl, difluorochloroacetyl, pentafluoropropionyl, heptafluorobutyryl, nonafluorovaleryl, 2,2,3,3-tetrafluoropropionyl, undecafluorohexanoyl, tridecafluoroheptanoyl, pentafluoropropionyl Decafluorooctanoyl, 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-promobutyryl, 2,2,3-trifluoropropionyl, 2,2,3-trifluorobutyryl 2,2,3,4-tetrafluorobutyryl, 2,2-difluoro-3-bromo-4-chlorobutyryl.

Preferred RO groups are trifluoroacetyl, difluoroacetyl, difluorochloroacetyl and 2.2.3.
3-tetrafluoropropionyl.

The starting materials used in this invention are prepared by known methods, some of which are commercially available.

These starting materials of the formula can be prepared by various synthetic steps necessary to introduce the desired substituents.

Most conveniently, one or both of the NH, groups can be introduced by conversion of the . It is also possible to introduce one or both of the amino groups by nitration followed by reduction. Target compounds in which R1 is other than hydrogen are generally prepared from diamine starting materials that already have the desired R1 group.

These starting materials can themselves be combined with the corresponding diamine starting materials as appropriate acyl halides or in which R1 is -C-0
-Y1 is produced by reacting with an appropriate lower alkyl haloformate or phenyl haloformate. These starting materials can also be prepared from o-nitroanilines of the formula by acylation and subsequent reduction, both known in the prior art. The compounds of the invention are suitable for use as herbicides, insecticides, spider killers, parasitic killers and anthelmintic agents.

These compounds can be used to achieve a wide range of herbicidal effects and therefore, in its broadest sense, the present invention does not apply to plant stems, leaves, flowers, fruits, roots, seeds or other similar developmental, reproductive A (2,2-difluoroalkanoyl)-0-phenylenediamine compound having a substituent on the ring can be applied to the unitary portion in one growth-inhibiting amount. However, these compounds can also be used to exploit selective patterns of herbicidal activity. As will be apparent to those skilled in the art, mixtures of one or more of these compounds can also be used to achieve herbicidal action. Using mixtures, the amounts of the individual compounds could be suitably reduced so that the mixture provides only the desired herbicidal effect. When using these compounds as herbicides,
It is not important to completely kill undesirable plants; it is sufficient to simply suppress the growth of unwanted plants.

Especially when selective activity is required, especially when combined with naturally occurring conditions such as limited humidity that are counterproductive to selective suppression of development over the crop, it is difficult to actually kill. Moderate suppression is sufficient. Compound of the present invention [
] are suitable for a wide variety of applications as herbicides.

That is, for example, when these compounds are used, for example, in cotton, at a usage rate (this usage rate will be more fully clarified below) that causes a selective action of these compounds.
It can be used as a selective herbicide in agricultural crops such as corn, sorghum and soybeans. In such uses, the application is by pre-emergent or preferably direct spray application methods to both crops and weeds.
It can be applied to crops after germination, and to weeds both before and after germination. In other applications, the compound of interest according to the invention may be applied to fallow land (including rotational fallow land in rotationally cultivated areas).

) can be used to provide a wide range of herbicidal activity against. For such so-called fallow applications, applications may be applied in the spring to suppress plant growth until planting in the fall or the following spring, or in the spring to suppress plant growth until planting in the spring or the following fall. It can be done in the fall.
In yet other applications, these compounds can be utilized to control weeds in harvest tree plantings, such as the planting of various citrus trees. In all of these various applications, and still others for which these compounds are suitable, another advantage is that these compounds do not need to be disked into the soil to be treated; It is sufficient simply to sprinkle one of these compounds or a composition containing one of these compounds onto the upper surface. However, if desired or expedient, these compounds can be disked or mixed mechanically with the soil. In addition to the previous terrestrial embodiments, the compounds of the invention can also be used as herbicides for aquatic plants. Compound of the present invention [
] as a herbicide can in some cases be carried out with unprepared compounds, but good results are generally obtained by using the compounds in prepared form, i.e. in compositions formulated to satisfy the plant growth inhibitory effect. It is necessary to use it as a component of

Thus, for example, the active ingredient can be mixed with water or other liquid or liquids, preferably with the aid of the use of surfactants. The active ingredient can also be mixed with a finely divided solid that is a surfactant to obtain a wettable powder, which can be dispersed in water or other liquids, or mixed as part of a finely divided powder that can be applied directly. be able to. Other methods of making compositions are known in the art and can be used with these compounds. The precise amount of active ingredient used is not critical and will vary depending on the type of growth inhibition effect desired, the plant itself, the particular active ingredient used and the weather conditions.

Generally, a wide range of growth control effects are obtained at rates of 0.5 to 20 pounds of active ingredient per acre or more, and such rates are suitable and effective for controlling plant growth in fallow fields. When it is desired to obtain selective growth control effects on weeds in areas with crops such as corn, soybeans and cotton, rates of 0.5 to 10 pounds generally give good results. In a typical mode of operation, the active ingredient is used in a composition comprising the active ingredient, and the concentration and total amount of the composition used is sufficient to provide a suitable amount of the active ingredient on a per acre basis. Otherwise, the precise concentration of active ingredients in the compositions may not be critical.
Generally, liquid compositions contain 0.5-10% active ingredient.
or higher concentrations, 1.0 to 5.0% of active ingredient in fine powders, granules or other dry compositions.
Good results are obtained when using compositions containing the same or higher concentrations. More concentrated compositions can be produced and, depending on the particular application and special concentration planned, can often serve both as concentrated compositions for shipping and storage purposes and as final processing compositions. preferable. Thus, for example, the composition may contain a surfactant and an active ingredient of the invention, the latter being present in an amount of 0.5 to 99.5% by weight, or an inert finely divided solid and an active ingredient of the invention, the latter being present in an amount of 0.5 to 99.5% by weight. It is often preferred that 1.0 to 99% by weight be present. Such compositions can be used directly in some applications, as already mentioned, but they can also be diluted and then used in many other applications. Liquid compositions containing the desired amount of the active ingredients of the invention can be prepared by dissolving the substances in an organic liquid or by dissolving the substances in water with or without the aid of suitable surfactant dispersants such as ionic or non-ionic emulsifiers. It is manufactured by dispersing in Such compositions may also contain modifiers that serve as spreading agents and adhesives to plant leaves. Suitable organic liquid carriers include agricultural spray oils and petroleum distillates such as diesel fuel, kerosene, fuel oil naphtha and Studdard solvents. Among such liquids, petroleum fractions are generally preferred. Aqueous compositions are one of the water-immiscible solvents for toxic compounds.
may include one or more. In such compositions, the carrier comprises an aqueous emulsion such as water, an emulsifier and a water-immiscible solvent. The selection of dispersants and emulsifiers and the amounts thereof used are directed by the nature of the composition and the agent's ability to facilitate dispersion of the active agent into the carrier to produce the desired composition. Dispersing and emulsifying agents that can be used in the compositions include condensation products of alkylene oxides with phenols and organic acids, alkylaryl sulfonates, polyoxyalkylene derivatives or zorbitan esters, and complex ether alcohols.
Representative surfactants suitable for use in the practice of this invention include U.S. Pat. No. 3,095,299, column 2, lines 25-36;
This is confirmed by the description in column 5 of No. 2655447 and columns 4 and 5 of No. 2412510. In the production of fine powder compositions, the active ingredient [ ] must be closely mixed with clay, talc,
Disperse in finely divided solids such as limestone, cast, limestone, birchstone fines or perlite.

One method of effecting such dispersion is to mechanically mix or grind the finely divided carrier with the active ingredient. Similarly, fine powder compositions containing drug compounds can be prepared with some of the solid surfactant dispersants such as bennite, fuller's earth, attapulgite, and other clays.

Depending on the proportions of the ingredients, these fine powder compositions can be used as concentrates or subsequently further diluted with solid surfactant dispersants or silica, talc or cast to achieve the desired concentration in a composition suitable for use in plant growth suppression. Amounts of active ingredient can be obtained and used. Such fine powder compositions can also be dispersed in water to form spray mixtures with or without the aid of dispersants. The composition containing the object compound of the present invention [ ] can be prepared by incorporating therein an effective amount of a surfactant that facilitates dispersion and spraying of the composition onto the leaves of plants and mixing of the composition into plants. It is often advantageously further prepared.

The active ingredient can be dispersed in the soil or other growth medium in any convenient manner.

Application can be by simply mixing with a medium, applying to the surface of the soil and then rake or discing to the desired depth in the soil, or by using a liquid carrier to achieve penetration and injection. can. The spraying and application of the fine powder composition to the surface of the earthen mound or to the parts of the plants or to the living surface of the plant may be carried out in the usual manner, for example by means of surface or aerial application with powder spreaders, boom sprayers or manual sprayers and spray spreaders. I can do it. However, while such conventional application methods can be used, they are not necessary. It is an advantage of the compounds of the present invention that they are active and effective as herbicides simply by being placed on the soil surface without further treatment to aid incorporation. Thus, these compounds have essentially the same efficacy regardless of whether they are applied to the surface only or applied to the surface and then disked into the soil. Distribution of the active agent into the soil can also be achieved by incorporating it into the water used to irrigate the land.

In such methods, the amount of water varies depending on the porosity and water holding capacity of the soil to obtain the desired depth of distribution of the agent. The object compound of the present invention [ ] exhibits lower toxicity to mammals than the corresponding benzimidazole.

Additionally, the target compound [ ] can be dispersed as an aerosol composition containing one or more of its active ingredients. Such compositions are prepared by conventional methods of dispersing the reagents in a solvent and mixing the resulting dispersion in a liquid state with a propellant. Variations such as the particular agent used and the nature of the plants being treated will determine the desired solvent and concentration of agent therein. Examples of suitable solvents include water, acetone, isopropanol and 2-ethoxyethanol. Satisfactory results are obtained when the active compounds according to the invention [] or compositions consisting of such active ingredients are combined with other agricultural substances for application to plants, plant parts or their habitat.

Such substances include fertilizers, fungicides, insecticides, other herbicides and soil conditioners. Various target compounds [ ] used as active herbicides were applied to various plants before emergence and evaluated.

For this evaluation, soil was prepared by mixing one part of sand obtained from a masonry construction site and crushed topsoil together in a cement mixer. Place one gallon of this soil in a 25 x 35 cm galvanized flat and tap it with flush pliers until level. Approximately 2 of the flat drums using a marking tool in 3 rows.
/2.5C on the 5th side! ! Create a groove with a depth of L.

Crop seeds consisting of 4 corn, 5 cotton seeds and 5 soybean seeds are placed in these furrows.

Four rows of templates are then placed on top of the remaining soil and the next number of seeds are planted, one in each plot. Foxtail (F
Oxtailmllet) 80-100 seeds; Velvetleleaf 40-50 seeds;
Pigxeed 150-250 seeds and large Crabgrass 100
~150 seeds. Add enough soil to cover the entire flat. For example, weed seeds are about 6]! covered to a depth of l,
The rich crop seeds are covered to a depth of about 3C1n. For testing the effectiveness of the composition as a pre-emergent herbicide, the flatbread prepared as described above is placed on the day of planting or the next day in a chamber equipped with a rotating table and an exhaust system.

Improved DeVillbiss with a spray-type emulsion or wettable powder herbicidal composition connected to an air source
Apply flat with a sprayer.

Compositions tested 12.577! Apply to each flat on the day of planting or the next day. Damage assessment and observation for type of damage was performed 11-12 days after treatment.
The damage grading scale used is as follows. 0...
・No damage 1...slightly damaged 2...slightly damaged 3...severely damaged 4...withering Scored more than once on the given scale. If so, the average damage grade was calculated.

Each compound evaluated was prepared into a spray solution in one of the following ways. In one test, a particular compound was ground and moistened in a mortar with one part polyoxyethylene sorbitan monolaurate.

500 parts of water was gradually added to the resulting creamy paste to obtain an aqueous dispersion containing 0.2% surfactant.

This dispersion was quite satisfactory for spray application. In the second method, the compound was dissolved in 1 volume of acetone and the acetone solution was diluted with 19 parts of water containing 0.1% polyoxyethylene sorbitan monolaurate. In the following table showing the results of the evaluation, the first column is the name of the compound tested, the second column is the pounds per acre usage rate of the compound applied to the test flats, and the remaining columns are the names of the compounds tested. Damage to specific plant seeds or germinating seeds measured on a scale.

The target compound [] was evaluated for post-emergence application to plants including corn and some weeds.

After preparing the test solution and sowing the seeds in a flat field, approximately 9-12
Evaluation was performed according to the above test method except that the test method was applied after 1 day. The results are shown in the table below. N2-(2,2,3,3-tetrafluoropropionyl)-N1-methoxycarbonyl-3'-nitro-5'-trifluoromethyl-0-
Phenylenediamine was evaluated as a post-emergence herbicide. Evaluations were conducted using the test method described above, but with different species (tomato, crabgrass, pigweed) at a single high usage rate (15 pounds per plant). The identified compounds completely killed each of the specified species. The above herbicidal compounds can be formulated and used with other classes of known herbicides. The ratios of the individual components of such compositions to each other are not critical; all ratios provide compositions with useful plant growth-altering properties. However, generally preferred compositions have a ratio of components of 1:10 to 10:1, especially 1:5.
5:1 such that a substantial portion of each component is present in the composition. Known herbicides that are preferably combined with the target compound [] include N-N-di-n-propyl-2,6-dinitro-4-(trifluoromethyl)aniline, N-N-di-n-propyl -2,6-dinitro-
4-methylaniline, N-ethyl-N-butyl-2.6
-dinitro-4-(trifluoromethyl)aniline, N
-N-di-n-propyl-2,6-dinitro-4-(methylsulfonyl)aniline, N-N-di-n-propyl-2,6-dinitro-4-sulfamoylaniline, N
-N-di-n-propyl-2,6-dinitro-4-isopropylaniline, N-N-di-n-propyl-2,6
-dinitro-4-Tert-butylaniline and N-
N-bis(2-chloroethyl)-2,6-dinitro-4
-Contains methylaniline.

These possible combinations are illustrated in the following way.

N1-(pentafluoropropionyl)-3'-1nitro-5'-(trifluoromethyl)-0-phenylenediamine and N-N-di-n-propyl-2,6-dinitro-
The combination with 4-(trifluoromethyl)aniline was evaluated using pre-emergence applications on plants of various species.

The soil was prepared by mixing one part of sand obtained from a masonry construction site and one part of crushed topsoil together in a cement mixer.

One gallon of this soil was then placed in a 21.5 x 31.5 mm galvanized flat and tapped with a bench brush until level. The rows were marked, and one seed was sown in each row except in the case of a mixture, and the mixture was similarly sown in one row. The species used were cotton (two separate rows), morning glory (
IpOmeapurpurea), Foxtail (FOXtai)
JimsOn), JimsOn
weed), velvet leaf
and SicklepOd, Pigweed, and IpOd.
meaquamOclit) and Crotolaria (Cr
It was a mixture of OtOlaria). The compounds from which the treated soil cover was prepared were each prepared separately by suspending a mixture of two sulfonate nonionic surfactants in a 1:1 solution of acetone and ethanol containing a small amount. Each suspension was further successively diluted with aqueous solutions of the same surfactant mixture so that the surfactant mixture was uniformly reduced to a total concentration of 0.5.
5%, acetone and ethanol each at a uniform concentration of 4.15%, and multiple aqueous treatment solutions containing various concentrations of each compound were prepared. The treatment solution containing each compound was sprayed onto a small amount of soil of the same type as above while rotating in a cement mixer. Rotation continued for 5-7 minutes. Each portion of the treated mound was then spread onto a flatbed to a depth of 3/8 inch. Other flatbeds were planted in the same manner, but no soil was applied for control purposes. All drumsticks were kept in regular greenhouse conditions for 13 days and damaged and observed for type of damage. The damage grading scale used is as follows. 0
...No damage 1-3...Slightly damaged 4-6...Slightly damaged 7-9...Severely damaged 10...Withered B: Dry N: No germination R: Reduced germination S: Growth inhibition The following table shows the results of the evaluation of the treated flats. .

In the control drumstick, the test plants were developing healthy. N1
-(pentafluoropropionyl)-3'nitro-5
Similar results are achieved when '-(trifluoromethyl)-0-phenylenediamine or other compounds of the invention [] are combined with the dinitroaniline compounds listed above. Generally, N-(2・2-
Good results are obtained using combinations that provide 0.5 to 8.0 pounds of difluoroalkanoyl)-0-phenylenediamine and 0.25 to 2.50 pounds of dinitroaniline per acre. When the following representative compounds of the object compounds of the present invention [] are evaluated, essentially the same results as detailed in the above tests are obtained.

N1-(2,2-difluoro-3-bromopropionyl)-N2-(2-chloro-4-Tertbutylbenzoyl)-3'-nitro-5'-trifluoromethyl-10
-Phenylenediamine.

N1-difluorochloroacetyl-N2-(phenoxycarbonyl)-3'-nitro-5'-(difluoromethyl)-0-phenylenediamine.

N1-trifluoroacetyl-N2-naphthol-3'
-Nitro-5'-trifluoromethyl-10-phenylenediamine. N1-trifluoroacetyl-N2-(p
-n-butoxybenzoyl)-4'-trifluoromethyl-6'-nitro-0-phenylenediamine.

N1-trifluoroacetyl-N2-(p-nitrobenzoyl)-4'-trifluoromethyl-6/nitro-0
-Phenylenediamine. N1-Heptafluorobutyryl-3'-nitro5'-trifluoromethyl-10-phenylenediamine N1-Pentafluoropropionyl-3'
-Nitro-5'-trifluoromethyl-10-phenylenediamine.

N1-trifluoroacetyl-N2-methoxycarbonyl-1-trifluoromethyl-6'-nitro-0-phenylenediamine.

N1-Pentadecafluorooctanoyl-3'nitro-5'-trifluoromethyl-10-phenylenediamine.

N1-trifluoroacetyl-N2-benzoyl-3'
1-fluoromethyl-5'-nitro-0-phenylenediamine.

N1-1fluoroacetyl-N2-naphthol-l-
1-fluoromethyl-6'-nitro-0-phenylenediamine.

The compound of the present invention [ ] also has insecticidal and arachnidal activity.

These compounds are useful in the control of insect and arachnid pests, and the proportions of their use should be chosen to avoid toxicity to the plant. Can be used for control. These compounds are active against arachnids such as red spiders, mites, citrus mites, scrotum mites, Pacific mites, clover mites, chicken mites, various mites, and various arachnids. The above target compounds can also be used for ladybugs, Mexican cottonseed weevils, corn root beetles,
Grass leaf beetle, small beetle, borer, Colorado potato capetle, grain beetle, alpha alpha weevil, red beetle, confused flower beetle, needle beetle, black weevil, scarab beetle that damages roses, plum weevil , white aphid, melon aphid, rose aphid, white fly, grain aphid, corn leaf aphid, pea aphid, mealybug, scale insect, leaf louse, citrus aphid, hunter alpha aphid, green peach aphid, bean aphid, hemipteran of the genus Asclepias Insect, Tarnishedplantbug
), ash maple, bed bugs, stink bugs, long-tailed bugs, house flies, yellow fever mosquitoes, stable flies, horn flies, cabbage maggots, carrot rust flies, armyworms, sink moths, root cutworms, burrs, corn meal moths, leafhoppers, corn・Earworm (Cornear)
wOrm), European corn borer, cabbage inchworm, cotton wool beetle, bagworm, leafworm, fall armyworm, German aphid, and American aphid.

In addition to their use in the control of plant pests, the target compounds can also be incorporated into inks, adhesives, soaps, polymeric materials, cutting oils or oil or latex paints.

The product can also be dispersed in textiles, cellulosic materials or grains, and can also be used for injection into trees and timber. Furthermore, it can be applied to plant seeds. In still other methods, the product can be evaporated or sprayed or dispersed in the air or in contact with air onto a surface as an aerosol. Applied in this manner, these compounds exhibit the useful properties described above. The method of using these insecticidal and arachnidal compounds is to contact the insect or arachnid with an inactivating amount of the compound of interest.

Contact with one of these products on insect or arachnid habitat
This is achieved by applying one or more of the following: Typical habitats include soil, air, water, food, plants, inert objects, stored materials such as grains, and other animal organisms. Inactivation can lead to immediate or delayed death or to a lethal state in which the insect or arachnid is rendered incapable of carrying out one or more of its normal life processes. means. Known insecticides typically exhibit this latter mechanism, in which biological systems, often the divine system, are seriously violated. On the other hand, although the exact mechanism of the compounds that make up this active substance is unknown,
The effectiveness as an insecticide and arachnid is not limited by any method of operation. When the target compound is used in an amount that inactivates insects, it exhibits decisive effectiveness as an insecticide and arachnicide.

Inactivating amounts can sometimes be used to administer the compound in unprepared form. However, often the desirable insecticidal and acaricidal properties of this class of compounds are such that, as in the case of herbicidal properties, one or more of these compounds may be combined with one or more adjuvant substances. It can only be used when compounding. The composition and adjuvants are as described above. When the insecticidal and arachnidal compounds are used for the control of insects and arachnids that attack plants, it is preferred that any adjuvants in the formulated composition be essentially non-toxic to the plants. . 1
one of the above target compounds in a composition with one or more adjuvants;
The exact concentration of one or more of these compounds can be varied, provided that one or more of these target compounds is administered in an amount sufficient to inactivate the insect or arachnid. .

In many situations, compositions comprising 0.000001% of active ingredient are effective to administer to insect and arachnid pest organisms in inactivating amounts. 0.000001
Of course, compositions containing higher concentrations of active agent, such as concentrations of ~0.5%, can be used.

In still other operations, compositions containing 0.5-98% by weight of one compound or a total of 0.5-98% of one or more compounds are often used. Such compositions can be applied to insects, arachnids and their habitats as treatment compositions, or as concentrates and subsequently diluted with adjuvants to form the final treatment composition. suitable for manufacturing. One or more of the compounds, or compositions containing one or more of the compounds, can be applied directly to the pest to be controlled, or in any suitable manner, such as by hand applicator, sprayer, or simply mixed into the food ingested by the organism. applied to one or more parts of the habitat in a suitable manner.

Application to the foliage of plants is preferably carried out with power spreaders, boom sprayers and fume sprayers. In such foliar applications, the composition used must not contain any amount of phytotoxic diluent. For large-scale operations, fine powder or low-volume sprays can be applied from airplanes. Also compositions consisting of one or more of these active compounds, supplements and other biologically active substances such as insecticides, fungicides, acaricides, bactericidal agents and nematocidal agents. It is possible to use one or more. The compounds evaluated for insect and arachnid control detailed in the tests below are formulated by the following method.

Introduction A mixture of two nonionic sulfonate emulsifiers 5
5f7 to cyclohexanone 1f! Mix with. 0.9TfL1 of the resulting mixture was further mixed with 90η of the test compound and diluted to 90WLI with distilled water.
It is contained at a concentration of PPM. To evaluate even lower concentrations, this mixture is further diluted with a diluted composition consisting of 41 d of distilled water and a total of 1.8 d of the same two nonionic sulfonate emulsifiers. The insecticidal and arachnidal activities of the compound [] of the present invention will be illustrated by the following tests against representative insects and arachnids.

Mexican ladybird (Epilachnavariv)
estis) (Coleoptera): Four kidney bean plants, 6 days after germination and having two leaves with a leaf surface of about 5 square inches, are cut and placed in water.

The leaves are sprayed and moistened with about 5-10 TfL1 of the composition containing a predetermined amount of the test compound. Half of the composition is applied to the upper surface of the leaf and half to the underside of the leaf.
vilbiss) sprayer at 10 psi and approximately 18 inches from the leaves. Once the leaves are dry, cut them from the stem and place them separately in a Petri dish. Ten unmolted third instar Mexican lady beetle larvae are placed on each kidney bean leaf. Controls were two leaves sprayed with 5 ml of a 500 ppm composition of S-(1,2-dicarbethoxyethyl)o-o-dimethylphosfluorodithioate (reference standard) and two leaves sprayed with a composition without active ingredient. It consists of one leaf and two leaves that served as an untreated control. Calculate the mortality rate after 48 hours and record the number of leaves eaten.

Dyed larvae are counted as dead. The following toxicity grading scale is used: The test compounds, their usage ratios, and evaluation results are shown in the table below.

When a given usage rate is evaluated more than once, the evaluation result described for that usage rate is the average of several evaluation results. Armyworm (PrOden)
iaeridania) (Lepidoptera): 10 uniform armyworm larvae of about 1-1.5 C1 L length grown on Henderson lima bean are placed on a cut bean leaf in a Petri dish.

The bean leaves are obtained in a manner similar to the leaves of the test plant (beans whose pods are eaten) in the Mexican lady beetle test and sprayed with an insecticide. The control sample in this case is 100p
These are leaves sprayed with pm(7) DDT solution. Mortality was calculated 48 hours after spraying, and larvae that were dying were considered dead. Larvae that were no longer visible and were probably eaten were assumed to be alive. The same grading scale was used as in the Mexican ladybug★ test. The test compounds, their usage ratios, and evaluation results are shown in the table below.

If a given usage rate is evaluated more than once, the evaluation result described for that usage rate is the average of several evaluation results. Melon Aphid (Aphi)
Medicinal effect against Blue sgOssypii (Hemiptera): Each container contains 4 pieces of Blue ossypii (Blu
Plant the (ehubbardsquash) seeds and water from the bottom of the container.

Cut out the two weakest plants after 6 days and remove one cotyledon and first leaf from each of the two remaining plants.

By training the remaining cotyledons on the cotyledons of the chestnut squash that have been infested with aphids and transferring the melon aphids from the colony, 100 melon aphids from the rearing colony are allowed to grow on the remaining cotyledons. After transferring, remove the leaves where colonies were present. After 48 hours, compositions containing insecticides in various proportions were applied to the infested leaves by Devilbis.
Moisten the plants by spraying them with an ILBISS sprayer at 10 Psi from 12 to 15 inches from the plants.

2 plants that attract insects and do not spray,
and S-(1,2-dicarboethoxyethyl)o-o
- Two plants sprayed with a composition containing 100 ppm of dimethyl fluorodithioate and infested with insects serve as control samples. Mortality rate was evaluated 24 hours after spraying by observing using a dissecting microscope at 10x magnification. The same grading scale was used as before. The test compounds, their usage ratios, and evaluation results are shown in the following table.

If a given usage rate is evaluated more than once,
The evaluation results listed for the usage rate are the average of several results. Tetravch spider mite (Tetravch)
Medicinal efficacy against Acarinae:
1. The spider mites are reared on mung bean plants and then transferred to chestnut squash plants. Store the chestnut squash plants for two days to ensure they are well-infested with insects. Next, the test compound was added to the insect-infested Curica bochia plant*? A test composition having the following properties is sprayed according to the test method described above. Mortality is determined 48 hours after spraying. The same grading scale was used as in other test methods. The test compounds, their usage ratios, and evaluation results are shown in the following table.

Milkweed ladybug (0nc0pe1itisfas)
ciatus) (Hemiptera): 10 adult milkweed ladybugs are chilled and placed in a test cage.

5 ml of the test composition containing a pre-measured amount of insecticide was applied to the insect cage using a DeVilbis sprayer at 10 psi.
spray from the top of the basket. After drying the basket,
Provide food and water to the insects for 48 hours. A composition containing 500 ppm of 2-(1,2-dicarbethoxy*ethyl)o-0-dimethylphosfluorodithioate was used as a reference sample, and a cage that was not sprayed was used as a control sample.

Mortality was calculated 48 hours after spraying. The dying adults were considered dead. The same grading scale was used as before. The tested compounds, their usage ratios, and evaluation results are shown in the following table. Medicinal efficacy against Muscad Omestica (Diptera) (Diptera): A breeding cage containing adult house flies 4 days after emergence is cooled to 2-4° C. for about 1 hour.

One hundred houseflies are transferred from the rearing cage to each test cage using a small scoop shovel.

House flies in cages are kept at 21-27°C for 1-2 hours.
The cages are sprayed with 5 Wt of the test composition in the same manner as described for the milkweed ladybug test. Two unsprayed cages j1 were used as controls, and two cages sprayed with 50 ppm of the DDT composition were used as control samples.

Mortality calculations were performed 24 hours after spraying. All house flies that did not fly and did not crawl up from the bottom of the cage were considered to be on the verge of death. A grading scale similar to that described above was used. The test compounds, their usage ratios, and evaluation results are shown in the following table. If the evaluation was performed more than once, the evaluation results listed for the usage percentage are the average of several results.

Mexican boll weevil (AnthOnOmusgra)
Medicinal efficacy against (Coleoptera) (Coleoptera). The procedure is the same as that used for the Mexican ladybug and armyworm, except that 10 adult Mexican boll weevils are placed on two cotton leaves that have been previously soaked in the composition of the test compound.

The same * (grading scale was used. The test compounds, their usage proportions and the results obtained are shown in the following table.

If the evaluation was performed more than once, the evaluation results listed for the usage percentage are the average of several results.

Essentially the same results as listed in the above table are obtained when the following compounds are evaluated in the same manner.

N1-(2,2-difluoro-3-bromopropionyl)-N2-(2-chloro-4-Tertbutylbenzoyl)-3'-nitro-5'-trifluoromethyl-0-
Phenylenediamine. Nl -difluorochloroacetyl-N2-(phenoxycarbonyl)-3'-nitro-
5'-difluoromethyl-0-phenylenediamine〇N
1-Trifluoroacetyl-N2-naphthol-y-nitro-5'-trifluoromethyl-10-phenylenediamine.

N1-trifluoroacetyl-N2-(P-n-butoxybenzoyl)-4'-trifluoromethyl-6'-nitro-0-phenylenediamine.

N1-trifluoroacetyl-N2-(P-nitrobenzoyl)-l-trifluoromethyl-6'nitro-0
-Phenylenediamine. N1-Heptafluorobutyryl-3'-nitro5'-trifluoromethyl-10-phenylenediamine N1-Pentafluoropropionyl-13
'-Nitro-5'-trifluoromethyl-10-phenylenediamine.

N1-trifluoroacetyl-N2-methoxycarbonyl-l-trifluoromethyl-6'-nitro-0-phenylenediamine.

N1-pentadecafluorooctanoyl-3'nitro-
5'-trifluoromethyl-10-phenylenediamine.

Furthermore, the compound of the present invention [ ] is a parasite-killing agent useful for the systemic control of insects and mites that damage living tissues of animals.

These compounds have the ability to penetrate the living tissues of the host animal to which they are administered. Insect and mite parasites that deplete the blood or other living tissues of host animals ingest these compounds penetrated into the tissues and are thereby killed. Presumably, the compounds are dispersed into the host animal by blood, but the fact that non-blood-sucking parasites such as fly larvae are killed by these compounds means that these compounds are dispersed in the blood as well as other Indicates that it penetrates the tissue. Some parasites, such as most mites, spend most of their life feeding on the living tissues of their host animals.

Other parasites, such as the American fly larva, live only in the larval stage by feeding on the host. A third group of parasites, such as blood-sucking flies, survive by feeding on animal hosts only during the adult stage. When the compound of the present invention [] is administered to a host animal,
It is possible to kill living parasites at any stage of their life by feeding on the living tissues of animals. All species of insect and mite parasites that live by feeding on the living tissues of animals are killed by the target compound.

Parasites that live by making holes and feeding on animal tissues, parasites that suck the blood of host animals, and parasites that invade through natural openings, attach to mucous membranes, and become parasitic there, such as the larvae of the horse fly. All are equally effectively killed. This will be clarified by mentioning some of the parasites specific to the various host animals that are controlled using these target compounds. The period of parasitism and the method of infecting the host animal are indicated for each parasite. Horse parasitic pigeon: adult (blood-sucking).

Stable fly: Adult (blood sucking). Blackfly: Adult (blood-sucking). Horse blood-sucking lice: immature, adult (blood-sucking). Nymph,
Adult worms (live by making holes in the skin). Bacteria: Adults (feeding on the skin). Common horse fly: Larva (migrate through the gastrointestinal tract).
Chinfly: Larva (migrates through the gastrointestinal tract) 3 Horse fly that invades the nasal cavity: Larva (migrates through the gastrointestinal tract). Cattle parasite hornworm: adult (blood-sucking).

Bovine lice: Adult (feeds on the skin). Bovine blood-sucking lice: nymphs, adults (blood-sucking). Tsetse fly: Adult (blood sucking). Stable fly: Adult (blood sucking). Horse fly: Adult (blood sucking). Cattle mites: Adults (live by making holes in the skin) Cattle mites: Larvae, nymphs (blood suckers). Ear mite: Nymph (blood sucking). Gulf Coast tick: Adult (blood-sucking). Rotsuki Ilsan spotted fever mite:
Adult (blood-sucking). American tick: adult (blood-sucking). Peel fly larva (migrate throughout the body). Bombfly: Larva (migrate throughout the body).
Greenfly: Larva (stags on wounds). Red-backed assassin bug (
Pig lice: nymphs, adults (blood-sucking).

Sand flea: Adult (blood sucking). Parasites in sheep and goats Blood-sucking body lice; adult (blood-sucking).

Vampire foot lice: Adult (blood sucking). Sheep tick: Adult (blood-sucking). Sheep mites: Nymphs, adults (skin-feeding).
Nasal fly: Larva (migrating through the sinuses). King fly: Larva (
(It hurts.) American fly: larva (feeds on wounds). Second stage of the American fly: Larva (staying on the wound). Bed bug parasites of poultry: nymphs, adults (blood sucking).

Nampou chick flea: Adult (blood-sucking). Chicken mite: Nymph (blood sucking). Baby chicken mites: nymphs, adults (blood-sucking). Skellyrethugmite: Adult (lives by making holes in the skin). Hairless mites: Adults (live by making holes in the skin). Dog fly parasite: adult (blood-sucking).

Stable fly: Adult (blood sucking). Mites: nymphs, adults (
live by making holes in the skin). Dog mite: Adult (
They live by making holes in the hair follicles). Fleas: Adult (blood-sucking).
It will be appreciated that the parasites described above are not confined to a single host animal, each of which has been identified in the past. Although each parasite has a favorite host, most parasites live in different types of hosts. For example, mites can be found on at least horses, dogs, mules, humans, dogs, cats, foxes, and rabbits.
Attacks sheep and cattle. The horse fly flies freely,
Attacks mules, cows, pigs, dogs and most other animals. The compounds of the present invention [ ] can be used to kill the above-mentioned host animals as well as the above-mentioned types of parasites inhabiting other host animals. For example, these compounds are found in cats,
Effective in goats, camels and zoo animals. Host animals in which these compounds are preferably used are ticks, fleas,
Dogs, cattle, to control flies or American flies
Be a sheep or a horse.

The timing, manner, and rate at which these compounds are effectively administered vary widely. A detailed description of the methods in which these compounds are used is provided below. These compounds are administered to animals at a dosage rate of about 1-100 W9/Kg. The best dose rate to kill a given parasite in an animal must be determined on an individual basis, but in most cases the optimum dose rate will be within the preferred range of about 2.5-50 η/Kg. It will be discovered. The optimal dosage rate in a given case will depend on factors such as the susceptibility of the parasite, the sacrifices that the animal is capable of taking and the degree of control desired, which are primarily concerned with the health of the animal being treated. Lower rates are safer for the host animal, less costly,
Although often easy to administer, they tend to provide incomplete or minimal parasite control, resulting in reinfestation. On the other hand, high rate administration provides more complete parasite control but is more costly and imposes stress on the treated animals. The compound of the present invention [ ] is effective when administered to animals of any age at any time of the year.

It is also possible to administer these compounds to the animals continuously, such as constantly feeding them with a feed containing one of the target compounds, thus ensuring that all parasites that come into contact with the treated animals are killed. Such administration is by no means economical, and it will usually be found that these compounds are best administered at a time when parasite control is best rewarded for the compounds consumed. . Certain parasites, such as peel fly and bomb fly larvae (maggot fly larvae that parasitize cattle), are known to have active seasons attacking animals. If such parasites are of primary importance, the active compounds of the invention can be used only during that season to ensure parasite control all year round. Other parasitic insects, such as ticks, attach to and bite animals essentially all year round. Control of such parasites can also be achieved over a relatively short period of time, by administering the compounds of the invention to all animals in a farm or area for a short period of time, for example 2 to 3 weeks. It is expected that all 5 generations of parasites will be killed in this way and that the animals will remain parasite-free for a considerable period of time, e.g. until reinfested by parasites that arrived with imported animals. be done. The compounds of the present invention may be administered by any oral or transdermal route.

It should be noted that many of these compounds undergo chemical changes as they pass through the rumen of ruminants.
When administered orally to ruminants, it is preferred to protect these compounds from the ruminal environment by special compositions. Such a composition will be described later. Methods of formulating compositions containing biologically effective compounds and administering them to animals are very old and well-developed techniques.

Some descriptions of different compositions and administration methods are presented to enable the implementation of all parasite control using these compounds. Transdermal administration of the compounds of the present invention [ ] is carried out by methods common in the art of treating veterinary diseases.

It is preferable to use a water-soluble salt of the target compound [ ], so that there is no need to painstakingly prepare the composition. On the other hand, if a water-insoluble compound is desired, it is practical to dissolve the compound in a physiologically acceptable solvent such as polyethylene glycol. Similarly, it is practically suitable to prepare an injectable suspension of the desired compound by suspending the desired compound as a fine powder in a composition of a physiologically acceptable non-solvent, a surfactant, and a suspending agent. . The non-solvent is for example a vegetable oil such as peanut oil, corn oil or sesame oil, a glycol such as polyethylene glycol or water;
It is selected depending on the target compound to be administered.

Appropriate physiologically acceptable excipients are required to suspend the compound.

The adjuvants are selected from emulsifiers such as dodecylbenzene sulfate and toluene sulfonate salts, ethylene oxide adducts of alkylphenols and oleates and laurate esters and dispersants such as naphthalene sulfonate salts, lignin sulfonates and fatty alcohol sulfates. Bulking agents such as carboxymethylcellulose, polyvinylpyrrolidone, gelatin, and alginates are also used as adjuncts to injectable suspensions. Many classes of surfactants serve to suspend compounds in the same manner as described above. For example, lecithin and polyoxyethylene sorbitan esters are useful surfactants. Transdermal administration is also readily accomplished by subcutaneous, intramuscular, and intravenous injection of injectable compositions.

Conventional needle-type injection devices as well as needleless air injection devices are also useful. It is possible to delay or sustain the penetration of the compound of the present invention into the living tissue of an animal by using an appropriate composition.

For example, highly insoluble compounds are used. In that case, the small solubility of the compound is responsible for the prolonged action, since the body fluids of the animal can always dissolve only a small amount of the compound. A sustained action of the compound of the present invention can also be obtained by incorporating the compound into a matrix that physically inhibits dissolution.

The formulated matrix is injected into the body, where it remains as a reservoir from which the compounds gradually dissolve. Matrix compositions now well known in the art are formulated in waxy semisolids such as vegetable waxes and high molecular weight polyethylene glycols. An even more effective sustained action is obtained by introducing pellets containing the compound into the animal. Such pellets are now well known in veterinary disease treatment technology and are usually made from silicone-containing rubber. The compound is dispersed in solid rubber pellets or contained within hollow pellets. Care must be taken to choose a compound that will dissolve in the rubber from which the pellets are made, since the compound will first dissolve and disperse in the rubber and then leach from the rubber into the body fluids of the treated animal. The rate at which the compound is released from the pellet, and therefore the length of time that the pellet remains active, is very precisely controlled by the concentration of the compound in the pellet, the surface area of the pellet, and the polymer composition from which the pellet is made. managed by

Administration of the compound by pellet is a particularly preferred embodiment. Such administration is very economical and effective since a properly designed pellet maintains a constant concentration of the compound in the tissues of the host animal. Pellets can be designed to provide compound for several months and are easily inserted into animals. There is no need to further handle the animal or worry about dosage after inserting the pellet. Oral administration of the compound of the present invention is carried out by mixing the compound with the animal's feed or drinking water, or by administering an oral dosage form such as a drink, tablet, or capsule.

When the compounds of the invention [ ] have to be administered orally to ruminants, it is necessary to protect them from the deleterious consequences of ruminal processes.

The veterinary disease treatment art now knows effective coating and encapsulation methods to protect these compounds from the rumen. For example, Grant et al. disclose coating materials and coating methods in US Pat. No. 3,697,640. Gran R describes a method for protecting compositions from the effects of the rumen by coating them with a film of cellulose propionate 3-morpholinobutyrate.

Such films can be used to protect compounds. In conventional manner, tablets or capsules containing the compound [] are coated with this film in a coating pan or fluid bed spray apparatus.

Pellets of the antiparasitic agent can be coated with a film and filled into capsules. Alternatively, a solid mixture of the compound and film-forming agent is prepared and ground or ground into small particles, each consisting of the compound contained in a matrix of film-forming agent. The particles may be filled into capsules or made into oral suspensions for oral administration. Additive compositions to animal feed for the treatment of livestock diseases are a very well known technology.

It is usually first formulated as a premix in which the target compound is dispersed in a liquid or particulate solid carrier. This premix should contain about 1 to 400 V per pound depending on the desired concentration in the feed. As is known in the art, many compounds are hydrolyzed or otherwise degraded by animal feed ingredients. Such compounds are routinely formulated into a protective matrix, such as gelatin, before being added to the bremix. This premix is subsequently formulated into a feed by dispersing it into the feed mixture in a conventional mixer. The exact amount of compound and therefore the amount of premix to be mixed into the feed is easily calculated taking into account the weight of the animal, the approximate daily feed intake of each animal and the concentration of the compound in the premix. Similarly, the amount of compound to be administered in the animal's drinking water is calculated taking into account the weight of the animal and the amount each animal drinks per day.

Water-soluble salts of the compound [ ] are best used for drinking water therapy. If such salts are not preferred, a suspendable composition of the desired compound must be prepared. The composition is a suspension in concentrated form, which is mixed into drinking water, or a dry formulation that is mixed and suspended in drinking water. In any case, the compounds are in finely divided form and the compositions follow the same principles as the injectable suspensions described above. These compounds can be readily formulated into tablets and capsules by conventional methods, which need not be discussed here.

The drug composition is dissolved or dispersed in an aqueous liquid mixture. It is also best to prepare a drink by dissolving a water-soluble salt of the compound [ ]. However, dispersions of the compounds prepared in the same manner as in the preparation of the drinking water compositions may also be used and are equally effective. The following examples demonstrate the effectiveness of the compounds in the control of many parasites that commonly affect commercial animals.

This compound was tested against American fly larvae, stable flies, mosquitoes, and American dog ticks. The American fly and the stable fly are insects, and the dog tick is a typical mite. Stable flies are common, free-flying blood-sucking parasites, and the American tick is a typical blood-sucking parasite that spends the nymph and adult portions of its life cycle attached to a host animal, usually a cow.

American fly larvae are attracted from eggs laid by free-flying insects near wounds in host animals. The larvae burrow into healthy flesh through exposed wounds,
They spend part of their life cycle inside, feeding on the host's flesh and blood. Stable flies infect horses, mules, cattle, pigs, dogs, cats, sheep, goats, rabbits, and humans.

American ticks are originally parasites of cattle, but
Also attacks mules and sheep. American fly larvae attack any injured animal, but are particularly harmful to cattle, pigs, horses, mules, sheep, and goats. The following test demonstrates the efficacy of compound [] when administered to cattle.

Most of the test examples in this test were conducted by inducing parasitism. 15η/K of N1-(2,2,3,3-tetrafluoropropionyl)-3'-nitro-5'-trifluoromethyl-10-phenylenediamine
Calves are treated with one subcutaneous injection of g. The compound is administered as a 10% polyvinylpyrrolidone suspension. Place the adult stable fly in a cage completely surrounded by wire mesh. Two or more cages, each containing 60-100 stable flies, are held in contact with the shaved back of a calf 24 hours after compound administration. The flies are kept for a predetermined period of time by feeding on the calves, and then the cages are observed, and the flies are kept for a certain period of time. Determine fly mortality by counting the number of live and dead flies after exposure to the calf's back. Each set is done separately.
The results of the mortality rate were as follows.

When the above method was repeated using mosquitoes instead of stable flies, the results were as follows.

The above method was carried out in 10% polyvinylpyrrolidone at 25η/1.
When repeated using <g, the results were as follows.

N1 -(2,2,3,3-tetrafluoropropionyl)-3'-nitro-5'-trifluoromethyl-10-
Phenylene diamine was tested against stable flies in calves at 10W9/Kg in rubber oil.

The method was modified from that described above, and a wire mesh cage was placed on the back of the calf 24 hours after compound administration. The results are shown in the table below. The above test shows the long-term control of insects and mites obtained using the compound [].

Administration of these compounds has been shown to kill parasites that feed on the treated animals, even at very low rates, even days after compound administration. It is also noteworthy that the control obtained is so complete that all or essentially all of the living parasites feeding on the animal are killed. The following steps record representative results of the bioassay test.

American fly larvae were used as test organisms in the bioassay test system.

The test was conducted by administering the compound of the present invention to a calf by subcutaneous injection once. Blood samples were taken from the calves daily after compound administration, and American fly larvae were reared on each blood sample. The last day of sustained efficacy to kill 90% or more of American fly larvae was recorded as the end point of the study. The results are shown in the table below. Furthermore, using the compound [],
The in vitro tests conducted to evaluate the control of adult stable fly parasites are described below.

Adult stable flies that have been fasted for 18 hours are reared in a Petri dish containing a blood sample pad or in a fly cage.

The blood in the vat is collected from the medicated calf at predetermined time intervals and used. After exposure to the blood feed pad, the mortality rate of stable flies is determined at predetermined ρ time intervals. The percent mortality at these times ★ is compared to normal mortality (control) obtained in Petri dishes or fly cages containing blood from unmedicated calves. The compound used in this test is N1-(2.2.3.3-tetrafluoropropionyl)-y-nitro-5'-trifluoromethyl-10-phenylenediamine. The results are shown in the table below. In the above test, instead of directly parasitizing the animal's body with parasites, blood was collected from the animal to which the drug had been administered, and the blood was indirectly parasitized with the parasite.

However, the control obtained is clearly as significant as if the parasite had sucked blood directly from the animal's body. Parasite control for several days was obtained with a single administration of compound [ ], so
This study clearly demonstrates the value of protecting animals from the highly harmful parasite, the American fly. weeding,
In addition to insecticidal and parasitic activity, the compounds according to the invention [ ] exhibit anthelmintic and nematocidal activity.

Regarding anthelmintic activity, internal parasites that parasitize warm-blooded animals,
Especially the whirling strongyle (Haem Onchsc OntOrtus).
), Syphacia Obvelata, Nematospiroides
The activity of the compound [] can be observed by administering it to control intestinal parasites such as P. ides dubius.

The preferred method of administration is oral administration, either in the feed or by administering only the compound to be used separately, or by combining it into a tablet or large pill. Typically, a single dose will contain 5-500 η/
Good results are obtained with doses of Kg and 0.001-0.05% in the feed. In a typical method, the mice's diet is supplemented with N1-trifluoroacetyl-3'-nitro-5/1-trifluoromethyl-10-phenylenediamine at a concentration of 0.01%. This modified diet is fed to a group of four mice, and the unmodified diet is fed to another group of four mice as a control. Approximately 7 days after starting feeding
time to infect Nematopyloides juubius. The breeding continues for 8 days, and on the 9th day all mice are necropsied and the upper gastrointestinal tract is examined for the presence of Nematospiroides jujubius and, if present, their number.

No larvae were found in the modified diet group of mice and an average of 28 larvae per mouse in the control group. Similar results can be obtained with compounds other than the above. Compound of the present invention []
is Rootnot Nematode (ROOt-KnOt-
NematOde), Stem Nematode (Stemn)
ematoOde), Fusarium rootrot (F
It can be used in the control of diseases caused by fungi and nematodes, such as Rhizoctonia (UsariumrOOt-ROt) and RhizOctOnia.

Generally control is achieved at a rate of 1 to 40 pounds per acre. In standardized test methods, the following compounds were found to exhibit complete or essentially complete control of root knot nematodes at the specified usage rates. N1-trifluoroacetyl-N2-naphthol-l-trifluoromethyl-6'-nitro, -0 phenylenediamine (
20 pounds per acre) N1 -trifluoroacetyl-N2-(3.4 dichlorobenzoyl)-4'-trifluoromethyl-6'-nitro-0-phenylenediamine (20 pounds per acre).

Next, specific embodiments of the method for producing the object compound of the present invention will be described with reference to Examples.

Example 1 Finely ground 3-trimethyl-5-nitro-0-
Phenylene diamine 2.27, triethylamine 1.0
ml and 10 ml of chloroform were mixed, and while stirring, trifluoroacetic anhydride (2-
3TfL1).

The addition is done dropwise over 20 minutes at room temperature. The resulting reaction mixture is filtered to separate the desired product, N1-trifluoroacetyl-3'-trifluoromethyl-5'-nitro-0-phenylenediamine, and recrystallized from benzene. Melting point 201-202℃ o Elemental analysis, C, H, F6N3O3
Calculated value (%): C1-34.08; Hll. 5
8; Nll3.24, actual value (%): Cl34.24;
Hll. 6O;Nll3.24.

Example 2 5.0y of 3-nitro-5-trifluoromethyl-0-phenylenediamine is mixed with 15d of pyridine and the mixture is cooled to O<0>C.

Chlorodifluoroacetyl chloride 3TrLe is then added with stirring over a period of 20 minutes. After standing at 20°C for about 1.5 hours, the reaction mixture was mixed with ice 150V and hydrochloric acid 20T1L.
Upon mixing with 2, the desired product N1-chlorodifluoroacetyl-3'-nitro-5'-trifluoromethyl-10-phenylenediamine is precipitated.

Separate this and recrystallize from benzene. Melting point 186-1
88°C Example 3N2-benzoyl-6-nitro-4
-trifluoromethyl-0-phenylenediamine 3.2
Mix r with excess trifluoroacetic anhydride and leave overnight.

Excess trifluoroacetic anhydride and the corresponding by-product acid were evaporated under reduced pressure to separate the target product N1-trifluoroacetyl-N2-benzoyl-6'-nitro-l-trifluoromethyl-0-phenylenediamine. , recrystallized from benzene. Melting point: 193-195°C. Example 4 Using similar starting materials and following the method of the above examples, further target compounds other than those mentioned above can be prepared.

The obtained compounds are illustrated below. N1-trifluoroacetyl-3'-nitro-5'-trifluoromethyl-o-phenylene produced by reacting trifluoroacetic anhydride with 3-nitro-5-trifluoromethyl-0-phenylenediamine Diamine. Melting point 194-19
5℃. N1-trifluoroacetyl-N2-naphthol-6'-nitro- prepared by reacting trifluoroacetic anhydride with N2-naphthol-6nitro-4-trifluoromethyl-0-phenylenediamine
4'-trifluoromethyl-10-phenylenediamine.

Melting point: 200-204° C.O Example 5 Other target compounds produced by the methods described in the previous Examples include, for example, the following.

N1-Trifluoroacetyl-N2-(p-n-butoxybenzoyl)-1-trifluoromethyl-6'-nitro-0-phenylenediamine.

Melting point: 172-174°C. N1-trifluoroacetyl-
N2-(p-nitrobenzoyl)-l-trifluoromethyl-6'nitro-0-phenylenediamine.

Melting point: 210-212°C. N1-heptafluorobutyryl-3'-nitro5'-trifluoromethyl-10-phenylenediamine.

Melting point 118-120'CONl-pentafluoropropionyl-3'-nitro-5'-trifluoromethyl-10
-Phenylenediamine.

Melting point 161-163℃0N1-trifluoroacetyl-
N2-Methoxycarbonyl-4'-trifluoromethyl-6'-nitro-10-phenylenediamine.

Melting point 129-130℃0N1-pentadecafluorooctanoyl-3'nitro-5'-trifluoromethyl-10
-Phenylenediamine. Melting point 111-113°C. N1
-(2,2,3,3-tetrafluoropropionyl)-
N2-Methoxycarbonyl-6'-nitro-4'-trifluoromethyl-10-phenylenediamine.

Melting point: 129-130°C. N1-(2,2,3,3-tetrafluoropropionyl produced by reacting 2,2,3,3-tetrafluoropropionyl bromide with 3-nitro-5-trifluoromethyl-o-phenylenediamine) )-3'-nitro-5'-trifluoromethyl-10-phenylenediamine.

N produced by reacting pentafluoropropionyl bromide with 3-nitro-5-trifluoromethyl-0-phenylenediamine, melting point 144-145°C
1-pentafluoropropionyl-3'-nitro-5'
Monotrifluoromethyl-10-phenylenediamine.

Melting point 161-163℃0N2-(3,6-dichloro-2
N1-trifluoroacetyl-N2-(3,6-dichloro-2-methoxy benzoyl)-6'-nitro-l-trifluoromethyl-0-phenylenediamine.

Claims (1)

[Claims] 1 A compound represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and an acylating agent or its active derivative represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , Formula: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Process for producing N-(2,2-difluoroalkanoyl)-o-phenylenediamine derivative, characterized by obtaining a compound represented by [II] [wherein R ^0 is a 2,2-difluoroalkanoyl group (where Y is chlorine, fluorine, difluoromethyl, or perfluoroalkyl having 1 to 6 carbon atoms) represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ represent. R^1 is hydrogen, formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼
(where Y^1 is alkyl having 1 to 4 carbon atoms), benzoyl, naphthol, or substituted benzoyl represented by the formula: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (where Z' is Each independently represents chlorine or nitro, Z″ is alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, p is 0, 1 or 2
, q are 0 or 1, and the sum of p and q is 1-3. ). However, NO_2 and CF_ in formula [II]
3 are in meta positions to each other, and when R^1 is hydrogen, NO is in the ortho position to the -NH-R^1 group on the ring.
Either _2 or CF_3 is present. ].