DE2213058A1 - Aromatic amine compounds, their preparation and their use - Google Patents

Description

PATENT AGENCY OFFICE

HOMSEN

TEL. (0811) 530211 «30212

TiEDTKE - BüHLING TELEX: 5-24303 topat PATENT LAWYERS

Munich:

Dipf.-Chem. Dr. D. Thomien Dipl.-Ing. H. Tledtke Dipl.-Chem. G. BQhling DipiVtng. R. Kinne Dipl.-Chem. Dr. U. Eggers

Frankfurt / M .:

Dipl.-Ing. W. Welnkauff (Fuchthohl 71)

8 0 0 0 SMALL

Kaiier-Ludwlg-Platz 6 March 17th, 1972

Imperial Chemical Industries Limited London »Great Britain

Aromatic amine compounds, their preparation and their

use

The invention relates to diphenylamine derivatives, on pesticide preparations »which contain these derivatives, and on methods for controlling pests using these derivatives or these preparations.

In British patent specification 868 165 there is one Class of diphenylamine derivatives of the general formula:

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Verbal agreements, especially by telephone, require written confirmation Po »ttcheck (Munich) Account 1198 74 Dresdner Bank (Munich) Account 5 Me 709

2213Q58

described »in which Hal is a fluorine, chlorine or bromine atom; Alk is an alkyl radical with up to 4 carbon atoms; R is hydrogen or an alkyl radical with up to 4 carbon atoms; m and ρ are integers from 1 to 3; η is zero or an integer up to 6; and q is zero or an integer up to 3; where m, η, ρ and q together are an integer not over Io; and all substituents >> except R, are core substituents.

It is stated that these compounds have an insecticidal effect, in particular a mite-ovicidal effect. All examples listed have a 2-nitro subatituent «

It has now been found that within the compound class defined above, a group of compounds exist which have very superior pesticidal effectiveness, including a broad spectrum of insecticidal and fungicidal properties.

According to the invention, compounds of the formula:

ζ -

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_ ₃ _ 22 * 43058

created, in which Z is a halogen-substituted naphthyl radical or the radical of the formula:

means, where X, X, X and X, which are the same or different can be, are halogen atoms; and Y is halogen, trifluoromethyl, nitro, or alkyl.

According to a preferred embodiment of the invention are compounds of the formula:

1 2 ⁷ I Ί created, in which X, X, X - and X, which can be the same or different, are halogen atoms; and Y is halogen, trifluoromethyl, nitro, or alkyl.

According to an even more preferred embodiment of the invention are compounds of the formula:

-Ö: O

' V

F V

20984 O / 12 07

created, in which Y fluorine, trifluoromethyl, nitro or Is methyl.

The invention includes compounds of the formula I in which Z is a halogen-substituted thiaphthyl group, or is a group of the formula II in which the latter X, X, X and X, which can be the same or different, are halogen atoms; and Y is halogen, trifluoromethyl, nitro, or alkyl. The compounds and the preparations containing these compounds are pesticidal.

- (/ 7—

no «

Specific examples of the invention are those whose structural formulas are summarized in Table I below with the melting points in degrees Celsius for each compound, are given:

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I ,

121301

Νϊ »

F.

Cf

W /

al

F F CF,

- V- 2-m j

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Table I.

Connection mr,

Structural formula

Melting point

V- r

ψ ex

F., F

en,

> x \

F F

FF Ci

F. F. F.
Λ Tl F. - Lj 1-naphthy! Isomeres) ι
F. ι
F. (or

2098A0 / 1207

The compounds of the invention can be prepared by adding iJ-nitro-2-trifluoroniethylaniline treated with a halogen-substituted naphthalene or with a compound which has the formula:

Shark

owns, in which Hai is a halogen atom and X, X, X, X and Y have the above meanings. The process is facilitated by the presence of a base, e.g. sodium hydride, and the process is carried out usually in the presence of a solvent or diluent, for example dimethylformamide or Tetrahydrofuran, by.

According to a preferred method, 4-nitro-2-trifluoromethylaniline is treated with the base and the Treatment product is treated further with a halogen-substituted one Naphthalene or with the compound of the formula:

Shark

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2213G58

Treat after another, optional operation
if one delts a compound of the formula:

or a halogen-substituted naphthylamine with 2-halogen-5-nitro-cx.Oi.o (-trifluorotoluene, the reaction being facilitated by the presence of a base.

The compounds themselves can be used to combat
Pests are used, but the compounds are more conveniently used in the form of preparations in which the active ingredient is mixed with a diluent or a carrier material.

According to a further embodiment, the invention therefore provides pesticidal preparations which are used as active
Component of a compound of the formula:

ψ -j «;

have, where in the formula Z is a halogen-substituted Naphthyl radical or the radical of the formula:

2 0 9 8 4 0/1 207

means in which the latter X ₁ X >> X ⁵ and X, which may be the same or different, are halogen atoms; and Y is halogen, trifluoromethyl, nitro, or alkyl

According to a preferred embodiment of the invention pesticidal preparations are created, which as an active ingredient a compound of the formula:

have, in which X, X, X ^ and. X, which one is the same or may be different, are halogen atoms; and Y is halogen, trifluoromethyl, nitro, or alkyl.

According to an even more preferred embodiment, the invention provides pesticidal preparations which

2G9840 / 12Ü '?

- Io -

before ala active ingredient a compound of the formula:

have, in which Y fluorine »trifluoromethyl, nitro or is methyl.

According to an even more preferred aspect of the invention, pesticidal preparations are provided, which have one of the compounds listed in Table I as the active ingredient.

The compounds according to the invention and the preparations which contain these compounds are very toxic to insect pests and other invertebrate pests, including for example the following:

Tetranychus telarius (red spider mites)

Plutella maculipennis (brilliant butterfly)

Aphis fabae (black aphid)

Pieris brassicae (cabbage white caterpillar)

Blattella germanica (cockroaches)

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Megoura viciae Phaedon cochleariae Tribolium confusum Musca domestica Aedes aegypti Agriolimax reticulatus Calandra granaria (greenfly)

(Mustard beetle)

(Flour beetle)

(Housefly)

(Mosquitoes)

(gray snail)

(Grain beetle).

The compounds according to the invention and the preparations which have or contain these compounds, have activity against a wide variety of plant leaf diseases and fungal and bacterial diseases post-harvest, including, for example, the following specific diseases:

Puccinia recondita Botrytis cinerea Phytophthora infestans Podosphaera leucotricha Uncinula neeator Piricularia oryzae Plasmopara viticola Venturia inaequalis Botrytis tulipae Nigrospora sphaerica Phomopsis citri Alternaria citri

2098

(Rust) on

(Chocolate stain) on f (later fire) on (powdery meltau) on (powdery meltau) on (fire) on

(downy meltau) on (scab)

(Fire)

(Splash)

(Scab)

(End rot)

40/1207

on on on on on

tomatoes

thick bananas

thick bananas

Apples

Wine

rice

Wine

Apples

Onions

Bananas

Citrus

Citrus

Phytophthora citrophthora Penicillium digitatum Gloeosporium musarum Fusarium caeruleum Botrodiplodia theobromae Ceratocystis paradoxa Phoma exigua Phytophthora parasitica Xanthomonas oryzae

Xanthomonas malvacearum Erwinia amylovora Erwinia carotovora

Pseudomonas phaseolicola Pseudomonas syringae Pseudomonas mors-prunorum

Corynebacterium michinganense (brown rot) (green mold) (black end) (Dry rot) (stem rot) (gangrene) (rot)

(gray mold) (bacterial leaf burn) (Schwärζarm) (fire blight) (bacterial soft rot) (ring burn) (drought)
(bacterial sponge) (bacterial sponge)

on citrus on citrus on bananas on potatoes on bananas on potatoes on pineapple on citrus

on rice

on cotton

on pear and apple

on vegetables on beans of pome fruit

of pome fruit

on potatoes

Streptomyees scabies (scab)

Agrobacterium tumefaciens (crown ball apple)

Fusarium culmorum (falling sickness) pea seedlings.

The compounds are also algicidal.

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In use, the compounds according to the invention or the preparations which contain these compounds can be used to control pests in a variety of ways. So the pests themselves, or the location of the pests or the habitat of the pests are treated to control the pests.

According to a further feature, the invention therefore provides a method for controlling pests which the pests, the location of the pests, or the habitat of the pests with a compound or a Preparation is treated according to the invention.

The invention also provides a method of treating plants with a compound of the invention or preparation to make the plants less susceptible to damage by pests, which may have already occurred (i.e. treatment to eradicate an infestation or infection) or their Is expected to occur (i.e. treatment to protect the plant from infestation or infection).

According to a still further feature, the invention therefore provides a method for treating plants, in order to make them less susceptible to damage by pests, whereby the plants or the seeds, the sprouts, the onions, the tubers, the sausages

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treated zirconia or other propagating parts of the plants with a compound or preparation according to the invention.

If desired, the medium in which the plants grow can be treated in a similar manner with a compound or preparation according to the invention.

According to a further feature, the invention therefore provides a method for treating a medium in which plants grow or are intended to grow, wherein a compound or preparation according to the invention is applied to the medium.

The compounds or preparations according to the invention can be used for agricultural or horticultural purposes and the compound or type of preparation which is used in any case depends on the particular purpose for which the compound or preparation is used should be used.

Preparations which contain the compounds according to the invention can be in the form of dust powders or granules in which the active ingredient is mixed with a solid diluent or carrier. Suitable solid diluents or carriers can be, for example, kaolinite (China clay), montmorillonite, attapulgite,

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TaIkUB ₅ pumice, silicon dioxide, calcium carbonate, gypsum, powdered magnesia, fuller's earth, Hewitt-earth and Diatom _e enerde
be. Preparations for preparing seeds, for example, can have an agent which the adhesion of the
Preparation on the seed supports, for example a mineral oil.

The preparation can also be in dispersible form
Powders or granules are present which, in addition to the active ingredient, contain a wetting agent in order to facilitate the dispersion of the powder or granules in liquids. Such powders or granules can include fillers, suspending agents, and the like.

The preparations can also be in the form of liquid preparations which are intended to be used as dips or sprays and which are generally aqueous
Dispersions or emulsions are those which contain the active ingredient in the presence of one or more wetting agents, dispersing agents, emulsifying agents or suspending agents.

Wetting agents, dispersants and emulsifiers
can be cationic, anionic or nonionic. to
suitable cationic agents include, for example
quaternary ammonium compounds, for example cetyltrimethylammonium bromide. Suitable anionic agents include, for example, soaps, salts of aliphatic monoesters of sulfuric acid, for example sodium lauryl sulfate, salts of sulfonated ones

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aromatic compounds, for example sodium dodecylbenzenesulfonate, Sodium, calcium or ammonium lignosulfonate, butylnaphthalene sulfonate, and a mixture of the Sodium salts of diisopropyl and triisopropyl naphthalenesulfonic acids.

Suitable nonionic agents include, for example, the condensation products of ethylene oxide Fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkylphenols such as octylphenol, nonylphenol and octyl-cresol. Other nonionic agents are the partial esters, which are derived from long chain fatty acids and hexitol anhydrides derive the condensation products of these partial esters with ethylene oxide, the lecithins and block copolymers of ethylene oxide and propylene oxide.

Suitable suspending agents are, for example, bentonite, pyrogenic silicon dioxide and hydrophilic colloids, for example polyvinylpyrrolidone and sodium carboxymethyl cellulose, and the vegetable gums such as gum acacia and gum tragacanth.

The aqueous solutions, dispersions or emulsions can be prepared by adding the active ingredient or dissolves the active ingredients in an organic solvent which contains one or more wetting, dispersing or emulsifiers may contain, and then the mixture thus obtained is added to water, which in similar

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One or more wetting, dispersing or emulsifying agents may contain. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, Diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichlorethylene.

The compounds according to the invention can be formulated into masses which are capsules or microcapsules j which contain any of the active ingredients and which according to any of the known encapsulation or microencapsulation techniques are prepared.

The preparations to be used as a spray can also be in the form of aerosols, in which the formulation in a container under pressure in the presence of a propellant such as, for example, fluorine trichloromethane or trichlorodifluoromethane is held »

By incorporating suitable additives, for example to improve distribution and adhesion and the resistance to rain on the treated surfaces, the different preparations can be used for the manifold Purposes for which they are intended, better adapted.

The compounds of the invention can be useful can be formulated by adding to fertilizers. One

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preferred mass of this type consists of fertilizer granules, in which a compound of the invention is incorporated, for example by adding such a compound to the fertilizer material is covered. The fertilizer can for example consist of nitrogen or phosphate-containing substances.

According to yet another feature of the invention, there is therefore provided a pesticidal preparation which is considered to be active Component of a compound according to the invention in a mixture having a fertilizer material.

The preparations which are to be used in the form of aqueous dispersions or emulsions are im generally supplied in the form of a concentrate, which has a high proportion of active ingredient or active Contains ingredients, this concentrate has to be diluted with water before use.

These concentrates are often necessary in order to be stable in storage and to allow them to be diluted with water to be capable of aqueous preparations which remain homogeneous for a sufficient time to enable them to to be applied by conventional spray equipment. The concentrates can expediently Io - 85 wt. of the active Ingredient or active ingredients, and generally 25-60 Gew.Jf of the active ingredients. For education

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aqueous formulations diluted, such preparations varying amounts of the active ingredient or ingredients may be included, depending on the purpose for which they are to be used, but one can use an aqueous preparation containing between ο, οοοΐ and l, O wt.% of the active ingredient or ingredients.

The pesticide preparations according to the invention can of course be used in addition to one according to the invention Compound, one or more other compounds with biological activity.

The invention is now illustrated by the following exemplary embodiments illustrated. It is not intended to go with these examples beyond the scope of the invention to say something.

Example I.

This example illustrates the preparation of ^: 2.3.5.6-Tetrafluoro-2'.4-bistrifluoromethyl-4'-nitrodiphenylamine (Compound No. 3, Table I) with the formula:

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- 2ο -

4, the above 2-amino-5-nitrobenzotrifluoride in solution in dry Trimethylformamid, is added with stirring added to a suspension of 1.56 g of sodium hydride in dimethylformamide at 0 ⁰ C. When the foaming has stopped, the mixture is allowed to warm to 15 to 18 ° C. and then stirred for 45 minutes. After the mixture has ^{cooled down again to 0} ° C., 4.58 g of octafluorotoluene in solution in dry dimethylformamide are carefully added. When the addition is complete, stir the mixture for 4 hours at ambient temperature and then pour it onto a mixture of ice, salt and water (about 600 ecm). Acidification of the mixture thus produced results in a reddish-yellow precipitate which is recrystallized twice from a mixture of methylene chloride and petroleum ether (boiling range 40 ° -60 ° C.). This results in 2.3 x 5 x ^{6-tetrafluoro-1} 2 ^{.4-bis-trifluoromethyl-l} -nitrodiphenylamin 4 having a melting point of 128.5 to 132.5 ⁰ C.

Example II

The procedure illustrated in Example I is used to prepare other compounds according to the invention under

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Turn the appropriate respondents listed below to prepare:

4.4 · -Dinitro-2.3.5.6-tetrafluoro-2 · -trifluoromethyldiphenylamine (Compound No. 1, Table I) from pentafluoronitrobenzene and 2-amino-5-nitrobenzotrifluoride.

4.4'-Dinitro-2.3.5 · 6-tetrachloro-2'-trifluoromethyldiphenylamine (Compound No. 2, Table I) from pentachloronitrobenol and 2-amino-5-nitrobenzotrifluoride.

4-Bromo-4'-nitro-2.3.5.6-tetrafluoro-2 * -trifluoromethyldiphenylamine (Compound No. 4, Table I) from pentafluorobromobenzene and 2-amino-5-nitrobenzotrifluoride.

3,5-Difluoro-4'-nitro-2.4.6-trichloro-2'-trifluorodiphenylamine (Compound No. 5, Table I) from 1.3.5-trichloro-2.4.6-trifluorobenzene and 2-amino-5-nitrobenzotrifluoride.

4-Methyl-4 · -nitro-2.3.5.6-tetrafluoro-2'-trifluoromethyldiphenylamine (compound no. 6, Table I) from 2.3.4.5.6-pentafluoro- ¹ 'toluene and 2-amino-5-nitrobenzotrifluoride.

4'-nitro-2.3.4.5.6-pentafluoro-2'-trifluoromethyldiphenylamine (Compound No. 7, Table I) from hexafluorobenzene and 2'Amino-5-nitrobenzotrifluoride.

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2 (2-heptafluoronaphthylamino) -5-nitrobenzotrifluoride, or the corresponding 1 (2-heptafluoronaphthylamino isomers, (Compound No. 8, Table I) from octafluoronaphthalene and 2-amino-5-nitrobenzotrifluoride.

Example III

The effectiveness of a number of compounds is shown against a number of insect pests as well tested other invertebrate pests. The compounds are used in the form of a liquid preparation, which contains 0.1 wt. 3t of the compound, with the exception the tests with Aedes aegypti and Meloidogyne incognita, where the preparations o, ol by weight of the compound contain. The preparations are made by putting each of the compounds in a mixed solvent dissolves, which consists of four parts by volume of acetone and one part by volume of diacetone alcohol. The solutions are then diluted with water containing o, ol% by weight of the wetting agent "Lissapol" NX (trade mark) until the liquid preparations contain the required concentration of the compound. '

The test procedure used for each pest is basically the same and passes in keeping a number of the pests on a medium which is usually a host plant or a Is the nutrient on which the pests feed,

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and that either the pests or the medium or both are treated with the preparations.

The mortality of the pests is then estimated in periods of time, which are usually from one to three Days after treatment.

The results of the tests are given in Table II below. In this table, the first column gives the Name of the pest species. Each of the following columns indicates the host plant or the medium on which the Pest is held, the number of days which one after the. Letting treatment pass before mortality the pest estimates, and the results obtained for each of the compounds listed in Table I above be achieved. The estimate is expressed in whole numbers, which are in the range 0-3.

0 means less than 30 % kill

1 means 3o - 49 % destruction

2 means 50 - 90 % destruction i

3 means over 90 % kill.

A dash (-) in Table II indicates that ke.in Test was performed. The symbol "A" in Table II indicates that an anti-nutritional effect was observed.

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- 24 Table II

Pest type Carrier- number
the 1 2 link
(Tabel 3 1" 5 6th 5 No.
I) 8th ■ ■ · - ν Days 3 O 3 3 3 1 7th 1 Tetranychus telarius
(Red spider mites
adult animals) Fire bean 3 3 O 3 O O O O O Tetranychus telarius
(Red spider mites
Eggs) Fire bean 3 O O 3 O O O 3 O Aphis fabae
(greenfly) thick bean 2 O O 3 O O O 3 O Megoura viceae
(black aphid) thick bean 2 3 3 3 3 3 O O O Aedes aegypti
(Mosquito larvae) water 1 O O 3 O O O O O Aedes aegypti
(Mosquito, fully awake
sene animals) plywood 1 1 1 3 2 O O 1 O Musca domestica
(Housefly,
Contact test *) Milk/
sugar 2 O O 3 O O O 1 - Musca domestica
(Housefly,
Aftermath test *) plywood 2 O
A. O
A. 3
A. 3 3 O - O Pieris brassicae
(Cabbage caterpillars) Cabbage 2 O 3
A. 3
A. 3
A. 3
A. O O O Plutella maculipennis
(Brilliant butterfly larvae) mustard 2 O ro 2
A. O
A. 1
A. O 3
A. O Phaedon cochleariae
(Mustard beetle) mustard 2 O 3 3 O O O O O Calandra granaria
(Grain beetle) grain 2 - 2 3 O O O O - Blatella germanica
(Cockroaches) - 1 - - 3 O O O O O Tribolium confusum
(Flour beetle) grain 2 - - - 3 2 - O Meloidogyne incognita
(Roundworms) water 1 O

* In the contact test, the flies are sprayed directly; in the aftermath test the Flieuse.rv. brought to a medium which previously dealt with »209840/1207

Example IV

The compounds according to the invention are tested against a number of plant leaf diseases caused by fungi. The technique used consists in spraying the foliage of the non-diseased plants with a solution of the test compound and also soaking the soil in which the plants grow with another solution of the same test compound. All solutions for spraying and for soaking contain 0.01 % of the test compound. The plants are then infected with the disease which it is desired to control and, after a period of days depending on the particular disease, the extent of the disease is assessed visually. The results are given in Table III below, with the extent of the disease being given in the form of a rating as follows:

Assessment of the extent of the disease as a percentage '

0 - 61 to loo

1 26 to 6o

2 6 to 25

3 ο to 5

In table III the disease is given in the first column and the time is given in the second column which has elapsed between infection of the plants and assessment of the extent of the disease, ίαοο / λ / ιοπί

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Table III

Disease and plant Time interval
(Days) Ill it s code letter
(Table IVa) Puccinia recondita
(Wheat) Io A. Phytophthora infestana
(Tomato) 3 B. Podosphaera leucotrichc
(Apple) Io C. Uncinula necator
(Wine) Io D. Plasmopara viticola
(Wine) 7th E. Piricularia oryzae
(Rice) 7th P. Botrytis cinerea
(Bean) 3 β

Table IHa

No. of
link
Table I. Disease Code Letter (Table III) A. B. C. D. E. P. G 1 1 3 3 0 3 2 3 2 0 3 - 3 OJ 2 2 3 2 - 3 3 3 - O 0 O 0 - 3 - O 5 1 O 2 1 3 - O 6th 0 O 1 1 1 - 1 7th 0 3 2 2 3 - O θ 0 0 2 1 O I. O

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The compounds are also active against apple scab, Venturia inaequalis.

example V

The culture of Fusarium culmorum is maintained on 2 x malt agar in test tubes at 2 ° C. Thirteen to seventeen days before testing the chemical, the culture is transferred to ground grain meal, consisting of 4oo g of 5% corn meal in John Innes seed compost, at a rate of 2 grain meal to 3 buckets of compost (buckets with 7.6 1 capacity). The seeds are prepared by placing 10 g of wheat seeds in 25% china clay preparation (where the chemical is a powder), or in 12.5% china clay (where the chemical is a liquid) at a rate of 1 ooo parts by weight per million rolls, (ζ.Β 4o mg of the 25 pound preparation on 10 g of seed). To test the chemical substance, one puts about. Loo g of the mixed soil in a fiber pot, one puts 20 seeds on the surface and another about loo g one puts on the seeds. This is repeated three times, making a total of four productions. The pots are kept in a greenhouse between 16 and 20 C. After ten days the number of germinated seeds is recorded and after seventeen days the roots are uncovered and

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the health number recorded. These records
one compares with untreated seeds and seeds that have been treated with mercury (Agrosan) and calculations are made in order to obtain an assessment of the disease control. The ratings applied
are the same as those of the previous example. Compound No. 3 (Table I) gives a rating of 2.

Example Vl

The activity of the compounds according to the invention against a number of bacterial and fungal diseases Post-harvest saprophytic diseases on plants is investigated by in vitro tests as follows: 5 mg

of the connection under test are given in Io cm

2
Dissolved or suspended acetone and 2 cm of this solution

or suspension is added to 18 cm nutrient agar (for bacterial diseases) and 16 cm 25% malt agar
(for the fungal diseases) added so that a final concentration of 50 parts per million of the under test

borrowed connection results. 2 cm of a streptomycin preparation with a content of 100 units per cm ² is used
added to the malt agar to prevent bacterial contamination of the fungal tests.

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The agar preparations are dried overnight in Petri dishes and inoculated with the the following morning bacterial or fungal diseases using of a multipoint vaccine. The antibacterial activity is after 5 days and the antifungal activity after Estimated 6 days.

The results of the tests are shown in the table below V (antibacterial activity) and listed in Table VI (antifugal activity). The results will be evaluated as in Example IV above. The names of the disease organisms are given in Table IV.

Table IV

Bacterial disease
is called organism code
Table V Pungaler sick
is called organism code
Table VI Agrobaoteri in
tuaifaciena Bl Higrospora
aphaerica Fl
I.
F2
F3
Th Corynebac teritun
oichiganenae
Erwinia
oarotoTora B2
B4
B5 Phytophthore *
Citrophthora
Alternaria.
Citri
Diplodia
natalan XanthoBonas
orysae

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- 3ο -

Table IV

Bacterial disease
ness§organism code
Table V Fungal sick
health organism code
Table VI Paendoaonas
• yringa B6 Phoaopsis
eitri F6
P7
f8
F9
PlO
NS
F12 Streptoaycac
scabies B7 Ceratocjstis
paradox·
ßloeosporiua
■ usarua
Penicilliu "
digitatuB FtMtdOMOtlM
■ ora-prunoruB ΒΘ Phoea exigua Pteudooonas
phaaeolieola B9 Botryti
tulipae
Botrodlplodia
theobroMM
FusariuK
caeruleuai Enrlnia
aaylovora BIO i
\ -. ... . . I. 1 ·

Table V

link
No,
Table I. Bl Disease code B2 B3 ΒΊ- B5 Bo (Tabel IV) 1 3 3 3 3 3 3 B7 B8 ι B9 BIO 2 1 2 0 1 ? 2 I ■
³ i ³ 3 0 2 0 2 0 2 3 | o ο; o
I. 0 y O
1 0 <O
I.
i

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- 31 Table VI

link . Disease code F2 * 3 3 (Tabel F6 IV) F8 F9 FlO FIl F12 No. 3 3 3 3 3 3 3 3 3 Table I. Fl 3 3 2 F5 O F7 3 O 3 3 1 1 3 2 2 3 O 3 2 2 2 2 2 2 3 3 3 3 2 2 2

Example VII

Compounds according to the invention are considered potential Algicide tested. A mixed algae culture is treated with an amount of an aqueous suspension of the test below compound in such a way that the culture contains 20 parts per million of the compound. It is found that compound No. 2 (Table I) contributes to algae growth this concentration is fully combated.

The following examples illustrate pesticidal preparations according to the invention.

Example VIII

This example illustrates a concentrate which consists of a miscible oil and which

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can be easily converted into a liquid preparation suitable for spraying purposes by dilution with water. That Concentrate has the following composition:

Weight * compound no. 1 of Table I 25, ο

"LUBROL" L (alkylphenol / xethylene oxide condensate; "Lubrol" is a trademark) 2.5

Calcium dodecylbenzenesulfonate 2.5

"AROMASOL" H (alkylbenzene solvent "Aromasol" is a trademark) 7o, o

Ιοο, ο

Example IX

This example also illustrates a concentrate in the form of a miscible oil. The composition of this concentrate is as follows:

Weight *

Compound no. 2 of Table I 25, ο "LUBROL" L 4.0

Calcium dodecylbenzenesulfonate 6, o

"AROMASOL" H 65, ο

Ιοο, ο

0 9 8 40/1 207

Example X

This example illustrates a wettable powder with the following composition: _Q -

Compound no. 3 of Table I 25, ο

Sodium silicate 5, ο

Calcium lignosulfonate 5, σ

China tone 65, ο

loo, ο

Example XI

This Example illustrates a dustable flow agent, which is a mixture consisting of 25 Gew.Ji of compound no. 1 of Table I and 75 wt.% Xylene.

Example XlI

This Example illustrates a dusting powder which may be applied directly to plants or other surfaces and consisting of 1 wt.% Of the compound

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No. 2 of Table X, and 99 wt.% Talcum.

Example XIII

25 parts by weight of compound no. Of Table I, 65 parts by weight of xylene and Io parts of des Alkyl-a ^ yl-polyether alcohols "Triton" X-loo (trademark) are mixed together. An emulsion concentrate is obtained, which can be mixed with water to form an emulsion suitable for use in agriculture suitable is.

Example XIV

5 parts by weight of compound no. 1 from table I thoroughly mix 95 parts by weight in a suitable mixer Talc mixed in. A dust powder is obtained in this way.

Example XV

Io parts by weight of compound no. 7 from Table I, Io parts of the ethylene oxide / octylphenol condensate "Lissapol" NX (trademark) and 80 parts by weight of diacetone alcohol thoroughly mixed together. You get such a con-

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concentrate, which when mixed with water forms an aqueous dispersion results, which is suitable for application as a spray in the control of insect pests.

Example XVI

This example illustrates a concentrated liquid preparation in the form of an emulsion. The below The components listed are mixed with one another in the specified proportions and the whole is stirred until the ingredients are dissolved.

Weight *

Compound No. 5 of Table I 2o

"Lubrol" L 17

Calcium dodecylbenzenesulfonate 3

Ethylene dichloride 15

"Aromasol" H 15

ioo

Example XVII

The components listed below are ground together in the specified proportions, resulting in a powdered mixture that is easily dispersible in liquids:

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Weight %

Compound No. 1 of Table I 50

"Dispersol" T (Trade Mark) 5

China tone iJ5

loo

Example XVIII

A mass in the form of grains, which are easily dispersible in a liquid (e.g. water), is prepared by grinding the first four of the ingredients listed below together in the presence of water and then mixing in the sodium acetate. The mixture is dried and passed through a tyty to loo mesh sieve (British Standard) to achieve the desired grain size:

Gew.i

Compound No. 2 of Table I 50

"Dispersol" T

Calcium lignosulfonate

Calcium Dodecylbenzenesulfonate Sodium Acetate

12th , 5 5 12th 2o loo

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Example XIX

A mass suitable for use as a seed dressing agent is prepared by adding all three of the following ingredients in the given Mixed proportions:

Weight *

Compound No. 1 of Table I 8o

Mineral oil 2

China tone 18

Io ο

Example XX

A mass suitable for use as a seed dressing is prepared by adding all of the three of the ingredients listed below mixed in the specified proportions:

Compound No. 2 of Table I 8o

Mineral oil 2

China tone 18

loo

Example XXI

Granules are prepared by dissolving the active ingredient in a solvent obtained solution sprayed on pumice granules, and the solvent evaporates:

Compound No. 2 of Table I 5

Pumice granules 95

Example XXII

An aqueous dispersion formulation is prepared by adding the ingredients listed below to the specified proportions mixed and ground:

Weight %

Compound No. 3 of Table I Ho

Calcium Lignosulfonate Io

Water 5o

In the following an explanation of the masses or substances is given to which here in the preceding Examples with indication of trademarks and trade names Is referred to -.

"LUBROL" L is a condensate of 1 mole of nonylphenol with .13 molar Proportions of ethylene oxide.

"AROMASOL" H is a mixed solvent of alkylbenzenes.

"DISPERSOL" T is a mixture of sodium sulphate and a condensate of formaldehyde with the sodium salt of naphthalenesulfonic acid,

"LISSÄPOL" NX is a condensate of 1 mole of nonylphenol with 8 moles of ethylene oxide.

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Claims (1)

-Ho- Claims ! / Aromatic amine compounds of the formula: in which Z denotes a halogen-substituted naphthyl radical or the radical of the formula: denotes in which X ¹ , X ² , X ⁵ and X, which may be the same or different, are halogen atoms; and Y is halogen, trifluoromethyl, nitro, or alkyl. ' 2. Compounds according to claim 1 of the formula: 209840/1207 in which X, X, X ^J and X, which can be the same or different, are halogen atoms; and Y is halogen, trifluoromethyl 1, nitro or alkyl. 3. Compounds according to claim 1 of the formula: CF. in which Y is fluorine, trifluoromethyl, nitro or methyl. k. Compound according to Claim 1, characterized in that it is 2,3,5,6-tetrafluoro-2 '.H-bis.-trifluoromethyl-H' nitrodiphenylamine. 5. Process for the preparation of the compounds according to Claim 1 to 4, characterized in that 4-nitro-2-trifluoromethylaniline is substituted with a halogen
Naphthalene or with a compound of the formula: Shark 209840/1207 1 p treated, in which Hal is a halogen atom and X, X _3, X, X and Y have the meanings given in claim 1. 6. The method according to claim 5 »characterized that it is carried out in the presence of a base. 7. The method according to claim 6, characterized in that the base used is sodium hydride. 8. The method according to claim 5 to 7, characterized in that that it is carried out in the presence of a solvent or diluent. 9. The method according to claim 8, characterized in that that the solvent or diluent used is dimethylformamide or tetrahydrofuran. Io. Method according to claim 6 to 9, characterized in that that 4-nitro-2-trifluoromethylaniline is treated with the base, and the product of the treatment is treated with an ι halogen-substituted naphthalene or with the compound of the formula: Shark 209840/1207 further treated. 11. Process for the preparation of a compound according to Claim 1 to M, characterized in that a compound is used the formula: or a halogen-substituted naphthylamine with 2-halogen-5-cx »QUx-trifluorotoluene treated, 12. The method according to claim 11, characterized in that it is carried out in the presence of a base. 13 · Use of the compounds according to claims 1 to k as pesticidal agents or as active ingredients in pesticidal preparations. 14. Use according to claim 13, wherein the agents or preparations include one or more wetting, dispersing or emulsifying agents. 209840/1207 15 · Use according to claim 13 and 1H , wherein the agents or preparations have one or more other compounds which have biological effectiveness. 16. Use according to claim 13 to 15, wherein the agents or preparations have a fertilizer material. 17. Use according to claim 13 to 15, wherein the agents or preparations ο, οοοΐ up to 85% by weight of the active Have constituent or active ingredients. 18. Use according to claim 17, wherein the agents or preparations 10 to 85 Gew.Jt of the active ingredient or the active ingredients. 19. Use according to claim 17, wherein the means or preparations 0.00οί to l, o wt.? of the active ingredient or the active ingredients. 20. Use according to claim 13 to 19 for pest control, wherein the pests, the location of the pests or the habitat of the pests with the agent
or the preparation is treated. 21. Use according to claim 13 to 19 for treating plants to prevent them from being damaged by
To make pests less susceptible, characterized in that the plants or the seeds, the sprouts, 209840/1207 the bulbs, the tubers, the rhizomes or others themselves reproductive parts of the plants treated with the agent or preparation. 22. Use according to claim 13 to 19 for treating a medium in which plants grow or are to grow, characterized in that the agent or the preparation is applied to the medium. 209840/1207