DE2026807A1 - l, 2, l (-Tricyan-3,5,6-trihalogenobenzenes and their use as biocides - Google Patents

Description

DR. ELISAIETH 3UNG

DR. VOLKER VOSSIUS

DR. 30RGEN SCHIRDEWAHN

PATENT ADVOCATE!

• Munich 13,

Telephone: MM «7

u.z .: F 224 G (Vo / kä)

DIAMOND SHAMROCK CORPORATION Cleveland, Ohio, V.St.A.

and its use as a

Biocides "

Priority: June 2, 1969, V.St.A., no.829

The. The invention relates to new 1,2,4-tricyan-3,5,6-trihalogenobenzo-Ie of the general formula I.

in which X is a fluorine, chlorine, bromine or iodine atom. Examples for these compounds, hereinafter referred to as trihalotrimellitonitriles for short are designated are 5-bromo-3 »6-dichlorotrimellitonitrile, 6-chloro-3,5-difluoro-trimellitonitrile, 3,5,6-trichlorotrimellitonitrile, 3,5-uibromo-6-chloro-trimellitonitrile, 3,5,6-tribromotrimellitonitrile, 3,6-dichloro-5-3odtrimellitonitrile, 3,5-diiodo-6-chloro-trimellitonitrile, 3,5,6-! Rifluorotrinellitonitrile and 6-bromo-3,5-difluorotrimellitonitrile.

009851/2233

BATH ORIGINAL

The compounds of general formula I can be prepared in this way be that one l-iodine-JiSjö-trichloro-isophthalic acid dinitrile conaensated with a metal cyanide such as copper (I) cyanide or l ^^ - Trieyan- ^ jSfö-trichlorobenzene with an alkali metal fluoride, bromide or iodide in a molar ratio of 1 s 1 up to 1: 3 for implementation. The reaction of tricyantrichlorobenzene with the alkali metal fluoride, bromide or iodide is at room temperature or higher and in an aprotic solvent, such as acetone, dimethylformamide, K-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone or sulfolane, or in the absence carried out a solvent. The number of halogen substituents introduced into the end product depends on the haul ratio of the alkali metal halides to the tricyanotri-chlorobenzene, the reaction time and the reaction temperature and in "some cases on the solvent and the stirring speed.

The invention also relates to the use of the compounds of general formula I as biocides or in biocidal agents. The compounds can be used, for example, to control plant pests, insects, nematodes, microorganisms or fungi will. The compounds of the invention can be used in undiluted form Apply form to plants or other material to be protected. However, they are often used together with fixed ones or liquid inert carriers. For use as The compounds of the invention can be fungicidal, for example in the form of a dispersion in an aqueous or organic solvent spray on the plants. To protect wood, the compounds can be painted on in the form of a solution or dispersion or sprayed on. You can also put the wood in the solution

009 851/223 3, _y

or dip in dispersion. The choice of the suitable solvent depends, among other things, on the desired concentration of the active ingredient, the required volatility of the solvent, the cost of the solvent and the type of material treated. Examples of suitable organic solvents which can be used as carriers for the compounds of the invention are hydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil, heating oil and petroleum naphtha, ketones such as acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons, λ as carbon tetrachloride, chloroform, trichlorethylene and perchlorethylene, Carbonsäureester, such as ethyl acetate, amyl acetate and butyl acetate, ethylene glycol and diethylene glycol from the föonoalkylather, for example, the Honomethyl- or Konoäthyläther, as well as alcohols, such as j ethanol, isopropanol, and amyl alcohol.

The compounds of the invention, together with inert solid excipients or Trägerstofien ,, such as talc, pyrophyllite, attapulgite, kieselguhr, chalk, diatomaceous earth, calcium oxide, CaI-carbonate, bentonite, kaolinite, cottonseed hulls, wheat λ flour, soybean flour, pumice, tripoli, Sawdust, walnut shell flour or lignin can be applied to plants and other materials as a pesticide.

It is often desirable to add a surface to the biocidal agents. to incorporate active agent. These surfactants are preferably incorporated in both solid and liquid preparations. The surfactant can be an anion-active, be cationic or nonionic wetting agent.

0098 5 1/2233 "

BAP OBI (SINAL

Typical surfactants are alkyl sulfonates, alkyl aryl sulfonates, Alkyl sulfates, alkyl amide sulfonates, alkylaryl polyether alcohols fatty acid esters of polyhydric alcohols, ethylene oxide adducts of these esterp addition products of ethylene oxide to long-chain mercaptans, sodium arkylbenzenesulfonates with 14 to 18 carbon atoms, addition products of ethylene oxide condensed on alkylphenols, ZoB, with 10 ethylene oxide units p-Isooctylphenol, and soaps ^ such as sodium stearate and Sodium oleate.

The solid and liquid preparations can be made according to conventional methods Be prepared, so the active ingredients can be in finely divided solid form together with a finely divided solid Carrier material are mixed in a tumble mixer «, solutions, Dispersions, emulsions or suspensions of the active ingredients can be mixed with a finely divided solid carrier material in such amounts offset so that the finished dust is free-flowing

Possess properties.

When using solid preparations, these should be in finely divided form as possible in order to deal with a Hindestmenge of the preparation, place a large Gebie.t "The dusts are to have gewöhnlieh such a particle size that they pass through a sieve of mesh aperture 0 ₉ 83 mm. Dusts that pass through a sieve with a mesh size of G.074 mm also give satisfactory results.

Dusts contain the active ingredient preferably in amounts of 5 to 50% by weight, based on the total weight, concentrations

009851/2233 *

BATH ORIGINAL

I 1

outside this range are also suitable. There come Agents with an active ingredient content of 1 to 99 wt .- ^ into consideration. The remainder can consist of carriers or other additives or auxiliaries exist. The wetting agent is preferably in an amount of 0.5 Ms 1.0 wt .- ^, based on the total weight of the Preparation, used.

For the production of sprays, the active ingredient can be used in one liquid carrier such as water or another suitable liquid, dissolved or dispersed. The active ingredient can ™ also be in the form of a solution, suspension, dispersion or emulsion in an aqueous or non-aqueous medium. Preferably the spray contains 0.5 to 1.0 percent by weight of a surface-active compound.

The surface-active agent can be used as an adjuvant in any desired amount, for example up to 250% by weight, based on the active ingredient. When the surfactant is only used to improve wetting properties, e.g. B. in a spray, even 0.05 wt .- j6 or ^ less are sufficient. The use of larger amounts of a surface-active agent does not depend on the wetting properties, but is a function of the physiological behavior of the surface-active compounds. This plays a special role in the treatment of plants. In the case of liquid preparations, the active ingredient content is often no more than 30% by weight, it can be 10% by weight or even just 0.01% by weight.

^009851/2233

^: .. ^: 202 * 807

The compounds of the invention can be used in biocidal compositions are "containing other pesticides, especially fungicides, insecticides and bactericides, e.g. phenothiazine, Pyrethrum ingredients, Rotenone or DDT.

Halogen-substituted benzonitriles such as tetrafluoroterephthalic acid dinitrile and 2,3,4,6-tetrachloroisophthalic acid dinitrile have been proposed as active ingredients of fungicidal, hematocidal and herbicidal agents; ., cf. German Auslegeschrift No. 1 44} 721. It is known to have herbicidal and insecticidal efficacy of polychlorinated benzonitriles as well as Chlorphthalsaureestem and their N-substituted amides which also exhibit nematicidal activity and ^7; See French patent specification No. 1,265,053 and USA patent specification No. 2,923,634. In practical use, however, the active ingredients have in many cases been found to be inferior to the compounds according to the invention, for which reference is made to the examples section of the present description.

009851/2233

BATH

The examples illustrate the invention. Unless otherwise stated, parts are by weight.

example 1

Core division of 3.5, 6-trichlorotrimellitonitrile. A slurry of 1610 g of 1- _{iodo-3 f} Srö-trichloroisophthalic acid nitrile in dimethylformamide was heated to 65 ° C. with stirring. Thereafter, copper (I) cyanide was added and the temperature raised to 95 to 1oc ⁰ C. After 3 hours it was determined by gas chromatography that the reaction was complete. The i'asets mixture was diluted with 3 liters v / water, cooled and then filtered. The product was washed with water and then allowed to dry. It was then extracted several times with a total of 4 liters of hot toluene. The toluene extracts were combined, washed with water, dried over magnesium sulfate, treated with activated charcoal and filtered. The yellow solution obtained was evaporated to dryness. Yield 733 g of crude trichlorotrimellitonitrile. After recrystallization from 2 liters of toluene 449.g ..eines product was obtained from P. 232-236 ⁰ C. A sample used for analysis had a melting point of 240.5 to 242.5 ° C.

(256, 5); ber .: 41 Cl N , 3 C ₉ Cl ₅ N ₃ found: 41 , 6 16 , 2. , 5 16

009 85 1/2233

BATH ORIGINAL Example 2

Preparation of 5-bromo-3 ₁ 6-dichlortrimellitonitril A mixture externa's Trichlortrimellitonitril 8.0 g and 10.2 g of sodium bromide in 50 ml of dimethylformamide was heated at 40 to 55 ⁰ C. The conversion was followed by gas chromatographic analysis. When significant amounts of the dibrominated product appeared, the reaction mixture was diluted with 4 volumes of water and filtered. The crude product was washed with water and dried; Yield 9.3g. After recrystallization from methyl ethyl ketone were obtained from P. 254-256 ⁰ C 4.3 g of 5-bromo-3 »6-dichlortrimellitonitril. The gas chromatographic analysis showed that the product was a mixture of 63 $ S-bromo-6-dichlorotrimellitonitrile, 29 $ trichlorotrimellitonitrile and 8,6 3,5-dibromo-6-chlorotrimellitonitrile.

Example 3

Manufacture; of 6-chloro-3,5-difluorotrimellitonitrile A mixture of 8.0 g of trichlorotrimellitonitrile and 6.3 g of dry potassium fluoride in 50 ml of dimethylformamide was stirred at room temperature (about 25 ° C.) for 2 hours. After adding a further 6.3 g of potassium fluoride, the mixture was stirred for a further 16 hours. The mixture was then diluted with 250 ml of ice water and filtered. The product was washed with water and air dried; Yield 6.0g. After recrystallization from carbon tetrachloride, 2.1 g of 6-Clilor _<s were obtained -3-5 difluortrimellitonitril from P. 109 to 111 ⁰ C.

C ₉ ClP ₂ N ₃ (223.56); her.ϊ

found s 19V2

009851/2233

Example 4 ,

Production of 3 _{t of} 5 ~ diprom ~ 6 ~ chlorotrimellitonitrile and tribromotrimellitonitil ·

A mixture of 10.1 g of trichlorotrimellitonitrile and 12.4 g of sodium bromide in dimethylformamide was heated to 100 ° C. for 18 hours with stirring. A further 12.4 g of sodium bromide were then added and the mixture was ^{stirred at 120 °} C. for a further 4 hours. The reaction mixture was then cooled to room temperature, diluted with 300 ml of iJiswasser and filtered. λ The product was washed with water and dried and then recrystallized from acetonitrile. Yield 4.0 g of a product from P. 235 to 295 ⁰ G. Gas chromatography showed that the product was a mixture of 4 ί> trichlorotrimellitonitrile, 29 i> S-bromine ^^ - dichlorotrimellitonitrile, 48.5 £ 3.5- Dibromo-6-chlorotrimellitonitrile and 18.5 # tribromo trimellitonitrile. was.

Example 5

Production of 3.6-dichloro-5-iodotrimellitonitrile Ä

A mixture of 30.0 g of trichlorotrimellitonitrile and 21.0 g of sodium iodide in 200 ml of dimethylformamide was ^{heated to 50 °} C. for 8 hours with stirring. Then additional 21.0 g * sodium iodide were added and the whole thing was stirred for a further 6.5 hours at 50 to 55 ° C. while the reaction was carried out by gas chromatography.

was awake. The mixture was then diluted with 1 liter of ice water and filtered. The product was washed with water, dried and recrystallized from benzene. 17 »4 g of a yellow solid with a P. 246 to 249 ^° C. were obtained.

. 009851/2233

··· '■:'. " ^{: ::} - ^.; 'i 2025307

C H

C ₉ Cl ₂ JN ₃ (347.93); calc .: 31.1 0.0

found: 32.6 0.7

Example 6

In this example, the insecticidal activity of the investigated Connection to the Mexican bean beetle Epilachna varivestis.

Larvae of the fourth instar are less than 1 day old examined.

Paired, fully extended seed leaves that have been cut out from bean plants are dipped into the preparation and stirred until they are completely wetted. The preparation contains the compound to be examined, acetone, a stock solution of the emulsifier and distilled water. The concentration of the active ingredient in this preparation is up to 2000 parts / million. Lower concentrations of the active ingredient are obtained by diluting the preparation with distilled water. The leaves are then dried and the paired leaves are separated from one another. One leaf is placed in a Dixle beaker, and up to 10 "* randomly selected larvae are placed in each Dixie beaker. The Dixie beaker is then covered with a lid of a Petri dish. The Dixie beakers are kept for 3 days 21 ⁰ C allowed to stand Thereafter, the mortality and the appetite suppression is determined the appetite suppression is compiled an indication of the repulsive properties of the compound under study "in the table below Bind the results of the insecticide activity..:

0098 51/2233

■ -11 - ■■ ■■. ■■

Investigated compound concentration, mortality,

3,6-dichloro-5-iodotrimellitonitrile 500 40

• ■.

Example 7

Test preparations are the growth of Erwinia amylpvora (Ea), Xanthomonas phaseoli (Xp) _f Staphylococcus aureus (Sa) and Escherichia coli (Ec) tested for inhibition in various concentrations. The starting preparation contains 0.15 g of the active ingredient, 4.0 ml of acetone, 2.0 ml of an emulsifier stock solution (0.5 # Triton X-155 in V / water) and 94.0 ml of distilled water. The concentration of the active ingredient in this preparation is 1250 ppm. Lower concentrations of the active ingredient are obtained by diluting the starting preparation with distilled water.

2 ml of each preparation are placed in a test tube which is placed in a 44 ° hot water bath. 8 ml of a 20 # Kähr agar are added to the test tube from a stock preparation which has also been warmed to 44 ° C. A 1: 5 dilution and a final concentration of 250 ppm of the active ingredient in the agar are obtained. The contents of the tube is still warm URTD mixed thoroughly with a vortex mixer immediately -hierauf ± n a sterile petri dish poured (χ 100 15 mm) of polystyrene. As soon as the agar has solidified, suspensions of each organism are spread onto the surface of the agar at the same time. The plate is then ^{incubated at 30 °} C. for 24 to 48 hours. The growth inhibition of each organism is then determined visually. The percentage growth inhibition is in the. Relation to the growth of streak colonies on control plates

009851/2233

estimated that are obtained during individual attempts. The following results are obtained.

Conc Mixture of $ 4 Trichlortrimelli 250 . dimethyl ester H 250 Stunted growth X.Po S.a. , % - - link tration, tonitrile, $ 29 5-bromo-3,6-dichloro- bromo-6-chlorotrlmellitonitrile and 128 250 100 TpM trimellitonitrile, $ 48.5 3,5-di- $ 18.5 tribromo trimellitonitrile 128 E.a. 100 100 E.c. 100 Mixture of $ 63 5-bromo-3,6- Trichlorotrimellitonitrile 64 100 100 dichlorotrimellitonitrile, $ 29 128 32 100 100 100 _ Trichlorotrimellitonitrile and 64 250 100 100 8 $ 3 »5-dibromo-6-chlorotrimelli ~ 32 2 2.3 »5 * 6-tetrachloroterephthalic acid loo 50 100 100 tonitrile dimethylamide 100 100 100 3,6-dichloro-5-iodtrimellito ™ 250 100 100 100 0 nitrile 128 100 100 100 0 64 100 100 100 • 32 100 100 0 6-chloro-3 »5-difluorotrimellito- 250 50 nitrile 128 0 100 100 100 0 100 100 0 100 100 50 - 100 50 100 - 100 100 100 - 100 100 100 0 100 50 - 100 100 0 " 2 50 ο 21. -8th. ίο

Example 8 ". .. -.""

To determine the Nachauf "activity running dynamics of the test compound, the so \ vie on the leaves of seedlings was" on the ground in which these seedlings grew applied _i%> are planted two mixtures of seeds in sterilized, composted greenhouse Earth » One seed mixture contains 3 types of broad-leaved plants (buckwheat, beets and asters) and the other seed mixture contains 3 types of grass (sorghum, Italian millet and perennial shark grass) ", the soil is divided diagonally into two equal areas,. And the broad-leaved plant - < zen are on one surface and the grass on the other

Sown area. Then the seeds are evenly mixed with a

009851/2233

about 6.35 mm thick layer of earth covered and watered. Thereafter put them in a greenhouse and let them grow until the first correct leaf is on the slowest growing one broad-leaved plant species appears. This takes about 9 to 14 days, depending on the time of year. Once the seedlings have this Have reached development stage, the container at a pressure of 0.7 kg / cm with 40 ml of the test preparation in a Evenly sprayed dose up to 27 kg / ha. The preparation contains the active ingredient, equal parts by volume of water and acetone and drops of the emulsifier, Triton X-155.

Two weeks after the treatment, the percent suppression will be and the effects in terms of phytotoxicity, growth control and other effects noted. It

the following results are obtained:

Connection concentration _β suppression, j »

tion, kg / ha broad-leaved _r ^ T. Weeds - eraser 6-chloro-3,5-difluor- _{1Ά λη} . . _β trimellitonitrile ^{Lö 4Ü} none

Example 9

Bs becomes the ability of to _. "^ " _ Investigating compound intended to protect tomato leaves against the causative agent of the potato blotch disease in Alternaria solani (Eil. And Mart.) Jones and Grout and the causative agent of late blight of the potato Phytophthora infestans (Mont.) DeBary This method uses tomato plants that are 13 to 18 cm tall and are 4 to 6 weeks old.

seeking pathogen with different doses of the test preparation- * - 009851/22 3 3

2023307

tes sprayed at a pressure of 2.8 kg / cm »with the plant being rotated on a turntable in a fume cupboard. The center of the turntable is 114 cm from the nozzle of the spray gun. The preparation to be examined, which contains the active ingredient, acetone, an emulsifier or stock solution and distilled water, is used in concentrations of up to 2000 ppm of the active ingredient. Lower concentrations of the active ingredient are obtained by using less active ingredient and larger amounts of water. The concentration of acetone and emulsifier is kept the same. The plants are then allowed to dry and the treated plants as well as the control plants, which have been sprayed with a preparation without active ingredient, are sprayed on a turntable while turning with a spore suspension containing about 20,000 conidia of A «

Sporangia
solani / ml or 150,000 / of P / infestans / ml. The spray gun used sprays 20.ml within 30 seconds. The plants are kept in a moisture-saturated atmosphere for 24 hours at 21 ^° C. (plants infected with A. solani) and at 16 ° C. (plants infected with P. infestans) for spore germination and infection before they are transferred to a greenhouse. 2 days after the start of the experiment with A. solani and 3 days after the start of the experiment with P. infestans "*, the injuries on the top three fully expanded leaves are counted. The values are expressed as a percentage of disease suppression, based on the number of Injuries obtained in control plants, converted. The doses and the percentage suppression are given in the table below!

009851/2 233

ORiOiMAL INSPECTED

link

Dose, percent suppression P 'A.solani P.infestans

Trichlorotrimellitonitrile

Mixture of 63 $ 5-brora ~ 3,6-dichlorotrinvellitonitrile,
29 '/' Trichlorotrimellitonitrile
and & p 3 »5- ^ ibroin-6-ciilortrimellitonitrile

3,6-l) icülor-5-joütrimellitonitril

6-chloro-3,5-difluorotrimellitonitrile

1000

128

32

256

64

16

256

64

16

256

128

64

Mixture of 4 # trichlorotrimellitonitrile, 29>'i 5-bromo-3, b-dichloro-25i> trimellitonitrile, 48.5 # 3,5-di-64 broru-6-chlorotriuellitonitrile and 16 18.5' / * tribronitrine. ellite nitrile 4

2 # 3t5> 6-tetrachloroterephthalic acid

d line t hy I amid 2000

2, J5,5,6-tetrachloroterephthalic acid

tetraethylamide 400

2000 2,3 »^ j6-Tetrachloroisophthalic acid

- dinitrile 8

2i3,5-trichloroterephthalic acid dimethyl ester ■ 10 to 100

100

93

74

100

100

75

37

100

100

34

79

0
0

100

82

32

9
20th

100 99

100 57

100

100

99

56

100

100

94

49

100 75 37

100 92

71 6

25 0

Example 10 .

Ih this example is the ability of the too

investigated compound determines the mycelial growth of soil fungi to inhibit * Pasteurized earth is made with Rhizoctonia solani » Sclerotium rolfsii and Pythium species inoculated on a Mixture of shark meal and sand grew in 450 ml vessels. The desired inoculuni level is achieved by a number of vessels of the cornmeal sand culture of a particular Amount of earth admits. The inoculum and the soil are then thoroughly mixed together and placed in suitable containers. ·. 00985 1/2233

BATH

filled in. After that, the earth with the appropriate amount of a diluted preparation containing the test compound, acetone, emulsifier stock solution and distilled water contains. This preparation is poured onto the surface of the earth in the container. For example, 19.9 ml of a preparation with a Active ingredient content of 1000 ppm on soil poured into a 120 ml flat Dixie beaker. This amount corresponds to one dose of 54 kg / ha. The concentration of the active ingredient in this preparation is up to 2000 ppm. Lower drug concentrations are obtained by diluting the preparation with distilled water.

As soon as the containers with the preparations are watered, they become Set in a chamber with high humidity at 21 ° C. for 48 hours. After this time, the mushroom mycelium has the surface the soil in the control containers completely overgrown. The degree of inhibition of mycelial growth is on a scale of 0 (complete inhibition) to 10 (growth of the control samples) determined. These values are called the percentage inhibition of growth expressed. The following results are obtained.

Compound Concentration- Percentage inhibition of the

tion, kg / ha of growth . ..

R. "S. Pythium _: sol ani ro lfsii sp.

Trichlorotrimellitonitrile 72 92 28 60

36 96 36 40 18 30 2 8

Example 11

To determine the fungicidal activity., After leaf contact and, Soil soaking in relation to the compound to be investigated, pea flour tau Erysiphe polygoni, a Yersuclis approach of 150 "ml

009851/2233

"■" '' * 202B807

made both for soaking the soil and for spraying the leaves. Each contained 100 ml of the test batch 0.24 g of the compound to be tested, 4.0 ml of acetone, 2.0 ml Emulsifier stock solution (0.5 volume $ Triton X-155 in water) and 94.0 ml of distilled water. Kidney bean plants of the cultivar Tendergreen at a height of about 10 to 15 cm, each of which 4 plants grown in a flower pot were treated. At least one day before treatment, the plants were with Pea powdery mildew Erysiphe polygoni infected from crops kept in the greenhouse in an environment where the spores ^ are constantly available to trigger the disease.

In the treatment by soaking the soil, the soil surface of each pot was soaked with 17.5 ml of the composition, which corresponds to an application of the test compound in an amount of 72 kg / ha. The four pots were then simultaneously sprayed with the remaining 80 ml (20 ml per pot) of the test batch on a turntable under a fume cupboard and under a pressure of 2.8 atm. The spray solution for spraying the leaves contained 2400 ppm of the compound to be tested, 7 to 14 days after the treatment, the percentage suppression of powdery mildew was estimated by macroscopic observation. In the loading · \-powered approach yielded the following results:

Investigated compound dosage percentage

. mg / ha TPM suppression

Mixture of $ 63 5-bromo-3,6-di-

chlorotrimellitonitrile, 29 # tri- - 1200 78

chlorotrimellitonitrile and 8 #

3,5-dibromo-6-chlorotrimellitonitrile

Irichlorotrimellitonitrile

72 1200 80 _ 100 part ₁₈ 300 78 150 100 009 851/223 3 * 100

■ ■ 2028307

- l8 -

Example 12

Foliar spray experiment on the Mexican bean beetle This experiment explains the insecticidal effect of the compounds to be investigated against the Mexican bean beetle Epilachna varivestis.

One day old larvae of the Mexican bean beetle are examined. Paired, fully expanded cotyledons, the were cut from bean plants of the Pintο variety kept in aquapics and sprayed on a turntable under a hood with 50 ml of the test preparation. The experimental preparation contained 0.1 g of the substance to be examined, 4.0 ml acetone, 2.0 ml emulsifier stock solution (0.5 volume # Triton X-155 in water) and 94.0 ml of distilled water. The concentration of the active ingredient in this preparation is 1000 ppm. Lower concentrations of active ingredients are obtained by diluting the preparation with distilled water.

After the sprayed substance has dried on the leaves the paired leaves were separated from each other and only either one was used for the experiment. This sheet was placed on agar containing 1.5 # water (15 ml ~ *, each disposable Petri dish made of polystyrene with a diameter of 100 mm), and filled with 10-day-old larvae of the Mexican bean beetle. she were kept at 21 C for 3 days; subsequently became mortality and appetite inhibition. The appetite suppressant is a Signs of the repulsive properties of those to be examined Links. The results of the insecticidal effect are summarized in the following table:

009851/2233

ORIGINAL WSPECTED

· ■■ ·. · ■ '' ^: 202R807

Investigated compound concentration, mortality,

TpM $>

3,6-Lachlor-5-iodotrimellitonitrile 500 40

Example 13 Try -, e ^ enover plant rust

This experiment is used to determine the effectiveness of the too investigating compounds as systemic agents against bean and corn grate. The host / rust systems used are: Puccinia sorghi on quays of the Varietas Golden X Bantam and Uromyces phaseoli on Phaseolus vulgaris, Varietas Pinto, which in 10 cm clay plugs were examined. There was one watering solution for each pot with a dose of 45 ml of the test liquid, accordingly 45 mg of substance or 72 kg / ha applied. The test liquid contained 0.1 g of the substance to be examined, 4.0 ml of acetone, 2.0 ml emulator stock solution (0.5 volume # Triton X-155 in water) and 94.0 ml of distilled water. The concentration of active ingredient in this test liquid is IOCC TpM. Lower Active ingredient concentrations can be achieved by diluting the test liquid with distilled water. f

24 hours after application of the substance to be investigated

the plants inoculated by dusting on the plant leaves a single aqueous suspension, the uredospore species contained. Thereafter, the plants were allowed to incubate overnight kept at 16 C and 100 ^ -iger relative humidity. ^ 7 to 10 days after the inoculation, the spots that had formed were counted, with the suppression of Percentage of Diseases Suppressed

on the development of spots on untreated comparison plants, • 0 0 9 951/2233

0BK3ANAL

was designated. In addition, the phytotoxicity of the substance to be examined with regard to the plant was determined by visual observation, with a 12-point evaluation number sequence being used: In it, 0 means no damage to the plant and 13 means complete destruction of the plant. The results are summarized in the following table i

dosage TpM Suppression, % Beans Investigated connection kg / ha 500
250 Corn 90 3,6-dichloro-5-iodotrimellito-
nitrile 250
125 100
100 success
rich
100
100 Mixture of $ 63 5-bromo-3,6-
dichlorotrimellitonitrile,
$ 29 trichlorotrimellitonitrile
and $ 8 3,5-dibroni-6-chloro-
trimellitonitrile 18th
9
4.5 500
250 90
0 90
90 6-chloro-3,5-difluorotrimelli
tonitrile f 100
100

0 Q 9? I · / 2.2 2 3.

BATH ORIGINAL

Claims (2)

Claims pfc *. 1,2,4-Tricyaji-3,5 »6-tr! Halobenzenes of the general formula in which X is a fluorine, chlorine, bromine or iodine atom. 2. Use of the compounds according to claim 1 as biocides. 009851/2233