HU217638B - Aryl-pyrrol derivatives, preparation thereof, insecticide, acaricide and anthelmintic compositions containing them as active components and method for controlling insects and acarina - Google Patents

Abstract

The arylpyrrole derivatives of the present invention in the formula (I): X is hydrogen, bromo or chloro, Y is chloro-trifluoromethyl, W is cyano or nitro, A is mono-substituted alkyl substituted with cyano, trihalogenalkoxy. , alkoxycarbonyl or alkoxycarbonyl-oxy, with the proviso that A is other than C 1 -C 4 alkoxycarbonylmethyl, L is H, M and R are independently hydrogen, chloro, or trifluorine. methyl, with the proviso that when X is hydrogen and A is a C1-4 alkyl group substituted with cyano, the general group (b) wherein L, M and R are as defined above is a pyrrole ring. It is linked to its two position positions near the nitrogen atom. ŕ

Description

The present invention relates to insecticides, acaricides and nematodes containing novel arylpyrrole derivatives of the formula I; The present invention also relates to compounds of formula (I) and a process for their preparation, as well as a method for controlling insects and mites.

In the formula I, X is hydrogen, bromine or chlorine,

Y is chlorine or trifluoromethyl,

W is cyano or nitro,

A is a monosubstituted C 1 -C 4 alkyl group substituted with cyano, C 1 -C 4 trihaloalkoxy, (C 1 -C 4 alkoxycarbonyl or C 1 -C 6 alkoxy) carbonyloxy, with the proviso that A is other than (C 1-4 alkoxy) carbonylmethyl,

L is hydrogen,

M and R are each independently hydrogen, chlorine or trifluoromethyl, provided that when X is hydrogen and A is a C 1 -C 4 alkyl substituted with cyano, then the group of formula (b) wherein L, M, and R have the same meaning as defined above - attached to one of the two positions adjacent to the nitrogen atom of the pyrrole ring.

Compounds of formula (I) are prepared by reacting a compound of formula (VIII) wherein X, Y, W, L, M, and R are as defined herein, with at least one molar equivalent of compound (IX). wherein A is as defined herein, Hal is halogen, in the presence of at least one molar equivalent of an alkali metal base and in a solvent suitable for the preparation of the desired compound of formula (I).

Similar to compounds of formula (I) are disclosed in Braz. Pedido Pl BR 88 03,788 (February 2, 1989), European Patent Application Publication No. 312,723 (April 26, 1989), and British Patent Specification 2,141,709 (March 3, 1985). .

However, the compounds known in the literature differ in their structure from the compounds of the invention, and the use of the new compounds is advantageous in that the use of the new compounds reduces the likelihood of habituation and the lower doses applied are environmentally friendly.

A preferred group of novel arylpyrrole derivatives of the present invention are those compounds of formula II wherein A, L, M, R, W, X and Y are as defined above.

Another preferred group of novel arylpyrrole derivatives of the present invention are compounds of formula III wherein A, L, M, R, X and Y are as defined above and W = NO ₂ .

A further preferred group of novel arylpyrrole derivatives of the present invention are those compounds of formula IV wherein A, L, M, R, W, X and Y are as defined above.

Another preferred group of novel arylpyrrole derivatives of the present invention include those compounds of Formula V wherein A, L, M, R, W, X, and Y are as defined above and include those of Formula VI. and compounds of Formula VII wherein A, L, M, R, W, X and Y are as defined above.

Preference is given to compounds of formula I in which

W is cyano or nitro,

L is hydrogen,

X is chlorine or bromine, and Y is chlorine or trifluoromethyl,

M is hydrogen, chlorine,

R is chlorine or trifluoromethyl.

Particularly preferred insecticides, acaricides and / or nematodes are those compounds of formula I wherein L is hydrogen,

M is hydrogen or chlorine,

R is chlorine or trifluoromethyl,

W is cyano,

X and Y are as defined above.

Highly active insecticides, acaricides and / or nematodes are compounds of the formula II in which

L is hydrogen,

M is hydrogen or chlorine,

R is chlorine or trifluoromethyl,

W is nitro,

X is chlorine or bromine, and Y is chlorine or trifluoromethyl.

Representative compounds of the insecticides, acaricides and nematodes produced by the process of the present invention include the following arylpyrrole compounds: [2,3-dichloro-4-cyano-5- (3,4-dichlorophenyl) pyrrol-1-yl methyl pivalic acid, m.p. 143-145 ° C; 4,5-dichloro-1- (hydroxymethyl) -2- (4- (trifluoromethyl) phenyl) pyrrole-3-carbonitrile acetate (ester); 4-Bromo-2- (4-chlorophenyl) -1-hydroxymethyl-5- (trifluoromethyl) pyrrole-3-carbonitrile pivalate (ester), m.p. 127.5 ° C;

4-Bromo-3- (3,4-dichlorophenyl) -1-hydroxymethyl-5- (trifluoromethyl) pyrrole-2-carbonitrile pivalate (ester), m.p. 93-94 ° C. ;

3,4-dibromo-5- (4-chlorophenyl) -1-hydroxymethylpyrrole-2-carbonitrile pivalate (ester), m.p.

130-132 ° C;

[2,3-Dichloro-4-cyano-5- (4-trifluoromethyl-phenyl) -pyrrol-1-yl] -pivalic acid methyl ester, m.p.

153-157 ° C;

3-bromo-5-cyano-4- (3,4-dichlorophenyl) -2- (trifluoromethyl) pyrrole-1-acetonitrile, m.p. 95-97 ° C;

2,3-dichloro-4-cyano-5- (4- (trifluoromethyl) phenyl) pyrrole-1-acetonitrile, m.p. 137.5-139 ° C;

3-bromo-5- (4-chlorophenyl) -4-cyano-2- (trifluoromethyl) pyrrole-1-acetonitrile, m.p. 142-144 ° C;

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2.3-dichloro-4-cyano-5- (3,4-dichlorophenyl) pyrrole-1-acetonitrile, m.p. 197-199 ° C;

3-bromo-5- (4-bromophenyl) -4-cyano-2- (trifluoromethyl) pyrrole-1-acetonitrile, m.p. 110.5-113 ° C; [3-Bromo-5-chloro-4-cyano-2- (3,4-dichloro-phenyl) -pyrrol-1-yl] -pivalic acid methyl ester, m.p.

119-122 ° C;

2.3-dichloro-5- (4-chlorophenyl) -4-cyanopyrrol-1-ylacetonitrile, m.p. 175-177 ° C;

[2- (3,4-Dichlorophenyl) -3-nitro-5- (trifluoromethyl) pyrrol-1-yl] -pivalic acid methyl ester, m.p.

116-119 ° C;

4-Bromo-2- (4-chlorophenyl) -1- [2,2,2-trifluoroethoxy) methyl] 5- (trifluoromethyl) pyrrole-3-carbonitrile.

European Patent Application 0 303 863 discloses a process for the preparation of a compound of formula I wherein A is hydrogen.

The N-substituted arylpyrrole compounds of formula (I) may be prepared by reacting an appropriately substituted arylpyrrole of formula (VIII) wherein L, M, R, W, X and Y have the same meanings as defined above. Reaction with an alkylating agent of formula IX and a suitable base. The alkylating agent may be (C 1 -C 4 haloalkyl) chloromethyl ether and the base may be potassium hydride. In another similar reaction, the compound of formula VIII is substituted with a-bromoacetonitrile to give the arylpyrrole derivative of formula I substituted with a cyanomethyl group on the nitrogen atom. The reaction is illustrated in Scheme 1; in the reaction scheme, L, M, R, W, X and Y are as defined above for the compound of formula (I) and A is (C 1 -C 4 haloalkoxy) methyl or cyanomethyl.

The following examples illustrate the preparation of compounds which can be prepared by the above reaction scheme.

The arylpyrrole compounds of the present invention are useful in the control of insects, mites and nematodes, as well as in the protection of standing or harvested plants against the above pests.

The arylpyrrole of formula (I) and its isomers of formula (II), (III), (IV), (V), (VI) and (VII) are generally used in practice in a concentration of 10 to 10,000 ppm by weight. . The active ingredient is dispersed in water or other inexpensive liquid pesticidal effective carrier for application to plants or their place of production to control insects, mites and / or nematodes. These agents can also be used against lawns such as larvae and bugs.

The arylpyrrole compounds of formula (I) produced by the process of the present invention are effective for controlling insects, mites or nematodes by treating the foliage of the plant and / or the site of production of the plant. The application rate is from 0.100 kg / ha to 4.0 kg / ha. Larger amounts can be used, but this is generally unnecessary and results in material waste.

The arylpyrrole compounds of the present invention can be used alone or in combination with other biologically active agents, including other insecticides, acaricides or nematodes, to control insects, mites or nematodes.

The arylpyrrole compounds of the present invention can be effectively coupled or associated with, for example, phosphates, carbamates, pyrethroids, formamidines, chlorinated hydrocarbons, halobenzoyl ureas.

The arylpyrrole active compounds of the present invention may be formulated in dry compacted granules, liquid formulations, granular formulations, wettable powders, powder concentrates, microemulsions and the like. Any formulation can be applied to soil, water and / or foliage, and each provides appropriate plant protection.

Compositions containing the active compounds of the present invention may also contain inert, agriculturally acceptable solid or liquid diluents.

For example, wettable powder, powder or powder concentrate formulations containing the active compounds of the present invention are prepared by co-milling 3-20% by weight of an arylpyrrole compound of formula I and 3-20% by weight of a solid anionic surfactant. Anionic surfactants include sodium sulfo-succinic acid dioctyl ester such as Aerosol OTB from American Cyanamid Company. These compositions may also contain from 60% to 94% by weight of inert solid diluents such as montmorillonite, attapulgite, chalk, talc, kaolin, diatomaceous earth, limestone or silicates.

Compact granules for application to soil or water are prepared by grinding about 60-94% by weight of gypsum with approximately the same amount, typically 3 to 20 parts by weight of arylpyrrole and solid surfactant. The resulting mixture is compacted into small granular granules of about 400 to 1000 microns or larger.

In addition to the anionic sodium di-succinic acid dioctyl ester, nonionic block copolymers of ethylene oxide and propylene oxide can be used as surfactants in the compositions containing the active ingredient of the present invention. Particularly effective in the preparation of compact granules are the Pluronic 10R8, 17RR8, 25R8, F38, F68, F77 or F87 branded by BASF Wyandotte Corporation.

In addition to powder and concentrate formulations, water-dispersible, wettable powders and liquid formulations are well suited for the uses described above. Preferably, the liquid compositions are applied at the site of plant growth by spraying the aqueous composition on a leaf of the plant to be protected. Spraying agents may also be applied to the seed, or to the presumed nutrient or locus of the insect and mite.

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When the compositions containing the active compounds of the present invention are used in combination with other plant protection products, the composition comprising the mixture of components or the separate compositions are applied sequentially to the site to be treated.

Similarly, arylpyrrole-containing liquid formulations used in combination with other pesticides are used separately in tank mixes or liquid formulations.

The liquid sprays of the present invention contain from 0.001 to 0.1% by weight of arylpyrrole active ingredient.

The following examples illustrate the process of the present invention in more detail.

Example 1

4-Bromo-2- (4-chlorophenyl) -1 - [(2,2,2-trifluoroethoxy) methyl] -5- (trifluoromethyl) pyrrole-3-carbonitrile The procedure is illustrated in Scheme 2. according to.

4-Bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile (1.0 g, 0.003 mol) was dissolved in anhydrous tetrahydrofuran and the resulting mixture was treated with 1.25 molar equivalents of potassium. -hydride containing tetrahydrofuran dispersion. The reaction mixture was stirred for 10 minutes, treated with chloromethyl (2,2,2-trifluoroethyl) ether (0.54 g, 0.0036 mol), stirred at room temperature for 48 hours and then poured into a large volume of water and extracted with ether. . The ether extract was washed with brine, dried over magnesium sulfate and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, 1: 1 methylene chloride: hexane) to give 0.90 g (68%) of a white solid, m.p. 124.6-125.3 ° C. .

By following the procedure described above, but employing the appropriately substituted phenylpyrrole-3-carbonitrile or 3-nitro-2- (substituted) phenylpyrrole and the appropriate alkylating agent, the following compounds of general formula (II) were prepared.

Compounds of Formula II (W = CN)

THE L M R X Y Melting point, C -CH ₂ COOC ₂ H ₅ H 3-C1 4-C1 cl cl 118-120 -CH ₂ OCOC (CH ₃ ) ₃ H 3-C1 4-Cl cl cl -ch ₂ ococh ₃ H H 4-CF ₃ cl cl -ch ₂ cn H H 4-C1 Br cf ₃ 142-144 -CHjCN H H 4-CFj cl cl 137-139 -ch ₂ cn H H 4-Br Br cf ₃ 110-113

Compounds of formula IIA

THE L M R X Y Melting point, C -CH ₂ OCOC (CH ₃ ) ₃ H 3-C1 4-C1 H cf ₃ 116-119

Example 2

Insect and acaricidal test The test was performed with technical grade materials. The concentration values refer to the concentration of the active ingredient. The tests were performed at 27 ° C.

Spodoptera eridania; Developmental Larvae 3 A 7-8 cm Sieva Urna bean leaf was immersed in the suspension to be examined for 3 seconds while stirring and then placed under a suction cup to dry.

The leaf was then placed in a 100x10 mm Petri dish containing wet filter paper at the bottom and 10 aphids. The cup was allowed to stand for 5 days and then evaluated for mortality, loss of nutrition, or any disturbance of normal molting.

Spodoptera eridania; Residue after 7 days Plants subjected to the treatment described in the above study were kept in a greenhouse under high intensity light for θθ for 7 days. The brightness of the lights was twice the June daylight in New Jersey, and we counted the number of daylight hours to 14. Leaves were sampled after 7 days and evaluated according to the procedure described above.

Aphis fabae; dishes containing mixed larva cm high sphynx (Tropaeolum sp.) were infected with 100-200 lice 1 day before the test. The vessels were sprayed with the test composition. Spraying was performed under a suction cup on a rotating table at 4 rpm with 154 DeVilbiss nozzles at 2 rpm. The end of the spray tube was kept 15 cm from the plant and the spray was applied to the entire surface of the plants and lice. The dishes were placed on a white enamel tray, allowed to stand for two days, and then evaluated for mortality.

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Tetranychus urticae (P-resistant strain)

We picked 7-8 cm primary Sieva lima bean leaves and placed one leaf in each dish. Small leaves were cut from a leaf of the main lice, and one was placed on the leaf of the plant to be examined. This was done 2 hours before treatment to allow the lice to permeate the leaves and lay eggs. The leaf pieces were cut to contain about 100 lice each. During treatment, the pieces of lice for relocation were removed and discarded. Plants infected with the roof were immersed in the test solution for 3 seconds with stirring and then placed under a suction cup to dry. The plants were allowed to stand for 2 days, and then some of the leaves were evaluated for adult lice mortality. The remainder of the leaves were allowed to stand for another 5 days and then evaluated for mortality of eggs and / or newly hatched individuals.

Diabrotic undecimpunctata howardi; 3. larval stage of development

Into a 3 ml wide mouth screw bottle was added 1 ml of fine talc. To the talc, a suspension of acetone containing the active ingredient was pipetted to give 1.25 mg of active ingredient and 0.25 mg of active ingredient. The vials were placed in a gentle air stream to evaporate the acetone. The dry talc was loosened and 1 ml of millet seed was fed as an insect food and 25 ml of moist soil was added to each of the jars. The vials were sealed and the contents shaken with a Vortex Mixer. Next, larvae of stage 3 larvae were placed in each of the vials, and the vials were loosely sealed to allow air exchange.

The vials were then allowed to stand for 6 days and the death rate was evaluated. Missing larvae were considered dead because they were not found due to their rapid decay. The application rates are 50 kg / ha and 10 kg / ha respectively.

The rating scale is as follows:

0 = ineffective = 10-25% mortality

2 = 26-35% mortality

3 = 36-45% mortality

4 = 46-55% mortality

5 = 56-65% mortality

6 = 66-75% mortality

7 = 76-85% mortality

8 = 86-99% mortality

9 = 100% mortality

R = reduced nutrition

The evaluation data are summarized in Table 1.

Table 1

Insecticide and acaricide

agent Aphis fabae Spodoptera eridania P. Copper lice Diabrotic undecim- punctate rootworm (Ppm) 100 (Ppm) 1000 (Ppm) 100 7 days (Ppm) 300 (Kg / ha) 50 1,2,3-Dichloro-4-cyano-5- (3,4-dichlorophenyl) pyrrole-1-acetonitrile 4 9 9 9 0 0 2. 4,5-Dichloro-1- (hydroxymethyl) -2- (alpha, alpha, alpha-trifluoro-p-tolyl) pyrrole-3-carbonitrile acetate (ester) 0 9 9 9 9 9 3. 2,3-Dichloro-4-cyano-5- (4- (trifluoromethyl) phenyl) pyrrol-1-ylacetonitrile 0 9 9 9 9 0 4. 3-Bromo-5- (4-chloro-phenyl) -4-cyano-2-trifluoromethyl-pyrrol-1-yl-acetonitrile 0 9 9 9 0 0 5. 2,3-Dichloro-4-cyano-5- (3,4-dichlorophenyl) pyrrol-1-yl pivalic acid methyl ester 0 9 9 9 0 4 6. 3-Bromo-5-cyano-4- (3,4-dichloro-phenyl) -2-trifluoromethyl-pyrrol-1-yl-acetonitrile 0 9 9 9 0 6 7. 4-Bromo-3- (3,4-dichlorophenyl) -1-hydroxymethyl-5- (trifluoromethyl) pyrrole-2-carbonitrile pivalate 0 9 9 9 9 8 8. 2,3-Dichloro-5- (4-chlorophenyl) -4-cyanopyrrol-1-ylacetonitrile 0 9 9 9 0 0

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Table 7 (continued)

agent Aphis fabae Spodoptera eridania P. Copper lice Diabrotic undecim- punctate rootworm (Ppm) 100 (Ppm) 1000 (Ppm) 100 7 days (Ppm) 300 (Kg / ha) 50 9. 4-Bromo-2- (4-chlorophenyl) -1- (hydroxymethyl) -5- (trifluoromethyl) -pinO1-3-carbonitrile pivalate (ester) 0 9 9 9 9 9 10. 3,4-Dibromo-5- (4-chlorophenyl) -1-hydroxymethylpyrrole-2-carbonitrile pivalate (ester) 0 9 9 9 0 0 11. 2,3-Dichloro-4-cyano-5- (alpha, alpha, alpha-trifluoro-p-tolyl) -pyrrol-1-yl-pivalic acid methyl ester 0 9 9 9 9 7 12.2- (3,4-Dichlorophenyl) -3-nitro-5-trifluoromethylpyrrol-1-yl-pivalic acid methyl ester 0 9 9 9 - 0 13. 3-Bromo-5- (p-bromophenyl) -4-cyano-2-trifluoromethyl-pyrrol-1-yl-acetonitrile 0 9 9 9 0 8 15. 3-Bromo-5-chloro-4-cyano-2- (3,4-dichlorophenyl) pyrrol-1-yl pivalic acid methyl ester 0 9 9 9 0 4

Example 3

Investigation of insecticidal activity

Heliothis virescens; 3. larval stage of development

Cotton cotyledons were immersed in the test preparation and dried under a suction cup. The dry leaves were cut into squares, and 10-10 of these were placed in a 30ml, 5-7mm wet dental cord. Each of the bowls was loaded with stage 3 butterfly larvae and the cups were covered with a card. The plates were then allowed to stand for 3 days and then evaluated for larval mortality and loss of nutrition.

Empoasca abrupta; an adult

A 3 cm long Sieva lima bean leaf was immersed in the preparation to be examined for 3 seconds with stirring and then dried under a suction cup. The leaves were then placed in a 100 χ 10 mm Petri dish containing wet filter paper on the bottom. 10 insects were placed in each cup and allowed to stand for 3 days. An evaluation of the extent of death was then performed.

Blattella germanica; bait test, adult

0.1% by weight baits were prepared by pipetting 1 g of corn into a 30 ml wide mouth bottle and pipetting 1 ml of 1000 ppm active compound to be tested in acetone. The bottle was placed in a gentle air stream to evaporate the acetone. The bait was then transferred to a 0.5 liter wide mouth Mason bottle containing 10 adult insects.

The bottle was closed with a sieve lid and a small piece of cotton dipped in 10% honey was placed on top of the sieve lid. Mortality was assessed after 3 days of standing.

Blattella germanica; residual examination, adult individuals

To the bottom of a 150 χ 15 mm Petri dish was slowly pipetted 1 mL of 1000 ppm acetone solution, distributing the solution as evenly as possible on the bottom of the dish. The acetone was evaporated and 10 adult insects were placed in each cup and the cups were covered. Mortality was assessed after 3 days of standing.

Spodoptera eridania; systemic absorption assay, larval stage 3 development

A formulation containing 0.1 g of the active ingredient, 0.2 g of Emulphor EL-620 (BASF AG, Ludwigshafen, Germany), 10 ml of acetone and 90 ml of water was prepared. This was diluted 10-fold with water to give a test solution containing 100 ppm of active ingredient. Subsequently, additional dilutions of 10-fold were made with the required amount of water.

7-8 cm long Sieva lima bean primary leaves were cut at the plant's height above the ground level so as to avoid disturbance of the soil bacteria on the plant stem during the test. Each stalk was put in a piece of cotton bur60 to hold the stems at the bottom of the bottle and

EN 217 638 Β evaporate the active ingredient. The bottles were stored at 27 ° C for 3 days for absorption of the drug into the plant. A leaf was then cut off and placed with 10 larvae in a 10 x 100 cm petri dish.

The degree of mortality and loss of nutrition were evaluated on days 3 and 5 after treatment.

Empoasca abrupta; adult, systemic absorption study

An emulsion formulation containing 0.1 g of the test substance, 0.2 g of Emulphor EL-620, 10 ml of acetone and 90 ml of water was prepared. This emulsion was diluted 10-fold with water to give a test emulsion containing 100 ppm of active ingredient. Subsequently, additional dilutions of 10-fold were made with the required amount of water.

7 to 8 cm long Sieva lima bean primary leaves were cut off at a plant height of 3 cm above the ground so as to avoid disturbing the soil bacteria on the plant stem. The cut stems were placed in the emulsion to be tested. Each stalk was wrapped in a piece of cotton cloth to keep the stems at the bottom of the bottle and to reduce evaporation of the active ingredient. The bottles were maintained at 27 ° C for 3 days for absorption of the drug into the plant. A leaf was then cut off from the plant and placed in a 10 χ 100 mm Petri dish along with 10 insects. After 3 days, mortality was assessed.

For evaluation, the scale described in Example 2 was used.

The results obtained are summarized in Table 2.

Table 2

Rovarölőhatás test

agent Empoasca abrupta Heliothis virescens systemic Blattella germanica Spodoptera eridonia Empoasca abrupta bait the rest (Ppm) 100 (Ppm) 1000 (Ppm) 100 (Ppm) 100 (Ppm) 100 (Ppm) 1000 (Ppm) 1000 2,3-Dichloro-4-cyano (3,4-dichlorophenyl) pyrrol-1-ylacetonitrile 0 9 9 0 - 0 7 3-Bromo-5- (4-chloro-phenyl) -4-cyano-2-trifluoromethyl-pyrrol-1-yl-acetonitrile - 9 9 0 0 9 9 4,5-Dichloro-1- (hydroxymethyl) -2- (4-trifluoromethyl-phenyl) -pyrrole-3-carbonitrile acetate (ester) 9 9 9 0 0 9 9 2,3-Dichloro-4-cyano-5- (4- (trifluoromethyl) phenyl) pyrrol-1-ylacetonitrile 9 9 9 0 7 6 9 2,3-Dichloro-4-cyano-5- (3,4-dichlorophenyl) -pyrrol-1-yl-pivalic acid methyl ester 0 9 9 0 0 8 9 3-Bromo-5-cyano-4- (3,4-dichlorophenyl) -2- (trifluoromethyl) pyrrol-1-ylacetonitrile 8 9 7 0 0 5 9 4-Bromo-3- (3,4-dichlorophenyl) -1- (Hydroxymethyl) -5- (trifluoromethyl) - pyrrole-2-carbonitrile, pivalate ester 9 9 9 0 0 9 8 2,3-Dichloro-5- (4-chlorophenyl) -4-cyanopyrrol-1-ylacetonitrile 0 9 9 0 0 0 9 4-Bromo-2- (4-chlorophenyl) -1-hydroxymethyl-5- (trifluoromethyl) pyrrole-3-carbonitrile pivalate (ester) 9 9 9 0 0 7 9 3,4-Dibromo-5- (4-chlorophenyl) -1-hydroxymethylpyrrole-2-carbonitrile pivalate (ester) 9 8 0 0 0 0 0 2,3-Dichloro-4-cyano-5- (4- (trifluoromethyl) phenyl) pyrrol-1-yl pivalic acid methyl ester 0 9 - 0 0 5 9

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Table 2 (continued)

agent Empoasca abrupta Heliothis virescens Szisztcmikus Blattella germanica Spodoptcra eridonia Empoasca abrupta bait the rest (Ppm) 100 (Ppm) 1000 (Ppm) 100 (Ppm) 100 (Ppm) 100 (Ppm) 1000 (Ppm) 1000 Methyl 2- (3,4-dichlorophenyl) -3-nitro-5-trifluoromethylpyrrol-1-ylpivalic acid 9 9 9 6 0 6 9 3-Bromo-5- (4-bromophenyl) -4-cyano- 2- (trifluoromethyl) pyrrole Title-l-yl- acetonitrile 7 9 9 0 - - 0 3-Bromo-5-chloro-4-cyano-2- (3,4-dichloro-phenyl) -pyrrol-1-yl-pivalic acid methyl ester 9 9 9 0 9 0 3

Example 4

Examination of the effect of yarnworm

Maintenance breeding Culture

C. Elegant culture (strain from J. Lewis) was maintained at 20 ° C in E. coli culture on NG Agar plates. A new breeding culture was prepared weekly.

The culture worms were washed for 4-5 days. The wash was performed with Fresh Ascaris Ringers Solution (FARS) (Fresh Ascaris Fingers Solution = Cattle Anti-Tapeworm Solution). The resulting culture was further washed with gentamicin-containing FARS to reduce bacterial contamination and centrifuged to separate the worms from solution. This procedure was repeated three times. The washed worms were then added to a C. briggsae Maintenance Medium (CbMM) (C. briggsae Maintenance Medium = C. briggsae maintenance solution, manufactured by GIBCOa) containing 600 units / ml gentamicin and 0.5 mg / ml micostatin.

The assay was conducted with a mixture of three active ingredients obtained from another high-throughput screening program to reduce lab and drug overhead costs.

The active compounds were dissolved in acetone and the solutions were made up to volume with equal volumes of water. The resulting mixture contained 150 ppm of test compound for each drug. Μΐ ^25-b of the test substance to one well of a sterile tissue culture 96-well plate (COSTAR) mikropipettáztuk. These "treated" plates were used immediately or stored in a freezer to prevent damage to the active ingredient.

50 µg of freshly prepared C. elegans were micropipetted into each well and a few control wells per plate. The culture plate was incubated at 20 ° C.

The efficacy assay was performed under a resolution microscope with 4, 24, and 48 hours post immersion. Immediately before reading, the plates were lightly probed to stimulate the movement of the worms. The drug effect was determined subjectively but semi-quantitatively by testing the motility of adult individuals or larvae.

The following criteria were used;

8 = immobile

7 = 95% of worms have significant immobility 6 = reduced mobility

5 = slightly reduced mobility 0 = normal mobility, identical to control

The effect was well demonstrated by other factors such as worm death, rigidity, cramping, twisting, paralysis, abnormal screwing and within 48 hours worm population and other abnormal behaviors.

Elegance of Caenorhabditis test procedure

Day 0: Inoculation of E. coli-NG Agar dish at 30-50 C.

elegant

- incubation at 20 ° C

Day 4: - Collection of a new C. elegans population

- antibiotic washing

- Transfer to CbMM

- Micropipetting of C. elegans into the wells containing the substance 00 25-100 μΐ

- impact assessment at 4 hours post-immersion

O> hole containing active substance: fresh or pre-prepared and stored in a refrigerator

Day 5: - Impact assessment

Day 6: - Impact assessment

The results obtained are summarized in Table 3.

Table 3

Impact test on nematodes

C. elegant effect [2,3-Dichloro-4-cyano-5- (3,4-dichloro-phenyl) -pyrrol-1-yl] -pivalic acid methyl ester 0

HU 217 638 Β

Table 3 (continued)

C. elegant effect 4,5-Dichloro-1- (hydroxymethyl) -2- (4-trifluoromethyl-phenyl) -pinO1-3-carbonitrile acetate (ester) the 4-Bromo-2- (4-chlorophenyl-1- (hydroxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile pivalate (ester) 0 4-Bromo-3- (3,4-dichlorophenyl) -1-hydroxymethyl-5- (trifluoromethyl) pyrrole-2-carbonitrile pivalate (ester) 0 3,4-Dibromo-5- (4-chlorophenyl) -1-hydroxymethylpyrrole-2-carbonitrile pivalate (ester) 0 [2,3-Dichloro-4-cyano-5- (a, a, atrifluoro-p-tolyl) -pyrrol-1-yl] -pivalic acid methyl ester 0 3-Bromo-5-cyano-4- (3,4-dichlorophenyl) -2- (trifluoromethyl) pyrrol-1-ylacetonitrile 0 2,3-Dichloro-4-cyano-5- (4- (trifluoromethyl) phenyl) pyrrol-1-ylacetonitrile the 3-Bromo-5- (4-chloro-phenyl) -4-cyano-2-trifluoromethyl-pyrrol-1-yl-acetonitrile the 2,3-Dichloro-4-cyano (3,4-dichlorophenyl) -pyrrol-1-yl-acetonitrile 0 [3-Bromo-5-chloro-4-cyano-2- (3,4-dichloro-phenyl] -pyrrol-1-yl] -pivalic acid methyl ester 0 3-Bromo-5- (4-bromo-phenyl) -4-cyano-2-trifluoromethyl-pyrrol-1-yl-acetonitrile the 2,3-Dichloro-5- (4-chlorophenyl) -4-cyanopyrrol-1-ylacetonitrile 0 [2- (3,4-Dichlorophenyl) -3-nitro-5-trifluoromethylpyrrol-1-yl] pivalic acid methyl ester -

- not effective a - effective - not tested

Claims (10)

PATENT CLAIMS A process for the preparation of arylpyrrole derivatives of the formula I wherein X is hydrogen, bromine or chlorine, Y is chlorine or trifluoromethyl, W is cyano or nitro, A is a monosubstituted C 1 -C 4 alkyl group substituted with a cyano group, C 1 -C 4 trihaloalkoxy, (C 1 -C 4 alkoxycarbonyl or C 1 -C 6 alkoxy) carbonyloxy, provided that A is (C 1 -C 4 alkoxy) carbonyl; other than methyl, L is hydrogen, M and R are each independently hydrogen, chlorine or trifluoromethyl, provided that when X is hydrogen and A is a C 1 -C 4 alkyl substituted by cyano, the group of formula (b) wherein wherein L, M, and R are as defined above, at one of the two positions adjacent to the nitrogen atom of the pyrrole ring, wherein X, Y, W, C, M, and R are as defined above. with at least one molar equivalent of a compound of formula IX, wherein A is as defined in the foregoing, Hal is halogen, in the presence of at least one molar equivalent of an alkali metal base and in a solvent suitable for preparing the desired compound of formula I. A process for the preparation of a compound of formula (II) according to claim 1, wherein A, L, M, R, W, X and Y are as defined in claim 1, using the appropriate starting materials. A process for the preparation of a compound of formula (III) according to claim 1, wherein A, L, M, R, W, X and Y are as defined in claim 1, using the appropriate starting materials. 4. An insecticide, acaricide, and nematode composition comprising at least one compound of formula I in an amount of from 0.05% to 95% by weight as an active ingredient, wherein X is hydrogen, bromine or chlorine, Y is chlorine or trifluoromethyl, W is cyano or nitro, A is a monosubstituted C 1 -C 4 alkyl group substituted with a cyano group, C 1-4 trihaloalkoxy, (C 1-4 alkoxy) carbonyl or (C 1-6 alkoxy) carbonyloxy, provided that A is (C 1-4 alkoxy) carbonyl other than methyl, L is hydrogen, M and R are each independently hydrogen, chlorine or trifluoromethyl, provided that when X is hydrogen and A is a C 1 -C 4 alkyl substituted with cyano, the group of formula (b) wherein L, M, and R are as defined above, being attached to one of the two positions adjacent to the nitrogen atom of the pyrrole, and one or more commonly used solid and / or liquid carriers, preferably natural or artificial ground and / or inert solvents, surfactant (s), preferably anionic or nonionic emulsifying and / or dispersing agents and optionally other non-synergistic pesticides. Composition according to claim 4, characterized in that it contains as active ingredient at least one compound according to the method of claim 2. HU 217 638 Β 6. A composition according to claim 4, characterized in that it contains as active ingredient at least one compound according to the method of claim 3. 7. An insect and mite control method, wherein the insect and mite breeding site, food or residence is a compound of formula (I) wherein A, L, M, R, W, X and Y are A composition according to claim 4 containing the same compound as claimed in claim 1, applied at a concentration of 0.100 kg / ha to 4 kg / ha of the active ingredient at a concentration of 10-10,000 ppm, either on exposed plants or on the soil at the place of production. treating the water with a liquid composition containing from 10 to 10,000 ppm by weight of the active ingredient of formula (I). 8. A process according to claim 7 wherein the active ingredient is a compound of formula II prepared by the process of claim 2. 9. The process of claim 7 wherein the active ingredient is in the form of a liquid formulation. An arylpyrrole derivative of formula (I) wherein: X is hydrogen, bromine or chlorine, Y is chlorine or trifluoromethyl, W is cyano or nitro, A is a monosubstituted C 1 -C 4 alkyl group substituted with cyano, C 1 -C 4 trihaloalkoxy, (C 1 -C 4 alkoxy) carbonyl or (C 1 -C 6 alkoxy) carbonyloxy, provided that A is other than (C1-C4) alkoxy-carbonylmethyl, L is hydrogen, M and R are each independently hydrogen, chlorine or trifluoromethyl, provided that when X is hydrogen and A is a C 1 -C 4 alkyl substituted with cyano, the group of formula (b) wherein wherein L, M and R are as defined above - bonded to one of the two positions adjacent to the nitrogen atom of the pyrrole ring.