HU217654B - 4-halogen-2-phenyl-1-(alkoxymethyl)-5-(trifluormethyl)-pyrrol-derivatives, and their intermediates process for their preparation and insecticidal compositions containing one compound as active ingredient and processes using them - Google Patents

Abstract

In the compounds of formula (Ib) of the present invention, R1 is alkyl and L is halogen. In the present invention, compounds of formula (Ia) are prepared in which R1 and L are as defined above and X is bromine or chlorine, wherein a compound of formula (II) wherein L is as defined above has at least one equivalent of a halogen of formula X2. In which X is a bromine atom or a chlorine atom in the presence of a solvent, the resulting 2-phenyl-1-methylpyrrole is reacted with at least one additional molar equivalent of fentanyl and the resulting 2-phenyl-4-halo-1-methylpyrrole radical in the presence of an initiator, reacting with at least a molar equivalent of the above halogen and reacting the resulting 2-phenyl-4-halo-1- (halomethyl) pyrrole with an alkali metal alkoxide. Also within the scope of the invention are insecticidal compositions containing the above compounds as intermediates, as well as intermediates of formula (VI) of the compounds of formula (Ia). ŕ

Description

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GB 217,654 Β amount X ₂ halogens of the formula - are reacted in a solvent, the resulting 2-phenyl-l-methylpyrrole is reacted with at least one additional molar equivalent of above and halogens, and the resulting 2-phenyl -, wherein X is Br or Cl; -4-halo-1-methylpyrrole is reacted with at least a molar equivalent of the above halogen in the presence of a radical initiator and the resulting 2-phenyl-4-halo-1- (halomethyl) pyrrole is reacted with an alkali metal alkoxide.

The invention also relates to insecticidal compositions containing one of the above compounds as active ingredients, as well as intermediates of formula VIa.

The present invention relates to 4-halo-2-phenyl-1- (alkoxymethyl) -5-trifluoromethylpyrrole derivatives, to processes for the production of these compounds and to methods for inhibiting the growth of mite, nematode and insect pests, and crop and cultivated plants against the above insect pests.

Certain substituted arylpyrrole compounds and their use as insecticidal, acaricidal, and nematicidal agents are described in US-A-5,010,098. 2-Aryl-1 (unsubstituted) - (5-trifluoromethyl) pyrrole is disclosed in U.S. Pat. US-A-5,030,735 via the azalactone intermediate.

There is a need for potent agents against mite, nematode and insect pests, which can be produced in high yield and purity in an environmentally friendly manner.

Accordingly, the present invention provides a compound of formula (Ib) wherein R 1 is C 1 -C 6 alkyl and L is halogen.

The invention further provides a process for the preparation of a compound of formula (Ia) wherein R 1 is C 1-6 alkyl,

X is a bromine atom or a chlorine atom, and L is a halogen atom, wherein a compound of formula II wherein L is reacted with at least one equivalent of a halogen of formula X ₂ wherein X is a bromine atom or a chlorine atom reacting the resulting 2-phenyl-1-methylpyrrole with at least one additional molar equivalent of the above halogen, then reacting the resulting 2-phenyl-4-halo-1-methylpyrrole with at least a molar equivalent of the above halogen in the presence of a radical initiator; The 4-halo-1- (halomethyl) pyrrole is reacted with at least one molar equivalent of an alkali metal (C 6) alkoxide.

A variant of the process of the invention is illustrated in Scheme A. The compound of formula (I) may be reacted with halogen in the presence of an aprotic solvent at elevated temperature to produce an arylpyrrole insecticide of formula (2) and of formula (III) wherein X is chlorine. Further halogen can be added to continue the reaction using a radical initiator such as benzoyl peroxide, 2,2'-azobisobutyronitrile or photochemical illumination to give the corresponding 1-halomethylpyrrole compound of formula (le) which can be reacted with an alkali metal alkoxide such as sodium ethoxide, potassium methoxide or the like to produce an insecticide of the arylpyrrole of formula (1d). The insecticidal 4-halo-2- (p-chlorophenyl) -1- (substituted) -5- (trifluoromethyl) pyrrole-3-carbonitrile compounds of formula (Ic) and (ld) are compounds of formula (I) wherein L is chloro and A is halomethyl or C 1-4 alkoxymethyl.

By varying the substituents, the halogen reaction partner and the reaction conditions, a variety of arylpyrrole insecticides, nematodes and acaricides can be prepared from derivatives of the compound of formula (1). The compounds obtained in the above reaction are particularly effective in inhibiting the growth of insect, mite and nematode pests and protecting agricultural crops against the damage caused by these insect pests, both in cultivated and harvested crops. Processes for the preparation of the compounds generally involve halogenation of a 2-aryl-5- (trifluoromethyl) pyrrole-3-carbonitrile halogenating agent such as hypohalite, halogen or sulfuryl halide to give the corresponding 4-halopyrrole intermediate, and alkylating the resulting intermediate with a suitable chloromethyl (C 1 -C 6) alkyl ether.

It has been found that the derivatives of the compound of formula (I) can readily and efficiently produce the compounds of formula (Ia), especially those wherein X is chlorine, by gradually adding the corresponding halogen (V) in the presence of a solvent, preferably at elevated temperature. To prepare the 4-halo-1-methylpyrrole intermediate of formula (VI), further halogen is added by reacting the intermediate of formula (V) in situ in the presence of a radical initiator to give the 4-halo-1- (halomethyl) pyrrole intermediate (VI). with an alkali metal (C1-C6) alkoxide. Surprisingly, the desired compound of formula (Ia) is obtained in high yield with high purity. This process according to the invention is illustrated in Scheme B.

It has been found that the gradual addition of halogen has a favorable effect on the reaction yield and product purity. By avoiding the use of certain unwanted reagents, such as chloromethylether, the process of the present invention enhances the safety of the environment and the operator during the preparation of starting materials. The method of the invention further comprises an effective insect, nematode and mite2

A process for the preparation of 2- (p-chlorophenyl) -4-chloro-1-ethoxymethyl-5- (trifluoromethyl) pyrrole-3-carbonitrile, a killing agent.

Suitable solvents for the process of the present invention include aprotic solvents including halogenated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene and the like, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform, 1,2-dichloroethane. and the like. Preferred solvents are halogenated aromatic hydrocarbons such as chlorobenzene and halogenated hydrocarbons such as carbon tetrachloride. Exemplary radical initiators include light illumination, peroxides such as dibenzoyl peroxide, di-tert-butyl peroxide and the like; azo compounds such as azobis-isobutyronitrile and the like. Preferred radical initiators include benzoyl peroxide and light illumination. The alkali metal alkoxides useful in the process of the present invention include sodium ethoxide, potassium methoxide and the like.

In the process of the invention, the reaction rate increases with increasing temperature, so that elevated temperatures in the range of 55 ° C to 210 ° C, preferably 70 ° C to 120 ° C, allow efficient and satisfactory oxidation, ring halogenation and side-chain halogenation. at a rapid rate without causing unnecessary adverse side effects.

The process of the present invention obviously includes an insect, nematode and acaricidal agent, 2- (chlorophenyl) -4-chloro-1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. production. Pyrrole-3-carbonitrile is effective in inhibiting the growth of mites, lepidoptera, colioptera, hemiptera and the like. It is effective against the following insect pests: potato beetle, golden owl, cabbage moth, cotton owl, corn moth, southern weed owl, cotton-seeded owl moth and the like. Fruits protected by the compound of the invention include lettuce, broccoli, corn, cabbage, kelp, tomato, cotton and so on.

In practice, 2- (p-chlorophenyl) -4-chloro-1 is usually dispersed in amounts of 10 to 10,000 ppm, preferably 100 to 5,000 ppm, in water and / or other suitable liquid carriers such as conventional organic solvents, especially ketones, especially acetone. (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, when used on crop or crop soils, is effective in preventing attack by insects, mites and nematodes. The compound is also useful for protection against garden pests such as lawns, larvae, woodpeckers and the like.

The amount used will vary depending on the external conditions, such as temperature and humidity. The amount of active compound can vary within wide limits, but can be in the range of 0.06-50 kg / ha, but also outside this range.

While 4-chloro-1-ethoxymethylpyrrole can be used alone to inhibit the growth of insects, mites and nematodes, it can be used in combination with other insecticides, including other nematodes and acaricides. The compound of the present invention may be used effectively in combination with, for example, other arylpyrroles, phosphates, carbamates, pyrethroids, formamidines, chlorinated hydrocarbons, halobenzoylureas and the like.

The following non-limiting Examples illustrate the preparation of starting compounds. NMR stands for Nuclear Magnetic Resonance and HPLC stands for High Pressure Liquid Chromatography. Unless otherwise indicated, parts are by weight.

Example 1

Preparation of 4-Chloro-1-chloromethyl-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile (Scheme C)

To a solution of 2.85 g (0.01 mol) of 2- (p-chlorophenyl) -1-methyl-5- (trifluoromethyl) -2-pyrroline-3-carbonitrile in o-dichlorobenzene was added 0.8 g Chlorine (0.011 mol) was added and the resulting solution was stirred at room temperature for 1 hour, heated slowly to 90 ° C over a period of about 2 hours, then cooled to 50 ° C with additional chlorine (0.8 g, 0.11 mol). The reaction mixture is then treated for 24 hours at 110 ° C, cooled to room temperature, treated with additional chlorine and a small amount of benzoyl peroxide and maintained at 110 ° C for 4 hours or until the reaction is complete by chromatography. The resulting solution was cooled, washed with sodium disulfite solution, and concentrated in vacuo to a residue, to which heptane was added to crystallize the title product as a white solid.

Melting point: 107-108 ° C.

Example 2

Preparation of 4-Chloro-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile (Scheme D)

A solution of 2.6 g (0.0074 mol) of 4-chloro-1- (chloromethyl) -2- (p-chlorophenyl) -5- (trifluoromethyl) -pinO1-3-carbonitrile in tetrahydrofuran was treated with sodium ethoxide 3. , Treated with 21% (w / w) solution of denatured ethanol (6 ml, 0.0096 mol), stirred at room temperature for 1 hour, treated with 2 to 3 additional drops of sodium ethoxide solution, kept at reflux for 1 hour, cooled and poured into water. The resulting precipitate was filtered, dried and recrystallized from isopropanol to give 1.6 g of the title compound as a white solid.

Yield: 60%.

Melting point: 104.0-104.5 ° C.

Example 3

Preparation of 2- (p-Chlorophenyl) -1-methyl-5- (trifluoromethyl) pyrrole-3-carbonitrile (Scheme E)

A mixture of 2.87 g (0.01 mol) of 2- (p-chlorophenyl) -1-methyl-5- (trifluoromethyl) -2-pyrroline-3-carbonitrile in chlorobenzene was treated with a mixture of 1.76 g (0.011 mol). moles) of bromine in chlorobenzene and for 4-5 hours (until the reaction is complete as determined by HPLC analysis)

HU 217 654 Β

Keep at 100 ° C. The reaction mixture was cooled to room temperature, diluted with water and extracted with ethyl acetate. The organic extracts were combined, washed successively with water, sodium disulfite and water, dried over anhydrous magnesium sulfate and concentrated in vacuo to give a pale yellow solid. The solid was recrystallized from a mixture of heptane and ethyl acetate to give 2.4 g of the title compound as pale yellow crystals.

Yield: 84.2%.

129.5-130 ° C.

Example 4

Preparation of 4-Bromo-2- (p-chlorophenyl) -1-methyl-5- (trifluoromethyl) pyrrole-3-carbonitrile (Scheme F) a mixture of 2- (p-chlorophenyl) -1-methyl-5- (trifluoromethyl) -2-pyrroline-3-carbonitrile (0.01 mol) in carbon tetrachloride and 3.2 g (0.015 mol) in bromine 2 After refluxing for 1 hour, cooled to room temperature, treated with additional 3.2 g (0.015 mol) of bromine, refluxed for 6-7 hours (until the reaction was complete as determined by HPLC analysis), then cooled to room temperature, aqueous sodium disulfide. solution and concentrated in vacuo to give a residue. The residue was recrystallized from heptane to give the title product as white crystals.

Melting point: 131-131.5 ° C.

Example 5

Preparation of 4-Chloro-1- (chloromethyl) -2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile (Scheme G)

To a solution of 2.85 g (0.01 mol) of 2- (p-chlorophenyl) -1-methyl-5- (trifluoromethyl) -2-pyrroline-3-carbonitrile in chlorobenzene is 0.8 g (0.011 mol). Chlorine was added, stirred at room temperature for 1 hour, kept at 90 ° C for 2 hours, then cooled to room temperature, treated with additional 1.1 g (0.015 mol) of chlorine, kept at 110 ° C for 24 hours, then cooled to room temperature. , Treated with 4 g (0.02 mol) of chlorine and a catalytic amount of benzoyl peroxide and maintained at 110 ° C until the reaction is complete according to HPLC analysis. The mixture was cooled to room temperature, washed with an aqueous solution of sodium disulfite, dried over anhydrous magnesium sulfate, and concentrated in vacuo to give a residue. The residue was recrystallized from heptane to give the title product as a white crystalline solid.

Melting point: 107-108 ° C.

Example 6

Preparation of 4-Bromo-1- (bromomethyl) -2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile (Scheme H)

A solution of 2.85 g (0.01 mol) of 2- (p-chlorophenyl) -1-methyl-5- (trifluoromethyl) -2-pyrroline-3-carbonitrile in carbon tetrachloride with stirring at room temperature

Treated with 1.1 molar equivalents of bromine, kept at 70 ° C for 2 hours, then cooled to room temperature, treated with additional 1.5 molar equivalents of bromine, maintained at reflux for 6-12 hours, and cooled to room temperature with additional 1.5 molar equivalents of bromine. The reaction mixture was illuminated at 2 ° C for 2-4 days or until the reaction was complete according to HPLC analysis, then cooled to room temperature and washed with an aqueous solution of sodium disulfite. The organic phase is concentrated in vacuo to give a residue which is recrystallized from heptane to give the title product as white crystals.

Melting point: 131.0-131.5 ° C.

Example 7

Preparation of 4-Bromo-1- (ethoxymethyl) -2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile (Scheme I)

A mixture of 4.42 g (0.01 mol) of 4-bromo-1- (bromomethyl) -2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile in absolute ethanol (0.715 g) was added. 0.01 mole) of sodium ethoxide in 21% w / w ethanol, kept at 80 ° C for 15-20 minutes, cooled to room temperature, then diluted with water and ether. The organic layer was dried over anhydrous magnesium sulfate and concentrated in vacuo to give a solid residue which was recrystallized from heptane to give 3.45 g of the title product as a white solid.

Yield: 85%.

M.p. 91-92 ° C.

Example 8

Evaluation of insect and acaricidal effects

All tests were performed with technical grade material. The concentration data given refer to the active substance. All tests were performed at 27 ° C.

Spodoptera eridania, Southern weed owl 3. Larvae of Sieva lima beans grown to 7-8 cm in length are immersed in the mixed test suspension for 3 seconds and placed in a drying rack. The dried leaf is placed in a 100x10 mm Petri dish containing wet filter paper at the bottom and ten caterpillars. After 5 days of storage of the thus prepared cup, the caterpillars are observed for mortality, loss of nutrition, and possible disturbances in normal shedding.

Spodoptera eridania, 7 days survival

Plants treated as described above were kept in the greenhouse under high-intensity light for 7 days. These lamps double the effect of New Jersey's cloudless, sunny June days, resulting in a test period of 14 days. After a test period of 7 days, the foliage of the plants was harvested and evaluated as described above.

Tetranychus urticae (P-resistant strain), 2-spotted spider mite

Specimens of bean plants of Sieva lima type having a first leaf 7-8 cm long 4 are selected

HU 217 654 Β gore, leave one plant per dish and infect it with about 100 mites per leaf. Plants infected with the mite are immersed in the mixed test preparation for 3 seconds and placed in a suction cup. After a test period of two days, the first leaf is determined for the death of adult mites. After a further 5 days, the second leaf is examined for mortality of eggs and / or newly developed larvae.

Diabrotic undecimpunctata howardi, 3rd root nematode larvae cm ³ of fine talc is placed in a 30 ml wide-bore with a screw cap glass jar. 1 ml of acetone suspension of test substance is pipetted onto talc to give 1.25 and 0.25 mg of active ingredient per dish, respectively. Air is bubbled into the vessels in a gentle stream until the acetone evaporates. The dry talc is loosened, 1 cm ³ of the insect-fed millet kernel and 25 ml of wet soil are added to each dish. The vessel is sealed and the contents are thoroughly mixed with a Vortex mixer. Indirectly, 10 larvae from each of the third larvae of the rootworm are placed and the dishes loosely covered to allow the larvae to exchange air. After 6 days of treatment, death is determined. Missing larvae are considered dead because they decay rapidly and cannot be found. The concentrations used in this study are approximately 50 kg / ha and 10 kg / ha respectively.

Aphis fabae, mixed larvae of bean aphids

Single dishes containing plants of Arctic fescue (Tropaeolum sp), approximately 5 cm high, were inoculated with 100-200 aphids one day before the test. Each vial was sprayed with the test formulation using a # 154 DeVilbiss nebulizer, sprayed at two revolutions per minute of a rotating turntable. The tip of the atomized spray is approximately 15 cm from the plant and the spray is directed so that the plants and aphids are completely covered with spray. The sprayed pots were placed on white enamel coated trays, and after 2 days the mortality rate was determined.

Empoasca abrupta, adult field cicadas

A leaf of about 5 cm in length from a Sieva lima bean is immersed in the test formulation for 3 seconds with stirring and placed in a suction cup. The leaf is placed in a Petri dish of 100 χ 10 mm with wet filter paper at the bottom. Ten adult cicadas were placed in each dish and mortality was determined after a three day study period.

Heliothis virescens, cotton owl 3. larvae

The cotyledons of cotton plants are immersed in the test preparation and dried in a suction cup. When dry, each cotyledon is cut into four parts and ten leaves are placed in 30 ml plastic medicine cups each,

They contain a dental swab of 5-7 mm in length. A third caterpillar is placed in each cup, and the cup is covered with a cardboard sheet. After a 3-day study period, death was determined and the reduction in leaf chewing damage assessed.

Heliothis virescens, cotton owl eggs

An approximately 6 to 7 cm long young cotton leaf was dipped in the mixed test suspension for 3 seconds. Collect the eggs on a tulle cut into squares of 10 to 20 mm, containing approximately 50 to 100 eggs (6 to 30 hours). One square of the tulle eggs is also dipped in the assay suspension and placed on the treated leaf. The test set-up thus created was dried and placed in a cup (240 ml, 6 cm high, 9.5 cm top and 8 cm lower) containing a 5 cm long dental swab. A clear plastic lid was placed on the dish and mortality was determined after a test period of three days.

Blattella germanica, bait test, adult male German cockroach

0.1% bait is prepared by pipetting 1 ml of a 1000 ppm solution of the test compound in acetone into 1 g of corn pellet in a 30 ml wide neck flask. The baits are dried by directing a weak stream of air into the flask. The baits were placed in a 470 mL wide aperture Mason bottle and ten adult male cockroaches were added. The glass is covered with a grid and a small piece of cotton cloth soaked in 10% honey is placed on the grid. Mortality was determined after a 3 day study period.

Blattella germanica, Residue Assay, Adult Male German Cockroach 1 ml of a 1000 ppm acetone solution of the test substance is slowly pipetted into the bottom of a 150x15 mm Petri dish to ensure a smooth coat. After the precipitate from evaporation of the solution has dried, ten adult male cockroaches are placed in each cup and the cup is covered. Mortality was determined after a 3 day study period.

Rating scale: 0 = ineffective 1 = 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 data obtained from the above definitions are shown in Table I.

The following comparative tests are described for the 4-chloro-2- (p-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrolecarbonitrile (hereinafter "4-chloro compound") of the present invention. and 4-bromo-2- (p5) as described in Hungarian Patent Application No. 204,971

EN 217,654 Β chlorophenyl) -1-ethoxymethyl-5- (trifluoromethyl) pyrrole carbonitrile (hereinafter referred to as "4-bromo compound").

Experiment 1

Determination of contact activity in Lepidopteran larvae

The residual drug was investigated to determine the cuticular contact toxicity of the two pyrrole derivatives in cotton owl larvae 1 (Heliothis virescens) and cotton-seeded owl larvae 3 (Helicoverpa zea). The inner surface of 20 ml glass ampoules was coated with technical grade insecticides diluted with acetone. After drying the surface of the ampoules (i.e., evaporation of acetone), each vial contained a single H. zea larva 3 or up to 10 H. virescens larvae 1 with a small bait. The larvae were then allowed to move on the treated surface of the ampoules for 3 days and the percentage of larvae death was determined for each treatment. Each insecticide was studied at a concentration of 3-4 (ppm by weight / volume of acetone).

Based on LC ₅₀ and non-overlapping confidence intervals, the contact activity of the 4-chloro compound in H. virescens and H. zea is 2-3 times that of the 4-bromo compound (see Table II).

Experiment 2

Toxicity to spider mites

Toxicity of the two pyrrole derivatives to two-spotted spider mites (Tetranychus urticae) was determined by leaf immersion test. The leaves of beans of the Lima type were dipped in a technical grade insecticide diluted 50:50 by volume in acetone: water. After the leaves had dried, 30-70 mites were placed on 1 leaf. After 3 days of study, the percent mortality was determined. Each treatment was performed at a concentration of 4 (active ingredient weight / acetone volume).

Based on LC ₅₀ and non-overlapping confidence intervals, the toxicity of the 4-bromo derivative to mites was 3 times that of the 4-chloro derivative (see Table II).

Experiment 3

Combating Lepidoptera in a cotton plantation

The efficacy of the two pyrrole derivatives against Heliothis virescens in cotton plantations has been investigated in field trials in the USA and Brazil. (The two pyrroles were formulated as a 24% suspension concentrate.) The cotton crop was spray treated with water-diluted concentrate when the density of the pests warranted it. After each treatment, the damage caused by pests to the crop was determined. For each study, the treatment was repeated four times on randomly arranged experimental plots, each measuring 4 rows wide and 12 m long.

The 4-chloro derivative showed greater activity against H. virescens than the 4-bromo compound in the cotton plantation (see Tables IV and V).

Experiment 4

Combating mites in a cotton plantation

The efficacy of the two pyrrole derivatives in cotton plantations against red spider mites (Tetranyhus cinnabarinus) was tested in field trials in the USA. (The two pyrroles were formulated as a 24% suspension concentrate.) By spraying the water-diluted concentrate, the cotton crop was treated when required by pest control. For two weeks following treatment, the extent of infection with the mites was studied. The treatments were repeated four times on randomly arranged experimental plots for 4 replicates per treatment.

The efficacy of the 4-bromo compound against mites was higher than that of the 4-chloro compound (see Table VI).

The above laboratory and field experiments clearly show that the yield of Lepidopteran spp. for larvae, the 4-chloro compound from the preferred red, especially when the pests can be controlled by contact toxicity (such as H. virescens in cotton).

In contrast to mites, the crop is preferably protected by the prior art 4-bromo compound.

Therefore, based on the known 4-bromo compound, no difference in toxicity and efficacy could be predicted for the 4-chloro compound.

Table I

Determination of insecticidal and acaricidal activity of 2- (p-chlorophenyl) -4-chloro-1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile

test evaluation 1000 100 10 1 o, l (ppm) Southern weed owl 3. larvae 9 9 9 0 - 7-day survival 9 9 6 - - Two-spotted spider mite - - 9 0 - bean - 9 4 0 - Cicada - 9 9 9 - Tobacco budworm ovule 7 0 - - - 3. larvae 9 9 9 - - German cockroach bait 0 - - - - the rest 9 0 - - 50 kg / ha 10 kg / ha 1 kg / ha Root- nematode 9 7 0

HU 217 654 Β

II. spreadsheet

Contact toxicity of selected pyrroles in H. virescens larva 1 and H. zea larva 3

Treatment n ¹ LC _SO (ppm, 95% Cl) H. virescens 4-Chloro Compound 210 0.35 (0.31-0.39) 4-bromo compound 206 1.06 (0.97-2.15) H. zea 4-Chloro Compound 45 1.70 (1.22 to 2.34) 4-bromo compound 45 3.84 (3.21-4.83)

^{1 is} the number of larvae tested

III. spreadsheet

Toxicity of selected pyrroles in the mobile forms of two-spotted spider mites (T. urticae)

Treatment LC ₅₀ (ppm, 95% Cl) 4-Chloro Compound 2.46 (1.27 to 4.90) 4-bromo compound 7.35 (7.10-7.60)

ARC. spreadsheet

Eradication of H. virescens in a cotton plantation (Louisiana, USA, 1991)

Treatment Damage to parcels (%) Damage to cotton (%) 08/06/06 June 28 5/9/09 9/11/11 9/20/2010 4-Chloro- compound, 0.39 kg / ha 0 * 6 * * 4 2 * * 1 4-Bromo- compound, 0.39 kg / ha * 1 8 * * 3 4 5 untreated 8 20 21 11 9

August 2, September 20 th September 2

2 * Significantly different from untreated controls (ANOVA, P = 0.05)

Table V.

Control of H. virescens in a cotton plantation (Brazil, 1992)

Treatments ¹ Final damage of plants (%) after treatment 3 days 7 days 4-Chloro Compound 0.35 kg / ha 10 7 0.45 kg / ha 8 3 4-bromo compound 0.35 kg / ha 20 15 0.45 kg / ha 12 10 untreated 26 13

VI. spreadsheet

Combating Red Spider Mites (T. cinnabarinus) in a cotton plantation (Texas, USA, 1991)

Treatments ¹ Average number of mites / leaves after treatment 1 week 2 weeks 4-bromo compound 0.06 kg / ha 8.0 45.3 0.11 kg / ha 1.5 32.4 0.23 kg / ha 0.6 3.9 4-Chloro Compound 0.06 kg / ha U 4 58.4 0.11 kg / ha 7.4 63.5 0.23 kg / ha 2.6 34.9 untreated 48.0 77.6

¹ June 17

Claims (8)

PATENT CLAIMS CLAIMS 1. Compounds of formula Ib wherein R 1 is C 1-6 alkyl and L is halogen. A compound of formula (Ib) according to claim 1, which is 4-chloro-1- (ethoxymethyl) -2- (chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. Preparing the third procedure (Ia) Compounds of general formula - wherein R _t is 1 to 6 carbon atoms, X is bromo formula or chloro, and L is a halogen atom, characterized in that (II) is a compound of formula - wherein L is a tangible with at least one equivalent of a halogen of formula X ₂ wherein X is bromine or chlorine, the resulting 2-phenyl-1-methylpyrrole is reacted with at least one additional molar equivalent of the above halogen and -phenyl-4-halo-1-methylpyrrole is reacted with at least a molar equivalent of the above halogen in the presence of a radical initiator, and the resulting 2-phenyl-4-halo-1- (halomethyl) pyrrole is at least one molar equivalent of an alkali metal with C) )alkalkoxide. 4. 4-Chloro-1- (chloromethyl) -2- (chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile (4) and 4-bromo-1- (bromomethyl) (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile intermediate -2-. 5. A method for protecting crops from attack by insects, nematodes and acarids, wherein 10 -10,000 ppm of 4-chloro-1- (ethoxymethyl) -2- (p-chlorophenyl) -5- ( a composition comprising trifluoromethyl) pyrrole-3-carbonitrile is applied to the foliage of the plants or to the soil or water used to grow the plants. 6. A method for inhibiting the growth of insects, nematodes and mites, comprising 10 to 10,000 ppm of 4-chloro-1- (ethoxymethyl) -2- (p-chlorophenyl) 7. HU 217 654 Β The composition comprising 5- (trifluoromethyl) pyrrole-3-carbonitrile is contacted with insects, nematodes and mites, their breeding grounds, food or place of occurrence. 7. A composition for protecting crops against insects, nematodes and mites, characterized in that the active ingredient used as an insect, nematode or mite is 4-chloro-1- (ethoxymethyl) 2- (p-chlorophenyl) -5-. (trifluoromethyl) pyrrole-3-carbonitrile It contains from 10 to 10,000 ppm in an agronomically acceptable carrier. 8. An insect, nematode, and acarid growth inhibitory composition, wherein the active ingredient is 4-chloro-1- (ethoxymethyl) -2- (p-chlorophenyl) -5- ( trifluoromethyl) pyrrole-3-carbonitrile in an amount of 10 to 10,000 ppm with an agronomically acceptable carrier.