Derivates of arylpyroli n-acilates, preparation process thereof and method for the controlling of the insects, acariens, nematodes, fungus and molluscs

The present invention relates to N-acylated arylpyrrole derivatives, a process for obtaining them and a method for combating insects, mites, nematodes and molluscs. 5

They are known as arylpyrrole derivatives used to combat the various pests that attack plants.

Of these we mention N-acylated 3-phenylpyrrole derivatives with fungicidal activity, of which 1-acetyl-3-cyano-4- (2-chlorophenyl] pyrrole is the most active [US 4229465],

Said compound can be obtained by a conventional acetylation reaction starting from suitable starting materials, namely, from o-chloro-cinnamic nitrile, methyltosyl isocyanide with pyrolysis ring closure, followed by acetylation.

Also known are derivatives with fungicidal, insecticidal, acaricidal and 20 herbicidal activity, of the class N-acetyl-3-aryl-4-cyanpirols [GB. 2024824],

Pesticides from the aryl class of pyrolols of the formula below are known.

<img file="RO110818B1_D0001.tif" />

wherein: X halogenated sphincter, CF₃, Y = X, CN; W 35 is CN, NO₂; A is selected from H, substituted alkyl or phenyl, L is selected from H, F, Cl, Br, M; R is H, alkyl alkoxy, alkylthio, alkyl sulfinyl, CN, alkyl sulfonyl, CN, halogen, · ·· N0₂. CF₃, and when M and R are adjacent 40 form 0CH groups₂0, 0CF20 [EP

312723],

The present invention extends the range of compounds intended to control insects, mites. nematodes and molluscs, and refers to N-acylated arylpyrrole derivatives that have

<img file="RO110818B1_D0002.tif" />

is H, F, Cl or Br, and M and Q are each, individually H, C alkyl₁-C₃ C 1 -C 6 alkoxy, C 1 -C 6 alkyl, C 1 -C 8 alkylsulfinyl, C 1 -C 6 alkylsulfonyl.₂C0 or NR₃R₄, and when M and Q are bonded to the carbon atoms adjacent to a phenyl ring, they can together with them form a ring in which MQ represents an OCH-type structure.₂O-, - 0CF₂0 - or z is S [C]_n or O, R₃ is H, F, CHF₂, CHFCI or CFg, R₂ is C 1 -C 6 alkyl_rC₃ or NR₃R₄, R₃ is H or C alkyl_rC3, R4 is H, C1 alkyl₁-C₃ or RsCG, Rs is H or CȚ-Cg alkyl, n is an integer chosen from O, 1 or 2, and R is C alkyl._rC₆which can be substituted with one to three halogen atoms, one hydroxyl, one cyan, one or two C alkoxy groups_q-C₄ optionally substituted with one to 3 halogen atoms, one alkylthio group one phenyl group, optionally substituted one to three halogen atoms, one to three C alkyl groups_rC₄ or with one to three CȚ-C ^ alkoxy groups, a phenoxy group, optionally substituted with one to three halogen atoms, with one to three C alkyl groups₃C₄ or with one to three C 1C alkoxy groups₄, a benzyloxy group, optionally substituted on the phenyl ring with one to three halogen atoms, with one to three C alkyl groups_qC₄ or with one to three C 1 C alkoxy groups₄, a C 1 -C 6 alkyl carbonyloxy group optionally substituted with one to three halogen atoms, a C 2 -C 6 alkenyl carbonyloxy group, optionally substituted with one to three halogen atoms, a phenylcarbonyloxy group optionally substituted with one to three halogen atoms, with one to three C 1 -C 6 alkyl groups₄ or with one to three C. alkoxy groups₄a C 1 -C 8 alkoxycarbonyl group, optionally substituted with one to three halogen atoms or one to three alkoxy groups;_Ίΐ₄, a benzyloxycarbonyl group, optionally substituted on the phenyl ring with one to three halogen atoms, with one to three C 1 -C 6 alkyl groups.₄ or with one to three C 1-4 alkoxy groups₄, is C alkenyl₂-C_B possibly substituted with one to three halogen atoms or a group wherein: X is HF, Cl.Br, I or CF₃, Y is

F, Cl, Br, I or CF₃, W is CN or NO2, L

Phenyl, is a C 1-6 alkynyl group₃-C_B, optionally substituted with one to three halogen atoms or a phenyl group, is a C cycloalkyl group₃-C₆, is a phenyl group. possibly substituted with one to three halogen atoms, with one to three alkyl groups Ο &lt;C₄, a C 1-6 alkyl group₅-C 2, one or two C 1 -C 6 alkoxy groups₄, or a phenoxy, C 1 -C 4 alkylthio, trialkylsilyl, 0_η-0₄ alkylsulfinyl, C. | -C₄alkylsulfonyl, carbo-C 1 -alkoxy-carboxy, CF₃, CN, ΝΟ_ξ, of [C 1 -C 4 alkyljamino, or C_n-C₄alkanoylamino, is phenoxy optionally substituted with one to three halogen atoms, one or two C groups_rC₄ alkyl, one or two C 1-4 alkoxy groups₄₁ trialchilsilil, CN, N0₂CF₃ or to the group of (C -] - C₄ alkyl) amino or C_q-C₄ alkanoylamino, is phenoxy optionally substituted with one to three halogen atoms, one or two C groups.₄alkyl, one or two C alkoxy groups_rC₄trialchilsilil, CN, N0₂, CF₃ or groups of (C₁-C₄alkyl) amino or C, -C₄ alkanoylamino, is 1 or 2-naphthyl, is 2-, 3- or 4-pyridyl, optionally substituted with one to three halogen atoms, a 5-atom heteroaromatic ring containing oxygen, nitrogen or sulfur and optionally substituted with one to three halogen atoms is a C 1 -C 6 alkoxy group, optionally substituted with one to three halogen atoms; or is a C alkenyloxy group₂-C_B, possibly substituted with one to three halogen atoms.

Another object of the present invention is the process for obtaining N-acylated arylpyrrole derivatives of formula I, which consists in the reaction of an arylpyrrole derivative of the formula

<img file="RO110818B1_D0003.tif" />

in which: L, M, Q, W, X and Y have the above meanings, with an excess of alkali metal hydride or alkali metal t-butoxide, in the presence of an anhydrous inert organic solvent, forming a first reaction mixture, a mixture which heat, then cool and add a suitably substituted carbonyl chloride having RCOCI, wherein R is a substituent with the same meanings as in formula (I), after which the second reaction mixture is heated with the formation of the arylpyrrole derivative N. acylated.

The present invention relates to a method for the control of insects, mites, nematodes, fungi and molluscs, which consists in the application on the mentioned pests, on their soil of development, on their food or habitat, of insecticidal, acaricidal effective amounts. , nematicide, fungicide or molluscide, preferably in an amount from 0.1 kg / h to 4.0 kg / ha, active ingredient.

The invention has an advantage in that the N-acylated arylpyrrole derivatives have better solubility and can be more easily formulated for application, as well as a higher hydrolytic stability and reduced phytotoxicity, compared to the non -acylated arylpyrrole derivatives.

The present invention relates to novel N-acetylated arylpyrroles described by formula I:

<img file="RO110818B1_D0004.tif" />

wherein: X is H, F, Cl, Br, I. or CF₃; Y is F, Cl, Br.l, or CF₃; W is CN, or N0₂: L is H, F, Cl, or Br; and M is Q are each in part H, C_rC₃ alkyl, C 1 -C 6 alkoxy, C 1 -C 6 thioalkyl, Οη-C 3 alkylsulfinyl, C_rC₃ alkylsulfonyl, cyan, F, C1, Br, I, nitro, CFg.RqCFgZ, R₂C0 or NR₃R₄; and when M and Q are bonded to the carbons adjacent to the phenyl ring and taken together with the carbon atoms they are bound to, they can form a ring in which MQ represents the structure:

-0CH₂0-, -OCF₂0- or Z is S (O)_n or

A; R_q is H, F, CHF₂, CHFCI, or CF₃;

R₂ is Οη-Cg alkyl, C 1 -C 6 alkoxy, or NR₅R₄;

R₃ is H or C 1 -C 6 alkyl; R₄ is H, C 1 -C 3 alkyl, or R₅CO; R₅ is H or 0_η-0₃ alkyl;

and n is an integer of 0.1 or 2; and R is C., - C_B alkyl possibly substituted with one at

RO 110818 With three halogen atoms, a hydroxyl, a cyan, one or two C groups.₄ alkoxy possibly substituted with one to three halogen atoms; a Ci-C₄ alkylthio; a phenyl group optionally substituted with one to three halogen atoms, one to three C-alkyl groups_q-C₄ or one to three C alkoxy groups_n-C₄; a phenoxy group optionally substituted with one to three halogen atoms, one to three C alkyl groups_n-C₄ or one to three C alkoxy groups₄-C₄; a benzyloxy group optionally substituted on the phenyl ring with one to three halogen atoms, one to three C 1 -C 6 alkyl groups₄ or one to three C 1 -C 4 alkoxy groups; a C 1-6 alkyl carbonyloxy group_rC₆ possibly substituted with one to three halogen atoms; a C alkenylcarbonyloxy group₂-C₆ optionally substituted with one to three halogen atoms; a phenylcarbonyloxy group optionally substituted with one to three halogen atoms, one to three alkyl groups or one to three C alkoxy groups_q-C₄; an alkoxycarbonyl group C_rC₆optionally substituted with one to three halogen atoms, or one to three alkoxy groups or one benzyloxycarbonyl group optionally substituted on the phenyl ring with one to three halogen atoms, one to three C alkyl groups., - C₄ or one to three C alkoxy groups_rC₄, C₂-C₆ alkenyl optionally substituted with one to three halogen atoms or with a phenyl group, C₃-C_B alkynyl optionally substituted with one to three halogen atoms or a phenyl group, C₃-C₆ cycloalkyl, phenyl optionally substituted with one to three halogen atoms, one to three C 1-4 alkyl groups, one C 1 -C 4 alkyl group, one to two Οη-ϋή alkoxy groups, or one phenoxy group, C 1 -C 6 alkyl.₄, trialkylsilyl, alkylsulfinyl C., - C₄, 0-4 alkylsulfonyl, C 1 -C 6 alkoxy, carboxy, CF₃, CN, N0₂, of (C₄-C₄ alkyl) amino. or phenoxy alkanoylamino optionally substituted with one to three halogen atoms, one or two C 1 -C 6 alkyl groups₄, one or two C 1 -C 6 alkoxy groups₄, trialchylsilyl, CF₃, CN, N0₂, or groups of (C_rC₄ alkyl) amino, or alkanoylamino C_q-C₄, 1-naphthyl or 2-naphthyl, 2,3-, or 4-pyridyl optionally substituted with one to three halogen atoms, a 5-atom heteroatomic ring containing an oxygen, nitrogen, or sulfur atom, and optionally substituted with one to three halogen atoms, the alkoxy-Cg group optionally substituted with one to three halogen atoms; or C alkenyloxy group₂-C₆ optionally substituted with one to three halogen atoms.

Preferred group of compounds of this invention is characterized by structural formula II, which can be illustrated as follows:

<img file="RO110818B1_D0005.tif" />

wherein: L, M, Q, W, X, Y and R have the same meanings as in formula I above.

Another preferred group of compounds of the present invention has structural formula II. where W is CN; X is HF Cl, Br, or CF₃; Y is H, CI, Br. or CF₃; L is H. CI. F, or Br; M and Q are each independent, H, halogen or CF₃; and R is phenyl optionally substituted with one to three halogen atoms, one to three C alkyl groups_rC₄. one to two C 1 -C 6 alkoxy groups, or a phenoxy group. thioalkyl C_rC₄, trialkylsilyl, alkylsulfinyl C., - C₄, C 1-6 alkylsulfonyl_rC₄, carboC ^ -alkoxy, carboxy, CF₃, CN, N0₂, d / (C₁-C₄C 1-6 alkyl, or alkanoylamino₄-C₄; 1 naphthyl or 2-naphthyl. or 2-, 3-, or 4-pyridyl optionally substituted with one to three halogen atoms, a 5-atom heteroaromatic ring containing an oxygen, nitrogen or sulfur atom, and optionally substituted with one to three halogen atoms.

Preparation of the N-acylated arylpyrroles of this invention generally involves the acylation of an arylpyrrole having structural formula III:

<img file="RO110818B1_D0006.tif" />

wherein: L, M, Q, W, X and Y have the same meanings as in formula I.

RO 110818 Bl

The acylation of arylpyrrole of formula (III) can be achieved by its reaction with an alkali metal hydride or alkali metal t-butoxide and an acylating agent having the structure: RCOC1 where R has the above meaning.

In the reaction, alkali metal hydride or alkali metal t-butoxide is generally dispersed in an anhydrous organic solvent such as tetrahydrofuran, dimethoxyethane, dimethylformamide, dimethylsulfoxide, or the like, and the mixture.

<img file="RO110818B1_D0007.tif" />

thus formed it is then heated to reflux temperature. The reaction mixture is cooled, generally between 20 ° and 3D ° C and the acylating agent, RCOCI, is added, wherein R is described above. Then the mixture thus prepared is heated at reflux temperature until arylpyrrole Nacylate is formed. The reactions are preferably conducted under an inert gas cushion such as nitrogen or argon. The reactions can be illustrated by

<img file="RO110818B1_D0008.tif" />

(I)

The N-acylated arylpyrroles of formula I according to the present invention are effective in controlling a wide variety of plant pests that destroy all types of vegetation, including field crops, fodder crops, cotton, cucumber, cereals, ornamental plants, cabbage crops, shrubs and the like.

Among these pests are insects and mites, which feed on the foliage, stems, fruits, flowers and sap of plants. These insects and mites are generally in the following order:

Coleoptera, Dipteo, Thysanoptera, Homoptera, Hymenoptera, Lepidoptere and Orthoptera. Other pests that destroy the plants, but are easily controlled by the N-acylated arylpyrroles of formula I, according to the present invention, are soil pests such as nematodes, root worms, long worms and the like, which attack and destroy the root system of plants, and molluscs, especially of the gastropathic class, which include snails (without a home), kauri, molluscs (with univalve shell) and snails, which are devouring, with an appetite for plant seedlings, in particular, ornamental. It has also been found that the arylpyrrole Nacylates of this invention have the additional advantage that they can also be used to control fungal organisms, in order to protect the plants against the ravages of fungal diseases.

It has been found that in order to combat the above-mentioned pests and / or to ensure the protection of the plants from their attack, the N-acylated arylpyrroles according to the present invention may be conditioned in the form of aqueous or non-aqueous liquid formulations and applied to the plants and / or soil where grow by spraying or watering, aqueous or liquid, containing from about 10 ppm to about 10,000 ppm and preferably about 50 ppm to 4000 ppm arylpyrrole N-acylate of formula I. These liquid compositions are usually applied in an amount sufficient to provide about 0.1 kg / ha to about 4.0 kg / ha of active ingredient at the treatment site.

Derivatives according to the present invention can be conditioned as solid formulations, such as compact granules, powders, powder concentrates and bait formulations that can be applied to the soil where the plants are to be protected, or, in the case of powders or powder concentrates, be applied to the foliage of plants.

The aqueous or liquid compositions useful in the practice of this invention may initially be formulated as a solid or liquid concentrate, which is dispersed in water or another inexpensive liquid diluent. generally in place

RO 110818 Treatment bl, for application by spray or watering.

The concentrates useful for the preparation of solutions for spraying or watering are in the form of a wettable powder, an emulsifiable concentrate, a granular formulation which can be fluidized in water or dispersible in water.

□ Typical suspension concentrate formulation can be prepared by grinding together about 5% to 25% by weight N-acylated arylpyrrole of formula I, about 3% to 20% by weight anionic surfactant such as dodecyl benzene sulfonic acid , about 1% to 5%, by weight, nonionic surfactant such as an ethylene oxide block copolymer having an ethoxylation degree of from 8 to 11 moles, about 1% to 5%, by weight, polyethylene oxide condensed alkylphenol, with an ethoxylation degree of 9 to 10 moles and up to 100% aromatic solvent, from petroleum.

A preferred group of ethylene oxide / propylene oxide block copolymers for use in the compositions of this invention are butyl-omega-hydroxypoly (oxypropylene) polymer block with poly (oxyethylene) having an average molecular weight in the range of 2400 to 3500, with block copolymer. / t-butyl-omega-hydroxyethylene oxide-propylene oxide having a HLB of 12 and viscosity at 25 ° C of 2000 CPS, (TOXIMUL ™ 8320, Stepan Chemical Co.) being one of the most preferred compounds of this class of emulsifiers.

The condensed compounds, alkylphenolpolyethylene oxide, preferred for use in the compositions of the invention are: nonylphenol ethoxylates, ethoxylated nonylphenol (9 to 10 moles ethylene oxide) (FLO M0 (^R) 9N, DeSoto, Inc.Sellers Chemical Div.) Being one of the most preferred compounds of this class of emulsifiers.

Among the most preferred aromatic petroleum solvents used in the preparation of suspension concentrates containing N-acylated arylpyrrols, according to the invention, are:

1 / mixture of aromatic hydrocarbons (C9-C12 aromatic, distillation range 183-210PC) (AROMATIC ™

15O, Exxon)

2 / mixture of aromatic hydrocarbons (C₈-C_g aromatic, distillation range 155-173 ° C) (AROMATIC ™

1OO, Exxon)

3 / mixture of aromatic hydrocarbons (C₁₀ the C₁₃ aromatic, distillation range 226-279 ° C) (AROMATIC ™ 200)

4 / mixture of aromatic hydrocarbons (C_B-Cg aromatic, boiling point 148.9 ° C) (TENNEC0 ™ T500 / -100) aromatic hydrocarbon mixture (TENNECO ™ T400) hydrocarbon mixture (distillation range 177-277 ° C) (HAN ™ Exxon)

5 / mixture of aromatic hydrocarbons (distillation range 21O-288 ° C) (PANASOL ™ AN-3N, Amoco)

6 / mixture of aromatic hydrocarbons (distillation range 179-21 B ° C (Shell CYCLO SOL ™ 63).

The fluidizable formulations can be prepared by mixing about 5% to 50% and preferably about 10% to 25%, by weight, of N-acylated arylpyrrole of formula I, from about 2% to 3%, by weight, of naphthalene sulfonic condensate. , about 0.1% to 0.5% by weight, nonionic polyethoxylate nonionic, about 0.1% to 0.5%, xanthan gum, about 0.1% to 0.5% clay with swelling properties, such as bentonite, about 5% to 10% by weight of propylene glycol, about 0.1 to 0.5%, by weight, silicone anti-foaming agent, about 0.1% to 0.3%, by weight, an aqueous solution of dipropylene glycol of 1,2-benzizothiazolin-3-one (preservative) and up to 100% water.

An wettable powder can be prepared by grinding together about 5% to 25%, by weight, arylpyrrole Nacylate of formula I · about 3% to 15%, by weight, anionic surfactant, such as dodecylbenzene sulfonic acid, about 3% to 10 % nonionic block copolymer ethylene oxide, about 1% to 3%, by weight, ethoxylated nonylphenol having 8 to 10 moles ethoxylate and about 47% to 88%, by weight, solid inert diluent such as montmorilonite, atapulgite, diatomite, talc or others also.

In addition to the suspension concentrates, the fluidizable aqueous compositions and the wettable powders described above, can be prepared and used for plant protection against the attack of the aforementioned pests and other formulations, such as water dispersible granules, emulsifiable concentrates and granular formulations.

RO 110818 Bl compacted.

From the point of view of practical use and application, several advantages derive from acylation of pyrolines of insecticidal character, described in the present invention. In one case, N-derivatization leads to improved solubility of the product in organic solvents, thus allowing greater ease of formulation of the product for application. In those cases where the base pyrol has little or no phytotoxicity to agricultural crops, it is necessary to pay little attention to the hydrolytic stability of the resulting derivative, as long as the stability allows formulation in a non-aqueous environment and sufficient stability in the mixing vessel. large to allow application. Such a situation has been found, for example, for compound A. In this case, the compound is harmful to plants. Due to the reduced solubility properties, compound A, illustrated below, is difficult to formulate. When A is acetylated to give compound B, the solubility in organic solvents is enhanced, allowing the specialist greater freedom in choosing an appropriate agent for the application of the product. Such formulations may be dispersed in water, as is customary, and applied immediately, although acetylated pyrol B will largely return to the base compound A, if left for several days in a homogeneous mixture with water and a miscible solvent as acetone.

<img file="RO110818B1_D0009.tif" />

Δ

<img file="RO110818B1_D0010.tif" />

B

If a pyrol, for example, compound A is benzoylated to give product C, the solubility properties are again enhanced. In addition to the fact that both A and C have comparable insecticidal activity against southern shrub and tobacco budworm at the larval stage, it has also been found that C is effective against the red spider at a concentration of 100 ppm. . It is different from A which has no activity even at 300 ppm. It has also been found that benzoyl pyrols, such as C, have a much higher hydrolytic stability than those derived from aliphatic carboxylic acids. This difference is of little interest when the pyrolysis base is not phytotoxic and a small amount of the hydrolysis-generated base compound would not harm the plants that are protected by insects. In a number of cases pyrols have been found that are very active against insects but harmful to the plants for which they are designated to protect them. An example is compound D, a broad-spectrum, high-efficiency insecticide that cannot be used due to severe plant damage. Because even small concentrations of this pyrol are not acceptable in a formulation, the derivative must be non-phytotoxic and hydrologically stable. In this case, the benzoylated product E provides a harmless product for plants. The danger of in situ hydrolytic generation of the phytotoxic base compound is very low because

Compound E has been found to have a half-life, in a homogeneous mixture of aquacetonitrile, measured in years. In this case, there is also the added benefit of reduced toxicity for mammals, which for base compound D is 31.0 mg / kg compared to 54.0 mg / kg for E, expressed as the dose required to kill.

50% of mice fed orally.

<img file="RO110818B1_D0011.tif" />

<img file="RO110818B1_D0012.tif" />

<img file="RO110818B1_D0013.tif" />

The following are 3 examples of embodiment of the invention.

Example 1. Preparation of 1-Benzoyl 4-bromo-2-chloro-5- (p-chloro-phenyl] pyrrole-3-carbonitrile

<td>NC</td><td>br</td><td></td>

<td></td><td>I</td><td>IIIWTHF 2) PhCoCI Δ</td>

<td></td><td>and H</td><td></td>

<img file="RO110818B1_D0014.tif" />

To a suspension of sodium hydride 35 (0.21 g of a 60% dispersion, 5.3 mmol) in 50 ml of dry tetrahydrofuran contained in a 100 ml round-bottomed flask with a single neck provided with a a condenser and a nitrogen inlet connection are added to 40 portions [1.0 g, 3.2 mmol] 4-bromo-2-chloro-5 (p-chlorophenyl] pyrrole-3-carbonitrile. Stir for 15 minutes. min. at room temperature, before adding by pipetting 3 ml of hexamethylphosphoramide (HMPA) followed immediately by 45 [0.75 g, 5.4 mmol] benzoyl chloride, and then the reaction mixture is heated to reflux for 17 h. and allowed to cool. Evaporation in a rotary evaporator gives a crude semi-solid to which is added 15 ml diethyl ether and 15 ml water. Shake vigorously for 20 minutes, ^;then filtered in vacuo to isolate the product as a yellow solid (1.0 g. 2.4 mmol, 75%), mp 179-181 ° C.

Example 2. Preparation of 1-Benzoyl 4-bromo-2- (p-chlorophenyl) -5- {trifluoromethyl-pyrrole-3-carbonitrile

<img file="RO110818B1_D0015.tif" />

1) N »H _____

2) doori dc bctMM

Τϋί, Δ, K₂

<img file="RO110818B1_D0016.tif" />

In a 250 ml round bottom flask fitted with a magnetic stirrer and a refrigerant with a nitrogen adapter, 0.60 g NaH (60%) is introduced. The NaH was washed with about 50 ml of hexane, which was then decanted and replaced with 75 ml of tetrahydrofuran (THF). Some kind of boiling occurs after THF is added, so THF is not anhydrous. The flask is cooled in an ice-water bath and 2.04 g of 4-bromo-2- (plorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile are added in portions, and hydrogen is released. The reaction mixture was refluxed for 20 min, cooled to room temperature, then 2.3 ml of benzoyl chloride were added, followed by the reaction mixture refluxing overnight. The reaction mixture is cooled and poured into about 100 ml of cold water and extracted with 100 ml of ether. The aqueous extract 20 was washed with 100 ml saturated NaHCO solution^3, dry on K₂CO₃, filtered and concentrated in a rotary evaporator under reduced pressure. The excess benzoyl chloride is removed by distillation with a 25 Kugelrohr apparatus at lOCPC and 5 mmHg. The residue is then refluxed with 100 ml of hexane, heat filtered to remove most of the unreacted 4-bromo-2- (p-chlorophenyl) 5- (trifluoromethyl) pyrrole-3-carbonitrile. The reaction product is chromatographed on a silica gel column, by flash chromatography, eluted from 1 to 12 with a mixture of 10% ethyl acetate and 90% hexane. Fractions of 100 ml are collected and fractions 3 and 4 are combined and concentrated in a rotary evaporator under reduced pressure. Then add 5Q ml of hexane, reflux the mixture to bring the product to the solution, after which the solution is allowed to slowly crystallize overnight. After filtration, 1.58 g of white crystals of 1-benzoyl-4-bromo-2- (p-chlorophenyl) -5 (trifluoromethyl) pyrrole-3-carbonitrile are isolated. Melting point 1O5-1O7 ° C.

Example 3. Preparation of 4-Bromo-2 [p-chlorophenyl] -1-pivaloyl-5- (trifluoromethyl) pyrrole-3-carbonitrile

<img file="RO110818B1_D0017.tif" />

,

2) Ounn dc phtiod

ΤΗ1Δ

<img file="RO110818B1_D0018.tif" />

In a flask with a round bottom of 35 250 ml, equipped with a magnetic stirrer and a refrigerant with a nitrogen adapter, 1.20 g NaH (60%) is introduced. The NaH is washed with about 50 ml of hexane, after which the hexane is decanted and replaced with 75 ml of 40 tetrahydrofuran (THF). Some kind of boiling occurs after THF is added, so THF is not anhydrous. The flask is cooled in an ice-water bath and 4, Q8 g 4-bromo-2 - (/&gt; chlorophenyl) 5-45 (trifluoromethyl) pyrrole-3-carbonitrile are added in portions, with hydrogen being released. The reaction mixture is refluxed for 20 minutes, cooled to room temperature and 5.0 ml of pivaloyl chloride is added, after which 50 the reaction mixture is refluxed overnight. The progress of the reaction is evaluated by HPLC analysis of part of the mixture. When HPLC indicates that the reaction has advanced about 20%, 2 mL of hexamethylphosphoramide (HMPA) is added to speed up the reaction, and the reaction mixture is refluxed again overnight. The reaction mixture is cooled and poured into about 100 ml of cold water, then extracted with 100 ml of ether and 100 ml of hexane. The organic layer is washed three times with 100 ml water, then with 100 ml saturated NaCl solution, dried over K₂C0₃, filtered and concentrated in a rotary evaporator under reduced pressure. Then 100 ml of hexane is added to the residue. The mixture is refluxed, cooled and then filtered to obtain

RO 110818 Bl

3.54 g yellowish powder. The powder is crystallized twice from 50 ml of methylcyclohexane to give 2.75 g of 4-bromo-2-fp-chlorophenyl) -1-pivaloyl-5 (trifluoromethyl] pyrrole-3-carbonitrile as a yellow needle, with pt = 177-. 18th C.

Following the above procedure, but replacing: 4-Bromo-2- (p-chlorophenyl) -5 (trifluoromethyl) pyrrole-3-carbonitrile with the appropriate arylpyrrole and pivaloyl chloride with suitable RCOCI acid halide, the following compounds are obtained:

4 * Bromo-2- (p-chlorophenyl) -1-methacryloyl-5- (trifluoromethyl) pyrrole-3-carbonitrile; mp 132.5134 ° C;

4-Bromo-2- (p-chlorophenyl) -1-O-toluoyl-5- (trifluoromethyl) pyrrole-3-carbonitrile; mp 131.5134.5 ° C;

4-Bromo-1 - (m-chlorobenzoyl J-1 - (pclorophenyl) -5- (trifluoromethyl] pyrrole-3-carbonitrile;

pt88-90¾

4-Bromo-2- [p-chlorophenyl) -1- (2-furoyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; mp 152156 ° C;

4-Bromo-2- (p-chlorophenyl) 1-p-toluene-5 (trifluoromethyl) pyrrole-3-carbonitrile; for doors 6.5 °;

4-Bromo-2- (p-chlorophenyl) -5 (trifluoromethyl) pyrrole-1- (a, a, a-tr / fluoro-ptoluyl) pyrrole-3-carbonitrile; mp 11O-118 ° C;

4-Bromo-2- (p-chlorophenyl) -1- (p-nitrobenzoyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; mp 128-132 ° C;

Phenyl 3-bromo-5- (p-chlorophenyl) -4-cyano-2 (trifluoromethyl) pyrrole-1-carboxylate; mp 11612 ° C;

4-Bromo-1-ichlorobenzoyl} -2- (p-chlorophenyl) 5- (trifluoromethyl) pyrrole-3-carbonitrile; mp 115117 ° C;

4-Bromo-2- (p-chlorophenyl) 1 -. (Cyclohexylcarbonyl] -5- [trifluoromethyl) pyrrole-3-carbonitrile; pt141-142 ° C;

4-Bromo-2- (p-chlorophenyl) -1-pivaloyl-5- (trifluoromethyl) pyrrole-3-carbonitrile; mp 177183 ° C;

1-Acetyl-4,5-dichloro-2- (3,4-d-lorphenyl) pyrrole-3-carbonitrile; for decomposition 15 ° C;

Phenyl 2,3-dibrorrh4-cyano-5- (a, a, atrifluoro-p-tolyl) pyrrole-3-carboxylate; mp 148149 ° C;

4-Bromo-2- (p-chlorophenyl) -1 - (1-naphthoyl) -518 (trifluoromethyl) pyrrole-3-carbonitrile; mp 101108 ° C;

4-Bromo-2- (p-chlorophenyl) -1 - (mfluorobenzoyl) -5- (trifluoromethyl] pyrrole-3-carbonitrile;

Not less than-ii8 ° C:

4-Bromo-2- (p-chlorophenyl) -1 - (3,4-dichlorobenzoyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; mp 135-144 ° C;

1-Benzoyl-4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; mp 141-144 ° C;

4-Bromo-1 - (p-tert -butylbenzoyl) -2- (pclorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; mp 113-115.5 ° C; or

1-6enzoyl-4-bromo-2- (p-bromophenyl) -5 (trifluoromethyl) pyrrole-3-carbonitrile; mp 112117 ° C.

Evaluation of the insecticidal and acaricidal properties of arylpyrrole N-acylates in these tests, the evaluations were performed using the technical substances dissolved in a 50/50 water acetone mixture. All the concentrations expressed here refer to the active ingredient. All tests are conducted in a laboratory maintained at about 27 ° C. The assessment system used is the following:

Appreciation system

O = no effect = 10-25% destroying effect = 26-35% destroying effect = 36-45% destroying effect = 46-55% destroying effect = 56-65% destroying effect = 66-75% effect Destruction = 76-85% Destruction Effect = 86-99% Destruction Effect = 100% Destruction Effect

Where two or more tests are performed using the same compound, the average of the test results is reported.

The species of insects and mites tested, used in the present assessments, together with the specific testing procedures are described below.

Holiothis virescens, tobacco bud worm in the third stage of development.

The cotton swabs are submerged in the test solution and allowed to

RO 110818 Bl is dried in a niche. When they are dry, each is cut into quarters and ten sections are individually placed in 30 ml plastic capsules containing 5-7 mm long pieces of moist dental wicks. One omide is added in the third stage of development, in each capsule and a cardboard cap is applied to the capsule. The treatments are maintained for three days before calculating the mortality and estimating the reduction of the damages to the feeding.

Spodoptera eridania. southern humid (worms moving into large groups destroying grass, seeds and other crops] in the third stage of development.

□ Sieva leaf developed at 78 cm long is immersed in the test solution with stirring for 3 sec and placed in a niche for drying. The leaf is then placed in a 100 x 10 mm Petri dish containing on the bottom a moistened filter paper and ten worms in the third stage of development. The vessel is maintained for 5 days before any observations are made regarding mortality, reduced feeding, or any interference with normal changes in the stage of evolution.

Spodoptera eridania. residue after 7 days.

The plants treated in the above test are kept under high intensity lamps for 7 days in the greenhouse. These lamps duplicate the effect of a sunny day in June New Jersey and are maintained for 14 hours a day. After 7 days, leaf samples are taken and tested as in the test above.

Diabetic undecimpunctata howardi, corn rootworm in the third stage of development.

In a glass container with a wide mouth, provided with a lid with a 30 ml thread, put I cm³ of fine talc. Pipette 1 ml of the appropriate acetone solution over the talc so that 1.25 and 0.25 mg of active ingredient are obtained per container. The containers are fitted under a low flow of air until the acetone is evaporated. The dried talc is loose, and 25 ml of moist soil is added to each container. The container is covered and the contents are completely mixed with a Vortex mixer. After that, ten root worms are added in the third stage of development, in each container, and the containers are lightly coated to allow air exchange for larvae. The treatments are maintained for 6 days before making the mortality calculations. Missing larvae are presumed dead, meanwhile they decay rapidly and cannot be found. The concentrations used in this test correspond to approximately 50 and 10 kg / ha respectively.

Tetranychus urticae (OP-resistant species), the red spider

Bean plants of the Sieva lima species are selected with primary leaves grown at 6 - 8 cm and milled at one plant per pot. Cut a small piece from a leaf taken from the main colony and place it on each leaf of the test plants. This is done about two hours before treatment to allow the lice to move on the test plant and leave the eggs. The size of the cut piece varies to obtain about 100 buns per leaf. During the treatment, the piece of fungus used to transfer the lice is removed and left on one side. Plants infected with lice are immersed in the test solution for 3 s, accompanied by agitation and arranged in a niche for drying. Plants are kept two days before the estimates of the destruction of adults that are made using the first leaf. The second leaf is kept on the plant for another five days before observations are made on the destruction of eggs and / or new nymphs.

Empty the steep, western potato leaf fleas, adults.

A Sieva bean leaf about 5 cm long is immersed in a test solution for 3 s, accompanied by stirring and placed in a niche for drying. The leaf is placed in a 100 x 10 mm Petri dish containing damp filter paper on the bottom. About 10 adults of fleas are added to each vessel and treatments are maintained for three days before the mortality is calculated.

Blattella germanica, adult male beetle, residual test.

Pipette 1 ml of solution slowly

1000 ppm acetone test material on the bottom of a 150 x 15 mm Petri dish,

RO 110818 Bl was complete; - = the test could not be conducted;

free space = test not conducted and + = data not yet reported.

The data obtained are presented in the table

The compounds evaluated in these tests include:

so as to obtain as even coverage as possible. After drying the deposit, 10 adult male cockroaches are placed in each vessel and the lid is placed. Mortality is calculated after three days. 5 in these evaluations the symbols used have the following meanings: X = test no a

Compound no, ______________________________ Compound name____________________________________

1-Benzoyl-4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl] pyrrole-3-carbonitrile, pt 105-

D7 ° C;

4-Bromo-2- (p-chlorophenyl) -1-methacryloyl-5- (trifluoromethyl) pyrrole-3-carbonitrile, pt

132.5-134 ° C

4-Bromo-2- (p-chlorophenyl) -1-o-toluoyl-5- (trifluoromethyl) pyrrole-3-carbonitrile_it mp 131,5134.5 ° C;

4-Bromo-1-fn-chlorobenzoyl) -1-fp-chlorophenyl) -5- (trifluoromethyl] pyrrole-3-carbonitrile, mp 8890 ° C;

4-Bromo-2- {p-chlorophenyl) -1 - (2-furoyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, mp 152156 ° C;

4-Bromo-2- {p-chlorophenyl) -1-p-toluoyl-5- (trifluoromethyl) pyrrole-3-carbonitrile, mp 113 316.5 ° C;

4-Bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -1 (a, a_itα-trifluoro-p-toluene) -pyrrole-3-carbonitrile, mp 110-118 ° C;

4-Bromo-2 - (/&gt; chlorophenyl) -1-fp-nitrobenzoyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile_itpt128-132 ° C;

Phenyl 3-bromo-5- (p-chlorophenyl) -4-cyano-2- (trifluoromethyl) pyrrole-1-carboxylate, mp 11612DPC;

I □ 4-Bromo-1 - (p-chlorobenzoyl) -2-fp-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile,

pt115-117 ° C;

II 4-Bromo-2- (p-chlorophenyl] -1- {cyclohexylcarbonyl) -5- {trifluoromethyl] pyrrole-3-carbonitrile, mp 141-142 ° C;

1-Benzoyl-4-bromo-2-chloro-5- (p-chlorophenyl) pyrrole-3-carbonitrile, mp 179-181 ° C;

4-Bromo-2- (p-chlorophenylF1-pivaloyl-5- (trifluoromethyl pyrrole-3-carbonitrile, pt. 177-)

183 ° C;

1-Acets F4,5-dichloro-2- {3,4-dichlorophenyl) pyrrole-3-carbonitrile, with 15QPC decomposition:

Phenyl 2,3-dibrom-4-cyano-5- (a, a₁α-trifluoro-p-thiol) pyrrole-3-carboxylate, mp 148-, 149 ° C;

4-Bromo-2- (p-clophenyl) -1 - (1-naphthoyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, mp 101108 ° C;

4-Bromo-2- (p-chlorophenyl) -1- {m-fluorobenzoyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, mp 111-118 ° C;

4-Bromo-2- (p-chlorophenyl) -1- (3_it4-dichlorobenzoyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, mp 135-144 ° C;

4-Bromo-1- (p-tert-butylbenzoyl) -2- (p-chlorophenyl) -5- {trifluoromethyl) pyrrole-3-carbonitrile, pt

113 to 115.5 ° C; or

1 -Benzoyl-4-bromo-2- (p-bromophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, pt 112-

117 ° C.

RO 110818 Bl

Assessment of insecticidal and acaricidal activity of N-acylated arylpyrroles

<td>Compound</td><td colspan="2">Worm</td><td>Caterpillar</td><td colspan="2">Worm of</td><td colspan="2">OP doll</td><td>Flea</td><td>Beetle</td>

<td>number</td><td colspan="2">of buds</td><td>southern</td><td colspan="2">root</td><td colspan="2">resistance</td><td>of leaves</td><td>of</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>kitchen</td>

<td></td><td>in the stage</td><td colspan="2">Day 3 Day 5</td><td colspan="4">corn Adult Egg Nymph</td><td>Account</td><td>Residual</td>

<td></td><td>3rd</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>ppm</td><td>ppm</td><td>ppm</td><td>ppm</td><td>ppm</td><td>ppm</td><td>ppm</td><td>ppm</td><td>ppm</td>

<td></td><td> 1</td><td>1 R</td><td>1 R</td><td></td><td></td><td></td><td></td><td></td><td> 1</td>

<td></td><td> □1</td><td>□ 1 E</td><td>01 E.</td><td></td><td> 31</td><td> 31</td><td> 31</td><td> 1</td><td> 01</td>

<td></td><td> □01</td><td>001S</td><td>001S</td><td> 51</td><td> 001</td><td> 001</td><td> 001</td><td> □1</td><td> □01</td>

<td></td><td> 000</td><td>OOOi</td><td>OOOi</td><td> 001</td><td> 000</td><td> 000</td><td> 000</td><td> 001</td><td> 000</td>

<td> 1</td><td> 998</td><td> 9999</td><td> 9999</td><td> 954</td><td> 999</td><td> 099</td><td> 9-</td><td> 996</td><td> 997</td>

<td> 2</td><td> 999</td><td> 9999</td><td> 9999</td><td> 95-</td><td> 999</td><td> 999</td><td>x-</td><td> 990</td><td> 999</td>

<td> 3</td><td> □01</td><td> 9999</td><td> 9999</td><td> 998</td><td> 999</td><td> 998</td><td>x-9</td><td> 990</td><td> 993</td>

<td> 4</td><td> 996</td><td> 999</td><td> 9999</td><td> 970</td><td> 999</td><td> 099</td><td> 0-</td><td> 990</td><td> 966</td>

<td> 5</td><td> 997</td><td> 9009</td><td> 9999</td><td> 960</td><td> 999</td><td> 099</td><td> 9-</td><td> 990</td><td> 998</td>

<td> 6</td><td> 995</td><td> 9999</td><td> 9999</td><td> 980</td><td> 00</td><td> 99</td><td> -</td><td> 990</td><td> 996</td>

<td> 7</td><td> 999</td><td> 9999</td><td> 9999</td><td> 950</td><td> 999</td><td> 999</td><td>Ck</td><td> 980</td><td> 990</td>

<td> 8</td><td> 998</td><td> 9999</td><td> 9999</td><td> 940</td><td> 999</td><td> 098</td><td> 0-9</td><td> 999</td><td> 970</td>

<td> 9</td><td> 999</td><td> 9999</td><td> 9999</td><td> 985</td><td> 999</td><td> 499</td><td> 8-</td><td> 90</td><td> 870</td>

<td> 10</td><td> 95</td><td> 9999</td><td> 9999</td><td> 995</td><td> 999</td><td> 090</td><td> 0-8</td><td> 00</td><td> 20</td>

<td> 11</td><td> 999</td><td> 9999</td><td> 9999</td><td> 970</td><td> 099</td><td> 099</td><td> 0-</td><td> 995</td><td> 99</td>

<td> 12</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>

<td> 13</td><td> 2</td><td>9 9x</td><td>9 9x</td><td> 92</td><td> 5 0</td><td> 00</td><td> 5 0</td><td> 40</td><td> 30</td>

<td> 14</td><td> 990</td><td> 9999</td><td> 9999</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 90</td>

<td> 15</td><td> 990</td><td> 9979</td><td> 9989</td><td> 97</td><td> □</td><td> 0</td><td> 0</td><td> 0</td><td> 5</td>

<td> 16</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>

<td> 17</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>

<td> 18</td><td> 999</td><td> 9999</td><td> 999*</td><td> 9**</td><td> 0</td><td> 0</td><td> 0</td><td> 990</td><td> 950</td>

<td> 19</td><td> 992</td><td> 9999</td><td> 999*</td><td> 9**</td><td> 9**</td><td> □**</td><td> 9**</td><td> 994</td><td> 940</td>

<td> 20</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

claims