DE4321031A1 - Substituted pyridylpyrroles - Google Patents

Description

The present invention relates to novel substituted pyridylpyrroles, processes and new intermediates for their preparation and their use for control of animal pests, especially insects, arachnids and nemato those used in agriculture, forestry, storage and materials protection, and occur in the hygiene sector.

It has already become known that structurally similar cyanopyrroles as Molluscicides, fungicides and insecticides are effective (see, for example, EP-A 0 347 488, EP-A 0 358 047, EP-A 0 312 723, DE-A 41 17 752, EP-A 0 481182, EP-A 0 484 614). The effectiveness and range of action of these compounds is However, especially at low rates and concentrations are not always fully satisfactory.

There have now been new substituted pyridylpyrroles of the general formula (I) found

in which
R¹ and R² independently of one another are hydrogen or halogen, but at least one of the two radicals R¹ or R² is halogen,
R³ is hydrogen, halogen or optionally substituted alkyl,
R⁴ for hydrogen or

wherein R⁵ is hydrogen or optionally substituted alkyl and R⁶ is Hydrogen, optionally substituted alkyl or one of the radicals

wherein R⁷ and R⁸ independently of one another are hydrogen, alkyl, alkenyl, alkynyl, alkoxycarbonyl, alkenoxycarbonyl, alkynoxycarbonyl or acyl, where R⁷ and R⁸ together with the N-atom to which they are attached can also form a ring,
Pyr is optionally substituted pyridin-2-yl, pyridin-3-yl or pyridin-4-yl,
X¹ and X² independently represent hydrogen or halogen, and
n stands for 0, 1 or 2.

Furthermore, it has been found that the substituted pyridylpyrroles (I) - in Ab Dependent on the respective substituents - on different ways certain subgroups of end products of the formula (I) at the same time be intermediates in the production of other end products (I) can; an overview shows the following scheme 1:

This gives the substituted pyridylpyrroles of the general formula (Ia),

in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning and n = 1 or 2,
if you either

• A) Pyridylpyrroles of the formula (II) in which R³, X¹, X² and Pyr have the meanings given above and n = 1 or 2,
  reacted with halogenating agents (method A)
  or
• B) Pyridylpyrroles of the formula (III) in which R¹, R², R³, X¹, X² and Pyr have the meanings given above,
  reacted with oxidants (method B).
• C) Pyridylpyrroles of the formula (Ib) are obtained in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning and n = 1 or 2 and
  R⁹ for in which R⁵ and R⁶ have the abovementioned meaning,
  when pyridylpyrroles of the general formula (Ia) in which R 1, R 2, R 3, X 1, X 2 and Pyr have the abovementioned meaning and n = 1 or 2,
  with compounds of the formula (IV) in which
  R⁹ has the meaning given above and
  X³ is an anionic leaving group,
  if appropriate in the presence of bases and / or if appropriate in the presence of diluents (process C).
• D) Furthermore, pyridylpyrroles of the formula (Ic) are obtained in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning and
  R⁹ for where R⁵ and R⁶ are as defined above and n = 0,
  when pyridylpyrroles of the general formula (III) in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning,
  with compounds of the formula (IV) in which
  R⁹ has the meaning given above and
  X³ is an anionic leaving group,
  if appropriate in the presence of bases and / or if appropriate in the presence of diluents (Method D).
• E) In addition, the substituted pyridylpyrroles of the general formula (Id) are obtained in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning and n = 0,
  when pyridylpyrroles of the formula (V) in which R³, X¹, X² and Pyr have the abovementioned meaning,
  reacted with halogenating agents (method E).

(The substituted Pyridylpyrrole of the general formula (Id) are identical to the by the general formula (III) described precursors).

Finally, it has been found that the new substituted pyridylpyrroles of the formula (I) have pronounced biological properties and especially for Be control of animal pests, in particular insects, arachnids and Nematodes used in agriculture, in forests, in stocks and materials protection as well as in the hygiene sector are suitable.

Preference is given to substituted pyridylpyrroles of the above formula (I) in which
R¹ and R² independently of one another are hydrogen, bromine or chlorine, where at least one of the radicals R¹ or R² is bromine or chlorine,
R³ represents hydrogen, fluorine, chlorine, bromine or C₁-C₅-alkyl (which, if appropriate, is the same or different substituted by 1 to 5 fluorine, chlorine or bromine atoms),
R⁴ for hydrogen or

stands,
in which R⁵ is hydrogen or C₁-C₅-alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C₁-C₅-alkoxy, C₁-C₅-alkylthio, C₁-C₅-acyloxy, C₂-C₆-alkoxycarbonyl, Phenyl, cyano or nitro) and
R⁶ is hydrogen or C₁-C₆ alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C₁-C₈ alkoxy, C₁-C₈ alkylthio, C₁-C₆ acyloxy, C₂-C₈ alkoxycarbonyl, phenyl , Cyano or nitro) or R⁶ for

stands,
wherein R⁷ and R⁸ are independently hydrogen, C₁-C₈-alkyl, C₃-C₈ alkenyl or C₃-C₈-alkynyl (wherein the alkyl, alkenyl and alkynyl radicals are each optionally substituted by 1 to 6 identical or different halogen atoms, C₁-C₆ Alkoxy, C₁-C₆-alkylthio, C₁-C₆-acyloxy, (C₁-C₆-alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro are substituted), or for (C₁-C₈-alkoxy) carbonyl, ( C₃-C₈ alkenoxy) carbonyl or (C₃-C₈ alkynoxy) - carbonyl (where the alkoxy, alkenoxy and alkynoxy each, where appropriate, by 1 to 6 identical or different halogen atoms, C₁-C₆ alkoxy, C₁- C₆ Alkylthio, C₁-C₆-acyloxy, (C₁-C₆-alkoxy) -carbonyl, optionally substituted phenyl, cyano or nitro are substituted), or represent C₁-C₈-acyl (which is optionally substituted by 1 to 6 identical or different halogen atoms, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-acyloxy, (C₁-C₆-alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro), or in which R⁷ and R⁸ together with the N-atom to which they are attached form a 4- to 8-membered ring,
Pyr is pyridine-2-yl, pyridin-3-yl or pyridin-4-yl which is optionally mono- to disubstituted by identical or different substituents by halogen,
by C₁-C₈-alkyl, C₂-C₈-alkenyl or C₂-C₈-alkynyl (wherein the alkyl, alkenyl and alkynyl radicals are each optionally substituted by 1 to 6 halogen atoms, C₁-C₅-alkoxy, C₁-C₅-alkylthio or by C₁ -C₅-acyloxy are substituted, and wherein the alkoxy and alkylthio radicals may each be substituted by 1 to 6 halogen atoms),
by C₁-C₈-alkoxy, C₂-C₈-alkenoxy or C₂-C₈-alkynoxy (where the alkoxy, alkenoxy and alkyoxy are optionally substituted by 1 to 6 halogen atoms),
by C₁-C₈-alkylthio, C₂-C₈-alkenylthio or C₂-C₈-alkynylthio (wherein the alkyl thio, alkenylthio and alkynylthio radicals are each optionally substituted by 1 to 6 halogen atoms),
by C₂-C₈-acyloxy (which is optionally substituted by 1 to 6 halogen atoms),
by amino (which is optionally substituted by 1 to 2 identical or different alkyl radicals or haloalkyl radicals having 1 to 8 carbon atoms and optionally 1 to 6 halogen atoms),
through nitro or cyano,
and in which
X¹ and X² independently of one another represent hydrogen, fluorine, chlorine or bromine and
n stands for 0, 1 or 2.

Particular preference is given to substituted pyridylpyrroles of the formula (I) in which
R¹ and R² independently of one another are hydrogen, bromine or chlorine, where at least one of the two radicals R¹ or R² is bromine or chlorine,
R³ is hydrogen, fluorine, chlorine, bromine or C₁-C₄-alkyl (which where appropriate equal or not substituted by 1 to 5 fluorine, chlorine or bromine atoms),
R⁴ for hydrogen or

stands,
wherein R⁵ is hydrogen or C₁-C₄-alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-acyloxy, C₂-C₅-alkoxycarbonyl, Phenyl, cyano or nitro), and
R⁶ is hydrogen or C₁-C₅ alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C₁-C₆ alkoxy, C₁-C₆ alkylthio, C₁-C₅ acyloxy, C₂-C₆ alkoxycarbonyl, phenyl , Cyano or nitro), or wherein R⁶ is for

stands,
in which R⁷ and R⁸ independently of one another are hydrogen, C₁-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl (where the alkyl, alkenyl and alkynyl radicals are each optionally substituted by 1 to 5 fluorine and / or chlorine atoms, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-acyloxy, (C₁-C₄-alkoxy) -carbonyl, substituted or unsubstituted phenyl, cyano or nitro are substituted),
or (C₁-C₆-alkoxy) -carbonyl, (C₃-C₆-alkenoxy) - or (C₃-C₆-alkynoxy) - carbonyl (where the alkoxy, alkenoxy and Alkinoxyreste each, where appropriate, by 1 to 5 fluorine and / or chlorine atoms, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-acyloxy, (C₁-C₄-alkoxy) -carbonyl, optionally substituted phenyl, cyano or nitro are substituted),
or are C₁-C₆-acyl (which is optionally substituted by 1 to 5 fluorine and / or chlorine atoms, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-acyloxy, (C₁-C₄-alkoxy) - carbonyl, optionally substituted phenyl, cyano or substituted by nitro),
or R⁷ and R⁸, together with the N atom to which they are attached, may be linked through any point to form a 4- to 6-membered ring;
in which further
Pyr is pyridine-2-yl, pyridin-3-yl or pyridin-4-yl, which is optionally mono- to trisubstituted by identical or different substituents by fluorine, chlorine or bromine, or
by C₁-C₆-alkyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl (wherein the alkyl, alkenyl and alkynyl radicals are each optionally substituted by 1 to 5 fluorine and / or chlorine atoms, C₁-C₄-alkoxy, C₁-C₄ -Alkylthio or substituted by C₁-C₄-acyloxy, and wherein the alkoxy and alkylthio radicals may each be substituted by 1 to 5 fluorine and / or chlorine atoms),
by C₁-C₆-alkoxy, C₂-C₆-alkenoxy or C₂-C₆-alkynoxy (where the alkoxy, alkenoxy and alkynoxy radicals are optionally substituted by 1 to 5 fluorine and / or chlorine atoms),
by C₁-C₆-alkylthio, C₂-C₆-alkenylthio or C₂-C₆-alkynylthio (where the alkylthio, alkenylthio and alkynylthio radicals are optionally substituted by 1 to 5 fluorine and / or chlorine atoms),
by C₂-C₆-acyloxy (which is optionally substituted by 1 to 5 fluorine and / or chlorine atoms), by amino (which is optionally substituted by 1 to 2 identical or different alkyl radicals having 1 to 6 carbon atoms, which by 1 to 5 Fluorine and / or chlorine atoms may be substituted),
through nitro or cyano,
and in which
X¹ and X² independently represent hydrogen, fluorine or chlorine and
n stands for 0, 1 or 2.

The above listed general or preferred Remaining definitions or explanations apply to the end products and to the Starting and intermediate products accordingly. These remainder definitions can among each other, so also between the respective preferential ranges arbitrarily be combined.

Is used according to preparation process A 2- (6-chloropyridin-3-yl) -5- (chloro-di fluoromethylsulfonyl) -pyrrole and bromine as starting materials, the reaction Ver be reproduced by the following reaction scheme:

Using according to method B 2- (5,6-dichloro-pyridin-3-yl) -3,4-dibromo-5- (tri Fluoromethylthio) -pyrrole and m-chloroperbenzoic acid as starting materials, so can the Reaction course be represented by the following reaction scheme:

Is used according to method C 2- (6-chloropyridin-3-yl) -3-bromo-5- (chlorodifluor Methylsulfonyl) -pyrrole and (chloro-methyl) -ethyl ether as starting materials, so the Reaction course be represented by the following reaction scheme:

Using according to method D 2- (2,6-dichloropyridin-4-yl) -3,4-dibromo-5- (di fluorochloromethylthio) pyrrole and (chloromethyl) ethyl ether as starting materials, as may the course of the reaction is represented by the following reaction scheme:

Is used according to method E 2- (6-chloropyridin-3-yl) -5- (difluorochloromethyl thio) -pyrrole and bromine as starting materials, so the reaction can be through the the following reaction scheme are shown:

The process A for the preparation of compounds of the formula (Ia) is characterized in that pyridylpyrroles of the formula (H) are halogenated treated.

As diluent in process A, all conventional solvents can be used be set. Preferably used are hydrocarbons such as benzene and Hexane, halogenated hydrocarbons such as chloroform and methylene chloride, furthermore ethers such as dibutyl ether, tetrahydrofuran, dioxane, and also organic Acids, such as formic acid and acetic acid. Furthermore, water as Ver be used diluents.

Suitable halogenating agents are all customary halogenating agents become. Preferably, chlorine, bromine, sodium hypochlorite, potassium are used  hypochlorite, sodium hypobromite, potassium hypobromite, sulfuryl chloride, t-butyl hypo chlorite, N-chlorosuccinimide and N-bromosuccinimide.

The temperatures can be varied within a wider range. in the general works at temperatures from -10 ° C to + 120 ° C, preferably between 0 ° C and 70 ° C.

In carrying out the reactants of the formula (II) is added equimolar or excess amounts of a halogenating agent.

This reaction is generally carried out under normal pressure. In the event of of chlorine and bromine, the reaction can also be carried out at elevated pressure (up to 5000 hPa) be performed.

Process B for the preparation of compounds of formula (Ia) is characterized in that pyridylpyrroles of the formula (III) are oxidized implements.

As a diluent in process B, all customary solvents be set. Preferably used are hydrocarbons such as benzene and Hexane, halogenated hydrocarbons such as chloroform and methylene chloride, furthermore ethers such as dibutyl ether, tetrahydrofuran, dioxane, and also organic Acids, such as formic acid and acetic acid. Furthermore, water as Ver be used diluents.

As the oxidizing agent, all conventional oxidizing agents can be used. Preference is given to using m-chloroperbenzoic acid, potassium hydrogenperoxodi sulfate (oxone), magnesium monoperoxyphthalate, H₂O₂, atmospheric oxygen in the presence of catalysts, potassium permanganate or CrO₃.  

The temperatures can be varied within a wider range. in the general works at temperatures from -30 ° C to + 200 ° C, preferably between -10 ° C and + 80 ° C.

When carrying out the reaction, the reaction components of the formula (III) depending on depending desired oxidation state of sulfur with one or two equivalents of a Oxidant around. The oxidizing agents may optionally also in Über shot are used.

The process C for the preparation of compounds of the formula (Ib) is characterized characterized in that pyridylpyrroles of the formula (Ia) with compounds of Formula (IV), optionally in the presence of bases and optionally in Reacting the presence of diluents.

Suitable diluents in process C are all inert organic solvents medium in question. These include preferably hydrocarbons such as benzene, Toluene, xylene, furthermore ethers, such as dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, Dioxane, as well as polar solvents, such as dimethyl sulfoxide, acetonitrile, sulfolane, Dimethylformamide and N-methyl-pyrrolidone.

All common proton acceptors can be used as bases. Preferably usable are alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as magnesium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which also in the presence of phases transfer catalysts such. B. triethylbenzylammonium chloride, tetrabutylammonium bromide or 18-crown-6 can be used. Further, alkali metal and Alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and Calcium hydride, and also alkali metal alcoholates, such as sodium methoxide, Sodium ethoxide and potassium tert-butoxide can be used.  

The reaction temperatures can be carried out in a wider range be varied. In general, one works at temperatures between -10 ° C and 200 ° C, preferably between 0 ° C and 120 ° C.

In carrying out the reaction components of the formula (Ia), the deprotonating bases and the components of the formulas (IV) in general in about equimolar amounts. However, it is also possible, one way or another Component in a larger excess (up to 3 mol) to use.

The process C is generally carried out under normal pressure, but it can also be carried out at overpressure.

The process D for the preparation of compounds of the formula (Ic) is characterized in that pyridylpyrroles of the formula (IV) are reacted with compounds of the Formula (IV), optionally in the presence of bases and optionally in Reacting the presence of diluents.

Suitable diluents in process D are all inert organic Solvent in question. These include, preferably, hydrocarbons such as Benzene, toluene, xylene, furthermore ethers, such as dibutyl ether, tert-butyl methyl ether, tetra hydrofuran, dioxane, as well as polar solvents, such as dimethyl sulfoxide, aceto nitrile, sulfolane, dimethylformamide and N-methyl-pyrrolidone.

All common proton acceptors can be used as bases. Preferably usable are alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which also in the presence of Phase transfer catalysts such. B. triethylbenzylammonium chloride, tetrabutyl ammonium bromide or 18-crown-6 can be used. Further are  Alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, as well as alkali metal alcoholates such as sodium methylate, sodium and potassium tert-butoxide can be used.

The reaction temperatures can be carried out in a wider range be varied. In general, one works at temperatures between -10 ° C and 200 ° C, preferably between 0 ° C and 120 ° C.

In carrying out one sets the reaction components of the formula (III), the deprotonating bases and the components of the formula (IV) in general in about equimolar amounts. However, it is also possible, one way or another Component in a larger excess (up to 3 mol) to use.

The process is generally carried out under normal pressure, but it can be carried out under increased pressure.

Process E for the preparation of compounds of formula (Id) (= III) characterized in that pyridylpyrroles of the formula (V) with halogenation treated.

Suitable diluents in process E are all customary solvents be set. Preferably used are hydrocarbons such as benzene and Hexane, halogenated hydrocarbons such as chloroform and methylene chloride, furthermore ethers such as dibutyl ether, tetrahydrofuran, dioxane, and also organic Acids, such as formic acid and acetic acid. Furthermore, water can also Diluents are used.

Suitable halogenating agents are all customary halogenating agents become. Preferably, chlorine, bromine, sodium hypochlorite, potassium are used  hypochlorite, sodium hypobromite, potassium hypobromite, sulfuryl chloride, t-butyl hypo chlorite, N-chlorosuccinimide, N-bromosuccinimide.

The temperatures can be varied within a wider range. in the general works at temperatures from -10 ° C to + 120 ° C, preferably between 0 ° C and 70 ° C.

In carrying out the reactants of the formula (V) is added equimolar or excess amounts of a halogenating agent.

This reaction is generally carried out under normal pressure. In case of Use of chlorine or bromine as a halogenating agent may cause the reaction as well be carried out at elevated pressure (up to 5000 hPa).

The in the preparation of compounds of general formula (Ia) according to Ver drive A required starting materials of the general formula (II) are new; you get they, when pyridylpyrroles of the formula (V)

in which R³, X¹, X² and Pyr have the abovementioned meaning, with Converts oxidizing agents.

For example, using 2- (6-chloropyridin-3-yl) -5- (difluorochloromethylthio) - pyrrole and m-chloroperbenzoic acid as starting materials, so the reaction can be represented by the following reaction scheme according to this method.

The process for the preparation of compounds of the formula (II) is characterized characterized in that pyridylpyrroles of the general formula (V) with oxidizing agents implements.

Suitable diluents in this process are all customary solvents be used. Preferably usable are hydrocarbons such as benzene and hexane, halogenated hydrocarbons such as chloroform and methylene chloride, furthermore ethers such as dibutyl ether, tetrahydrofuran, dioxane, and also organic Acids, such as formic acid and acetic acid. Furthermore, water can also Diluents are used.

In this case, all customary oxidizing agents can be used as the oxidizing agent become. It is preferable to use m-chloroperbenzoic acid, potassium hydrogen peroxodisulfate (oxone), magnesium monoperoxyphthalate, H₂O₂, atmospheric oxygen in Presence of catalysts, potassium permanganate or CrO₃.

The temperatures can be varied within a wider range. in the general works at temperatures from -30 ° C to + 200 ° C, preferably between -10 ° C and + 80 ° C.

When carrying out the reaction components of the formula (V) depending on depending desired oxidation state of the sulfur with one or two equivalents of a  Oxidant around. The oxidizing agents may optionally also in Über shot are used.

The starting materials of formula (V) are new; you get it when you are Pyridylpyrroles of the general formula (VI)

wherein Pyr has the meaning given above,
with sulfenchlorides of the general formula (VII),

wherein X¹, X² and R³ have the abovementioned meaning, optionally in Presence of bases and optionally in the presence of diluents implements.

Is used according to this preparation method 2- (5,6-dichloro-pyridin-3-yl) - pyrrole and Trifluormethylsulfenchlorid as starting materials, so the reaction be represented by the following reaction scheme:

The process for the preparation of compounds of formula (V) is thereby in that pyridylpyrroles of the formula (VI) with sulfenchlorides of general formula (VII) optionally in the presence of bases and given if reacted in the presence of diluents.

Suitable diluents in this process are all inert organic solvents in question. These include preferably hydrocarbons such as benzene, Toluene, xylene, furthermore ethers, such as dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, Dioxane, as well as polar solvents, such as dimethyl sulfoxide, acetonitrile, sulfolane, Dimethylformamide and N-methyl-pyrrolidone.

As bases are z. B. alkali metal and alkaline earth metal amides and hydrides, such as Sodium amide, sodium hydride and calcium hydride, and also alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butylate used.

The reaction temperatures can be carried out in a wider range be varied. In general, one works at temperatures between -70 ° C and + 50 ° C, preferably between -30 ° C and + 30 ° C.

In carrying out the reaction components of the formula (VI) and (VII) in equimolar proportions. The reaction components of the formula (VII) may optionally be used in excess.  

The optionally used bases are generally in equimolar or used slightly excess amounts.

This reaction is generally carried out under normal pressure. In the event of of gaseous sulfenchlorides, the reaction can also be carried out at elevated pressure (until 5000 hPa).

The pyridylpyrroles of general formula (VI) are new; They get started to prepare known processes (see A. Gossauer, The chemistry of pyrroles, Springer-Verlag, Berlin 1974, p. 276; N. Engel, W. Steglich, Angew. Chem. 90 719 (1978)).

The sulfenchlorides of the general formula (VII) are known in part and leave can be prepared by methods known in principle (see Houben-Weyl, Georg Thieme Verlag Stuttgart, Vol. 9, p. 267 ff .; see. DE-A 40 36 515).

The substituted pyridylpyrroles (I) according to the invention are suitable with good plant compatibility and favorable toxicity to warm-blooded animals for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forestry, in the protection of stored products and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include:
From the order of Isopoda z. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of Diplopoda z. B. Blaniulus guttulatus.
From the order of Chilopoda z. Geophilus carpophagus, Scutigera spec.
From the order of Symphyla z. B. Scutigerella immaculata.
From the order of Thysanura z. B. Lepisma saccharina.
From the order of Collembola z. B. Onychiurus armatus.
From the order of Orthoptera z. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
From the order of Dermaptera z. B. Forficula auricularia.
From the order of Isoptera z. Reticulitermes spp. From the order of Anoplura z. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
From the order of Mallophaga z. B. Trichodectes spp., Damalinea spp.
From the order of Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.
From the order of Heteroptera z. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus auundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella,  Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp. Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of Diptera z. Aeses spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hippobosca spp., Stomoxys spp , Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of Siphonaptera z. Xenopsylla cheopis, Ceratophyllus spp.
From the order of Arachnida z. B. Scorpio maurus, Lactrodectus mactans.

From the order of Acarina z. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The substituted pyridylpyrroles (I) according to the invention not only act against Plant, hygiene and storage pests, but also on veterinary medical sector against animal parasites (ectoparasites) like ticks, Leather ticks, mange mites, mites, flies (stinging and licking), parasitic fly larvae, lice, hair pieces, featherlings, fleas.

They are against normal-sensitive and resistant species and tribes, as well as against all parasitic and non-parasitic developmental stages of the ectoparasites effective.

The substituted pyridylpyrroles (I) according to the invention are characterized by a high insecticidal activity. They can be planted with good success damaging insects such as the larvae of the horseradish leaf beetle (Phaedon cochleariae), against the green peach aphid (Myzus persicae) or against insert the black bean aphid (Aphis fabae). This show the invention appropriate active ingredients not only protective but also leaf systemic and root systemic properties.

In addition, the substituted pyridylpyrroles (I) according to the invention are also suitable for controlling soil insects and can be, for example, to combat of the onion fly (Phorbia antiqua) grubs in the soil.  

In addition, the substituted pyridylpyrroles (I) according to the invention have a high Effect against hygiene and storage pests and can be used for example Combat the German cockroach (Blatella germanica).

The substituted pyridylpyrroles (I) according to the invention can be converted into the customary Formulations, such as solutions, emulsions, suspensions, Powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, very fine encapsulation in polymeric substances and in encapsulants for seed, and also in fuel-burning formulations such as smoke cartridges, cans, spirals, etc., as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for. B. by mixing the substituted pyridylpyrroles (I) according to the invention with extenders, ie liquid solvents, liquefied gases under pressure and / or solid Carriers, optionally with the use of surfactants, ie Emulsifiers and / or dispersants and / or foam-forming agents. in the Case of using water as an extender z. B. also organic Solvent can be used as auxiliary solvent. As liquid solvents are essentially in question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. As petroleum fractions, alcohols such as butanol or Glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethyl formamide and dimethyl sulfoxide, as well as water; with liquefied gaseous stretch means or carriers are meant liquids which are normal Temperature and under atmospheric pressure are gaseous, z. B. aerosol propellant gas, such as Halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; when solid carriers are suitable: z. Natural minerals, such as kaolins,  Clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and ground synthetic minerals, such as fumed silica, alumina and silicates; As solid carriers for granules are: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well synthetic granules of inorganic and organic meals and granules from organic material such as sawdust, coconut shells, corn cobs and Tobacco stalks; suitable emulsifiers and / or foaming agents are: z. Nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. B. alkylarylpolyglycol ethers, alkylsulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: z. As lignin-sulphite liquors and methylcellulose.

It can in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospho lipids, such as cephalins and lecithins, and synthetic phospholipids, others Additives can be mineral and vegetable oils.

It can dyes such as inorganic pigments, eg. For example, iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc are used.

The formulations generally contain between 0.1 and 95% by weight. Active ingredient, preferably between 0.5 and 90%.

The substituted pyridylpyrroles (I) according to the invention can be used in their commercial formulations as well as in the formulations prepared from these formulations formulations in mixture with other active substances, such as insecticides, attractants,  Sterilizers, acaricides, nematicides, fungicides, growth regulators or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, by microorganisms produced substances u. a.

The substituted pyridylpyrroles (I) according to the invention can also be used in their commercially available formulations as well as in those prepared from these formulations Application forms in mixture with synergists are present. Synergists are Ver compounds, which increase the effect of the active ingredients without the added synergist itself must be active.

The active substance content of the users prepared from the commercial formulations can vary widely. The drug concentration of Use forms may range from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1 wt .-% are.

The application is done in a custom forms adapted to the application forms Wise.

When used against hygiene and storage pests, the Wirk stand out by an excellent residual effect on wood and clay as well as by a good alkali stability on limed substrates.

The substituted pyridylpyrroles (I) according to the invention are also suitable for Combating insects, mites, ticks, etc. in the field of animal husbandry and Livestock breeding, whereby by controlling the pests better results, eg. B. higher milk yield, higher weight, better animal coat, longer life etc. can be achieved.  

The application of the substituted pyridylpyrroles (I) according to the invention takes place in this field in a known manner, such as by oral application in the form of For example, tablets, capsules, potions, granules, by dermal or external Application in the form of, for example, diving (dipping), spraying (spraying), Pouring (pour-on and spot-on) and powdering as well as by parenteral Application in the form of injection, for example, and also by the feed In addition, an application as a shaped body (collar, Ear tag) possible.

The following examples serve to further illustrate the invention.

Preparation Examples Example 1 (Method A)

3 g (9.1 mmol) of 2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylsulfonyl) -pyrrole are dissolved in 30 ml of chloroform and mixed with 2 ml of bromine. The mixture is stirred for 20 h at room temperature, expels excess bromine with nitrogen gas, evaporated on a rotary evaporator and codistilled twice with toluene. The residue is chromatographed on silica gel (CH₂Cl₂ / methanol = 97: 3).
Yield: 1.7 g (= 46% of theory) of 3-bromo-2- (6-chloropyridin-3-yl) -5- (chlorodifluoro-methylsulfonyl) -pyrrole;
physical data see table 1.

Example 2 (Method C)

1.5 g (3.7 mmol) of 3-bromo-2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylsulfonyl) - Pyrrole are presented in 50 ml of tetrahydrofuran (THF) and with cooling with 0.5 g (4.4 mmol) of potassium tert-butoxide was added. For this purpose, then dripping a solution  of 0.4 ml (4.1 mmol) of chloromethyl ethyl ether in 10 ml of THF. It is stirred for 19 h Room temperature, poured into water, extracted with dichloromethane, dried MgSO₄ and the filtered organic solution is evaporated on a rotary evaporator. The Residue is chromatographed on silica gel (CH₂Cl₂).

Yield: 0.9 g (= 52% of theory) of 3-bromo-2- (6-chloropyridin-3-yl) -5- (chlorodifluoro-methylsulfonyl) -1- (ethoxymethyl) -pyrrole;
physical data see table 1.

Analogously to Examples 1 and 2 and according to the above general Information on the preparation processes A to E according to the invention can also be further compounds of the formula (I) listed in Table 1 below getting produced:

Production of precursors Example VI-1

21.8 g (0.101 mol) of allyl [chloro- (6-chloro-pyridin-3-yl) methylene] -amine of the formula (VII-1) are dissolved in 100 ml of dry tetrahydrofuran (THF) and dissolved at 0 ° C was added dropwise to a solution of 33.6 g (0.3 mol) of potassium tert-butoxide in 90 ml of dry THF. The mixture is stirred for 10 minutes at this temperature, poured into ice-water and extracted three times with dichloromethane. The combined organic extracts are dried over MgSO₄, then filtered and evaporated using a rotary evaporator. The residue is purified by chromatography on silica gel (CH₂Cl₂ + 2% methanol).
Yield: 8.6 g (= 48% of theory) of 2- (6-chloro-pyridin-3-yl) -pyrrole;
physical data see table 2.

In an analogous manner, the others in the following Table 2 mentioned precursors of formula (VI) are prepared:

Example V-1

5 g (28 mmol) of 2- (6-chloropyridin-3-yl) -pyrrole are dissolved in 30 ml of diethyl ether and treated with 3 g (28 mmol) of N₂CO₃. It is cooled to -30 ° C. and a solution of 3.1 ml (31 mmol) of chlorodifluoromethylsulfen chloride in 10 ml of diethyl ether is added dropwise. The mixture is stirred for 6 h at this temperature and then filtered from insolubles. The filtrate is washed with water, dried over MgSO₄ and concentrated.
Yield: 5.5 g (= 67% of theory) of 2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylthio) -pyrrole;
physical data see table 3.

In an analogous manner, the others in Table 3 below mentioned precursors of formula (V) prepared:

Example II-1

4.6 g (16 mmol) of 2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylthio) -pyrrole are dissolved in 50 ml of chloroform and cooled to -10 ° C. To this is added dropwise a solution of 7.7 g (32 mmol) of 55% strength m-chloroperbenzoic acid in 80 ml of chloroform. The mixture is stirred for 3 h at room temperature and then washed with Na₂SO₄ solution and Na₂CO₃ solution. After drying over MgSO₄, the solution is evaporated (using a rotary evaporator) and the residue is filtered through silica gel (CH₂Cl₂).
Yield: 4.2 g (= 82% of theory) of 2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylsulfonyl) -pyrrole;
physical data see table 4.

In an analogous manner, the others in Table 4 below prepared precursors of the formula (II):

applications

In the active compounds according to the invention, the example no. on the corresponding production examples.

Example A Phaedon larvae test

Solvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of Part active ingredient with the specified amount of solvent and the specified Amount emulsifier and dilute the concentrate with water to the desired Concentration.

Cabbage leaves (Brassica oleracea) are dipped in the preparation of active ingredient treated with the desired concentration and with horseradish leaf beetle larvae (Phaedon cochleariae) as long as the leaves are still moist.

After the desired time the kill is determined in%. This means 100% that all beetle larvae were killed; 0% means that no Beetle larvae were killed.

In this test, z. B. the following compounds of the preparation examples superior efficiency over the prior art: (2).  

Example B Plutella Test

Solvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of Part active ingredient with the specified amount of solvent and the specified Amount emulsifier and dilute the concentrate with water to the desired Concentration.

Cabbage leaves (Brassica oleracea) are dipped in the preparation of active ingredient treated with the desired concentration and with caterpillars of the cabbage (Plutella maculipennis), as long as the leaves are still moist.

After the desired time the kill is determined in%. This means 100% that all caterpillars have been killed; 0% means that no caterpillars are killed were.

In this test, z. B. the following compounds of the preparation examples superior efficiency over the prior art: (2).  

Example C Heliothis virescens test

Solvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of Part active ingredient with the specified amount of solvent and the specified Amount emulsifier and dilute the concentrate with water to the desired Concentration.

Soybean shoots (Glycine max) are dipped into the preparation of the active ingredient desired concentration and with the tobacco budworm (Heliothis virescens) as long as the leaves are still moist.

After the desired time the kill is determined in%. This means 100% that all caterpillars have been killed; 0% means that no caterpillars are killed were.

In this rest, z. B. the following compounds of the preparation examples superior efficiency over the prior art: (2).  

Example D cockroach test

Test animals: Blattella germanica or Periplaneta americana
Solvent:
35 parts by weight of ethylene glycol monomethyl ether
35 parts by weight Nonylphenolpolyglykolether

For the preparation of a suitable formulation, 3 parts by weight are mixed Active ingredient with 7 parts of the above solvent-emulsifier mixture and dilute the emulsion concentrate thus obtained with water to each desired concentration.

2 ml of this preparation of active ingredient are placed on filter paper discs (⌀ 9.5 cm) Pipetted, which are in Petri dishes of appropriate size. After drying of the filter discs 5 test animals are transferred to B. germanica or P. americana and covered.

After 3 days, the effectiveness of the preparation of the active ingredient is determined. The Effectiveness is expressed in%. 100% means that all cockroaches were killed; 0% means that no cockroaches have been killed.

In this test, z. B. the following compounds of the preparation examples superior efficiency over the prior art: (2).  

Example E flying test

Test animals: Musca domestica, strain WHO (N)
Solvent:
35 parts by weight of ethylene glycol monomethyl ether
35 parts by weight Nonylphenolpolyglykolether

For the preparation of a suitable formulation, 3 parts by weight are mixed Active ingredient with 7 parts of the above solvent-emulsifier mixture and dilute the emulsion concentrate thus obtained with water to each desired concentration.

2 ml of this preparation of active ingredient are placed on filter paper discs (⌀ 9.5 cm) Pipetted, which are in Petri dishes of appropriate size. After drying of the filter discs, 25 test animals are transferred to the Petri dishes and covered.

After 6 hours, the effectiveness of the preparation of the active ingredient is determined. The Effectiveness is expressed in%. 100% means that all flies are killed were; 0% means that no flies were killed.

In this test, z. B. the following compounds of the preparation examples superior efficiency over the prior art: (2).

Claims (11)

1. Substituted pyridylpyrroles of the general formula (I) in which
R¹ and R² independently of one another represent hydrogen or halogen,
but at least one of the two radicals R¹ or R² is halogen,
R³ is hydrogen, halogen or optionally substituted alkyl,
R⁴ for hydrogen or stands,
wherein R⁵ is hydrogen or optionally substituted alkyl and
R⁶ is hydrogen, optionally substituted alkyl or one of the radicals stands,
wherein R⁷ and R⁸ independently of one another are hydrogen, alkyl, alkenyl, alkynyl, alkoxycarbonyl, alkenoxycarbonyl, alkynoxycarbonyl or acyl, where R⁷ and R⁸ together with the N-atom to which they are attached can also form a ring,
Pyr is optionally substituted pyridin-2-yl, pyridin-3-yl or pyridin-4-yl,
X¹ and X² independently represent hydrogen or halogen, and
n stands for 0, 1 or 2. 2. Substituted pyridylpyrroles of the general formula (I) according to claim 1, characterized in that therein
R¹ and R² independently of one another are hydrogen, bromine or chlorine, where at least one of the radicals R¹ or R² is bromine or chlorine,
R³ is hydrogen, fluorine, chlorine, bromine or C₁-C₅-alkyl (which is optionally the same or different substituted by 1 to 5 fluorine, chlorine or bromine atoms),
R⁴ for hydrogen or stands,
where R⁵ is hydrogen or C₁-C₅-alkyl (which is optionally substituted by 1 to 5 identical or different halo genatome, by C₁-C₅-alkoxy, C₁-C₅-alkylthio, C₁-C₅-acyloxy, C₂-C₆- Alkoxycarbonyl, phenyl, cyano or nitro) and
R⁶ is hydrogen or C₁-C₆-alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C₁-C₈-alkoxy, C₁-C₈-alkylthio, C₁-C₆-acyloxy, C₂-C₈-alkoxy carbonyl, Phenyl, cyano or nitro) or R⁶ for stands,
where R⁷ and R⁸ independently of one another are hydrogen, C₁-C₈-alkyl, C₃-C₅-alkenyl or C₃-C₈-alkynyl (where the alkyl, alkenyl and alkynyl radicals are each optionally substituted by 1 to 6 identical or different halogen atoms, C₁-C₈-alkynyl C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-acyloxy, (C₁-C₆-alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro are substituted), or for (C₁ C₈-alkoxy) carbonyl, (C₃ -C₈-alkenoxy) carbonyl or (C₃-C₈alkinoxy) carbonyl (wherein the alkoxy, alkenoxy and Alkinoxyeste each optionally substituted by 1 to 6 identical or different halogen atoms, C₁-C₆-alkoxy, C₁-C₆-alkylthio , C₁-C₆ acyloxy, (C₁-C₆ alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro are substituted), or represent C₁-C₈ acyl (which may optionally be replaced by 1 to 6 identical or different halogen atoms, C₁-C Ac acyl C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-acyloxy, (C₁-C₆-alkoxy) -c arbonyl, optionally unsubstituted phenyl, cyano or nitro is substituted), or wherein R⁷ and R⁸ together with the N-atom to which they are attached form a 4- to 8-membered ring,
Pyr is pyridine-2-yl, pyridin-3-yl or pyridin-4-yl, which is optionally mono- to disubstituted by identical or different substituents by halogen,
by C₁-C₅-alkyl, C₂-C₈-alkenyl or C₂-C₈-alkynyl (wherein the alkyl, alkenyl and alkynyl radicals are each optionally substituted by 1 to 6 halogen atoms, C₁-C₅-alkoxy, C₁-C₅-alkylthio or by C₁ -C₅- acyloxy are substituted, and wherein the alkoxy and alkylthio radicals may each be substituted by 1 to 6 halogen atoms),
by C₁-C₈-alkoxy, C₂-C₈-alkenoxy or C₂-C₈-alkynoxy (where the alkoxy, alkenoxy and alkynoxy are optionally substituted by 1 to 6 halogen atoms),
by C₁-C₈-alkylthio, C₂-C₈-alkenylthio or C₂-C₈-alkynylthio (wherein the alkylthio, alkenylthio and alkynylthio radicals are each optionally substituted by 1 to 6 halogen atoms),
by C₂-C₈-acyloxy (which is optionally substituted by 1 to 6 halogen atoms),
by amino (which is optionally substituted by 1 to 2 identical or different alkyl radicals or haloalkyl radicals having 1 to 8 carbon atoms and optionally 1 to 6 halogen atoms),
through nitro or cyano,
and in which
X¹ and X² independently of one another represent hydrogen, fluorine, chlorine or bromine and
n stands for 0, 1 or 2. 3. Substituted Pyridylpyrrole of the general formula (I) according to claim 1, characterized in that therein
R¹ and R² independently of one another are hydrogen, bromine or chlorine, where at least one of the two radicals R¹ or R² is bromine or chlorine,
R³ is hydrogen, fluorine, chlorine, bromine or C₁-C₄alkyl (which is optionally the same or different substituted by 1 to 5 fluorine, chlorine or bromine atoms),
R⁴ for hydrogen or stands,
wherein R⁵ is hydrogen or C₁-C₄-alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-acyloxy, C₂-C₅-alkoxycarbonyl, Phenyl, cyano or nitro), and
R⁶ represents hydrogen or C₁-C₅-alkyl (which is unsubstituted or substituted by 1 to 5 identical or different halogen atoms, by C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₅-acyloxy, C₂-C₆-alkoxycarbonyl, Phenyl, cyano or nitro), or wherein R⁶ is for stands,
wherein R⁷ and R⁸ are independently hydrogen, C₁-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl (wherein the alkyl, alkenyl and alkynyl radicals are each optionally substituted by 1 to 5 fluorine and / or chlorine atoms , C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-acyloxy, (C₁-C₄-alkoxy) - carbonyl, optionally substituted phenyl, cyano or nitro are substituted),
or (C₁-C₆alkoxy) -carbonyl, (C₃-C₆alkeneoxy) - or (C₃-C₆alkynoxy) carbonyl (where the alkoxy, alkenoxy and alkynoxy radicals are each optionally substituted by 1 to 5 fluoro and / or chlorine atoms, C₁-C₄ alkoxy, C₁-C₄ alkylthio, C₁-C₄ acyloxy, (C₁-C₄ alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro are substituted),
or for C₁-C₆ acyl (which may be substituted by 1 to 5 fluorine and / or chlorine atoms, C₁-C₄ alkoxy, C₁-C₄ alkylthio, C₁-C₄ acyloxy, (C₁-C₄ alkoxy) carbonyl, optionally substituted phenyl, cyano or substituted by nitro),
or R⁷ and R⁸, together with the N atom to which they are attached, may be linked through any point to form a 4- to 6-membered ring;
in which further
Pyr is pyridine-2-yl, pyridin-3-yl or pyridin-4-yl, which is optionally mono- to trisubstituted by identical or different substituents by fluorine, chlorine or bromine, or
by C₁-C₆-alkyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl (wherein the alkyl, alkenyl and alkynyl radicals are each optionally substituted by 1 to 5 fluorine and / or chlorine atoms, C₁-C₄-alkoxy, C₁-C₄ Alkylthio or substituted by C₁-C₄-acyloxy, and wherein the alkoxy and alkylthio radicals may each be substituted by 1 to 5 fluorine and / or chlorine atoms),
by C₁-C₆-alkoxy, C₂-C₆-alkenoxy or C₂-C₆-alkynoxy (where the alkoxy, alkenoxy and alkyoxy are optionally substituted by 1 to 5 fluorine and / or chlorine atoms),
by C₁-C₆-alkylthio, C₂-C₆-alkenylthio or C₂-C₆-alkynylthio (where the alkylthio, alkenylthio and alkynylthio radicals are optionally substituted by 1 to 5 fluorine and / or chlorine atoms),
by C₂-C₆-acyloxy (which is optionally substituted by 1 to 5 fluorine and / or chlorine atoms),
by amino (which is optionally substituted by 1 to 2 identical or different alkyl radicals having 1 to 6 carbon atoms, which may be substituted by 1 to 5 fluorine and / or chlorine atoms),
through nitro or cyano,
and in which
X¹ and X² independently represent hydrogen, fluorine or chlorine and
n stands for 0, 1 or 2. 4. Process for the preparation of substituted pyridylpyrroles of the formula (I) in which
R¹ and R² independently of one another are hydrogen or halogen, but at least one of the two radicals R¹ or R² is halogen,
R³ is hydrogen, halogen or optionally substituted alkyl,
R⁴ for hydrogen or stands,
wherein R⁵ is hydrogen or optionally substituted alkyl and R⁶ is hydrogen, optionally substituted alkyl or one of the radicals stands,
wherein R⁷ and R⁸ independently of one another are hydrogen, alkyl, alkenyl, alkynyl, alkoxycarbonyl, alkenoxycarbonyl, alkynoxycarbonyl or acyl, where R⁷ and R⁸ together with the N-atom to which they are attached can also form a ring,
Pyr is optionally substituted pyridin-2-yl, pyridin-3-yl or pyridin-4-yl,
X¹ and X² independently of one another represent hydrogen or halogen,
and
n is 0, 1 or 2,
characterized in that (A / B) is obtained for obtaining pyridylpyrroles of the formula (Ia) in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning and n = 1 or 2,
either

• A) Pyridylpyrroles of the formula (II) in which R³, X¹, X² and Pyr have the meanings given above and n = 1 or 2,
  reacted with halogenating agents (method A)
  or
• B) Pyridylpyrroles of the formula (III) in which R¹, R², R³, X¹, X² and Pyr have the meanings given above,
  reacted with oxidizing agents (method B);
  or that one
• C) to obtain pyridylpyrroles of the formula (Ib) in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning and n = 1 or 2 and in which R⁵ and R⁶ have the abovementioned meaning,
  Pyridylpyrroles of the general formula (Ia) in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning and n = 1 or 2,
  with compounds of the formula (IV) in which
  R⁹ has the meaning given above and
  X³ is an anionic leaving group,
  if appropriate in the presence of bases and / or if appropriate in the presence of diluents (Method C);
  or that one
• D) for obtaining pyridylpyrroles of the formula (Ic) in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning and where R⁵ and R⁶ are as defined above and n = 0,
  Pyridylpyrroles of the general formula (III) in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning,
  with compounds of the formula (IV) in which
  R⁹ has the meaning given above and
  X³ is an anionic leaving group,
  optionally in the presence of bases and / or optionally in the presence of diluents (Method D);
  or that one
• E) for obtaining pyridylpyrroles of the general formula (Id) in which R¹, R², R³, X¹, X² and Pyr have the abovementioned meaning and n = 0,
  Pyridylpyrroles of the formula (V) in which R³, X¹, X² and Pyr have the abovementioned meaning,
  reacted with halogenating agents (method E).

5. pesticides, characterized by a content of at least one substituted pyridylpyrrole of the formula (I) according to claim 1 to 3. 6. Use of substituted pyridylpyrroles of the formula (I) according to Claims 1 to 3 for controlling animal pests. 7. A method for controlling animal pests, characterized characterized in that substituted pyridylpyrroles of the formula (I) according to claim 1 to 3 can act on animal pests and / or their habitat. 8. A process for the preparation of pesticides, characterized ge denotes that substituted pyridylpyrroles of the formula (I) according to Claims 1 to 3 with extenders and / or surface-active agents mixed. 9. Substituted pyridylpyrroles of the general formula (II) in which
n is 1 or 2,
Pyr is optionally substituted pyridin-2-yl, pyridin-3-yl or pyridin-4-yl,
R³ is hydrogen, halogen or optionally substituted alkyl and
X¹ and X² independently represent hydrogen or halogen. 10. Substituted pyridylpyrroles of the formula (V) in which
Pyr, R³, X¹ and X² have the meanings given in claim 9. 11. Pyridylpyrroles of the formula (VI) in which
Pyr is optionally substituted pyridin-2-yl, pyridin-3-yl or pyridin-4-yl.