WO1995000506A1

WO1995000506A1 - Substituted pyridylpyrroles and their use for controlling animal pests

Info

Publication number: WO1995000506A1
Application number: PCT/EP1994/001909
Authority: WO
Inventors: Hermann Uhr; Albrecht Marhold; Christoph Erdelen; Andreas Turberg
Original assignee: Bayer Aktiengesellschaft
Priority date: 1993-06-24
Filing date: 1994-06-13
Publication date: 1995-01-05
Also published as: DE4321031A1; AU7184794A

Abstract

New substituted pyridylpyrroles have the formule (I), in which n equals 0, 1 or 2; pyr stands for possibly substituted pyridin-2-yl, pyridin-3-yl or pyridin-4-yl; R?1 and R2¿ represent independently from each other hydrogen or halogen, but at least one of both residues R1 or R2 necessarily represents halogen; R3 stands for hydrogen, halogen or possibly substituted alkyl; X?1 and X2¿ represent independently from each other hydrogen or halogen; and R4 stands for hydrogen or the group (a), in which R?5 and R6¿ have the meanings given in the description. Also disclosed are a process and new intermediate products for preparing these compounds, as well as their use as pesticides.

Description

SUBSTITUTED PYRIDYLPYRROLE AND THEIR USE FOR CONTROLLING ANIMAL PEST

The present invention relates to new substituted pyridylpyrroles, processes and new intermediates for their preparation and their use for controlling animal pests, in particular insects, arachnids and nematodes, which protect in agriculture, in the forests, in supply and material and on occur in the hygiene sector.

It has already become known that structurally similar cyanopyrroles are effective as molluscicides, fungicides and insecticides (see, for example, EP-A 10 0 347 488, EP-A 0 358 047, EP-A 0 312 723, DE-A 4 1 17 752. EP-A 0 481 182, EP-A 0 484 614). The effectiveness and range of action of these compounds, however, is not always completely satisfactory, especially at low application rates and concentrations.

We have now found new substituted pyridylpyrroles of the general formula (I) 15

in which

R and R ~ are independently hydrogen or halogen, but at least one of the two radicals R ¹ or R ^{2 is}

20 halogen stands,

R ^{j represents} hydrogen, halogen or optionally substituted alkyl, R ⁴ for hydrogen or

5

R / - CH stands,

\

R wherein R ^{5 represents} hydrogen or optionally substituted alkyl and R ^{6 represents} hydrogen, optionally substituted alkyl or one of the radicals

7

R

/ _A

- N or -O-R stands,

\ 8 R wherein R ⁷ and R ⁸ independently of one another are hydrogen, alkyl, alkenyl, alkynyl, alkoxycarbonyl, alkenoxycarbonyl, alkynoxycarbonyl or acyl, where R ⁷ and R ⁸ together with the N atom to which they are attached also form one Can form a ring

Pyr for optionally substituted pyridin-2-yl, pyridin-3-yl or

Pyridin-4-yl,

X ¹ and X ^{2 are} independently hydrogen or halogen, and

n stands for 0, 1 or 2.

It has also been found that the substituted pyridylpyrroles (I) - depending on the respective substituents - can be prepared by different processes, certain subgroups of end products of the formula (I) also being intermediates in the preparation of other end products (I ) could be; the following diagram shows an overview: Scheme 1:

Oxidizing agent (V) (method E)

/ Halogenating agent

(la) (Ib)

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

in which R ¹ , R ", K ^~ , X ^] , X ² and Pyr have the meaning given above and n = 1 or 2,

if you either

A) pyridylpyrroles of the formula (II)

in which R ^J , X ¹ , X ² and Pyr have the meanings given above and n is 1 or 2,

reacted with halogenating agents (process A

or

B) pyridylpyrroles of the formula (III)

in which R ¹ . R ² . R ³ , X ¹ , X ² and Pyr have the meanings given above, reacted with oxidizing agents (method B).

Pyridylpyrroles of the formula (Ib) are obtained.

in which R, R ". R ^J , X, X" and Pyr have the meaning given above and n = 1 or 2 and

in which R ⁵ and R have the meaning given above,

if pyridylpyrroles of the general formula (Ia) in which R, R, R ^J , X, X "and Pyr have the meaning given above and n = 1 or 2,

with compounds of formula (IV)

9 3

R X (IV)

in which

R ^{9 has} the meaning given above and

X ^{3 represents} an anionic leaving group, if appropriate in the presence of bases and / or if appropriate in the presence of diluents ( ^" Process C).

Furthermore, pyridylpyrroles of the formula (Ic)

in which R ¹ , R ² , R ^J , X ¹ , X ² and Pyr have the meaning given above and

where R ⁵ and R ^{6 have} the meaning given above and n = 0,

if pyridylpyrroles of the general formula (III) in which R ¹ , R ² ,

R ^J , X ¹ , X ² and Pyr have the meaning given above,

with compounds of formula (IV)

R- (IV)

in which

R ^{9 has} the meaning given above and

X ' ^{1 represents} an anionic leaving group, if appropriate in the presence of bases and / or if appropriate in the presence of diluents (process D.

E) In addition, the substituted pyridylpyrroles of the general formula (Id)

in which R ¹ , R ² , R ³ , X ¹ , X ² and Pyr have the meaning given above and n = 0,

if pyridylpyrroles of the formula (V)

in which R ³ , X ¹ , X ² and Pyr have the meaning given above,

reacted with halogenating agents (process E).

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

Finally, it was found that the new substituted pyridylpyrroles of the formula (I) have highly pronounced biological properties and, above all, for combating animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in the forests, in the stocks and materials protection as well as in the hygiene sector.

Substituted pyridylpyrroles of the above formula (I) are preferred, in which R ¹ and R ^~ independently of one another represent hydrogen, bromine or chlorine, at least one of the radicals R ¹ or R ^{2 representing} bromine or chlorine,

R ^{J represents} hydrogen, fluorine, chlorine, bromine or C _j -C _j alkyl (which is optionally substituted identically or differently by 1 to 5 fluorine, chlorine or bromine atoms),

R ⁴ for hydrogen or

5

/ CH

\ 6

R stands

where R ^{3 is} hydrogen or C _j -C ₅ alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C _r C ₅ alkoxy, C _r C ₅ alkylthio, C _r C ₅ acyloxy, C ₂ -C ₆ alkoxycarbonyl, phenyl, cyano or by nitro) and

R ^{6 represents} hydrogen or C _j -C ₆ alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C _j -C ₈ alkoxy, C _] -C ₈ alkylthio, C _] -C ₆ - Acyloxy, C ₂ -C ₈ alkoxycarbonyl, phenyl, cyano or by nitro) or in which R ^{6 is}

7 κ ^R

- N ₈ or -oR is present,

R

~ η o where R and R are independently hydrogen, C _r C ₈ - alkyl, C ₃ -C ₈ - alkenyl or C ₃ -C ₈ alkynyl are (where the alkyl, alkenyl and alkynyl each optionally substituted by 1 to 6 identical or different halogen atoms, C, -C ₆ -alkoxy, C, -C ₆ -alkylthio, C _r C ₆ -acyloxy. (C, -C ₆ -alkoxy) -carbonyI, optionally substituted phenyl, cyano or nitro are substituted ), or for (C _r C ₈ alkoxy) carbonyl, (C ₃ -C ₈ alkenoxy) carbonyl or (C -, - C ₈ alkynoxy) carbonyl (where the alkoxy, alkenoxy and alkynoxy radicals each optionally with 1 to 6 identical or different halogen atoms, C, -C ₆ -alkoxy, C _r C ₆ -alkylthio, C- -C ₆ -acyloxy, (C _r C ₆ -alkoxy) carbonyl, if appropriate substituted phenyl, cyano or nitro are substituted), or are C, -C ₈ -acyl (which may be substituted by 1 to 6 identical or different halogen atoms, C ₁ -C ₆ -alkoxy, C, -C ₆ -alkyl) thi o, C - -C ₆ acyl oxy, (C _] -C ₆ alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro is substituted), or wherein R and R together with the N atom to which they are are bound to form a 4- to 8-membered ring,

Pyr represents pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, which is optionally substituted one to four times by the same or different substituents by halogen,

by C _j -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂ -C ₈ alkynyl (the alkyl, alkenyl and alkynyl radicals each optionally having 1 to 6 halogen atoms, C - C ₅ alkoxy, C, -C ₅ alkylthio or substituted by C _r C ₅ acyloxy, and wherein the alkoxy and alkylthio radicals can each be substituted by 1 to 6 halogen atoms),

by C *, - C ₈ -alkoxy, C ₂ -C ₈ -alkenoxy or C ₂ -C ₈ -alkynoxy (the alkoxy, alkene oxy and alkynoxy radicals optionally being substituted by 1 to 6 halogen atoms),

by C 1 -C ₈ -alkylthio, C ₂ -C ₈ -alkenylthio or C ₂ -C ₈ -alkynylthio (the alkylthio, alkenylthio and alkynylthio radicals each being optionally substituted by 1 to 6 halogen atoms),

by C ₂ -C ₈ 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 what X ¹ and X "independently of one another represent hydrogen, fluorine, chlorine or bromine and

n stands for 0, 1 or 2.

Substituted pyridylpyrroles of the formula (I) in which

R ¹ and R ² independently of one another represent hydrogen, bromine or chlorine, at least one of the two radicals R ¹ or R ^{2 representing} bromine or chlorine,

R ° stands for hydrogen, fluorine, chlorine, bromine or C C -alkyl (which may or may not be substituted in the same way or differently by 1 to 5 fluorine, chlorine or bromine atoms),

R ⁴ for hydrogen or

5

R /

-CH _ß stands,

wherein R ^{5 is} hydrogen or C _j -C ₄ alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C, -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C _j -C ₄ -Acyloxy, C ₂ -C ₅ alkoxycarbonyl, phenyl, cyano or by nitro), and

R represents hydrogen or C _j -C ₅ alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C _j -C ₈ alkoxy, C _j -C ₆ alkylthio, C -.- C ₅ - Acyloxy, C ₂ -C ₆ alkoxycarbonyl, phenyl, cyano or by nitro), or in which R ^{6 is}

7

R

-N _{χ 8} or -OR stands, R wherein R ⁷ and R ⁸ independently of one another are hydrogen, C - C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl (the alkyl, alkenyl and alkynyl radicals each optionally being represented by 1 to 5 fluorine and / or chlorine atoms, C, -C ₄ alkoxy, C - C ₄ alkylthio, C ₁ -C ₄ acyloxy, (C _r C ₄ alkoxy) carbonyl, optionally substituted phenyl, cyano or are substituted by nitro),

or represent (C _j -C ₆ alkoxy) carbonyl, (C ₃ -C ₆ alkenoxy) - or represent (C - <- C ₆ alkynoxy) carbonyl (the alkoxy, alkenoxy and alkynoxy radicals in each case optionally s through 1 to 5 fluorine and / or chlorine atoms, C - C ₄ alkoxy, C _r C ₄ alkylthio, C, -C ₄ acyloxy, (C _j -C ₄ alkoxy) carbonyl, optionally substitutable tuiertes phenyl, ^'cyano or nitro-substituted),

or represent C 1 -C ₈ -acyl (which is optionally substituted by 1 to 5 fluorine and / or chlorine atoms, C, -C ₄ -alkoxy, C, -C ₄ -alkylthio, C, -C ₄ -acyloxy, (C, -C ₄ - alkoxy) carbonyl, optionally substituted phenyl, cyano or substituted by nitro),

or R and R together with the N atom to which they are attached can be linked at any point to form a 4- to 6-membered ring;

in which further

• Pyr represents pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, which is optionally substituted one to three times by the same or different substituents by fluorine, chlorine or bromine, or

by C ** - C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl (the alkyl, alkenyl and alkynyl radicals each optionally having 1 to 5 fluorine and / or chlorine atoms, C _] -C ₄ alkoxy, C _j -C ₄ alkylthio or substituted by C _j -C ₄ acyloxy, and wherein the alkoxy and alkylthio radicals can in each case be substituted by 1 to 5 fluorine and / or chlorine atoms),

by C, -C ₆ alkoxy, C ₂ -C ₆ alkenoxy or C ₂ -C ₆ alkynoxy (where the alkoxy, alkenoxy and alkynoxy radicals are optionally substituted by 1 to 5 fluorine and / or chlorine atoms) , by C - C ₆ -alkylthio, C *, - C ₆ -alkenylthio or C ₂ -C _fi -alkynylthio (the alkylthio, alkenylthio and alkynylthio radicals optionally being substituted by 1 to 5 fluorine and / or chlorine atoms),

by C ₂ -C ₆ 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 can be substituted by 1 to 5 fluorine and / or chlorine atoms),

through nitro or cyano,

and in what

X ¹ and X ² independently of one another represent hydrogen, fluorine or chlorine and

n stands for 0, 1 or 2.

The general or preferred radical definitions or explanations listed above apply to the end products and to the starting and intermediate products accordingly. These residual definitions can be combined with one another, i.e. also between the respective preferred areas.

If 2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylsulfonyl) pyrrole and bromine are used as starting materials according to production process A, the course of the reaction can be represented by the following reaction scheme:

If 2- (5,6-dichloropyridin-3-yl) -3,4-dibromo-5- (trifluoromethylthio) pyrrole and m-chloroperbenzoic acid are used as starting materials in process B, the course of the reaction can be determined by the following Reaction scheme are reproduced:

If 2- (6-chloropyridin-3-yl) -3-bromo-5- (chlorodifluoromethylsulfonyl) pyrrole and (chloromethyl) ethyl ether are used as starting materials in process C, the course of the reaction can be represented by the following reaction scheme :

If 2- (2,6-dichloropyridin-4-yl) -3,4-dibromo-5- (di-fluorochloromethylthio) pyrrole and (chloromethyl) ethyl ether are used as starting materials in process D, the course of the reaction can be determined by the following reaction scheme are reproduced:

OC, 2H " 5 If 2- (6-chloropyridin-3-yl) -5- (difluorochloromethylthio) pyrrole and bromine are used as starting materials in process E, the course of the reaction can be represented by the following reaction scheme:

Process A for the preparation of compounds of the formula (Ia) is characterized in that pyridylpyrroles of the formula (II) are treated with halogenating agents.

All conventional solvents can be used as diluents in process A. 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 are preferably usable. Water can also be used as a diluent.

All conventional halogenating agents can be used as halogenating agents. Chlorine, bromine, sodium hypochlorite, potassium hypochlorite, sodium hypobromite, potassium hypobromite, sulfuryl chloride, t-butyl hypochlorite, N-chlorosuccinimide and N-bromosuccinimide are preferably used.

The temperatures can be varied within a wide range. In general, temperatures from -10 ° C to + 120 ° C are used. preferably between 0 ° C and 70 ° C.

When carrying out the reaction components of the formula (II) with equimolar or excess amounts of a halogenating agent.

This reaction is generally carried out under normal pressure. In the case of chlorine and bromine, the reaction can also be carried out at elevated pressure (up to 5000 hPa). Process B for the preparation of compounds of the formula (Ia) is characterized in that pyridylpyrroles of the formula (III) are reacted with oxidizing agents.

All conventional solvents can be used as diluents in process B. 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 are preferably usable. Water can also be used as a diluent.

All customary oxidizing agents can be used as the oxidizing agent. M-Chloroperbenzoic acid, potassium hydrogen peroxodisulfate (Oxone), magnesium monoperoxyphthalate, HO ₂ , atmospheric oxygen in the presence of catalysts, potassium permanganate or CrO _{3 are} preferably used.

The temperatures can be varied within a wide range. In general, 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) are reacted with one or two equivalents of an oxidizing agent, depending on the desired oxidation level of the sulfur. The oxidizing agents can optionally also be used in excess.

Process C for the preparation of compounds of the formula (Ib) is characterized in that pyridylpyrroles of the formula (Ia) are reacted with compounds of the formula (IV), if appropriate in the presence of bases and if appropriate in the presence of diluents.

All inert organic solvents can be used as diluents in process C. These preferably include hydrocarbons such as benzene, toluene, xylene, furthermore ethers such as dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, and also polar solvents such as dimethyl sulfoxide, acetonitrile, sulfolane, dimethylformamide and N-methyl-pyrrolidone. All common proton acceptors can be used as bases. 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 can also be used in the presence of phase transfer catalysts such as triethylbenzylammonium chloride, tetrabutylammonium bromide or 18-crown-6, are preferably usable can. 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 methylate, sodium ethylate and potassium tert-butoxide, can also be used.

The reaction temperatures can be varied within a wide range when carried out. In general, temperatures between -10 ° C and 200 ° C, preferably between 0 ° C and 120 ° C.

The reaction components of the formula (Ia), the deprotonating bases and the components of the formulas (IV) are generally employed in approximately equimolar amounts. However, it is also possible to use one or the other component in a larger excess (up to 3 moles).

Process C is generally carried out under normal pressure, but it can also be carried out under positive pressure.

Process D for the preparation of compounds of the formula (Ic) is characterized in that pyridylpyrroles of the formula (III) are reacted with compounds of the formula (IV), if appropriate in the presence of bases and if appropriate in the presence of diluents.

All inert organic solvents are suitable as diluents in process D. These preferably include hydrocarbons such as benzene, toluene, xylene, furthermore ethers such as dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, and also polar solvents such as dimethyl sulfoxide, acetonitrile, sulfolane, dimethylformamide and N-methyl-pyrrolidone.

All common proton acceptors can be used as bases. Alkali metal and alkaline earth metal oxides are preferably usable, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which can also be used in the presence of phase transfer catalysts such as triethylbenzylammonium chloride, tetrabutylammonium bromide or 18-crown-6. Furthermore, 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 methylate, sodium ethylate and potassium tert-butoxide, can also be used.

When carrying out the reaction components of the formula (III), the deprotonating bases and the components of the formula (IV) are generally used in approximately equimolar amounts. However, it is also possible to use one or the other component in a larger excess (up to 3 moles).

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

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

All conventional solvents can be used as diluents in process E. 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 are preferably usable. Water can also be used as a diluent.

All conventional halogenating agents can be used as halogenating agents. Chlorine, bromine, sodium hypochlorite, potassium hypochlorite, sodium hypobromite, potassium hypobromite, sulfuryl chloride, t-butyl hypochlorite, N-chlorosuccinimide, N-bromosuccinimide are preferably used. The temperatures can be varied within a wide range. In general, temperatures from -10 ° C to + 120 ° C, preferably between 0 ° C and 70 ° C.

When carrying out the reaction components of the formula (V) with equimolar or excess amounts of a halogenating agent.

This reaction is generally carried out under normal pressure. If chlorine or bromine is used as the halogenating agent, the reaction can also be carried out at elevated pressure (up to 5000 hPa).

The starting materials of the general formula (II) required for the preparation of compounds of the general formula (Ia) by process A are new; they are obtained if pyridylpyrroles of the formula (V)

in which R, X, X and Pyr have the meaning given above, reacted with oxidizing agents.

If, for example, 2- (6-chloropyridin-3-yl) -5- (difluorochloromethylthio) pyrrole and m-chloroperbenzoic acid are used as starting materials, the course of the reaction according to this process can be represented by the following reaction scheme.

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

All customary solvents can be used as diluents in this process. 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 are preferably usable. Water can also be used as a diluent.

All customary oxidizing agents can be used here as the oxidizing agent. M-Chloroperbenzoic acid, potassium hydrogen peroxodisulfate (Oxone), magnesium monoperoxyphthalate, H *, O ₂ , atmospheric oxygen in the presence of catalysts, potassium permanganate or CrO _{3 are} preferably used.

Depending on the desired oxidation level of the sulfur, the reaction components of the formula (V) are reacted with one or two equivalents of an oxidizing agent. The oxidizing agents can optionally also be used in excess.

The starting materials of formula (V) are new; they are obtained if pyridylpyrroles of the general formula (VI)

H in which Pyr has the meaning given above,

with sulfen chlorides of the general formula (VII), X

3 '

R— C-SCI (VII)

2

X wherein X ¹ , X ² and R ^{J have} the meaning given above, if appropriate in the presence of bases and if appropriate in the presence of diluents.

If 2- (5,6-dichloropyridin-3-yl) pyrrole and trifluoromethylsulfenchloride are used as starting materials in accordance with this production process, the course of the reaction can be represented by the following reaction scheme:

The process for the preparation of compounds of the formula (V) is characterized in that pyridylpyrroles of the formula (VI) are reacted with sulfenchlorides of the general formula (VII), if appropriate in the presence of bases and if appropriate in the presence of diluents.

All inert organic solvents can be used as diluents in this process. These preferably include hydrocarbons such as benzene, toluene, xylene, furthermore ethers such as dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, and also polar solvents such as dimethyl sulfoxide, acetonitrile, sulfolane, dimethylformamide and N-methyl-pyrrolidone.

Examples of bases which can be used are 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 methylate, sodium ethylate and potassium tert-butoxide. The reaction temperatures can be varied within a wide range when carried out. In general, temperatures between - 70 ° C and + 50 ° C, preferably between -30 ° C and + 30 ° C.

When carrying out the reaction components of the formula (VI) and (VII) are used in aquimolar ratios. The reaction components of the formula (VII) can optionally be used in excess

The bases which are optionally used are generally used in aquimolar or slightly excess amounts

This reaction is generally carried out under normal pressure. In the case of gaseous sulfen chlorides, the reaction can also be carried out under elevated pressure (up to 5000 hPa)

The pyridylpyrroles of the general formula (VT) are new, they can be prepared by processes known per se (cf. A. Gossauer, Die Chemie der Pyrrole, Springer-Verlag, Berlin 1974, p. 276; N. Engel, W. Steglich , Angew Chem. 90, 719 (1978))

Some of the sulfen chlorides of the general formula (VTI) are known and can be prepared by methods which are known in principle (cf. Houben-Weyl, Georg Thieme Verlag Stuttgart, Vol. 9, p. 267 ff; see also DE-A 4 036 515)

The substituted pyridylpyrroles (I) according to the invention are suitable with good plant tolerance and favorable warm-blood toxicity for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products and materials and in the hygiene sector. They are normal against sensitive and resistant species and effective against all or individual stages of development The pests mentioned above include

From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare,

Porcelho scaber

From the order of the Diplopoda, for example, Blaniulus guttulatus From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec. From the order of the Symphyla, for example, Scutigerella immaculata. From the order of the Thysanura, for example Lepisma saccharina. From the order of the Collembola, for example Onychiurus armatus. From the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria. From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera e.g. Reticulitermes spp .. From the order of the Anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp .. From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp ..

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci. From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp ..

From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae. Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticepellis, Laodiaiaeaeaiataiaieaiataiaieaiataiaiiataieaia Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp ..

From the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculitrella thyll ., 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 kuellellaiellaellaellaiellaellaiellaellaiellaellaiellaellaellaiellaellaellaiellaellaiellaellaiellaellaiellaellaellaiellaellaiellaellaiellaellaiellaellaiellaellaiellaellaiellaellae , Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana. From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrisousisamasppas, Atomic spp. , Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus holpp., Ptinus holpp. Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp ..

From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gasttophilus spp., Hippobosca spp., Stomoxys 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 the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp .. From the order of the Arachnida e.g. Scorpio maurus, Lactrodectus mactans.

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

The substituted pyridylpyrroles (I) according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary medical sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, space mites, running mites, flies (stinging and licking), and parasitic Fly larvae, lice, hair lice, featherlings, fleas. They are effective against normally sensitive and resistant species and strains, as well as against all parasitic and non-parasitic stages of development of the ectoparasites.

The substituted pyridylpyrroles (I) according to the invention are notable for high insecticidal activity. They can be used with good success against plant-damaging insects, such as, for example, against the larvae of horseradish leaf beetles (Phaedon cochleariae), against green peach aphids (Myzus persicae) or against black bean aphids (Aphis fabae). The active compounds according to the invention show 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 used, for example, for controlling the maggots of the onion fly (Phorbia antiqua) in the soil.

In addition, the substituted pyridylpyrroles (I) according to the invention have a high activity against hygiene pests and pests of stored products and can be used, for example, to control 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 substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds , also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the substituted pyridylpyrroles (I) according to the invention with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: Aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example 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, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example. Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: eg lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, natural phospholipids such as cephalins and lecithins, and synthetic phospholipids, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used. The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

The substituted pyridylpyrroles (I) according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.

The substituted pyridylpyrroles (I) according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.

The active ingredient content of the applications prepared from the commercially available formulations can be varied. The active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms.

When used against hygiene pests and pests of stored products, the active substances are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.

The substituted pyridylpyrroles (I) according to the invention are also suitable for controlling insects, mites, ticks, etc. in the field of animal husbandry and animal husbandry, better results being obtained by controlling the pests. eg higher milk yields, higher weight, more beautiful animal fur, longer lifespan etc. can be achieved. The substituted pyridylpyrroles (I) according to the invention are used in this field in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal or external use in the form of, for example, immersion (dipping), spraying (spraying) ), Pour-on and spot-on and powdering, as well as by parenteral use in the form of, for example, injection and furthermore by the “feed-through” method. In addition, use as a shaped body (collar, ear tag) is also possible.

The following examples serve to explain the invention further.

Manufacturing bed games

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 2 ml of bromine are added. The mixture is stirred for 20 h at room temperature, excess bromine is driven off with nitrogen gas, evaporated on a rotary evaporator and codistilled twice with toluene. The residue is chromatographed on silica gel (CH ₂ Cl, / methanol = 97: 3). Yield: 1.7 g (= 46% of theory) of 3-bromo-2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylsulfonyl) 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 placed in 50 ml of tetrahydrofuran (THF) and cooled with 0.5 g (4.4 mmol) potassium tert-butoxide added. A solution of 0.4 ml (4.1 mmol) of chloromethyl ethyl ether in 10 ml of THF is then added dropwise. The mixture is stirred at room temperature for 19 h, poured onto water, extracted with dichloromethane, dried over MgSO ₄ and the filtered organic solution is evaporated on a rotary evaporator. The residue is chromatographed on silica gel (CHXl * -,). Yield: 0.9 g (= 52% of theory) of 3-bromo-2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylsulfonyl) -l- (ethoxymethyl) pyrrole; physical data see table 1.

The other compounds of the formula (I) listed in Table 1 below can also be prepared analogously to Examples 1 and 2 and in accordance with the general information given above about the production processes A to E according to the invention:

Table 1

Table 1 - continued

Table 1 - continued

i-

Table 1 - continued

Manufacture of intermediate products

Example VI-1

(VII-1)

21.8 g (0.101 mol) of allyl- [chloro- (6-chloropyridin-3-yl) methylene] amine of the formula (VII-1) are dissolved in 100 ml of dry tetrahydrofuran (THF) and at 0 ° C 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 onto ice water and extracted three times with dichloromethane. The combined organic extracts are dried over MgSO ₄ , then filtered and evaporated using a rotary evaporator. The residue is purified by chromatography on silica gel (CH ₂ C1 ₂ + 2% methanol).

Yield: 8.6 g (= 48% of theory) of 2- (6-chloro-pyridin-3-yl) pyrrole; physical data see table 2.

The other precursors of the formula (VI) listed in Table 2 below can also be prepared in an analogous manner:

Table 2

_u

% ιvι CD

__σ m

ro .03

Example V-l

5 g (28 mmol) of 2- (6-chloropyridin-3-yl) pyrrole are dissolved in 30 ml of diethyl ether and 3 g (28 mmol) of Na ₂ CO _{3 are} added. The mixture is cooled to -30 ° C. and a solution of 3.1 ml (31 mmol) of chlorodifluoromethylsulfenchloride in 10 ml of diethyl ether is added dropwise. The mixture is stirred at this temperature for 6 h and then insoluble is filtered off. The filtrate is washed with water, dried over MgS0 ₄ and concentrated.

Yield: 5.5 g (= 67% of theory) of 2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylthio) pyrrole; physical data see table 3.

The other precursors of the formula (V) listed in Table 3 below are also prepared in an analogous manner:

Table 3

Table 3 - continued

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. A solution of 7.7 g (32 mmol) of 55% m-chloroperbenzoic acid in 80 ml of chloroform is added dropwise. The mixture is stirred for 3 h at room temperature and then washed with Na, SO ₄ solution and Na CO solution. After drying over MgSO ₄ , the solution is evaporated (using a rotary evaporator) and the residue is filtered through silica gel (CH ₂ C1,).

Yield: 4.2 g (= 82% of theory) of 2- (6-chloropyridin-3-yl) -5- (chlorodifluoromethylsulfonyl) pyrrole; physical data see table 4.

The other precursors of the formula (II) listed in Table 4 below are also prepared in an analogous manner:

Table 4

m σ> m ro

Table 4 - continued

Examples of use

In the case of the active compounds according to the invention, example no. on the corresponding manufacturing examples.

Example A Phaedon larval test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.

In this test, for example, the compound according to Preparation Example 2, with an exemplary active ingredient concentration of 0.1%, caused 100% killing after 7 days.

Example B

Plutella test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cabbage cockroach (Plutella maculipennis) while the leaves are still moist.

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

In this test, for example, the compound of preparation example 2, with an exemplary active compound concentration of 0.1%, caused 100% destruction after 7 days.

Example C

Heliothis virescens test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Soybean shoots (Glycine max) are treated by dipping into the active ingredient preparation of the desired concentration and populated with the tobacco bud caterpillar (Heliothis virescens) while the leaves are still moist.

For this remainder, for example, the compound according to Preparation Example 2, with an exemplary active compound concentration of 0.1%, caused 100% and 7 days to be killed.

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 of nonylphenol polyglycol ether

To produce a suitable formulation, 3 parts by weight of active compound are mixed with 7 parts of the solvent / emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the concentration desired in each case.

2 ml of this active ingredient preparation are pipetted onto filter paper discs (0 9.5 cm), which are located in Petri dishes of the appropriate size. After the filter discs have dried, 5 test animals are transferred to B. germanica or P. americana and covered.

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

In this test, for example, the compound according to Preparation Example 2, with an exemplary active ingredient concentration of 1000 ppm, caused a kill of 100%.

Example E Fly test

Test animals: Musca domestica, strain WHO (N)

2 ml of this active ingredient preparation are pipetted onto filter paper discs (0 9.5 cm), which are located in Petri dishes of the appropriate size. After the filter discs have dried, 25 test animals are transferred to the Petri dishes and covered.

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

In this test, e.g. the compound according to preparation example 2 with an exemplary active ingredient concentration of 1000 ppm a killing of 100%.

Claims

1. Substituted pyridylpyrroles of the general formula (I),

in which

R ¹ and R ² independently of one another represent hydrogen or halogen, but at least one of the two radicals R or R ^{~ represents} haloses,

R represents hydrogen, halogen or optionally substituted

Alkyl stands,

R ⁴ for hydrogen or

5

R /

- CH stands,

\ 6

R wherein R represents hydrogen or optionally substituted alkyl and

RR ⁶⁶ for hydrogen, optionally substituted alkyl or for one of the

Leftovers

7

- N / ^R o "der - OR stands,

\ 8 R wherein R ⁷ and R ^{8 are} independently hydrogen, alkyl, alkenyl, alkynyl, alkoxycarbonyl, alkenoxycarbonyl, alkynoxycarbonyl or acyl R ⁷ and R ⁸ together with the N atom to which they are attached can also form a ring,

Pyr represents optionally substituted pyridin-2-yl, pyridin-3-yl or pyridin-4-yl,

X ¹ and X ^{2 are} independently 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

R ¹ and R ² independently of one another represent hydrogen, bromine or chlorine, at least one of the radicals R ¹ or R ^{2 representing} bromine or chlorine,

R ^{3 represents} hydrogen, fluorine, chlorine, bromine or C _r C ₅ alkyl (which is optionally substituted identically or differently by 1 to 5 fluorine, chlorine or bromine atoms),

R ⁴ for hydrogen or

5 R CH

^R is where R ^{3 is} hydrogen or C, -C ₅ -alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C _j -C ₅ -alkoxy, C - -C ₅ - Al kyl thi o,

C _j -C ₅ acyloxy, C *, - C ₆ alkoxycarbonyl, phenyl, cyano or by nitro) and

R ^{6 represents} hydrogen or C _r C ₆ alkyl (which is optionally substituted by 1 to 5 or the same or different Hal ogenatom e, by C, -C ₈ -alkoxy, C - -C _s - AI ky 1 thio, C, -C ₆ -acyloxy, C ₂ -C ₈ alkoxycarbonyl, phenyl, cyano or by nitro) or wherein R ⁶ for

7

- ₈ or -oR stands,

R

where R ⁷ and R ^{8 are} independently hydrogen,

C.-C ₈ -alkyl, C ₃ -C ₈ -alkenyl or C ₃ -C ₈ -alkynyl (the alkyl, alkenyl and alkynyl radicals each optionally having 1 to 6 identical or different halogen atoms, C, -C ₆ Alkoxy, C _j -C ₈ alkylthio, C _j -C ₆ acyloxy, (C _j -C ₆ alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro are substituted), or for (C ₁ - C ₈ -alkoxy) -carbonyl, (C ₃ -C ₈ -alkenoxy) -carbonyl or (C ₃ -C ₈ -alkynoxy) -carbonyl (where the alkoxy, alkenoxy and alkynoxy radicals are each optionally 1 to 6 identical or various halogen atoms, C _j -C ^ alkoxy, C _j -C ₆ allythio, C, -C ₆ acyloxy, (C _j -C ₆ alkoxy) carbonyl, optionally substituted

Phenyl, cyano or nitro are substituted), or stand for C _j -C ₈ acyl (which may be by 1 to 6 identical or different halogen atoms, C, -C ₆ alkoxy, C ^ C ₈ alkylthio, C ^ C ₈ -Acyloxy, (C _] -C ₆ -alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro is substituted), or in which

R ⁷ and R ⁸ together with the N atom to which they are attached form a 4- to 8-membered ring,

by C, -C ₈ alkyl, C ₂ -C ₈ alkenyl or C *, - C ₈ alkynyl (the alkyl, alkenyl and alkynyl radicals each optionally having 1 to 6 halogen atoms, C, -C ₅ alkoxy , C, -C ₅ alkylthio or substituted by C _r C ₅ acyloxy, and wherein the alkoxy and Alkylthio radicals can each be substituted by 1 to 6 halogen atoms),

by C _j -C ₈ alkoxy, C ₂ -C ₈ alenoxy or C ₂ -C ₈ alkynoxy (the alkoxy, alkenoxy and alkynoxy radicals optionally being substituted by 1 to 6 halogen atoms),

by CC ₈ -alkylthio, C ₂ -C ₈ -alkenylthio or C ₂ -C ₈ -alkynylthio (where the alkylthio, alkenylthio and alkynylthio radicals are each optionally substituted by 1 to 6 halogen atoms),

by C *, - C ₈ -acyloxy (which is optionally substituted by 1 to 6 halogen atoms),

through nitro or cyano,

and in what

X ¹ and X ² independently of one another represent hydrogen, fluorine, chlorine or bromine and

n stands for 0, 1 or 2.

Substituted pyridylpyrroles of the general formula (I) according to Claim 1, characterized in that therein

R ¹ and R ~ independently of one another represent hydrogen, bromine or chlorine, at least one of the two radicals R ¹ or R- representing bromine or chlorine, R ^{J represents} hydrogen, fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl (which is optionally substituted identically or differently by 1 to 5 fluorine, chlorine or bromine atoms),

R ⁴ for hydrogen or

5

R /

-CH _β stands, R

wherein R ^{5 is} hydrogen or C, -C ₄ alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, du rc h C _j - C ₄ -alkoxy, C, - C ₄ -alkylene) io, C, - C ₄ - A cy l oxy, C ₂ -C ₅ alkoxycarbonyl, phenyl, cyano or by nitro), and

R ^{6 represents} hydrogen or C _j -C ₅ alkyl (which is optionally substituted by 1 to 5 identical or different halogen atoms, by C ₁ -C ₆ alkoxy, C _j -C ₆ alkylthio, C _j -C ^ Acyloxy, C ₂ -C ₆ alkoxycarbonyl, phenyl, cyano or by nitro), or wherein R ⁶ for

7

/ ^R

- N ₈ or -OR stands,

R

in which R ⁷ and R ⁸ independently of one another are hydrogen, C ₁ -C ₈ -alkyl,

C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl (the alkyl, alkenyl and alkynyl radicals each optionally having 1 to 5 fluorine and / or chlorine atoms, C, -C ₄ alkoxy, C , -C ₄ alkylthio, C _r C ₄ acyloxy, (C, -C ₄ alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro are substituted),

or for (C ** - C ₆ - alkoxy) -carbonyl, (C ₃ -C ₆ -alkenoxy) - or for (C ₃ -C ₆ - alkynoxy) -carbonyl (the alkoxy, alkenoxy and alkynoxy radicals in each case optionally by 1 to 5 fluorine and / or chlorine atoms, C, -C ₄ -alkoxy, CC ₄ -alkylthio, C, -C ₄ -acyloxy, (C - C ₄ alkoxy) carbonyl, optionally substituted phenyl, cyano or nitro are substituted),

or represent C _j -C ₆ -acyl (which is optionally substituted by 1 to 5 fluorine and / or chlorine atoms, C - C ₄ -alkoxy, C, -C ₄ -alkylthio, C - C ₄ -acyloxy, (C _j - _j - alkoxy) carbonyl, optionally substituted phenyl, cyano or substituted by nitro),

"7 R or R and R together with the N atom to which they are attached can be linked at any point to form a 4- to 6-membered ring;

in which further

Pyr stands for pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, which is optionally substituted one to three times by the same or different substituents by fluorine, chlorine or bromine, or

by C _r C ₆ alkyl, C ₂ -C ₆ alkenyl or C, -C ₆ alkynyl (the alkyl, alkenyl and alkynyl radicals each optionally having 1 to 5 fluorine and / or chlorine atoms, C _j -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or substituted by C ₁ -C ₄ -acyloxy, and where the alkoxy and alkylthio radicals can in each case be substituted by 1 to 5 fluorine and / or chlorine atoms),

by C _j ^ -C alkoxy, C ₂ -C ₆ -alkenoxy or C ₂ -C ₆ alkynoxy (where the alkoxy, alkenoxy and Alkinoxyreste are optionally substituted by 1 to 5 fluorine and / or chlorine atoms),

by C _j -C ₆ alkylthio, C ₂ -C ₆ alkenylthio or C ₂ -C ₆ alkynylthio (the alkylthio, alkenylthio and alkynylthio radicals optionally being substituted by 1 to 5 fluorine and / or chlorine atoms),

by C ₂ -C ₆ 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 can be substituted by 1 to 5 fluorine and / or chlorine atoms),

through nitro or cyano,

and in what

n stands for 0, 1 or 2.

4. Process for the preparation of substituted pyridylpyrroles of the formula (I)

in which

R ¹ and R ² independently of one another represent hydrogen or halogen, where at least one of the two radicals R or R represents halogen,

R represents hydrogen, halogen or optionally substituted

Alkyl stands,

R ⁴ for hydrogen or

5

R / - CH stands,

\ 6 R wherein R ^{3 represents} hydrogen or optionally substituted alkyl and R ^{6 represents} hydrogen, optionally substituted alkyl or one of the radicals

- N er -OR stands,

where R and R independently of one another are hydrogen, alkyl, alkenyl,

Are alkynyl, alkoxycarbonyl, alkenoxycarbonyl, alkynoxycarbonyl or acyl, where R and R together with the N atom to which they are attached can also form a ring,

X and X "independently of one another represent hydrogen or halogen, and

n represents 0, 1 or 2,

characterized in that (A / B) to obtain pyridylpyrroles of the formula (Ia)

in which R ¹ , R ² , R ³ , X ¹ , X ² and Pyr have the meaning given above and n = 1 or 2,

either

A) pyridylpyrroles of the formula (II)

in which R ^J , X ¹ , X ² and Pyr have the meanings given above and n = 1 or 2,

reacted with halogenating agents (process A

or

B) pyridylpyrroles of the formula (III)

in which R, R, R, X, X "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 R ¹ , R ² , R ³ , X ¹ , X ² and Pyr have the meaning given above and n = 1 or 2 and R

R ^v for

-CH

R stands in which R ⁵ and R ^{6 have} the meaning given above,

Pyridylpyrroles of the general formula (Ia) in which R, R, R ^J , X ¹ , X "and Pyr have the meaning given above and n = 1 or 2,

with compounds of formula (IV)

R X (IV)

in which

10 R ^{9 has} the meaning given above and

X ^{3 represents} an anionic leaving group,

if appropriate in the presence of bases and / or if appropriate in the presence of diluents (process C):

or that one

15 D) to obtain pyridylpyrroles of the formula (Ic)

in which R ¹ , R ² , PX, X ¹ , X ² and Pyr have the meaning given above and

R

R ^y for

-CH

\ 6

R is where R ⁵ and R ^{6 have} the meaning given above and n = 0,

Pyridylpyrroles of the general formula (III) in which R, R, R, X, X ^~ and Pyr have the meaning given above,

with compounds of formula (IV)

9 3

R X (IV)

10 in which

R ^{9 has} the meaning given above and

X ^{3 represents} an anionic leaving group,

if appropriate in the presence of bases and / or if appropriate in the presence of diluents (process D);

15 or that one

E) to obtain pyridylpyrroles of the general formula (Id)

Pyridylpyrroles of the formula (V)

in which R ³ , X ¹ , X ² and Pyr have the meaning given above,

reacted with halogenating agents (method EY

5. pesticide, characterized by a content of at least one substituted pyridylpyrrole of the formula (I) according to

Claims 1 to 3.

6. Use of substituted pyridylpyrroles of the formula (I) according to Claims 1 to 3 for combating animal pests.

7. A method for controlling animal pests, characterized in that substituted pyridylpyrroles of the formula (I) according to

Claims 1 to 3 can act on animal pests and / or their habitat.

8. A process for the preparation of pesticides, characterized in that substituted pyridylpyrroles of the formula (I) according to Claims 1 to 3 are mixed with extenders and / or surface-active agents. 9. Substituted pyridylpyrroles of the general formula (II)

in which

n represents 1 or 2,

Pyr for optionally substituted pyridin-2-yl, pyridin-3-yl or

Pyridin-4-yl,

R ^{3 represents} hydrogen, halogen or optionally substituted alkyl and

X ¹ and X ^{2 are} independently hydrogen or halogen.

10. Substituted pyridylpyrroles of the formula (V)

in which

Pyr, R, X and X "have the meanings mentioned in claim 9.

1 1. pyridylpyrroles of the formula (VI)

H in which

Pyr represents optionally substituted pyridin-2-yl, pyridin-3-yl or pyridin-4-yl.