EP1322604A1 - Delta 1-pyrrolines for use as pesticides - Google Patents

Abstract

The invention relates to novel Δ1 pyrrolines of formula (I), wherein R?1, R2, R3, R4, R5¿, n, r and s have the meanings given in the description, to several methods for producing these substances, to their use for controlling pests and to novel intermediate products.

Description

 DELTA 1-PYRROLINE FOR USE AS PESTICIDES

The present invention relates to new Δ'-pyrrolines, several ner processes for their preparation and their use as pesticides.

It is already known that numerous Δ'-pyrrolines have insecticidal properties (cf. WO 00/21958, WO 99/59968, WO 99/59967 and WO 98/22438). The effectiveness of these substances is good, but leaves something to be desired in some cases.

Δ'-pyrrolines of the formula (I)

found in which

n represents 0 or 1,

r and s independently of one another represent 0, 1 or 2,

R 'represents halogen or methyl,

R ^{2 represents} hydrogen or halogen.

R ³ and R ¹ independently of one another for halogen. Al yl. Haloalkyl, alkoxy or

Halogenalkoxy stand. R ^{5 represents} alkyl, haloalkyl, in each case optionally singly or multiply, identical or different phenyl substituted by radicals from the list W 'or represents -NR ⁶ R ⁷ ,

W 'for halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylcarboηyl,

Is alkoxycarbonyl or -S (O) R ⁸ ,

R ^{6 represents} alkyl or haloalkyl,

R ^{7 represents} hydrogen, alkyl or haloalkyl,

R ⁶ and R ⁷ also together represent alkylene or alkoxyalkylene,

R ^{8 represents} alkyl or haloalkyl and

q represents 0, 1 or 2.

Furthermore, it has been found that Δ'-pyrrolines of the formula (I) can be prepared by

A) aminoketones of the formula (II)

in which R ¹ , R \ R ³ , R, R \ n, r and s have the meanings given above. treated with a Lewis acid or protonic acid,

or

B) (Bi) phenols of the formula (III)

in which

R, R, R, R, n, r and s have the meanings given above,

with a sulfonylation reagent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,

or

C) that Δ'-pyrrolines of the formula (I-a)

R. R ", R. R, R, r and s have the meanings given above. obtained by using pyrrolines of the formula (IV)

in which

R, R, R and r have the meanings given above and

X represents Br, Cl, I, -OSO ₂ CF ₃ or -OSO ₂ (CF ₂ ) ₃ CF ₃ ,

first reacted with a diboronic ester in the presence of a catalyst, in the presence of an acid binder and, if appropriate, in the presence of a diluent and, if appropriate, after prior isolation of the resulting compounds of the formula (V)

in which

R, R, R and r have the meanings given above and

G for 4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yl, 5,5-dimethyl-l, 3,2-dioxaborinan-2-yl, 4,4,6-trimethyl 1, 3,2-dioxaborinan-2-yl or 1,3,2-benzodioxaborol-2-yl,

with iodides of the formula (VI) in which

R ⁴ , R ⁵ and s have the meanings given above,

in the presence of a catalyst, in the presence of a diboronic ester, in the presence of an acid binder and, if appropriate, in the presence of a diluent.

Finally, it was found that the compounds of the formula

(I) have very good insecticidal properties and can be used both in crop protection and in material protection to combat unwanted pests, such as insects.

Surprisingly, the Δ'-pyrrolines of the formula (I) according to the invention show a substantially better insecticidal activity than the constitutionally most similar, previously known Δ'-pyrrolines of the same action.

The Δ 'pyrrolines according to the invention are generally defined by the formula (I)

n is preferably 0 or 1.

r and s independently of one another are preferably 0, 1 or 2.

R 'preferably represents fluorine, chlorine, bromine or methyl.

R ^" preferably represents hydrogen. Fluorine. Chlorine or bromine. R ³ and R ⁴ independently of one another preferably represent fluorine, chlorine, bromine, C, -C ₆ -alkyl, C _r C ₆ -haloalkyl, C, -C ₆ -alkoxy or C, -C ₆ -haloalkoxy.

R ⁵ preferably represents C, -C ₆ -alkyl, C, -C ₆ -haloalkyl, in each case optionally one to four times, identical or different phenyl substituted by radicals from the list W 'or -NR ⁶ R ⁷ .

W 'preferably represents fluorine, chlorine, bromine, C, -C ₆ -alkyl, C _r C ₆ -haloalkyl, C, - C ₆ -alkoxy, C, -C ₆ -haloalkoxy, C, -C ₆ -alkylcarbonyl, C _r C ₆ alkoxycarbonyl or -S (O) _q R ⁸ .

R ⁶ preferably represents C _r C ₆ alkyl or C, -C ₆ haloalkyl.

R ⁷ preferably represents hydrogen, C, -C ₆ alkyl or C _r C ₆ haloalkyl.

R ⁶ and R ⁷ together also preferably represent C ₃ -C ₆ alkylene or C _r C ₄ alkoxy-C, -C ₄ alkylene.

R ⁸ preferably represents C, -C ₆ alkyl or C, -C ₆ haloalkyl.

q is preferably 0, 1 or 2.

n particularly preferably represents 0 or 1.

r and s independently of one another are particularly preferably 0, 1 or 2.

R ¹ particularly preferably represents fluorine, chlorine or methyl.

R ² particularly preferably represents hydrogen, fluorine or chlorine.

R 'and R ⁴ independently of one another are particularly preferably fluorine, chlorine, C, -

C-alkyl, C, -C ₄ haloalkyl. C, -C ₄ alkoxy, C, -C ₄ haloalkoxy. R ⁵ particularly preferably represents C, -C ₄ -alkyl, C, -C ₄ -haloalkyl, in each case optionally mono- to triple, the same or different phenyl substituted by radicals from the list W 'or -NR ⁶ R ⁷ .

W 'is more preferably fluorine, chlorine, C, -C ₄ -alkyl, C ₄ haloalkyl,

C, -C ₄ alkoxy, C, -C ₄ haloalkoxy, C, -C ₄ alkylcarbonyl, C, -C ₄ alkoxycarbonyl or -S (O) _q R ⁸ .

R ⁶ particularly preferably represents C, -C ₄ -alkyl or C, -C ₄ -haloalkyl.

R ⁷ particularly preferably represents hydrogen, C, -C ₄ -alkyl or C, -C ₄ -haloalkyl.

R ⁶ and R ⁷ together also particularly preferably represent C ₄ -C ₅ alkylene or - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -.

R ⁸ particularly preferably represents C _r C ₄ - alkyl or C _r C ₄ haloalkyl.

q particularly preferably represents 0, 1 or 2.

n very particularly preferably represents 0 or 1.

r and s independently of one another very particularly preferably represent 0 or 1.

R 'very particularly preferably represents fluorine or chlorine.

R ² very particularly preferably represents hydrogen or fluorine.

R 'and R ⁴ independently of one another very particularly preferably represent fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, Trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, trifluoromethoxy or trifluoroethoxy.

R ⁵ very particularly preferably represents methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl, trifluoroethyl, nonafluorobutyl, in each case, if appropriate, once or twice, the same or phenyl substituted by radicals from the list W 'or for -NR ⁶ R ⁷ .

W 'very particularly preferably represents fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl, trifluoroethyl,

Methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-

Butoxy, trifluoromethoxy, trifluoroethoxy, -COCH ₃ , -CO ₂ CH ₃ , -SCF ₃ ,

-SCHF ₂ , -SOCF ₃ , -SOCHF ₂ , -SO ₂ CF ₃ or -SO ₂ CHF ₂ .

R ⁶ very particularly preferably represents methyl, ethyl, n-propyl, i-propyl, n-

Butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl or trifluoroethyl.

R ⁷ very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, i-

Propyl, n-butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl or trifluoroethyl.

Compounds of the formula (I-a) are also preferred

in which

R. R ", R, R, R, r and s have the meanings given above. Compounds of the formula (Ib) are also preferred

in which

R ', R ² , R ⁴ , R ⁵ and s have the meanings given above.

Also preferred are compounds of the formulas (Ia) and (Ib) in which R ', R ² , R ³ , R ⁴ , R ⁵ , r and s each have the preferred meanings indicated above.

Also preferred are compounds of the formulas (Ia) and (Ib) in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , r and s each have the particularly preferred meanings given above.

Also preferred are compounds of the formulas (Ia) and (Ib) in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , r and s each have the very particularly preferred meanings given above.

Furthermore, (R) -configured compounds of the formulas (I-c) are very particularly preferred

in which

R ¹ , R ² , R ⁴ , R ⁵ and s have the meanings given above. Furthermore, (R) -configured compounds of the formulas (Id) are very particularly preferred.

in which

R ', R ² , R ³ , R ⁴ , R ⁵ , r and s have the meanings given above.

Enantiomerically pure compounds of the formulas (I-c) and (I-d) are obtained by customary processes for resolving racemates, for example by chromatography of the corresponding racemates on a chiral stationary phase. It is possible to break down both the racemic end products or racemic intermediates into the two enantiomers in this way.

Saturated hydrocarbon radicals, such as alkyl, can also be used in connection with heteroatoms, e.g. in alkoxy, where possible, be straight-chain or branched.

Optionally substituted radicals can be mono- or polysubstituted, whereby in the case of multiple substitutions the substituents can be the same or different. Several residues with the same indices, such as s residues R ⁴ for s = 2, can be the same or different.

The general definitions or explanations of residues or explanations listed above or in preferred areas can, however, also be combined as desired, that is to say between the respective areas and preferred areas. They apply accordingly to the end products as well as to the preliminary and intermediate products. If 4 '- [1 - [(tert-butoxycarbonyl) amino] -4- (2,6-difluorophenyl) -4-oxobutyl] -l, r-biphenyl-4-yl-trifluoromethanesulfonate and trifluoroacetic acid (TFA) are used as starting materials, the course of process (A) according to the invention can be illustrated by the following formula.

If 4 '- [5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] -l, 1' -biphenyl-4-ol and trifluoromethanesulfonic acid chloride (F ₃ CSO ₂ Cl) are used as starting materials, the course of process (B) according to the invention can be illustrated by the following formula.

If 5- (2,6-difluorohenyl) -2- (4-bromophenyl) -3,4-dihydro-2H-pyrrole, 4- is used

Iodophenyl trifluoromethanesulfonate, a palladium catalyst and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi-l, 3,2-dioxaborolane as starting materials, the process according to the invention can (C) can be illustrated by the following formula scheme.

Explanation of ner driving and intermediate products

Procedure (A)

Formula (II) provides a general definition of the amino ketones required as starting materials when carrying out process (A) according to the invention. In this formula, R ^1, R ^2, R ^3, R ^4, R ^5, n, r and s being preferred, particularly preferred and very particularly preferably has those meanings which have already in connection with the description of the substances according to the invention of the formula ( I) were mentioned as preferred, particularly preferred etc. for these radicals.

The amino ketones of formula (II) are new. They can be made by

a) Ν-Boc lactams of the formula (VII)

in which

R, R, R, n, r and s have the meanings given above,

with metallated aromatics of formula (VIII)

in which R ¹ and R ^{2 have} the meanings given above and

M represents Li, MgCl, MgBr, Mgl or ZnCl,

optionally in the presence of a diluent (e.g. tetrahydrofuran) at temperatures between -70 ° C and + 70 ° C.

Formula (VII) provides a general definition of the N-Boc lactams required as starting materials when carrying out process (a). In this formula, R ³ , R ⁴ , R ⁵ , n, r and s are preferred, particularly preferred or very particularly preferred for those meanings which are already in connection with the description of the substances of the formula (I) according to the invention for these radicals preferred, particularly preferred, etc. were mentioned.

N-Boc lactams of the formula (VII) are new. They can be made, for example, by

b) lactams of the formula (IX)

in which

R, R, R, n, r and s have the meanings given above,

with di-tert-butyl dicarbonate in the presence of a base (eg dimethylaminopyridine). if appropriate in the presence of a diluent (for example dichloromethane). Formula (VIII) provides a general definition of the metallated aromatics required as starting materials when carrying out process (a). In this formula, R 'and R ^{2 are} preferred, particularly preferred or very particularly preferred for those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention were. M preferably represents Li, MgCl, MgBr, Mgl, ZnCl, particularly preferably Li, MgCl, MgBr, Mgl, very particularly preferably Li, MgCl, MgBr.

Metallized aromatics of the formula (VIII) are known in some cases or can be prepared by known methods, e.g. Lithiation or Grignard reaction, can be prepared from the corresponding aromatics or halogen aromatics.

The lactams required as starting materials in carrying out process (b) are generally defined by the formula (IX). In this formula, R ³ , R ⁴ , R ⁵ , n, r and s are preferred, particularly preferred or very particularly preferred for those meanings which are already in connection with the description of the substances of the formula (I) according to the invention for these radicals preferred, particularly preferred, etc. were mentioned.

Lactams of the formula (IX) are new.

Lactams of the formula (IX-a)

in which

R ⁴ , R \ r and s have the meanings given above, can be made, for example, by

c) lactams of the formula (X)

in which

R ⁴ and s have the meanings given above,

α) with sulfonic acid halides of the formula (XI)

R ⁵ SO '2, - Y (XI)

in which

R ^{5 has} the meanings given above and

Y represents halogen,

or

β) with sulfonic anhydrides of the formula (XII)

(R ⁵ SO ₂ ) ₂ O (XU)

in which R ^{5 has} the meanings given above

in the presence of a base and in the presence of a diluent (cf. WO 98/22438, Synthesis 1993, 735 and the literature cited therein).

Lactams of formula (IX-b)

in which

R ³ , R ⁴ , R ⁵ , n, r and s have the meanings given above,

can be made, for example, by

d) 5-ethoxy-2-pyrrolidinone with biphenyls of the formula (XIII)

in which

R ³ , R ⁴ , R ⁵ , r and s have the meanings given above,

in the presence of hydrogen fluoride and optionally in the presence of a diluent (for example dichloromethane). The lactams required as starting materials in carrying out process (c) are generally defined by the formula (X). In this formula, R ⁴ and s are preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention ,

Lactams of the formula (X) are known and / or can be prepared by known processes (cf. WO 98/22438).

Formula (XI) provides a general definition of the sulfonic acid halides required as starting materials when carrying out process (c). In this formula, R ^{5 is} preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention. Y preferably represents fluorine or chlorine.

Sulfonic acid halides of the formula (XI) are known.

Those required as starting materials when carrying out process (c)

Formula (XII) generally defines sulfonic anhydrides. In this formula, R ^{5 is} preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.

Sulfonic anhydrides of the formula (XII) are known.

Formula (XIII) provides a general definition of the biphenyls required as starting materials when carrying out process (d). Stand in this formula

R ³ . R ⁴ , R ⁵ , r and s are preferred, particularly preferred or very particularly preferred for those meanings which have already been mentioned as preferred, particularly preferred etc. in connection with the description of the substances of the formula (I) according to the invention for these radicals.

Biphenyls of the formula (XIII) are known. They can e.g. manufacture by

e) hydroxybiphenyls of the formula (XIV)

in which

R ³ , R ⁴ , r and s have the meanings given above,

e-1) with sulfonic acid halides of the formula (XI)

R ⁵ SO-Y (XI)

in which

R ^{5 has} the meanings given above and

Y represents halogen,

or

e-2) with sulfonic anhydrides of the formula (XII)

(R ⁵ SO ₂ ) ₂ O (XU) in which

R ^{5 has} the meanings given above

in the presence of a base (e.g. potassium carbonate) and optionally in the presence of a diluent (e.g. acetonitrile) (cf. Synthesis 1993, 735 and the literature cited therein; see also WO 98/22438)

Formula (XIV) provides a general definition of the hydroxybiphenyls required as starting materials when carrying out process (e). In this formula, R ³ , R ⁴ , r and s are preferably, particularly preferably or very particularly preferably those meanings which, in connection with the description of the substances of the formula (I) according to the invention, are preferred, particularly preferred, etc. for these radicals . were called.

Hydroxybiphenyls of the formula (XIV) are known.

Suitable diluents for carrying out process (A) according to the invention are all customary inert, organic solvents. Halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, may optionally be used; Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;

Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sulfones such as sulfolane. Methylene chloride, chloroform, toluene, methanol or ethanol are particularly preferably used. When carrying out process (A) according to the invention, all customary Lewis acids or protonic acids are suitable. Boc elimination methods are generally known (cf., for example, TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, Ed. 3, New York, Wiley & Sons, 1999, pp. 520-525). Trifluoroacetic acid, HC1 or HBr are preferably used to split off the Boc protective group.

When carrying out process (A) according to the invention, the reaction temperatures can in each case be varied within a substantial range. In general, temperatures between -20 ° C and + 120 ° C, preferably between -10 ° C and 60 ° C.

When carrying out process (A) according to the invention, 100 moles of a protonic acid are generally employed per mole of compound of the formula (II). However, it is also possible to use the reaction components in other ratios. The processing takes place according to usual methods. In general, the reaction mixture is concentrated, taken up in a suitable solvent, adjusted to pH 12 with sodium hydroxide and the organic phase is washed with water, dried over sodium sulfate, filtered and concentrated.

The residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.

To prepare chiral compounds of the formulas (Ic) and (Id), the lactams of the formula (IX) can be subjected to racemate resolution. For example, preparative chromatography, preferably high performance liquid chromatography (HPLC), is used. For example, a chiral stationary silica gel phase is used. A silica gel derivative (for example mercaptopropyl silica gel) which has been modified with N-methacryloyl-L-leucine-D-menthylamide has proven to be particularly suitable for the separation of the compounds of the formula (IX). This separating material is known (cf. EP-A 0 379 917). All customary inert, organic solvents and mixtures of these can be considered as eluents. Halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, may preferably be used.

, Hexane, heptane, cyclohexane; Dichloromethane, chloroform; Alcohols, such as methanol,

5 ethanol, propanol; Nitriles such as acetonitrile; Esters such as methyl acetate or

Ethyl acetate. Aliphatic is particularly preferably used

Hydrocarbons, such as hexane or heptane, and alcohols, such as methanol or

Propanol, very particularly preferably n-heptane or isopropanol or mixtures of these. The (R) -configured enantiomers obtained are then used as starting materials for the synthetic route described.

Procedure (B)

Formula (III) provides a general definition of the (bi) phenols required as starting materials when carrying out process (B) according to the invention. In this formula, R ¹ , R ² , R ³ , R ⁴ , n, r and s are preferably, particularly preferably or very particularly preferably, those meanings which have already been associated with the description of the substances of the formula (I) according to the invention were mentioned as preferred, particularly preferred etc. for these radicals.

0 The (bi) phenols of the formula (III) are known and / or can be prepared according to known ones

Manufacture process (cf. WO 98/22438).

When carrying out process (B) according to the invention, sulfonylation halides of the formula (XI) and anhydrides of the formula (XII) are suitable as sulfonation reagents.

Suitable diluents for carrying out process (B) according to the invention are all customary inert, organic solvents. Halogenated aliphatic, alicyclic or U (hetero) aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, pyridine or decalin; Chlorobenzene, Dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-

Methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sulfones such as sulfolane. Pyridine, dichloromethane, chloroform, tetrahydrofuran or toluene are particularly preferably used. If appropriate, mixtures with water can be used and the reaction can be carried out in a two-phase system.

Suitable acid binders for carrying out process (B) according to the invention are all inorganic and organic bases customary for such reactions. Alkaline earth metal or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali metal or alkaline earth metal acetate such as sodium acetate, potassium acetate, calcium acetate, and also tertiary amines are preferably usable Trimethylamine, triethylamine, tributylamine, diethylisopropylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). Triethylamine, diethylisopropylamine, sodium hydroxide, potassium hydroxide or potassium carbonate are particularly preferably used.

The reaction temperatures can be varied within a substantial range when carrying out process (B) according to the invention. In general, temperatures between -70 ° C and + 110 ° C, preferably between -20 ° C and + 40 ° C. When carrying out process (B) according to the invention, 1 mol or a slight excess of sulfonylation reagent and 0.5 to 3 mol of acid binder are generally employed per mol of compound of the formula (III). However, it is also possible to use the reaction components in other ratios. The processing takes place according to usual methods. The general procedure is to decant, wash, dry, filter and concentrate the reaction mixture. The residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.

Process (C)

Formula (IV) provides a general definition of the pyrrolines required as starting materials when carrying out process (C) according to the invention. In this formula, R ¹ , R ² , R ³ and r are preferred, particularly preferred or very particularly preferred for those meanings which, in connection with the description of the substances of the formula (I) according to the invention, are preferred for these radicals, particularly preferred etc. were mentioned.

The pyrrolines of the formula (IV-a)

in which

R ', R ² , R ³ and r have the meanings given above and

X ^{1 represents} chlorine, bromine and iodine, are known and can be produced by known processes (cf. WO 98/22438).

The pyrrolines of the formula (IV-b)

in which

R, R, R and r have the meanings given above and

X ^{2 represents} -OSO ₂ CF ₃ or -OSO ₂ (CF ₂ ) ₃ CF ₃ ,

are new.

Pyrrolines of the formula (IV-b) are prepared by process (A).

Formula (VI) provides a general definition of the iodides required as starting materials when carrying out process (C) according to the invention. In this formula, R ⁴ , R ⁵ and s are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention were.

Iodides of the formula (VI) are generally known or are commercially available.

When carrying out process (C) according to the invention, a palladium catalyst is generally used, which in turn can be used with or without the addition of further ligands. Preferably used as Catalyst PdCl ₂ (dppf) [dppf = l, l'-bis (diphenylphosphino) ferrocene], Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , PdCl ₂ (CH ₃ CN) ₂ , Pd ₂ (dba) ₃ [dba - dibenzylidene acetone] or Pd (OAc) ₂ , particularly preferably PdCl ₂ (dppf), Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , or Pd (OAc) ₂ , very particularly preferably PdCl ₂ (dppf ) or Pd (PPh ₃ ) ₄ .

Triarylphosphines, trialkylphosphines or arsines are suitable as ligands. Dppf, PPh ₃ , P (t-Bu) ₃ , Pcy ₃ or AsPh _{3 are} preferably used, particularly preferably dppf.

As diboronic ester come 4,4,4 ', ^4', 5,5,5 ', 5'-octamethyl-2,2'-bi-l, 3,2-dioxaborolane,

5,5,5 ^ 5'-tetκιme hyl-2,2 ^, -bi-1, 2-dioxaborinan, 4,4,4 ', 4', 6,6'-hexamethyl-2,2'-bi- 1 , 3,2-dioxaborinan or 2,2'-Bi-l, 3,2-benzodioxaborol in question. All diborone esters are known.

Suitable acid binders for carrying out process (C) according to the invention are all inorganic and organic bases which are customary for such reactions. Alkaline earth metal or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali metal or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate, alkali metal and alkali metal, are preferably usable Tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). However, it is also possible to work without an additional acid binder, or to use the amine component in excess, so that it also acts as an acid binder. Barium hydroxide, tripotassium phosphate, cesium carbonate, potassium carbonate, sodium carbonate, potassium acetate, triethylamine, potassium tert-butanolate (KotBu), cesium fluoride or potassium fluoride are particularly preferably used. Suitable diluents for carrying out process (C) according to the invention are all customary inert, organic solvents. Halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Chlorobenzene, dichlorobenzene,

Dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-

Methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sulfones such as sulfolane. Acetone, dimethoxyethane, dioxane, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethanol, toluene or, if appropriate, mixtures of these diluents with water are particularly preferably used.

When carrying out process (C) according to the invention, the reaction temperatures can in each case be varied within a substantial range. In general, temperatures between 0 ° C and 140 ° C, preferably between

10 ° C and 120 ° C, particularly preferably between 20 ° C and 120 ° C.

The process (C) according to the invention can be carried out in two variants. In the first variant, a compound of the formula (IV) is first reacted with a diboronic ester. The intermediates of the formula (V) are obtained, which are then reacted in a second stage with iodides of the formula (VI). In the second variant, the intermediates of the formula (V) are not isolated, but instead reacted in situ with iodides of the formula (VI). In both variants it is also possible to use the iodides of the formula (VI) first and the pyrrolines of the formula (IV) only in the second stage. When carrying out process (C) according to the invention, 1 mol or a slight excess of a diborone ester and 1 mol or a slight excess of iodide of the formula (VI), and 3% of one, are generally employed per mol of compound of the formula (IV) Palladium catalyst. However, it is also possible to use the reaction components in other ratios. It can optionally be the

Compound of formula (IV) or the compound of formula (VI) are presented first. The processing takes place according to usual methods. In general, the procedure is such that the reaction mixture is diluted with water and extracted with ethyl acetate. The organic phase is washed with water, dried over sodium sulfate, filtered and concentrated. If necessary, the residue is freed of any impurities that may still be present using customary methods, such as chromatography or recrystallization. To isolate the intermediates of the formula (V), the mixture is worked up as described before the next reaction component is added.

When carrying out all the processes according to the invention, the procedure is generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.

The active compounds 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 can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:

From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber. From the order of the Diplopoda e.g. Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spp. 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 e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.

From the order of the Blattaria e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.

From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera e.g. Reticulitermes spp. From the order of the Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis. 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, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Maculiiphumumpp 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 the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonellella, Galleria mellonellaella, Galleria mellonellaella, Galleria mellonellaella, Galleria mellonellaella Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fu- miferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chryso-cephala, syllable, Or spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus sppium, sides., Nipt ., Tenebrio molitor, Agriotes spp.,

Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.

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., Gastrophilus spp., Hyppobosca spp., Stomox ., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp.

From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp. From the class of the Arachnida e.g. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllo-coptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., I ., Chorioptes spp., Sarcoptes spp., Tarsonemus spp.,

Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevi palpus spp.

Plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

The compounds of the formula (I) according to the invention are distinguished in particular by an excellent action against caterpillars, beetle larvae, spider mites, aphids and leaf miners.

If appropriate, the compounds according to the invention can also be used in certain concentrations or application rates as herbicides and microbicides, for example as fungicides, antifungal agents and bactericides. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and undesirable wild plants or crop plants (including naturally occurring crop plants). Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including those by

Plant variety rights of protectable or non-protectable plant varieties. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and plant parts according to the invention with the active substances takes place directly or by acting on their environment, habitat or

Storage room according to the usual treatment methods, e.g. by dipping, spraying, Vaping, atomizing, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by means of single or multi-layer coating.

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and also female encapsulations in polymeric substances ,

These formulations are made in a known manner, e.g. by mixing the active compounds according to the invention with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, 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.

The following are suitable as solid carriers: for example ammonium salts and 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, as solid carriers for granules are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and syn- synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stems;

as emulsifying and / or foaming agents are possible: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;

Possible dispersants are: e.g. Lignin sulfite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. 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 active compounds according to the invention, as such or in their formulations, can also be used in a mixture with other, also known active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides, for example the

To broaden the spectrum of activity or to prevent the development of resistance. In In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas, substances produced by microorganisms and others

The following connections can be considered as mixed partners:

Fungicides: Aldimoφh, Ampropylfos, Ampropylfos Potassium, Andoprim, Anilazine, Azaconazole,

azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic-isobutyl, bialaphos, bi- napacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulfide, capsimycin, captafol, captan, carbendazate (quinomethionate), carboxinionionvon, carboxinionionon, carboxinionionon, carboxinionionon, carboxinionionimone, carboxinionionon, carboxinionionon, carboxinionionon, carboxinionionon, carboxinionionon, carboxinionionon, carboxinionionon, carboxinionionof, , Chlobenthiazon, Chlorfenazol, Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinat, Clozylacon, Cufraneb, Cymoxanil, Cyproconazol, Cyprodinil, Cyprofuram,

Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomoφh, diniconazole, dinicenazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon

Dodine, Drazoxolon,

Ediphenphos, Epoxiconazol, Etaconazole, Ethirimol, Etridiazol, Famoxadon, Fenapanil, Fenarimol, Fenbuconazol, Fenfuram, Fenitropan, Fenpicclonil, Fenpropidin, Fenpropimoφh, Fentinacetat, Fentinhydroxyd, Ferbam, Fluorimolonid, Ferimzolonid

Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl-Alminium, Fosetyl-Sodium, Fthalide, Fuberidazole, Furalaxyl, Furametpyr, Furcarbonil, Furconazole, Furconazole-cis, Furmecyclox, Guazatin, Hexaconobolene, Hexazonymol Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,

Kasugamycin, Kresoxim-methyl, copper preparations such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and

Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazole, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin, Nickel-dimethyldithiochalamopropyl, Nitrile

Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin, Paclobutrazol, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Picoxystrobin, Pimaricin, Piperalin, Polyoxin, Polyoxorim, probenazol, Prochloronine, Proamazonol, Prochlorazinol Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon, Pyroxyfur,

Quinconazole, quintozen (PCNB), sulfur and sulfur preparations,

Tebuconazole, Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazole, Thiabendazole, Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutichlamidid, Triazoxid, Triazoxid

Tricyclazol, Tridemoφh, Trifloxystrobin, Triflumizol, Triforin, Triticonazol, Uniconazol,

Validamycin A, vinclozolin, viniconazole, zarilamide, zineb, ziram and Dagger G, OK-8705, OK-8801, α- (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H-1, 2.4 -triazole-1-ethanol, α- (2,4-dichloro-phenyl) -ß-fluoro-b-propyl-1 H-1, 2,4-triazole-1-ethanol, α- (2,4-dichloro-phenyl) - ß-methoxy-a-methyl-lH-l, 2,4-triazol-l-ethanol, α- (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) - phenyl] methylene] -IH-l, 2,4-triazole-1-ethanol,

(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (lH-l, 2,4-triazol-l-yl) -3-octanone, (E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,

{2-Methyl-l - [[[l- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid

1-isopropyl ester

1 - (2,4-Dichlθφhenyl) -2- (1 H- 1, 2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) -oxime, 1 - (2-methyl-1 - naphthalenyl) - 1 H-pyrrole-2,5-dione,

1 - (3, 5-Dichlθφhenyl) -3 - (2-propenyl) -2,5-pyrrolidinedione, l - [(diiodomethyl) sulfonyl] -4-methyl-benzene, l - [[2- (2,4 -Dichloφhenyl) -l, 3-dioxolan-2-yl] methyl] -lH-imidazole,

1 - [[2- (4-Chlθφhenyl) -3-phenyloxiranyl] methyl] - 1 H- 1, 2,4-triazole, 1 - [1 - [2- [(2,4-dichlorophenyl) methoxy] -phenyl] -ethenyl] - 1 H-imidazole, l-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,

2 ', 6 ^, -dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide,

2,2-dichloro-N- [l - (4-chlorothenyl) ethyl] -1-ethyl-3-methyl-cyclopropanecarboxamide, 2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate,

2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide,

2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,

2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1, 3,4-thiadiazole, 2 - [[6-deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl ) -aD-glucopyranosyl] -amino] -4- methoxy- 1 H-pyrrolo [2,3-d] pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2- (bromomethyl) -pentandinitril,

2-chloro-N- (2,3-dihydro-1,3,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide, 2-chloro-N- (2,6-dimethylphenyl) -N - (isothiocyanatomethyl) acetamide,

2-phenylphenol (OPP),

3,4-dichloro-l- [4- (difluoromethoxy) phenyl] -lH-pyrrole-2,5-dione,

3,5-dichloro-N- [cyano [(l-methyl-2-propynyl) -oxy] -methyl] -benzamide,

3 - (1,1-dimethyl propyl-1-oxo-1 H-indene-2-carbonitrile, 3- [2- (4-chloro-phenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,

4-chloro-2-cyan-N, N-dimethyl-5- (4-methylphenyl) -1 H-imidazole-1-sulfonamide, 4-methyl-tetrazolo [l, 5-a] quinazolin-5 (4H) -one,

8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4.5] decane-2-methanamine,

8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid 2- [(phenylamino) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, ice-1 - (4-chloro-phenyl) -2- (1 H-1, 2,4-triazole-1-yl) -cycloheptanol, cis-4- [3- [4- (1,1-dimethylpropyl) -phenyl -2-methylpropyl] -2,6-dimethyl-moφholin hydrochloride,

Ethyl [(4-chloro-phenyl) azo] cyanoacetate, potassium hydrogen carbonate,

Methantetrathiol sodium salt,

Methyl 1 - (2,3-dihydro-2,2-dimethyl-1 H-inden-1-yl) - 1 H-imidazole-5-carboxylate,

Methyl-N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,

Methyl-N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate, N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexane carboxamide.

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,

N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,

N- (4-cyclohexylphenyl) - 1, 4,5,6-tetrahydro-2-pyrimidinamine, N- (4-hexylphenyl) - 1, 4,5,6-tetrahydro-2-pyrimidinamine,

N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) -acetamide,

N- (6-methoxy) -3-pyridinyl) -cyclopropanecarboxamide,

N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide,

N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide, N-formyl-N-hydroxy-DL-alanine sodium salt,

O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat,

O-methyl-S-phenyl-phenylpropylphosphoramidothioate,

S-methyl-1, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] -l-benzopyran-2, r (3Η) -isobenzofuran] -3'-one, 4- [3,4-dimethoxyphenyl) - 3- (4-fluoφhenyl) acryloyl] -moφholin bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, popilliae azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin, Bacillus, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis .

Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomethrin, Biopermethrin, Bistrifluron, BPMC, Bromophos A, Butenoc, Carbofoxylbench, Carbofimosyl, Carbofimosyl, Carbofimosyl, Carbofimosin , Carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloφyrifos, chloφyrifos M, chlovaporthrin, chromafenozide, cis-resmethrin, cispermethrin, clocythrin, cloethocine rotin, cloethocine pyrin Cyhalothrin, cyhexatin, cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Dicofol, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulphoson, Docusat-sodium, Dofenapyn, Eflusilanate, Emaminopin, Endaminophen, Emaminopin, Emaminopin ., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,

Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fi- pronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxoxinon, Fluvalinoxuron, Flucythrinurin, Flucythrinurin, Flucytinurin, Flucytinurin, Flucytinurin, Flucyinhrin, Flucyinhrin, Flucyinhroxinon, Fluuminoxuron, Flucythrin, Flucyinhrin, Flucythrinur, Flucytinurin, Flucytinurin, , Fosmethilan, Fosthiazate. Fubfenprox, Furathiocarb,

granulosis Halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene, imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin, kempolyederviruses lambda-cyhalothrin, lufenuron malathion, mecarbam, metaldehyde, methamidophosphate, methamidophosphate, methamidophosphate

Metharhilic flavoviride, methidathione, methiocarb, methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, monocrotophos, naled, nitenpyram, nithiazine, novaluron omethoat, oxamyl mydyd

Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothrohrinos, Pothrohrinos, Pothrohrinate, Pothrohrinate , Pyridaben, pyridathione, pyrimidifene, pyriproxyfen,

Quinalphos, Ribavirin

Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Sulfotep, Sulprofos, Tau-fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachloradipinphonidone, Thetrachlorifinone Thiocyclam hydrogen oxalate, Thiodicarb, Thiofanox, Thuringiensin, Tralocythrin, Tralomethrin, Triarathene, Triazamate, Triazophos, Triazuron, Trichlophenidine, Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, Vanilipium lani, Vert

YI 5302

Zeta-cypermethrin, zolaprofos

(1 R-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) -furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate ( 3-phenoxyphenyl) methyl-2,2,3,3-tetramethylcyclopropanecarboxylat 1 - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2 (1 H) -imine

2- (2-chloro-6-fluoφhenyl) -4- [4- (l, l-dimethylethyl) phenyl] -4,5-dihydro-oxazol

2- (acetyloxy) -3-dodecyl-1,4-naphthalenedione 2-chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] benzamide

2-chloro-N - [[[4- (2,2-dichloro-l, l-difluoroethoxy) -phenyl] -amino] -carbonyl] -benzamide

3-methylpheny 1-propyl carbamate

4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene

4-Chloro-2- (l, l-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] - 3 (2H) pyridazinone

4-Chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) -pyridazinone

4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichloφhenyl) -3 (2H) -pyridazinone

Bacillus thuringiensis strain EG-2348 benzoic acid [2-benzoyl-1 - (1, 1-dimethylethyl) hydrazide

Butanoic acid 2,2-dimethyl-3- (2,4-dichloro phhenyl) -2-oxo-l-oxaspiro [4.5] dec-3-en-4-yl ester

[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide

Dihydro-2- (nitromethylene) -2H- 1,3-thiazine-3 (4H) -carboxaldehyde ethyl- [2 - [[1,6-dihydro-6-oxo-l- (phenylmethyl) -4 pyridazinyl] oxy] ethyl] carbamate

N- (3,4,4-trifluoro-l-oxo-3-butenyl) -glycine

N- (4-Chloφhenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-lH-pyrazol-

1-carboxamide

N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine N-methyl-N '- (1-methyl-2-propeny 1) - 1,2-hydrazinedicarbothioamide

N-methyl-N'-2-propenyl-1, 2-hydrazine dicarbothioamide

O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat

N-cyanomethyl-4-trifluoromethyl-nicotinamide

3,5-dichloro-l- (3,3-dichloro-2-propenyloxy) -4- [3- (5-trifluoromethylpyridin-2-yloχ \) - propoxyj-benzene A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds which increase the activity of the active compounds according to the invention without the added synergist itself having to be active.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. 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

Wise.

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

As already mentioned above, all plants and their parts can be treated according to the invention. In a preferred embodiment, plant species and plant cultivars and their parts occurring wildly or obtained by conventional organic breeding methods, such as crossing or protoplast fusion, are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetic modified organisms) and their parts are treated. The term “parts” or “parts of plants” or “parts of plants” was explained above. Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with certain properties (“traits”) which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also have additive (“synergistic”) effects. For example, reduced application rates and / or extensions of the

Spectrum of activity and / or an intensification of the action of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher crop yields , higher quality and / or higher nutritional value of the harvest products, higher shelf life and / or workability of the harvested products possible, which go beyond the expected effects.

The preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic modification which gives these plants particularly advantageous valuable properties (“traits”). Examples of such properties are better Plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and or higher nutritional value of the crop products, higher storability and / or workability Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants to certain herbicides Agents. As examples of transgenic plants, the important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, bims, citrus fruits and grapes) are mentioned, with corn, soybeans, potatoes and cotton and rapeseed are highlighted. The properties (“traits”) which are particularly emphasized are the plants' increased defense against insects by toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA (a), CryΙA (b), CryΙA (c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants"). The increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins are also particularly emphasized as properties ("traits"). As properties ("traits") ) are also particularly emphasized the increased tolerance of the plants to certain herbicidal active ingredients, for example imidazoline, sulfonylureas, glyphosate or phosphinotricin (for example "PAT" gene). The genes which confer the desired properties ("traits") can also be found in Combinations with each other occur in the transgenic plants. Examples of "Bt plants" are corn varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YIELD GARD ^® (e.g.

Corn, Cotton, Soybean), KnockOut ^® (e.g. corn), StarLink ^® (e.g. corn), Bollgard ^® (cotton), Nucotn ^® (cotton) and NewLeaf ^® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soy varieties which are sold under the trade names Roundup Ready ^® (tolerance against glyphosate, for example corn, cotton, soybeans), Liberty Link ^® (tolerance against

Phosphinotricin, such as rapeseed), IMI ^® (tolerance to imidazolinones) and STS ^® (tolerance to sulfonylureas, such as corn) are sold. Herbicide-resistant plants (bred conventionally for herbicide tolerance) plants also sold under the name Clearfield ^® varieties (eg maize) are mentioned. Of course, these statements also apply to those developed in the future or to the future Coming plant varieties with these or future-developed genetic traits.

The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.

The active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair linge, featherlings and fleas. These parasites include:

From the order of the Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the subordinates Amblycerina as well

Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.

From the order Diptera and the subordinates Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp.,

Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp ., Haematobia spp .. Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp .. Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp. From the order of the Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.

From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,

Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumoniassus spp., Stemostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp. Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

For example, they show an excellent effectiveness against the developmental stages of ticks such as Amblyomma hebraeum, against parasitic flies such as against Lucilia cuprina.

The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens. Turkeys, ducks, geese, bees, other pets such as Dogs, cats. Caged birds. Aquarium fish and so-called experimental animals, such as Hamsters, guinea pigs, rats and

Infest mice. By fighting these arthropods, deaths and Reduced output (for meat, milk, wool, skins, eggs, honey, etc.) are reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by Injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or

Bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, pumping in and with the help of shaped articles containing active ingredients, such as necklaces, ear tags, tail tags, limb tapes, holsters, marking devices, etc.

When used for cattle, poultry, pets, etc., the active compounds of the formula (I) according to the invention can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds according to the invention in an amount of 1 to 80% by weight, apply directly or after 100 to 10,000-fold dilution or use it as a chemical bath.

It has also been found that the compounds according to the invention have a high insecticidal action against insects which destroy industrial materials.

The following are examples and preferably - but without limitation -

Called insects:

Beetle like

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum. Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Emobius mollis, Priobium caφini.

Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes mgicollis, Xyleboms spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus bmnneus, Sinoxylon spec. Dinoderus minutus.

Skin wings like

Sirex juvencus, Uroceras gigas, Urocerus gigas taignus, Urocerus augur.

Termites like

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristle tails such as Lepisma saccharina.

In the present context, technical materials include non-living ones

Understand materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.

The material to be protected against insect infestation is very particularly preferably wood and wood processing products.

Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples:

Lumber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wooden products that are generally used in house construction or joinery. The active compounds according to the invention can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active compounds according to the invention with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally siccatives and UV stabilizers and optionally dyes and pigments and further processing aids.

The insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

The amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.

An organic-chemical solvent or solvent mixture and / or an oily or oily, low-volatile organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or serves as the solvent and / or diluent

Water and optionally an emulsifier and / or wetting agent.

The organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. Corresponding mineral oils are used as such low-volatility, water-insoluble, oily and oily solvents or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene.

Mineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C are advantageous. Teφentinöl and the like. For use.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or spindle oil and / or monochlomaphthalene, preferably α-monochloronaphthalene, used.

The organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced. Aliphatic organochemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used. In the context of the present invention, the known organic-chemical binders are the water-thinnable and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a Natural and / or synthetic resin is used.

The synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellents, odor correctors and

Inhibitors or anticorrosive agents and the like are used.

According to the invention, at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder. Are preferred according to the invention

Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are used.

All or part of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additions are said to be one

Prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as

Dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate phate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight glycol ether, glycerol ester and p-toluenesulfonic acid ester.

Fixatives are chemically based on polyvinyl alkyl ethers such as Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.

A particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure processes.

The ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.

The insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners. The compounds mentioned in this document are an integral part of the present application.

Insecticides such as chloφyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthronid, as well as thifloxiduron, and methifluorideuron, fifluorideuron, and methifluorideuron, as well as thifluorideuron, as well as fungloxidonuron, as well as fungloxidonuron, as well as fungloxidonuron, as well as fungalidium clonid, as well as Funglumidopuron, as well epoxyconazole,

Hexaconazole, Azaconazole, Propiconazole, Tebuconazole, Cyproconazole, Metconazole, Imazalil, Dichlorfluanid, Tolylfluanid. 3-iodo-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octyl-isothiazolin-3-one.

At the same time, the compounds according to the invention can be used to protect objects, in particular hulls, sieves, nets, structures, Quays and signaling systems that come into contact with sea or brackish water are used.

Overgrowth by sessile oligochaetes, such as lime tube worms, and by mussels and species of G ppe Ledamoφha (barnacles), such as various types of Lepas and Scalpellum, or by species of Gmppe Balanomoφha (barnacles), such as Baianus or Pollicipes species, increases the frictional resistance of ships and subsequently leads to a significant increase in operating costs due to increased energy consumption and, moreover, frequent dry dock stays.

In addition to fouling by algae, for example Ectocaφus sp. and Ceramium sp., vegetation by sessile Entomostraken groups, which are grouped under the name Cirripedia (barnacles), is of particular importance.

It has now surprisingly been found that the compounds according to the invention, alone or in combination with other active ingredients, have an excellent antifouling effect.

By using compounds according to the invention alone or in combination with other active ingredients, the use of heavy metals such as in bis (trialkyltin) sulfides, tri- / ι-butyltin laurate, tri- / ι-butyltin chloride, copper (I) - oxide, triethyltin chloride, tri-π-butyl (2-phenyl-4-chloφhenoxy) tin, tributyltin oxide. Molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl- (bispyridine) - bismuth chloride, tri-π-butylzinnfluorid, Manganethylenbisthiocarbamat, zinc di methyldithiocarbamate, Zinkethylenbisthiocarbamat, zinc and copper salts of 2 Pyridinthiol- 1 oxide, Bisdimethyldithiocarbamoylzinkethylenbisthiocarbamat, zinc oxide, copper (I) -ethylene thiocyanate. Copper thiocyanate, copper phthalate and tributyltin halides are omitted or the concentration of these compounds is significantly reduced. The ready-to-use antifouling paints may also contain other active ingredients, preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients.

Suitable combination partners for the antifouling agents according to the invention are preferably:

Algicides like

2-tert-butylamino-4-cyclopropylamino-6-methylthio-l, 3,5-triazine, dichlorophen, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen,

Quinoclamine and Terbutryn;

Fungicides like

Benzo [ό] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlofluanid, fluorofolpet, 3-iodo-2-propynyl butyl carbamate, tolyl fluanide and azoles such as

Azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and tebuconazole;

Molluscicides such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb; or conventional antifouling agents such as

4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethylthiocarbamoylthio) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridine thiol -l-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5, 6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6-trichloφhenylmaleimide ,

The antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular of 0.01 to 20% by weight. The antifouling agents according to the invention furthermore contain the usual constituents as described, for example, in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

In addition to the algicidal, fungicidal, molluscicidal and insecticidal active compounds according to the invention, antifouling paints contain in particular binders.

Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile Rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.

Paints may also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in sea water. Paints may also contain materials such as rosin to enable controlled release of the active ingredients. The paints may also contain plasticizers, modifiers that affect the rheological properties, and other conventional ingredients. The compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.

The active compounds according to the invention are also suitable for controlling animal pests, in particular insects, arachnids and mites, which occur in closed rooms, such as, for example, apartments, factory halls, offices, vehicle cabins and the like. You can fight these pests alone or in combination with other active ingredients in household insecticide products be used. They are effective against sensitive and resistant species and against all stages of development. These pests include:

From the order of the Scoφionidea e.g. Buthus occitanus. From the order of the Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp.,

Dermanyssus gallinae, Glyciphagus domesticus, Omithodoms moubat, Rhipice- phalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagides pteronissimus, Dermatophagoides forinae.

From the order of the Araneae e.g. Aviculariidae, Araneidae. From the order of the Opiliones e.g. Pseudoscoφiones chelifer, Pseudoscoφiones cheiridium, Opiliones phalangium.

From the order of the Isopoda e.g. Oniscus asellus, Porcellio scaber.

From the order of the Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp.

From the order of the Chilopoda e.g. Geophilus spp. From the order of the Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina,

Lepismodes inquilinus.

From the order of the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta austral- asiae, Periplaneta americana, Periplaneta brunnea, Periplaneta ftüiginosa, Supella longipalpa.

From the order of the Saltatoria e.g. Acheta domesticus.

From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera e.g. Kalotermes spp., Reticulitermes spp.

From the order of the Psocoptera e.g. Lepinatus spp., Liposcelis spp. From the order of the Coleptera e.g. Anthrenus spp., Attagenus spp., Dermestes spp.,

Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp. Calliphora erythrocephala. Chrysozona pluvialis. Culex quinquefasciatus, Culex pipiens. Culex tarsalis, Drosophila spp., Fannia canicularis. Musca domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia inteφunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella. From the order of the Siphonaptera e.g. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.

From the order of the Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum. From the order of the anoplura e.g. Pediculus humanus capitis, Pediculus humanus coφoris, Phthims pubis.

From the order of the Heteroptera e.g. Cimex hemiptems, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

The application in the field of household insecticides is carried out alone or in combination with other suitable active ingredients such as phosphoric acid esters, carbamates, pyrethroids, growth regulators or active ingredients from other known classes of insecticides.

They are used in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, fog machines, foggels, foams, gels, vaporizer products with vaporizer plates made of cellulose or plastic, liquid vaporizers, gel and membrane vaporizers, propeller-driven vaporizers, energy-free or passive evaporation systems, moth papers, moth bags and moth gels, as granules or sticks in litter edema or bait stations.

The preparation and use of the substances according to the invention can be seen from the following examples. Preparation Examples

Driving Ner (A)

example 1

Trifluoroacetic acid (185.37 g, 1.63 mol) is placed at 5 ° C. At this temperature a solution of 4- [l - [(tert-butoxycarbonyl) amino] -4- (2,6-difluoφhenyl) -

4-oxobutyl] phenyl trifluoromethanesulfonate (II-1) (42.55 g, 80.8% ig ≤ 0.06 mol) in dichloromethane (150 ml) was added dropwise and the mixture was then stirred at this temperature for 3 hours. The trifluoroacetic acid is distilled off under reduced pressure and the residue is adjusted to pH 12 with IN ΝaOH. The aqueous phase is extracted with dichloromethane (2 x 100 ml). The combined organic phases are dried over sodium sulfate, filtered and concentrated. The crude product is purified by chromatography on silica gel (mobile phase: n-hexane / ethyl acetate 3: 1 (v / v)).

15.83 g (65% of theory) of 4- [5- (2,6-difluorophene) -3,4-dihydro-2H-pyrrole-

2-yl] phenyl trifluoromethanesulfonate (I-1).

HPLC: Log P (pH 2.3) = 3.49 (100% purity). 'H-ΝMR: δ (CD, CΝ) - 1.80 (1H, m), 2.65 (1H, m), 3.07 (2H, m), 5.34 (1H, m),

7.08 (2H. M), 7.37 (2H, d), 7.50 (3H, m) ppm. Example 2

Analogously to Example 1, (2R) -4- [5- (2,6-Difluoφhenyl) -3,4-dihydro-2H-pyrrol-2-yl] phenyl-trifluoromethanesulfonate (I-2) is obtained.

HPLC: Log P (pH 2.3) = 3.55.

Rotation value: [α] _D = +34.1 (c = 0.92, chloroform), 20 ° C.

Example 3

Analogously to Example 1, 4 '- [5- (2,6-Difluoφhenyl) -3,4-dihydro-2H-pyrrol-2-yl] -l, 1' -biphenyl-4-yl-1, 1, 2,2,3,3,4,4,4-nonafluoro-1-butanesulfonate (1-3).

HPLC: Log P (pH 2.3) = 5.57 (100% purity).

Mp 68-69 ° C

'H NMR: δ (CD ₃ CN) = 1.85 (1H, m), 2.67 (1H, m), 3.06 (2H, m), 5.34 (1H, m),

7.09 (2H,), 7.46 (5H, d), 7.65 (2H, d), 7.77 (2H, d) ppm. Example 4

Analogously to Example 1, 4 '- [5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] -1, l'-biphenyl-4-yl-dimethylsulfamate (1-3 ). The crude product is purified by chromatography on silica gel (running agent: cyclohexane / ethyl acetate 1: 1) and subsequent stirring with isopropanol.

HPLC: Log P (pH 2.3) = 3.06 (100% purity).

Mp 131-133 ° C

'H NMR: δ (CD ₃ CN) = 1.83 (IH, m), 2.62 (IH, m), 3.06 (2H, m), 5.33 (IH, m),

7.07 (2H, m), 7.38 (2H, d), 7.42 (2H, d), 7.45 (IH, m), 7.65 (2H, d),

7.71 (2H, d) ppm.

Production of starting materials for process (A)

Aminoketones of formula (II)

Example (II-l)

1,3-difluorobenzene (11.04 g, 96.7 mmol) is placed in tetrahydrofuran (100 ml) and cooled to -70 ° C. At this temperature, n-butyllithium (61.3 ml, 96.7 mmol) is added dropwise. The reaction mixture is allowed to warm to -30 ° C. and a solution of tert-butyl-2-oxo-5- (4 - {[(trifluoromethyl) sulfonyl] oxy} phenyl) -l-pyrrolidinecarboxylate (VI -1) (36.0 g, 87.9 mmol) in tetrahydrofuran (100 ml). The reaction mixture is left to stir for 4 hours at -30 ° C. and then for 16 hours at room temperature. The reaction mixture is stirred into water (1000 ml) and extracted with ethyl acetate (2 x 500 ml). The combined organic phases are washed successively with 1N HCl, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution. The organic phase is dried over sodium sulfate, filtered and concentrated.

42.55 g (75% of theory) of 4- [l- [tert-butoxycarbonyl) amino] -4- (2,6-difluorophenyl) -4-oxobutyl] phenyl trifluoromethanesulfonate (II-1) are obtained.

HPLC: Log P (pH 2.3) = 4.38 (81% purity).

Example (H-2)

Analogously to Example (II-1), 4 - [(IR) -l- [tert-butoxycarbonyl) amino] -4- (2,6-difluorophenyl) -4-oxobutyl] phenyl trifluoromethanesulfonate (II-2) is obtained.

HPLC: Log P (pH 2.3) = 4.37. Example (H-3)

Analogously to Example (II-1), 4 '- [l - [(tert-butoxycarbonyl) amino] -4- (2,6-difluorophenyl) -4-oxobutyl] - 1, 1' -biphenyl-4- are obtained yl-1, 1, 2,2,3, 3, 4,4,4-nonafluoro-1-butanesulfonate (II-3). The crude product is purified by chromatography on silica gel (running agent: n-hexane / ethyl acetate 9: 1).

HPLC: Log P (pH 2.3) = 6.05 (97.60% purity).

Mp 90-92 ° C

Example (II-4)

Analogously to Example (II-1), tert-butyl 4- (2,6-difluoφhenyl) -l- (4 '- {[(dimethylamino) sulfonyl] oxy} -l, r-biphenyl-4-yl) is obtained -4-oxobutyl carbamate (II-4).

HPLC: Log P (pH 2.3) = 4.25. N-Boc lactams of the formula (VII)

Example (VII- 1)

4- (5-Oxo-2-pyrrolidinyl) phenyl trifluoromethanesulfonate (154.63 g, 0.50 mol) is initially charged at 0 ° C. in dichloromethane (600 ml) under an argon atmosphere. At this temperature, di-tert-butyl dicarbonate (218.25 g, 1.0 mol) and dimethylaminopyridine (6.10 g, 0.05 mol) are added in succession. Then at room temperature

Stirred for 48 hours. The reaction mixture is washed successively with 1N HCl (2 x 500 ml), saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution. The organic phase is dried over sodium sulfate, filtered and concentrated.

198.70 g (99% of theory) of tert-butyl-2-oxo-5- (4 - {[(trifluoromethyl) sulfonyl] oxy} phenyl) -1-pyrrolidinecarboxylate (VII-1) are obtained.

HPLC: Log P (pH 2.3) = 3.31 (98.80% purity).

Example (VII-2)

The racemate is separated from 4- (5-oxo-2-pyrrolidinyl) phenyltriιluormethanesulfonate at room temperature using liquid chromatography on a chiral stationary polyamide silica gel phase (based on the monomer N-methacryloyl-L-leucine-d-menthylamide, particle size: 10 μm, column dimension: 450 mm x 75 mm) using ethyl acetate as eluent (flow rate: 100 ml / min) and photometric detection (λ = 254 nm). A solution of 40 g of the racemate in 1 l of ethyl acetate is prepared for chromatography. 6 g (= 150 ml of the solution) are chromatographed. After analytical testing for enantiomeric purity, the eluate fractions are combined accordingly, largely evaporated in vacuo, the residues are filtered off and, after washing, dried with n-heptane.

4- (5-Oxo- (2R) -2-pyrrolidinyl) phenyltrifluoromethanesulfonate is obtained.

Rotation value: [α] _D = +22.8 (c = 0.9, methanol), 20 ° C.

The (R) -enantiomer is then reacted analogously to Example (VII- 1), so that tert-

Butyl-2-oxo- (5R) -5- (4 - {[(trifluoromethyl) sulfonyl] oxy} phenyl) -l-pyrrolidinecarboxy-lat (VII-2).

HPLC: Log P (pH 2.3) = 3.31.

Example (VII-3)

Analogously to Example (VII-1), tert-butyl-2- (4 '- {[(l, l, 2,2,3,3,4,4,4-nonafluorobutyl) sulfonyl] oxy} -l is obtained , r-biphenyl-4-yl) -5-oxo-l-pyrrolidine carboxylate (VII-3). The crude product is purified by chromatography on silica gel (mobile phase: n-hexane / ethyl acetate 3: 1). HPLC: Log P (pH 2.3) = 5.44 (98.6% purity).

Mp 115-117 ° C

Example (VII-4)

Analogously to Example (VII-1), tert-butyl 2- (4 '- {[(dimethylamino) sulfonyl] oxy} - l, r-biphenyl-4-yl) -5-oxo-l-pyrrolidinecarboxylate (VII- 4). The crude product is recrystallized from isopropanol.

HPLC: Log P (pH 2.3) = 3.31 (98.17% purity)

Mp 171-173 ° C

Lactams of formula (IX-b)

Example (IX-b-1)

Hydrogen fluoride (50 ml) is placed at 0 ° C. A solution of 5-ethoxy-2-pyrrolidinone (2.58 g, 0.02 mol) and 1,1'-biphenyl-4-yl-dimethylsulfamate (XII-2) (2.77 g, 0.01 mol) in dichloromethane (15 ml) is added dropwise and then the reaction mixture is stirred at room temperature. HF is removed under reduced pressure, the residue is taken up in dichloromethane and the latter is washed with saturated aqueous sodium bicarbonate solution. The organic phase is dried over magnesium sulfate, filtered and concentrated. The raw product is further implemented without purification.

3.20 g (59% of theory) of 4 '- (5-oxo-2-pyrrolidinyl) -l, l'-biphenyl-4-yl-dimethylsulfamate (IX-b-1) are obtained in a mixture with the " Ortho "isomer 2 '- (5-oxo-2-pyrrolidinyl) - 1, 1' -biphenyl-4-yl-dimethyl sulfamate.

HPLC (IX-b-1): Log P (pH 2.3) = 2.23 (66.49% purity)

HPLC ("Ortho" isomer): Log P (pH 2.3) = 2.28 (23.81% purity)

Example (IX-b-2)

Analogously to Example (IX-b-1), 4 '- (5-oxo-2-pyrrolidinyl) -l, r-biphenyl-4-yl are obtained

1, 1,2,2,3, 3, 4,4,4-nonafluoro-1-butanesulfonate (IX-b-2).

HPLC: Log P (pH 2.3) = 4.21 (88.60% purity)

Biphenyls of formula (XIII)

Example (XIII- 1)

4-Hydroxybiphenyl (1.70 g, 0.01 mol) and potassium carbonate (1.66 g, 0.012 mol) are suspended in acetonitrile (50 ml). 1,1,2,2,3,3,4,4,4-nonafluorobutane-l-sulfonyl fluoride (3.60 g, 0.01 mol) is added dropwise at room temperature and then stirred for 16 hours at room temperature. The acetonitrile is distilled off and water is added to the residue. The precipitate is filtered off and dried.

4.45 g (99% of theory) of l, l'-biphenyl-4-yl-l, l, 2,2,3,3,4,4,4-nonafluoro-l-butanesulfonate (XIII- 1).

HPLC: Log P (pH 2.3) = 5.81 (100% purity)

Example (XIII-2)

4-Hydroxybiphenyl (1.70 g, 0.01 mol) and potassium carbonate (1.66 g, 0.012 mol) are suspended in acetonitrile (50 ml), stirred at room temperature for 1.5 hours and then cooled to 0 ° C. Dimethylsulfamoyl chloride (1.44 g, 0.01 mol) is added dropwise and the reaction mixture is stirred at room temperature for 16 hours. The precipitate is filtered off and the acetonitrile is distilled off. The residue is recrystallized from isopropanol.

1.81 g (65% of theory) of l, l'-biphenyl-4-yl-dimethylsulfamate (XIII-2) with a melting point of 105-107 ° C. are obtained.

HPLC: Log P (pH 2.3) = 3.51 (99.6% purity) Procedure (B)

Example 5

4 '- [(2R) -5- (2,6-Difluoφhenyl) -3,4-dihydro-2H-pyrrol-2-yl] -l, 1' -biphenyl-4-ol (7.0 g, 0.02 mol) is suspended in toluene (150 ml). Sodium hydroxide solution (1.3 ml, 45% strength) is added at room temperature and the mixture is stirred at this temperature for a further 45 min. Trifluoromethanesulfonic acid chloride (2.34 ml, 0.022 mol) is added dropwise and at

Room temperature stirred for 1.5 h. The toluene phase is decanted from the solid residue, washed successively with 1 N NaOH, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous ammonium chloride solution, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product is purified by chromatography on silica gel (mobile phase: cyclohexane /

Ethyl acetate, 9: 1 v / v) and then purified by preparative HPLC (Kromasil 100-5 C18, 250 x 50 mm; CH ₃ CN / H ₂ O, 80:20 v / v).

2.36 g (25% of theory) of 4 '- [(2R) -5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] -l, r- biphenyl-4-yl trifluoromethanesulfonate (1-4) from the melting point

109 ° C.

HPLC: Log P (pH 2.3) = 4.27 (99.88% purity)

Rotation value: [α] _D = +31.8 (c = 0.39. MeOH); 20 ° C Example 6

4- [5- (2,6-Difluoφhenyl) -3,4-dihydro-2H-pyrrol-2-yl] phenol (2.00 g, 7.3 mmol) is suspended in toluene (30 ml). Sodium hydroxide solution (0.7 ml, 45% v / v) and 4- (trifluoromethoxy) benzenesulfonyl chloride (1.90 g, 7.3 mmol) are added in succession at room temperature. The reaction mixture is stirred at 45 ° C for 12 hours. After cooling to room temperature, the phases are separated. The aqueous phase is extracted with ethyl acetate. The combined organic phases are washed with water, dried over sodium sulfate, filtered and concentrated. The crude product is purified by chromatography on silica gel (mobile phase: toluene / ethyl acetate, 9: 1 v / v).

2.55 g (70% of theory) of 4- [5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-ylphenyl 4- (trifluoromethoxy) benzene sulfonate (1-5) are obtained.

HPLC: Log P (pH 2.3) = 3.83 (98.6% purity) 'H-NMR: δ (CD ₃ CN) = 1.75 (IH, m), 2.60 (IH, m), 3.05 (2H, m), 5.26 ( IH, m), 7.01 (2H, d), 7.07 (2H, m), 7.31 (2H, d), 7.48 (IH, m), 7.50 (2H, d), 7.93 (2H, d) ppm. Process (C)

Example 7

5- (2,6-difluorophenyl) -2- [4- (4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yl) phenyl] -3,4-dihydro-2H-pyrrole (VI) (0.96 g, 2.5 mmol), 4-iodophenyl trifluoromethanesulfonate (1.06 g, 3.0 mmol), aqueous sodium hydrogen carbonate solution (5 ml, 2 M) and 0 PdCl ₂ dppf (56 mg, 0.075 mmol) are dissolved in dimethoxyethane (30 ml) for 1.5 hours

60 ° C, and then heated for 1.5 hours at 80 ° C under an argon atmosphere. After cooling, the reaction mixture is mixed with water and with ethyl acetate. The organic phase is dried over sodium sulfate and filtered. Florisil (5 g) is added and the solvent is evaporated to dryness. The 5 crude product is chromatographed on silica gel (mobile phase: cyclohexane /

Ethyl acetate, 9: 1 v / v) purified.

0.62 g (52% of theory) of 4 '- [5- (2,6-Difluoφhenyl) -3,4-dihydro-2H-pyrrol-2-yl] -l, l'-biphenyl-4 are obtained -yl trifluoromethanesulfonate (1-7). 0

HPLC: Log P (pH 2.3) = 4.15 (96% purity)

Mp 73-75 ° C.

'H NMR: δ (CD3CN) = 1.88 (IH, m), 2.68 (IH, m), 3.06 (2H, m), 5.35 (IH, m),

7.08 (2H. D). 7.47 (5H, m), 7.65 (2H, m), 7.78 (2H, d) ppm. :>

In addition, a fraction of compound (1-7) of 0.20 g (14% of theory) with 87% purity is obtained. Manufacture of raw materials for ner driving (C)

4- [5- (2,6-Difluoφhenyl) -3,4-dihydro-2H-pyrrol-2-yl] phenyl trifluoromethanesulfonate (1-1) (60.80 g, 0.15 mol), bispinacol ethodiborone (41.90 g, 0.165 mol ), Potassium acetate (44.20 g, 0.45 mol), PdCl ₂ dppf (3.30 g, 4.50 mmol), diphenylphosphomoferrocene (2.50 g, 4.50 mmol) are heated in dioxane (900 ml) for 16 hours at 80 ° C under an argon atmosphere. After cooling, the reaction mixture is stirred into water (1000 ml) and extracted with ethyl acetate (2 x 600 ml). The combined organic phases are dried over sodium sulfate and filtered. Florisil (200 g) is added and the solvent is evaporated to dryness. The crude product is purified by chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate, 4: 1 v / v).

52.80 g (89% of theory) of 5- (2,6-difluorophenyl) -2- [4- (4,4,5,5-tetramethyl-1, 3, 2-dioxaborolan-2-yl ) phenyl] -3, 4-dihydro-2H-pyrrole (V-1).

HPLC: Log P (pH 7.5) = 4.46 (96.7% purity) 'H-NMR: δ (CD ₃ CN) = 1.32 (12H, s), 1.78 (IH, m), 2.59 (IH, m), 3.03 ( 2H, m),

5.30 (IH, m), 7.07 (2H, d), 7.35 (2H, m), 7.46 (IH, m), 7.70 (2H, d) ppm. The logP values specified in the tables and manufacturing examples above are determined in accordance with EEC Directive 79/831 Annex N.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.

The determination is carried out in the acidic range at pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile.

The determination is made in the neutral range at pH 7.5 with 0.01 molar aqueous

Phosphate buffer solution and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile.

The calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the

Retention times by linear interpolation between two consecutive alkanones).

The lambda max values were determined on the basis of the UN spectra from 200 μm to 400 nm in the maxima of the chromatographic signals.

applications

Example A

Aphis gossypii test

Solvent: 30 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 amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.

Cotton leaves (Gossypium hirsutum), which are heavily infested with the cotton aphid (Aphis gossypii), are treated by dipping into the active ingredient preparation of the desired concentration.

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

In this test, e.g. B. the following compounds of the preparation examples have good activity:

Active substances, active substance concentrations and test results are shown in the following table. Table A: Aphis gossypii test

Example B

Heliothis virescens test

Solvent: 30 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 amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

Soybean shoots (Glycine max) are treated by immersing them in the active ingredient preparation of the desired concentration and populating them with Heliothis virescens caterpillars 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.

Active substances, active substance concentrations and test results are shown in the following table.

Table B: Heliothis virescens test

Example C

Myzus Test

Solvent: .30 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 amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.

Cabbage leaves (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are treated by being dipped into the preparation of active compound of the desired concentration.

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

Active substances, active substance concentrations and test results are shown in the following table.

Table C: Myzus test

Example D

Meloidogyne Test

Solvent: 30 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 amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

Vessels are filled with sand, active ingredient solution, Meloidogyne incognita egg larva suspension and lettuce seeds. The lettuce seeds germinate and the plantlets develop. The galls develop at the roots.

After the desired time, the nematicidal effect is determined in% using the formation of bile. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.

Active substances, active substance concentrations and test results are shown in the following table.

Table D: Meloidogyne test

Example E

Panonychus test

Solvent; 3 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 amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

Approximately 30 cm high plum trees (Pmnus domestica), which are severely affected by all stages of the fruit tree spider mite (Panonychus ulmi), are sprayed with an active ingredient preparation of the desired concentration.

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

Active substances, active substance concentrations and test results are shown in the following table.

Table E: Panonychus test

Example F

Phaedon larvae test

Solvent: 30 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 amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

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

Active substances, active substance concentrations and test results are shown in the following table.

Table F: Phaedon larval test

Example G

Plutella Test

Solvent: 30 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 amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

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 cockroach (Plutella xylostella) 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.

Active substances, active substance concentrations and test results are shown in the following table.

Table G: Plutella test

Example H

Spodoptera exigua test

Solvent: 30 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 amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

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 army worm (Spodoptera exigua) 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.

Active substances, active substance concentrations and test results are shown in the following table.

Table H: Spodoptera exigua test

Example I

Spodoptera frugiperda test

5 solvents: 30 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 amounts of solvent and emulsifier, and 1.0 is diluted to the desired amount with water containing emulsifier

Concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of army worm 15 (Spodoptera frugiperda) 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. 20

Active substances, active substance concentrations and test results are shown in the following table.

Table I: Spodoptera frugiperda test

Example J

Tetranychus test (OP-resistant / immersion treatment)

Solvent: 30 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 amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

Bean plants (Phaseolus vulgaris), which are heavily infested with all stages of the common spider mite (Tetranychus urticae), are immersed in an active ingredient preparation of the desired concentration.

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

Active substances, active substance concentrations and test results are shown in the following table.

Table J: Tetranychus test

Example K

Diabrotica balteata test (larvae in the soil)

Limit concentration test / soil insects - treatment of transgenic plants

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, the specified amount is given

Amount of emulsifier and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is poured onto the floor. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (mg / 1). You fill the bottom in 0.25 1 pots and let them stand at 20 ° C.

Immediately after the preparation, 5 pre-germinated maize kernels of the YIELD variety are added to each pot

GUARD (trademark of Monsanto Comp., USA). After 2 days, the appropriate test insects are placed in the treated soil. After a further 7 days, the efficiency of the active ingredient is determined by counting the maize plants that have accumulated (1 plant = 20% activity). Example L

Heliothis virescens - test (treatment of transgenic plants)

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 level

Concentration.

Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are treated by dipping into the preparation of active compound of the desired concentration and populated with the tobacco bud caterpillar Heliothis virescens 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.

Example M

Blowfly larva test / development-inhibiting effect

Lucilia cuprina (48h / EH)

Test animals: Lucilia cuprina larvae

Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in one ml of dimethyl sulfoxide. To produce a suitable formulation, the active ingredient solution is diluted with water to the desired concentration.

About 20 Lucilia cuprina larvae are placed in a test tube containing approx. 1 cm ³ horse meat and 0.5 ml of the active ingredient preparation to be tested. After 48 hours, the effectiveness of the active ingredient preparation is determined as% larval mortality.

The test tubes are then transferred to beakers with a bottom covered with sand. After a further 12 days, the test tubes are removed and the dolls and flies are counted. The development inhibitory effect is the

Slip inhibition after 1.5 times the development time of an untreated control in% (ratio of pupae to hatched flies) stated.

Active substances, active substance concentrations and test results are shown in the following table. Table M: BIowfly larval test

Example N

Test with multi-host tick nymphs in the diving process

Amblyomma hebraeum (EH)

Test animals: sucked nymphs from Amblyomma hebraeum

Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in one ml of dimethyl sulfoxide. In order to produce a suitable formulation, the active ingredient solution is diluted with water to the desired concentration.

10 soaked nymphs are immersed in the drug preparation to be tested for 1 minute. The animals are transferred to petri dishes (0 9.5 cm) equipped with filter disks and covered. After 4 weeks of storage in an air-conditioned

Mortality is determined in space.

100% means that no animal has skinned normally. 0% means that all animals have skinned.

In this test, e.g. the compounds (I-1), (1-2), (1-5) and (1-7) of the preparation examples have a good effect.

Claims

claims

Δ-pyrrolines of the formula (I)

in which

n represents 0 or 1,

r and s independently of one another represent 0, 1 or 2,

R ^{1 represents} halogen or methyl,

R ^{2 represents} hydrogen or halogen,

R ³ and R ⁴ independently of one another represent halogen, alkyl, haloalkyl, alkoxy or haloalkoxy,

R ^{5 represents} alkyl, haloalkyl, in each case optionally singly or multiply, the same or different phenyl substituted by radicals from the list W ^1, or represents -NR ⁶ R ⁷ ,

W ^{1 represents} halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylcarbonyl, alkoxycarbonyl or -S (O) _q R ⁸ ,

R ^{6 represents} alkyl or haloalkyl, R ^{7 represents} hydrogen, alkyl or haloalkyl,

R ⁶ and R ⁷ also together represent alkylene or alkoxyalkylene,

R ^{8 represents} alkyl or haloalkyl and

q represents 0, 1 or 2.

2. Compounds of formula (I) according to claim 1, in which

n represents 0 or 1,

r and s independently of one another represent 0, 1 or 2,

R ^{1 represents} fluorine, chlorine, bromine or methyl,

R ^{2 represents} hydrogen, fluorine, chlorine or bromine,

R ³ and R ⁴ independently of one another represent fluorine, chlorine, bromine, C, -C ₆ -alkyl, C, - C ₆ -haloalkyl, C, -C ₆ -alkoxy or C, -C ₆ -haloalkoxy,

R ^{5 represents} CC ₆ -alkyl, C, -C ₆ -haloalkyl, in each case optionally up to four times, identically or differently, by phenyl substituted by radicals from the list W ^1, or represents -NR ⁶ R ⁷ ,

W ¹ for fluorine, chlorine, bromine, C, -C ₆ alkyl, C, -C ₆ haloalkyl, C, -C ₆ -

Alkoxy, C, -C ₆ -haloalkoxy, C, -C ₆ -alkylcarbonyl, C, -C ₆ -alkoxycarbonyl or -S (O) _q R ⁸ ,

R ^{6 represents} C, -C ₆ alkyl or C, -C ₆ haloalkyl, R ^{7 represents} hydrogen, C, -C ₆ alkyl or C, -C ₆ haloalkyl,

R ⁶ and R ⁷ also together represent C ₃ -C ₆ alkylene or C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkylene,

R ^{8 represents} C, -C ₆ alkyl or C, -C ₆ haloalkyl and

q represents 0, 1 or 2.

Compounds of formula (I) according to Anspmch 1, in which

n represents 0 or 1,

r and s independently of one another represent 0, 1 or 2,

R ^{1 represents} fluorine, chlorine or methyl,

R ^{2 represents} hydrogen, fluorine or chlorine,

R ³ and R ⁴ independently of one another for fluorine, chlorine, C, -C ₄ alkyl, C, -C ₄ -

Haloalkyl, C, -C ₄ -alkoxy, C, -C ₄ -haloalkoxy,

R ^{5 represents} C, -C ₄ -alkyl, C, -C ₄ -haloalkyl, each optionally mono- to triple, identical or different, phenyl substituted by radicals from the list W ¹ or represents -NR ⁶ R ⁷ ,

W ¹ for fluorine, chlorine, C, -C ₄ -alkyl, C, -C ₄ -haloalkyl, C, -C ₄ -alkoxy, C, - C ₄ -haloalkoxy, C _r C ₄ -alkylcarbonyl, C, -C ₄ -alkoxycarbonyl or -S (O) _q R ⁸ ,

R ^{6 represents} C, -C ₄ -alkyl or C _r C ₄ -haloalkyl, R ^{7 represents} hydrogen, C, -C ₄ alkyl or C, -C ₄ haloalkyl,

R ⁶ and R ⁷ also together represent C ₄ -C ₅ alkylene or - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -,

R ^{8 represents} C, -C ₄ alkyl or C, -C ₄ haloalkyl and

q represents 0, 1 or 2.

4. Compounds of formula (I) according to spoke 1, in which

n represents 0 or 1,

r and s independently of one another represent 0 or 1,

R ^{1 represents} fluorine or chlorine,

R ^{2 represents} hydrogen or fluorine,

R ³ and R ⁴ independently of one another for fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n- Propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, trifluoromethoxy or trifluoroethoxy,

R ⁵ for methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl, trifluoroethyl, nonafluorobutyl, in each case optionally one to two times, identically or differently, by radicals from the List W 'substituted phenyl or represents -NR ⁶ R ⁷ , W ¹ for fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n-propoxy, i-propoxy , n-butoxy, i-butoxy, s-butoxy, t-butoxy, trifluoromethoxy, trifluoroethoxy, -COCH ₃ , -CO ₂ CH ₃ , -SCF ₃ , -SCHF ₂ , -SOCF ₃ , -SOCHF ₂ , -SO ₂ CF ₃ or -SO ₂ CHF ₂

R ^{6 represents} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl or trifluoroethyl and

R ^{7 represents} hydrogen, methyl, ethyl, n-propyl, -i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl or trifluoroethyl.

5. Compounds of formula (I-a)

in which

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , r and s have the meanings given in one of claims 1 to 4.

6. Compounds of formula (I-b)

in which R ¹ , R ² , R ⁴ , R ⁵ and s have the meanings given in one of claims 1 to 4.

7. Δ'-pyrrolines of the formula (I-c)

in which

R ¹ , R ² , R ⁴ , R ⁵ and s have the meanings given in one of claims 1 to 4.

Δ'-pyrrolines of the formula (I-d)

in which

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , r and s have the meanings given in one of claims 1 to 4.

A process for the preparation of compounds of formula (I) according to spoke 1, characterized in that

A) aminoketones of the formula (II)

in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , n, r and s have the meanings given in Claim 1,

treated with a Lewis acid or protonic acid,

or

B) (Bi) phenols of the formula (III)

in which

R ¹ , R ² , R ³ , R ⁴ , n, r and s have the meanings given in spoke 1,

with a sulfonylation reagent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,

or that Δ'-pyrrolines of the formula (Ia)

in which

n stands for 1 and

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , r and s have the meanings given in spoke 1,

obtained by using pyrrolines of the formula (IV)

in which

R, R, R and r have the meanings given above and

X represents Br, Cl, I, -OSO ₂ CF ₃ or -OSO ₂ (CF ₂ ) ₃ CF ₃ ,

first reacted with a diboronic ester in the presence of a catalyst, in the presence of an acid binder and, if appropriate, in the presence of a diluent and, if appropriate, after prior isolation of the resulting compounds of the formula (V) in which

R, R, R and r have the meanings given above and

G for 4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yl, 5,5-dimethyl-1, 3, 2-dioxaborinan-2-yl, 4,4,6- Trimethyl-1, 3, 2-dioxa-borinan-2-yl or l, 3,2-benzodioxaborol-2-yl,

with iodides of the formula (VI)

in which

R, R and s have the meanings given in spoke 1,

in the presence of a catalyst, in the presence of a diboronic ester, in the presence of an acid binder and, if appropriate, in the presence of a diluent.

10. Aminoketones of the formula (II)

in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , n, r and s have the meanings given in one of claims 1 to 4.

11. Pyrrolines of the formula (IV-b)

in which

R ¹ , R ² , R ³ and r have the meanings given in one of claims 1 to 4 and

X ^{2 stands} for -OSO ₂ CF ₃ .

12. Pyrrolines of the formula (IV-b)

in which R ¹ , R ² , R ³ and r have the meanings given in one of claims 1 to 4 and

X ^{2 stands} for OSO ₂ (CF ₂ ) ₃ CF ₃ .

13. N-Boc lactams of the formula (VII)

in which

R ³ , R ⁴ , R ⁵ , n, r and s have the meanings given in one of claims 1 to 4.

14. Lactams of the formula (IX)

in which

R ³ , R ⁴ , R ⁵ , n, r and s have the meanings given in one of claims 1 to 4.

15. pesticide, characterized by a content of at least one compound of the formula (I) according to spoke 1 in addition to extenders and / or surface-active substances.

16. Use of compounds of formula (I) according to spoke 1 for controlling pests.

17. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.

18. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to spoke 1 are mixed with extenders and / or surface-active substances.

19. Use of compounds of formula (I) according to spoke 1 for the production of pesticides.