DE10051395A1 - DELTA · 1 · -pyrrolines - Google Patents

Abstract

New DELTA · 1 · pyrrolines of the formula (I) DOLLAR F1 in which DOLLAR AR · 1 ·, R · 2 ·, R · 3 ·, R · 4 ·, R · 5 ·, n, r and s are those in the Description given meanings, DOLLAR A several processes for the preparation of these substances and their use for controlling pests.

Description

The present invention relates to new Δ ¹ -pyrrolines, several processes for their preparation and their use as pesticides.

It is already known that numerous Δ ¹ -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 ¹ -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 ^{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 phenyl which is monosubstituted or polysubstituted 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.

Furthermore, it was found that Δ ¹ -pyrrolines of the formula (I) can be prepared by

• 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 above,
  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 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 ¹ -pyrrolines of the formula (Ia)
  in which
  R ¹ , R ² , R ³ , R ⁴ , R ⁵ , r and s have the meanings given above,
  obtained by using pyrrolines of the formula (IV)
  in which
  R ¹ , R ² , R ³ 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 ¹ , R ² , R ³ and r have the meanings given above and
  G for 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl, 5,5-dimethyl-1,3,2-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 are useful both in crop protection as well as in material protection to combat unwanted pests, such as Insects, let use.

Surprisingly, the Δ ¹ -pyrrolines of the formula (I) according to the invention have a significantly better insecticidal activity than the constitutionally most similar, previously known Δ ¹ -pyrrolines having the same direction of action.

The Δ ¹ -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 ¹ preferably represents fluorine, chlorine, bromine or methyl.
R ² preferably represents hydrogen, fluorine, chlorine or bromine.
R ³ and R ⁴ are, independently of one another, preferably fluorine, chlorine, bromine, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy or C ₁ -C ₆ haloalkoxy.
R ⁵ preferably represents C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, in each case optionally up to four times phenyl substituted by radicals from the list W ¹ or for -NR ⁶ R ⁷ .
W ¹ preferably represents fluorine, chlorine, bromine, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylcarbonyl , C ₁ -C ₆ alkoxy carbonyl or -S (O) _q R ⁸ .
R ⁶ preferably represents C ₁ -C ₆ alkyl or C ₁ -C ₆ haloalkyl.
R ⁷ preferably represents hydrogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ haloalkyl.
R ⁶ and R ⁷ together also preferably represent C ₃ -C ₆ alkylene or C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkylene.
R ⁸ preferably represents C ₁ -C ₆ alkyl or C ₁ -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 ³ and R ⁴ independently of one another particularly preferably represents fluorine, chlorine, C ₁ - C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ -haloalkoxy.
R ⁵ particularly preferably represents C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, in each case optionally phenyl which is monosubstituted to trisubstituted by radicals from the list W ¹ or represents -NR ⁶ R ⁷ .
W ¹ particularly preferably represents fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkoxy, C ₁ -C ₄ -alkylcarbonyl, C ₁ -C ₄ alkoxy carbonyl or -S (O) _q R ⁸ .
R ⁶ particularly preferably represents C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl.
R ⁷ particularly preferably represents hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ halogen alkyl.
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 ₁ -C ₄ -alkyl or C ₁ -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 ¹ very particularly preferably represents fluorine or chlorine.
R ² very particularly preferably represents hydrogen or fluorine.
R ³ 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 optionally from one to two times from residues the list W ¹ substituted phenyl or for -NR ⁶ R ⁷ .
W ¹ 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.

Furthermore, (R) -configured compounds of the formulas (Ib) 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 (Ic) are very particularly preferred

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

Enantiomerically pure compounds of the formulas (I-b) and (I-c) are obtained by Conventional processes for resolving racemates, such as by chromatography of the corresponding racemates on a chiral stationary phase. It is possible both the racemic end products or racemic intermediates on them Way to decompose into the two enantiomers.

Saturated hydrocarbon residues such as alkyl can, also in combination with Heteroatoms, e.g. B. in alkoxy, as far as possible, in each case straight-chain or be 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 or priority areas listed above However, definitions or explanations can also be made among themselves, i.e. between the respective areas and preferred areas can be combined as desired. they seem for the end products as well as for the preliminary and intermediate products accordingly.

If 4 '- [1 - [(tert-butoxycarbonyl) amino] -4- (2,6-difluorophenyl) -4-oxobutyl] -1,1'-biphenyl-4-yl-trifluoromethanesulfonate and trifluoroacetic acid (TFA ) 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] -1,1'-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-difluorophenyl) -2- (4-bromophenyl) -3,4-dihydro-2H-pyrrole, 4-iodophenyl trifluoromethanesulfonate, a palladium catalyst and 4,4,4 ', 4', 5,5 are used , 5,5 ', 5'-octamethyl-2,2'-bi-1,3,2-dioxaborolane as starting materials, the method (C) according to the invention can be illustrated by the following formula.

Explanation of the processes and intermediates 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) N-Boc lactams of the formula (VII)
  in which
  R ³ , R ⁴ , R ⁵ , 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, MgI or ZnCl,
  if appropriate in the presence of a diluent (eg tetrahydro furan) at temperatures between -70 ° C and + 70 ° C.

Formula (VII) generally defines 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

• a) lactams of the formula (IX)
  in which
  R ³ , R ⁴ , R ⁵ , n, r and s have the meanings given above,
  with di-tert-butyl dicarbonate in the presence of a base (e.g. dimethyl aminopyridine), optionally in the presence of a diluent (e.g. dichloromethane).

Formula (VIII) provides a general definition of the metallated aromatics required as starting materials when carrying out process (a). In this formula, R ¹ and R ^{2 are} preferably, particularly preferably or very particularly preferably, 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 , M preferably represents Li, MgCl, MgBr, MgI, ZnCl, particularly preferably Li, MgCl, MgBr, MgI, very particularly preferably Li, MgCl, MgBr.

Metallized aromatics of the formula (VIII) are known in some cases or can according to known methods, such as. B. lithiation or Grignard reaction, from the ent speaking 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 ⁵ , r and s have the meanings given above,
can be made, for example, by

• a) lactams of the formula (X)
  in which
  R ⁴ and s have the meanings given above,
  • 1. 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
  • 2. β) with sulfonic anhydrides of the formula (XII)
    (R ⁵ SO ₂ ) ₂ O (XII)
    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

• a) 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. in connection with the description of the substances of the formula (I) according to the invention for these radicals.

Lactams of the formula (X) are known and / or can be prepared by known processes produce (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 preferably, particularly preferably or very particularly preferably represents 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.

Formula (XII) provides a general definition of the sulfonic anhydrides 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.

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

Biphenyls of the formula (XIII) are known. You can z. B. manufacture by

• a) Hydroxybiphenyls of the formula (XIV)
  in which
  R ³ , R ⁴ , r and s have the meanings given above,
  • 1. e-1) 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
  • 2. e-2) with sulfonic anhydrides of the formula (XII)
    (R ⁵ SO ₂ ) ₂ O (XII)
    in which
    R ^{5 has} the meanings given above
  in the presence of a base (for example potassium carbonate) and optionally in the presence of a diluent (for example 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 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.

Hydroxybiphenyls of the formula (XIV) are known.

Suitable diluents for carrying out the Ver according to the invention driving (A) all usual inert, organic solvents in question. virtue 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 acetic acid methyl ester or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sul fone, like Sulfolan. Methylene chloride and chloro are particularly preferably used form, toluene, methanol or ethanol.

When carrying out process (A) according to the invention, all come in each case usual Lewis acids or protonic acids in question. Boc elimination methods are generally known (see e.g. T. W. Greene, P. G. M. Wuts, Protective Groups in Organic Synthesis, Ed. 3, New York, Wiley & Sons, 1999, pp. 520-525). Prefers Trifluoroacetic acid, HCl or HBr are used to split off the Boc protective group on.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (A) can be varied over a wide range. In general  one works at temperatures between -20 ° C and + 120 ° C, preferably between -10 ° C and 60 ° C.

When carrying out process (A) according to the invention, the starting point is 1 mol Compound of formula (II) generally 100 moles of a protonic acid. It is however, it is also possible to incorporate the reaction components in other ratios put. The processing takes place according to usual methods. Generally done in a suitable manner by concentrating the reaction mixture Absorbs solvent, adjusts to pH 12 with sodium hydroxide and the orga Wash the phase with water, dry over sodium sulfate, filter and concentrate. The residue is, if necessary, by customary methods, such as chromatography or recrystallization, freed of any impurities that may still be present.

To prepare chiral compounds of the formulas (I-b) and (I-c), the Lactams of the formula (IX) are subjected to racemate resolution. It works one, for example, by methods of preparative chromatography, preferably according to the method of high performance liquid chromatography (HPLC). there z. B. uses a chiral stationary silica gel phase. As particularly suitable A silica gel derivative has been used for the separation of the compounds of the formula (IX) (e.g. mercaptopropyl silica gel) which is treated with N-methacryloyl-L-leucine-D-menthylamide has been modified. This separating material is known (cf. EP-A 0 379 917). All customary inert, organic solvents and mixtures come as eluents of these in question. Halogenated, if appropriate, are preferably usable aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, Hexane, heptane, cyclohexane; Dichloromethane, chloroform; Alcohols, such as methanol, 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 this. The (R) -configured enantiomers obtained are then called Starting materials used 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 are, 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 of formula (I) according to the invention for these residues were mentioned as preferred, particularly preferred etc.

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 come as sulfony lation reagents sulfonic acid halides of the formula (XI) and anhydrides of Formula (XII) in question.

Suitable diluents for carrying out the Ver according to the invention driving (B) all usual inert, organic solvents in question. virtue Halogenated aliphatic, alicyclic or (Hetero) aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclo hexane, 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-diethoxy ethane 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; ester such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sulfones, such as sulfolane. Pyridine is particularly preferably used, Dichloromethane, chloroform, tetrahydrofuran or toluene. One can if necessary  Use mixtures with water and the reaction in a two-phase system carry out.

Suitable acid binders when carrying out the process according to the invention driving (B) all inorganic and organic customary for such reactions Bases into consideration. Alkaline earth metal or alkali metal can preferably be used 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 or alkaline earth metal acetate such as sodium acetate, potassium acetate, calcium acetate, and also tertiary amines, such as Trimethylamine, triethylamine, tributylamine, diethylisopropylamine, N, N-dimethyl aniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). Especially Triethylamine, diethylisopropylamine, sodium hydroxide, potassium are preferably used hydroxide or potassium carbonate.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (B) can be varied over a wide range. In general one works at temperatures between -70 ° C and + 110 ° C, preferably between -20 ° C and + 40 ° C.

When carrying out process (B) according to the invention, the starting point is 1 mol Compound of formula (III) generally 1 mole or a slight excess of sulfonylation reagent and 0.5 to 3 mol of acid binder. However, it is also possible to use the reaction components in other ratios. The Refurbishment is carried out using customary methods. In general, one proceeds in the Way, that the reaction mixture is decanted, washed, dried, filtered and a concentrated. The residue is optionally by conventional methods such as Chromato graphy or recrystallization of any impurities that may still be present freed.  

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 are already preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention preferred etc. were mentioned.

The pyrrolines of the formula (IV-a)

in which
R ¹ , 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 ¹ , R ² , R ³ and r have the meanings given above and
X ^{2 represents} -OSO ₂ CF3 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. The catalyst used is preferably PdCl ₂ (dppf) [dppf = 1,1'-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 preferred 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.

Diboronic esters are 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi-1,3,2-dioxaborolane, 5,5,5 ', 5'-tetramethyl-2,2'-bi-1,3,2-dioxaborinane, 4,4,4', 4 ', 6,6'-hexamethyl-2,2'-bi - 1,3,2-dioxaborinan or 2,2'-Bi-1,3,2-benzodioxaborol in question. All diborone esters are known.

The acid binders used in carrying out the process according to the invention rens (C) each have all the usual inorganic and or ganic bases. Alkaline earth or alkali can preferably be used 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 or earth alkali metal acetates such as sodium acetate, potassium acetate, calcium acetate, alkali metal fluorides, and also tertiary amines, such as trimethylamine, triethylamine, tributyl amine, 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 is simultaneously acts as an acid binder. Barium hydroxide is particularly preferably used, Tripotassium phosphate, cesium carbonate, potassium carbonate, sodium carbonate, potassium acetate, triethylamine, potassium tert-butoxide (KotBu), cesium fluoride or Potassium fluoride.

Suitable diluents for carrying out the Ver according to the invention driving (C) all usual inert, organic solvents in question. virtue 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 acetic acid methyl ester or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sul fone, like Sulfolan. Acetone, dimethoxyethane are particularly preferably used. Dioxane, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, Ethanol, toluene or mixtures of these diluents mentioned with water.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (C) can be varied over a wide range. In general one works at 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 formula (IV) with a Diboronester implemented. This gives the intermediates of the formula (V), the then reacted in a second stage with iodides of the formula (VI). In the second variant, the intermediates of formula (V) are not isolated, but implemented in situ with iodides of the formula (VI). It is with both variants also possible first the iodides of the formula (VI) and only in the second stage Use pyrrolines of the formula (IV).

When carrying out process (C) according to the invention, the starting point is 1 mol Compound of formula (IV) generally 1 mole or a slight excess of a diborone ester and 1 mole or a slight excess of iodide of the formula (VI) and 3% of a palladium catalyst. However, it is also possible that To use reaction components in other ratios. It can optionally be the Compound of formula (IV) or the compound of formula (VI) presented first become. The processing takes place according to usual methods. Generally done one in such a way that the reaction mixture is diluted with water and with Extracted ethyl acetate. The organic phase is washed with water,  dried over sodium sulfate, filtered and concentrated. The backlog will optionally by customary methods, such as chromatography or recrystallization tion, freed of any contamination that may still be present. To isolate the Intermediates of formula (V) is added before the next reaction Component worked up as described.

In general, all procedures according to the invention are carried out under atmospheric pressure. But it is also possible, in each case under increased or to work under 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 goods and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species and against all or individual stages of development. The pests mentioned above include:
From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus.
From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spp.
From the order of the Symphyla z. B. Scutigerella immaculata.
From the order of the Thysanura z. B. Lepisma saccharina.
From the order of the Collembola z. B. Onychiurus armatus.
From the order of Orthoptera z. B. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
From the order of the Blattaria z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Reticulitermes spp.
From the order of the Phthiraptera z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus sppe, Phrosiphumumonpp., Macrosiphumum 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 z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisisppa, Fpp , Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Hofeannannionella, Tinea pellellaella Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephppis, Orphusus spp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Giptusibbium psol. Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. 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 z. B. Xenopsylla cheopis, Ceratophyllus spp.
From the class of the Arachnida z. B. Scorpio maunis, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., Ipp ., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.

The plant parasitic nematodes include z. B. 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 particularly noteworthy through an excellent effect against caterpillars, beetle larvae, spider mites, Aphids and leaf flies.

The compounds of the invention can optionally in certain con concentrations or application rates also as herbicides and microbicides, for example used as fungicides, antifungals and bactericides. You leave  optionally as intermediates or precursors for the synthesis of further Use active ingredients.

According to the invention, all plants and parts of plants can be treated. Under Plants are understood here as all plants and plant populations desired and undesirable wild plants or crops (including naturally occurring crops). Cultivated plants can be plants that by conventional breeding and optimization methods or by organic technological and genetic engineering methods or combinations of these Methods can be obtained, including transgenic plants and one finally, the plant that can or cannot be protected by plant breeders' rights zensorten. Plant parts should include all above-ground and underground parts and organs of the plants, such as shoot, leaf, flower and root, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes are listed. To the Plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.

The treatment according to the invention of the plants and parts of plants with the active ingredients substances takes place directly or by influencing their surroundings, living space or Storage room according to the usual treatment methods, e.g. B. by diving, spraying, Evaporation, atomization, scattering, spreading and with propagation material, especially in the case of seeds, still by 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 medium, pastes, soluble powders, granules, suspension emulsion concentrates, Active ingredient-impregnated natural and synthetic substances as well as very fine encapsulation in polymeric fabrics.  

These formulations are prepared in a known manner, e.g. B. by mixing of the active compounds according to the invention with extenders, that is to say liquid solvents and / or solid carriers, optionally using surfaces active agents, ie emulsifiers and / or dispersants and / or foam generating means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. 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 solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers:
z. B. 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, are suitable as solid carriers for granules: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and Ta bakstems;
as emulsifying and / or foam-generating agents come into question: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, poly oxyethylene fatty alcohol ethers, for. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

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

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan 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 Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be in commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, Acaricides, nematicides, fungicides, growth regulators or herbi ziden available. Insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms u. a.

Particularly cheap mixing partners are e.g. B. the following:

fungicides

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazon, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyphodinconol, cypodinconol, cypodinconol
Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxinodonine, dithorphononodine
Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, flurprimolol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfosolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusilazolutol, flusulfonol, flusilazolutol, flusulfazolutol, flusilazolutol, flusulfazolutol, flusilazolutol, flusulfazolutolol Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox, guazatin, hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Metrifuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazol, Pethrazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Polyoxorim, probenazole, Prochloraz, Procymidon, Propamocarb, Propanosine-Sodium, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyimyroxon, Pyrimethonil
Quinconazole, quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
uniconazole
Validamycin A, vinclozolin, viniconazole,
Zarilamid, Zineb, Ziram as well
Dagger G, OK-8705, OK-8801,
α- (1,1-dimethylethyl) -β- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-fluoro-b-propyl-1H-1,2,4-triazol-1-ethanol,
α- (2,4-dichlorophenyl) -β-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,
α- (5-methyl-1,3-dioxan-5-yl) -β - [[4- (trifluoromethyl) phenyl] methylene] -1H-1,2,4-triazol-1-ethanol,
(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone,
(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
{2-methyl-1 - [[[1- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester,
1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) oxime,
1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,
1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,
1 - [(diiodomethyl) sulphonyl] -4-methylbenzene,
1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,
1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,
1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazol-5-carboxanilide,
2,2-dichloro-N- [1- (4-chlorophenyl) 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) sulphonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,
2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -aD-glucopyranosyl] amino-4-methoxy-1H-pyrrolo [2,3-d] pyrimidine-5 carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) -pentandinitril,
2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridine carboxamide,
2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) -acetamide,
2-phenylphenol (OPP),
3,4-dichloro-1- [4- (difluoromethoxy) phenyl] -1H-pyrrole-2,5-dione,
3,5-dichloro-N- [cyano [(1-methyl-2-propynyl) -oxy] -methyl] -benzamide,
3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] -pyridine,
4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazol-1-sulfonamide,
4-methyl-tetrazolo [1,5-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 (1-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) oxy] -2,5-thiophene dicarboxylate,
cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,
cis-4- [3- [4- (1,1-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethylmorpholine hydrochloride,
Ethyl - [(4-chlorophenyl) azo] cyanoacetate,
potassium bicarbonate,
Methantetrathiol sodium salt,
Methyl-1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-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-cyclohexanecarboxamide,
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'-methoxy-methanimidamid,
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] -1-benzopyran-2,1 '(3'H) -isobenzofuran] -3'-one.

bactericidal

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Teclofta lam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Biethanoprofinoxhrin, Bethenomethrofin, Biobanomethrin Butyl pyridaben
Cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, Chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, Chlovaporthrin, cis-resmethrin, Cispermethrin, Clocythrin, cloethocarb, clofentezine, cyanophos, Cycloprene, cycloprothrin, cyfluthrin , Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn,
Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Eprinomectin, Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,
Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazuron, Flubrocythrinate, Flucycloxuron, Floxthrinofonate, Fufenzoxinhronate, Fufenoxthhronate, Fufenoxthonate, Fufronoxin, Fufone .
granulosis,
Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
Imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,
nucleopolyhedroviruses
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos,
Naled, Nitenpyram, Nithiazine, Novaluron,
Omethoate, oxamyl, oxydemethone M,
Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pyromhrhridos, Pymmethrofzin, Pymmethrofinos , Pyridathione, pyrimidifen, pyriproxyfen,
quinalphos,
ribavirin,
Salithion, Sebufos, Selamectin, Silafluofen, Spinosad, Sulfotep, Sulprofos,
Tau-fluvalinate, oxalate hydrogen tebufenozide, tebufenpyrad, Tebupirimiphos, teflubenzuron, tefluthrin, temephos, Temivinphos, terbufos, tetrachlorvinphos, theta cypermethrin, thiamethoxam, Thiapronil, Thiatriphos, thiocyclam, thiodicarb, thiofanox, thuringiensin, Tralocythrin, tralomethrin, triarathene, Triazamate, triazophos , Triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,
Vamidothion, Vaniliprole, Verticillium lecanii,
YI 5302,
Zeta-cypermethrin, zolaprofos,
(1R-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 (1H) - imine
2- (2-chloro-6-fluorophenyl) -4- [4- (1,1-dimethylethyl) phenyl] -4,5-dihydro-oxazol
2- (Acetlyoxy) -3-dodecyl-1,4-naphthalenedione
2-chloro-N - [[[4- (1-phenylethoxy) phenyl] amino] carbonyl] -benzamide
2-chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) phenyl] amino] carbonyl] -benzamide
3-methylphenyl propylcarbamate
4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene
4-chloro-2- (1,1-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-dichlorophenyl) -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-dichlorophenyl) -2-oxo-1-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-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate
N- (3,4,4-trifluoro-1-oxo-3-butenyl) -glycine
N- (4-chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide
N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine
N-methyl-N '- (1-methyl-2-propenyl) -1,2-hydrazindicarbothioamid
N-methyl-N'-2-propenyl-1,2-hydrazindicarbothioamid
O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

When used as insecticides, the active compounds according to the invention can also be used in their commercial formulations as well as in those formulations prepared application forms in a mixture with synergists. synergists are compounds through which the action of the active compounds according to the invention is increased without the added synergist itself having to be active.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary widely. The drug concentration of the Use forms can be from 0.0000001 to 95% by weight of active ingredient, preferably are 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 and storage pests, the effect is noticeable fabric through an excellent residual effect on wood and clay as well as through a good alkali stability on limed substrates.

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, mite mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas. These parasites include:
From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina z. B. 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 z. B. 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 z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.
From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata z. B. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp. Pneumonyssus spp., Sternostoma spp., Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia 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 excellent effectiveness against development stages of ticks such as Amblyomma hebraeum, against parasitic ones Flies such as against Lucilia cuprina, against fleas such as Ctenocephalides felis.

The active compounds of the formula (I) according to the invention are also suitable for combating of arthropods, the farm animals, such as. B. cattle, sheep, goats, Horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, Bees, other pets such as B. dogs, cats, house birds, aquarium fish as well as so-called experimental animals, such as. B. hamsters, guinea pigs, rats and Infest mice. By fighting these arthropods, deaths and Reductions in performance (for meat, milk, wool, skins, eggs, honey, etc.) can be reduced, so that by using the active compounds according to the invention more economical and easier animal husbandry is possible.  

The active compounds according to the invention are used in the veterinary sector in in a known manner by enteral administration in the form of, for example, tablets, Capsules, watering, drenching, granules, pastes, boluses, the feed-through process, suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, through nasal Application, by dermal application in the form of, for example, diving or Bathing (dipping), spraying (spray), pouring (pour-on and spot-on), des Washing, powdering and with the help of shaped articles containing active ingredients, such as Collars, ear tags, tail tags, limb straps, halters, Mar marking devices etc.

When used for cattle, poultry, pets, etc., you can the fiction active substances of the formula (I) as formulations (for example powder, emul sions, flowable agents), the active ingredients according to the invention in an amount Contain from 1 to 80 wt .-%, directly or after 100 to 10,000 times dilution apply or use it as a chemical bath.

It was also found that the compounds of the invention have a high Show insecticidal activity against insects that destroy technical materials.

The following insects may be mentioned by way of example and preferably, but without limitation:
Beetle like
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Specus Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.
Skin wings like
Sirex juvencus, Urocerus 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, woodworking products and paints.

The one to be protected against insect attack is very particularly preferably Material around 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, as such, in the form of concentrates or general formulations such as powders, granules, solutions, suspensions sions, emulsions or pastes.  

The formulations mentioned can be prepared in a manner known per se be, e.g. B. by mixing the active ingredients according to the invention with at least a solvent or diluent, emulsifier, dispersing and / or binding agent or fixative, water repellant, possibly desiccant and UV stabilizer gates and possibly dyes and pigments and other processing auxiliaries.

The insecticidal agents or used to protect wood and wood-based materials Concentrates contain the active ingredient 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 agents or concentrates used depends on the type and type come from insects and depending on the medium. The optimal amount to use can be determined by test series in the application. In general however, it is sufficient 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active ingredient, based on the material to be protected.

An organic chemical solution serves as the solvent and / or diluent medium or solvent mixture and / or an oily or oily low volatility organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or Water and optionally an emulsifier and / or wetting agent.

The organic chemical solvents used are preferably oily or oily ones Solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, used. As such volatile, Water-insoluble, oily and oily solvents become corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures preferably white spirit, petroleum and / or alkylbenzene used.  

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

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

The organic semi-volatile oily or oily solvents with a ver Evaporation number above 35 and a flash point above 30 ° C, preferably above half 45 ° C, can be partly due to slightly or medium volatile organic chemical Solvents are replaced, provided that the solvent mixture also an evaporation number above 35 and a flash point above 30 ° C preferably above 45 ° C, and that the insecticide-fungicide mixture in this solvent mixture is soluble or emulsifiable.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture or an aliphatic polar orga niche chemical solvent or solvent mixture replaced. Preferably come aliphatic containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ether, ester or the like. to use.

As an organic chemical binder in the present Er finding the known water-dilutable and / or in the used organic chemical solvents soluble or dispersible or emulsifiable Synthetic resins and / or binding drying oils, in particular binders  from or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, poly ester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indden Coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin used.

The synthetic resin used as a binder can be in the form of an emulsion, dispersion or solution. Bitumen or bitumi can also be used as binders nous substances up to 10 wt .-% can be used. In addition, in itself known dyes, pigments, water repellants, odor correctors and Inhibitors or anticorrosive agents and the like are used.

According to the invention, preference is given to at least one organic chemical binder an alkyd resin or modified alkyd resin and / or a drying vegetable Contain oil in the medium or in the concentrate. Are preferred according to the invention Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight.

The binder mentioned can be wholly or partly by a fixative (ge mix) or a plasticizer (mixture) can be replaced. These additions are said to be one Prevent volatilization of the active ingredients as well as 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, 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 Gly kolether, glycerol ester and p-toluenesulfonic acid ester.  

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

Water is also particularly suitable as a solvent or diluent, optionally mixed with one or more of the above organic chemical solvents or diluents, emulsifiers and dispersants.

A particularly effective wood protection is achieved through industrial impregnation processes, z. B. vacuum, double vacuum or printing process.

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

The additional mixing partners are preferably those in WO 94/29 268 Insecticides and fungicides mentioned in question. The ones mentioned in this document Connections are an integral part of this application.

Insecticides, such as chlorpyri, can be used as very particularly preferred mixing partners phos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, Permethrin, Imidacloprid, NI-25, Flufenoxuron, Hexaflumuron, Transfluthrin, Thia cloprid, methoxyphenoxide and triflumuron, and fungicides such as epoxyconazole, Hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, Metconazole, imazalil, dichlorfluanide, tolylfluanid, 3-iodo-2-propynylbutyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

At the same time, the compounds according to the invention can protect against fouling objects, especially hulls, sieves, nets, structures, Quayside and signal systems, which are connected with sea or brackish water come, be used.  

Overgrowth by sessile oligochaetes, such as lime tube worms and by mussels and species of the group Ledamorpha (barnacles), such as various Lepas and Scalpellum species, or by species from the group Balanomorpha (barnacles), such as Balanus or pollicipes species, increases the frictional resistance of ships and subsequently performs through increased energy consumption and beyond frequent dry dock stays for a significant increase in operating costs.

In addition to the growth by algae, for example Ectocarpus sp. and Ceramium sp., comes in particular the vegetation by sessile Entomostraken groups, which are summarized under the name Cirripedia (barnacles) their importance.

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

By using compounds according to the invention alone or in combination with other active ingredients, can rely on the use of heavy metals such. B. in bis- (trialkyltin) sulfides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper (I) oxide, Triethyltin chloride, tri-n-butyl (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, Molybdenum disulfide, antimony oxide, polymeric butyl titanate, phenyl (bispyridine) - bismuth chloride, tri-n-butyltin fluoride, manganese ethylene bisthiocarbamate, zinc di methyldithiocarbamate, zinc ethylene bisthiocarbamate, zinc and copper salts of 2- Pyridinthiol-1-oxide, bisdimethyldithiocarbamoylzinkethylenististhiocarbamate, zinc oxide, copper (I) ethylene bisdithiocarbamate, copper thiocyanate, copper naphthenate and Tributyltin halides are omitted or the concentration of this verbin reduced significantly.

The ready-to-use antifouling paints can also be used if necessary Active ingredients, preferably algicides, fungicides, herbicides, molluscicides or others Contain antifouling agents.  

Suitable combination partners for the antifouling agents according to the invention are preferably:
Algicides like
2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophene, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
Fungicides like
Benzo [b] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlofluanid, fluor folpet, 3-iodo-2-propynyl-butylcarbamate, tolylfluanid and azoles such as
Azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propi conazole and tebuconazole;
Molluscicides like
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-pyridinthiol- 1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6-trichlorophenylmaleimide.

The antifouling agents used contain the active ingredients according to the invention compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular from 0.01 to 20% by weight.

The antifouling agents according to the invention further contain the usual ones Components such as B. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.  

Antifouling paints contain algicidal, fungicidal, molluscicides and insecticidal active substances according to the invention, in particular binders.

Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in one Solvent system especially in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organi 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 chlorine rubber, chlorinated polypropylene and vinyl resins.

Paints may also contain inorganic pigments, organic Pigments or dyes, which are preferably insoluble in sea water. Further Paints can contain materials, such as rosin, to be controlled To enable release of the active ingredients. The paints can also be soft makers, modifiers influencing the rheological properties, and contain other conventional ingredients. Also in self-polishing antifouling Systems can be the compounds of the invention or those mentioned above Mixtures can be incorporated.

The active compounds according to the invention are also suitable for combating animal pests, in particular insects, arachnids and mites, which are found in closed rooms, such as, for example, apartments, factory halls, offices, driving cabins and the like. occur. To combat these pests, they can be used alone or in combination with other active ingredients and auxiliaries in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
From the order of the Scorpionidea z. B. Buthus occitanus.
From the order of Acarina z. B. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides formae.
From the order of the Araneae z. B. Aviculariidae, Araneidae.
From the order of the Opiliones z. B. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
From the order of the Isopoda z. B. Oniscus asellus, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus, Polydesmus spp.
From the order of the Chilopoda z. B. Geophilus spp.
From the order of the Zygentoma z. B. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
From the order of the Blattaria z. B. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
From the order of the Saltatoria z. B. Acheta domesticus.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Kalotermes spp., Reticulitermes spp.
From the order of Psocoptera z. B. Lepinatus spp., Liposcelis spp.
From the order of the Coleptera z. B. 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 z. B. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musaria domestica. , Stomoxys calcitrans, Tipula paludosa.
From the order of the Lepidoptera z. B. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
From the order of the Siphonaptera z. B. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
From the order of the Hymenoptera z. B. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
From the order of the Anoplura z. B. Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.
From the order of Heteroptera z. B. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

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

The application takes place in aerosols, unpressurized sprays, e.g. B. Pump and Atomizer sprays, automatic fog machines, foggers, foams, gels, vaporizers products with evaporator platelets made of cellulose or plastic, liquid evaporators, Gel and membrane evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth papers, moth bags and Moth angels, as granules or dusts, in lures or bait stations.

The manufacture and use of the substances according to the invention are based on following examples.

Preparation Examples

Procedure (A)

example 1

Trifluoroacetic acid (185.37 g, 1.63 mol) is placed at 5 ° C. At this tempera a solution of 4- [1 - [(tert-butoxycarbonyl) amino] -4- (2,6-difluorophenyl) - 4-oxobutyl] phenyl trifluoromethanesulfonate (II-1) (42.55 g, 80.8% ≅ 0.06 mol) in Dichloromethane (150 ml) was added dropwise and then at this temperature for 3 hours rature stirred. The trifluoroacetic acid is distilled off under reduced pressure and the residue was adjusted to pH 12 with 1N NaOH. The aqueous phase will extracted with dichloromethane (2 × 100 ml). The combined organic phases are dried over sodium sulfate, filtered and concentrated. The raw product is using chromatography on silica gel (mobile phase: n-hexane / ethyl acetate 3: 1 (v / v)) cleaned up.

15.83 g (65% of theory) of 4- [5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] phenyl trifluoromethanesulfonate (I-1) are obtained.
HPLC: Log P (pH 2.3) = 3.49 (100% purity).
¹ H-NMR: δ (CD ₃ CN) = 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-difluorophenyl) -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-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] -1,1'-biphenyl-4-yl-1,1 are obtained, 2,2,3,3,4,4,4-nonafluoro-1-butanesulfonate (I-3).
HPLC: Log P (pH 2.3) = 5.57 (100% purity).
Mp 68-69 ° C
¹ 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, m), 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] - 1,1'-biphenyl-4-yl-dimethylsulfamate (I-3 ). The crude product is purified by chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate 1: 1) and then stirring with isopropanol.
HPLC: Log P (pH 2.3) = 3.06 (100% purity).
Mp 131-133 ° C
¹ H-NMR: δ (CD ₃ CN) = 1.83 (1H, m), 2.62 (1H, m), 3.06 (2H, m), 5.33 (1H, m), 7.07 (2H, m), 7.38 (2H , d), 7.42 (2H, d), 7.45 (1H, m), 7.65 (2H, d), 7.71 (2H, d) ppm.

Production of starting materials for process (A)

Aminoketones of formula (II)

Example (II-1)

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) was added dropwise. The reaction mixture is allowed to warm to -30 ° C. and A solution of tert-butyl-2-oxo-5- (4 - {[(trifluor methyl) sulfonyl] oxy} phenyl) -1-pyrrolidine carboxylate (VI-1) (36.0 g, 87.9 mmol) in Tetrahydrofuran (100 ml). The reaction mixture is left for 4 hours at -30 ° C and then stir for 16 hours at room temperature. The The reaction mixture is stirred into water (1000 ml) and with ethyl acetate (2 x 500 ml) extracted. The combined organic phases are sequential with 1N HCl, saturated aqueous sodium hydrogen carbonate solution and saturated washed aqueous sodium chloride solution. The organic phase is over Dried sodium sulfate, filtered and concentrated.

42.55 g (75% of theory) of 4- [1- [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 (II-2)

Analogously to Example (II-1), 4 - [(1R) -1- [tert-butoxycarbonyl) amino] -4- (2,6-difluorophenyl) -4-oxobutyl] phenyl trifluoromethanesulfonate (II-2) is obtained.
HPLC: Log P (pH 2.3) = 4.37.

Example (II-3)

Analogously to Example (II-1), 4 '- [1 - [(tert-butoxycarbonyl) amino] -4- (2,6-difluorophenyl) -4-oxobutyl] -1,1'-biphenyl-4-yl is obtained -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-difluorophenyl) -1- (4 '- {[(dimethylamino) sulfonyl] oxy} -1,1'-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 added to 0 ° C in dichloromethane (600 ml) under an argon atmosphere. At this tempe rature is successively di-tert-butyl dicarbonate (218.25 g, 1.0 mol) and dimethyl aminopyridine (6.10 g, 0.05 mol) added. Then at room temperature Stirred for 48 hours. The reaction mixture is washed successively with 1N HCl (2 × 500 ml), saturated aqueous sodium hydrogen carbonate solution and saturated washed aqueous sodium chloride solution. The organic phase is over Dried 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 separation of the racemate from 4- (5-oxo-2-pyrrolidinyl) phenyltrifluoromethane Sulfonate is carried out by liquid chromatography on a chiral at room temperature stationary polyamide silica gel phase (based on the monomer N-methacryloyl-L- leucine-d-menthylamide, particle size: 10 µm, column dimension: 450 mm × 75 mm) using ethyl acetate as eluent (flow rate: 100 ml / min) and photometric detection (λ = 254 nm). Chromatography becomes a solution prepared from 40 g of the racemate in 1 l of ethyl acetate. 6 g (= 150 ml of the solution) are chromatographed. The eluate fractions are after analytical examination summarized accordingly on enantiomeric purity, largely in a vacuum evaporated, the residues filtered off and after washing with n-heptane dried.

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) -1 -pyrrolidine carboxy lat (VII-2) receives.
HPLC: Log P (pH 2.3) = 3.31.

Example (VII-3)

Analogously to Example (VII-1), tert-butyl-2- (4 '- {[(1,1,2,2,3,3,4,4,4-nonafluorobutyl) sulfonyl] oxy} -1, 1'-biphenyl-4-yl) -5-oxo-1-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} - 1,1'-biphenyl-4-yl) -5-oxo-1-pyrrolidinecarboxylate (VII - 17912 00070 552 001000280000000200012000285911780100040 0002010051395 00004 177934). 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-dimethyl sulfamate (XII-2) (2.77 g, 0.01 mol) in dichloromethane (15 ml) is added dropwise and then  the reaction mixture was stirred at room temperature. HF is under deducted reduced pressure, the residue taken up in dichloromethane and this washed with saturated aqueous sodium bicarbonate solution. The organic phase is dried over magnesium sulfate, filtered and concentrated. The Crude product is further implemented without purification.

3.20 g (59% of theory) of 4 '- (5-oxo-2-pyrrolidinyl) -1,1'-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) -1,1'-biphenyl-4-yl 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)

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-1 sulfonyl fluoride (3.60 g, 0.01 mol) is added dropwise at room temperature and on then stirred for 16 hours at room temperature. The acetonitrile is removed distilled and the residue mixed with water. The precipitate is suctioned off and dried.

4.45 g (99% of theory) of 1,1'-biphenyl-4-yl-1,1,2,2,3,3,4,4,4-nonafluoro-1-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) for 1.5 hours at room temperature stirred and then cooled to 0 ° C. Dimethylsulfamoyl chloride (1.44 g, 0.01 mol) is added dropwise and the reaction mixture for 16 hours at room temperature tur stirred. The precipitate is filtered off and the acetonitrile is removed distilled. The residue is recrystallized from isopropanol.

1.81 g (65% of theory) of 1,1'-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-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] -1,1'-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 the mixture is stirred at room temperature 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 by preparative HPLC (Kromasil 100-5 C18, 250 × 50 mm; CH ₃ CN / H ₂ O, 80:20 v / v) cleaned up.

2.36 g (25% of theory) of 4 '- [(2R) -5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] -1,1' are obtained -biphenyl-4-yl-trifluoromethanesulfonate (I-4) of 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-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] phenol (2.00 g, 7.3 mmol) suspended in toluene (30 ml). Successively, baking soda at room temperature lye (0.7 ml, 45% v / v) and 4- (trifluoromethoxy) benzenesulfonyl chloride (1.90 g, 7.3 mmol) added. The reaction mixture is at 45 ° C for 12 hours stirred. After cooling to room temperature, the phases are separated. The aqueous phase is extracted with ethyl acetate. The combined organi phases are washed with water, dried over sodium sulfate, filtered and constricted. The crude product is chromatographed on silica gel (run medium: toluene / ethyl acetate, 9: 1 v / v) purified.

2.55 g (70% of theory) of 4- [5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] phenyl-4- (trifluoromethoxy) benzenesulfonate (I- 5).
HPLC: Log P (pH 2.3) = 3.83 (98.6% purity)
¹ H-NMR: δ (CD ₃ CN) = 1.75 (1H, m), 2.60 (1H, m), 3.05 (2H, m), 5.26 (1H, m), 7.01 (2H, d), 7.07 (2H , m), 7.31 (2H, d), 7.48 (1H, 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-1,3,2-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, 2M) and PdCl ₂ dppf (56 mg, 0.075 mmol) are dissolved in dimethoxyethane (30 ml) Heated at 60 ° C for 1.5 hours, and then heated at 80 ° C for 1.5 hours 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 crude product is purified by chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate, 9: 1 v / v).

0.62 g (52% of theory) of 4 '- [5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] -1,1'-biphenyl-4 are obtained -yl trifluoromethanesulfonate (I-7).
HPLC: Log P (pH 2.3) = 4.15 (96% purity)
Mp 73-75 ° C.
¹ H NMR: δ (CD ₃ CN) = 1.88 (1H, m), 2.68 (1H, m), 3.06 (2H, m), 5.35 (1H, m), 7.08 (2H, d), 7.47 (5H , m), 7.65 (2H, m), 7.78 (2H, d) ppm.

In addition, a fraction of compound (I-7) of 0.20 g (14% of theory) is also obtained 87% purity.

Production of starting materials for process (C)

4- [5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] phenyl trifluoromethanesulfonate (I-1) (60.80 g, 0.15 mol), bispinacolatodiborone (41.90 g, 0.165 mol ), Potassium acetate (44.20 g, 0.45 mol), PdCl ₂ dppf (3.30 g, 4.50 mmol), diphenylphosphinoferrocene (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 × 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)
¹ H-NMR: δ (CD ₃ CN) = 1.32 (12H, s), 1.78 (1H, m), 2.59 (1H, m), 3.03 (2H, m), 5.30 (1H, m), 7.07 (2H , d), 7.35 (2H, m), 7.46 (1H, m), 7.70 (2H, d) ppm.

The specified logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on one Phase inversion column (C 18). Temperature: 43 ° C.

Eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

The calibration was 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 through linear interpolation between two consecutive Alkanones).

The lambda max values were determined using the UV spectra from 200 nm to 400 nm the maxima of the chromatographic signals determined.  

applications Example A Heliothis virescens test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water containing emulsifier to the desired level Concentration.

Soybean shoots (Glycine max) are dipped into the active ingredient preparation desired concentration treated and populated with Heliothis virescens caterpillars, as long as the leaves are still damp.

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

In this test, e.g. B. the compound (I-5) of the preparation examples good Effectiveness.  

Example B Meloidogyne Test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

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

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

In this test, e.g. B. the compound (I-5) of the preparation examples good Effectiveness.  

Example C Panonychus test, house tribe

Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water containing emulsifier to the desired level Concentration.

Approximately 30 cm high plum trees (Prunus domestica) that are strong of all stages the fruit tree spider mite (Panonychus ulmi) are infected with an active ingredient sprayed fabric 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 were killed.

In this test, e.g. B. the compound (I-2) of the preparation examples good Effectiveness.  

Example D Phaedon larvae test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water containing emulsifier to the desired level Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with larvae of the horseradish leaf beetle (Phaedon cochleariae) occupied 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 there are no beetle larvae were killed.

In this test, e.g. B. the compounds (I-2) and (I-5) of Her position examples good effectiveness.  

Example E Plutella Test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water containing emulsifier to the desired level Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars (Plutella xylostella) as long as 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 are killed were.

In this test, e.g. B. the compound (I-5) of the preparation examples good Effectiveness.  

Example F Spodoptera frugiperda test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water containing emulsifier to the desired level Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation of the desired concentration and treated with caterpillars of the army worm (Spodoptera frugiperda) occupied 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 are killed were.

In this test, e.g. B. the compound (I-5) of the preparation examples good Effectiveness.  

Example G Tetranychus test (OP-resistant / immersion treatment)

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water containing emulsifier to the desired level Concentration.

Bean plants (Phaseolus vulgaris), strongly of all stages of the common Spider mite (Tetranychus urticae) are infested in an active ingredient preparation 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 were killed.

In this test, e.g. B. the compound (I-5) of the preparation examples good Effectiveness.  

Example H Blowfly larva test / development-inhibiting effect Lucilia cuprina (48 h / EH)

Test animals: Lucilia cuprina larvae
Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in one ml of dimethyl sulfoxide. For manufacturing purposes a suitable formulation, the active ingredient solution is diluted with water to 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 placed in beakers with a bottom covered with sand transferred. After a further 12 days, the test tubes and the dolls are removed and counted flies. The development inhibitory effect is the Slip inhibition after 1.5 times the development time of an untreated control in% (ratio of dolls to hatched flies).

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

Example I 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. For manufacturing purposes a suitable formulation, the active ingredient solution is diluted with water to desired concentration.

10 fully soaked nymphs are in the test preparation for 1 minute dipped. The animals are placed on Petri dishes (∅ 9.5 cm) equipped with filter disks transferred 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 the animals have skinned.

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

Claims (12)

1. Δ ¹ -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 phenyl which is monosubstituted or polysubstituted 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. A process for the preparation of compounds of formula (I) according to claim 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 Claim 1,
  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 ¹ -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 Claim 1,
  obtained by using pyrrolines of the formula (IV)
  in which
  R ¹ , R ² , R ³ 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 ¹ , R ² , R ³ and r have the meanings given above and
  G for 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl, 5,5-dimethyl-1,3,2-dioxaborinan-2-yl, 4,4,6-trimethyl -1,3,2-dioxa borinan-2-yl or 1,3,2-benzodioxaborol-2-yl,
  with iodides of the formula (VI)
  in which
  R ⁴ , R ⁵ and s have the meanings given in Claim 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.

3. Δ ¹ -pyrrolines of the formula (Ib)
in which
R ¹ , R ² , R ⁴ , R ⁵ and s have the meanings given in Claim 1. 4. Δ ¹ -pyrrolines of the formula (Ic)
in which
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , r and s have the meanings given in Claim 1. 5. 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 Be. 6. N-Boc lactams of the formula (VII)
in which
R ³ , R ⁴ , R ⁵ , n, r and s have the meanings given in claim 1. 7. Lactams of the formula (IX)
in which
R ³ , R ⁴ , R ⁵ , n, r and s have the meanings given in claim 1. 8. Pesticides, characterized by a content of min least one compound of formula (I) according to claim 1 in addition to extenders and / or surfactants. 9. Use of compounds of formula (I) according to claim 1 for loading pest control. 10. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 on pests and / or their living space. 11. Process for the manufacture of pesticides, thereby ge indicates that compounds of formula (I) according to claim 1 with Extenders and / or surfactants mixed. 12. Use of compounds of the formula (I) according to Claim 1 for the preparation provision of pesticides.