KR100292446B1 - Substituted 1-H-3 arylpyrrolidine-2,4-dione derivatives - Google Patents

Abstract

The present invention relates to novel 1-H-3-arylpyrrolidine-2,4-dione derivatives of the following general formula (I), methods for their preparation and their use as pesticides.

In the above formula,

A and B represent cycles substituted with the carbon atoms to which they are attached,

X represents alkyl, halogen or alkoxy,

Y represents hydrogen, alkyl, halogen, alkoxy or halogenoalkyl,

Z represents alkyl, halogen or alkoxy,

n represents 0, 1, 2 or 3,

G is hydrogen (a) or a group

,

E represents 1 equivalent of metal ion or ammonium ion,

L and M represent oxygen and / or sulfur,

R ¹ may be interrupted by a heteroatom, in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or cycloalkyl, or optionally substituted phenyl, optionally substituted phenylalkyl , Substituted hetaryl, substituted phenoxyalkyl or substituted hetaryloxyalkyl,

R ² represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, or in each case optionally substituted phenyl or benzyl,

R ³ , R ⁴ and R ⁵ independently of one another in each case are optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio, or in each case optionally substituted phenyl , Phenoxy or phenylthio,

R ⁶ and R ⁷ independently of one another represent hydrogen, in each case optionally halogen-substituted alkyl, alkenyl, alkoxy or alkoxyalkyl, or optionally substituted phenyl or optionally substituted benzyl, or with adjacent N-atoms Or cycles which are optionally blocked by sulfur.

Description

[Name of invention]

Substituted 1-H-3-arylpyrrolidine-2,4-dione derivatives

Detailed description of the invention

The present invention relates to 1-H-3-arylpyrrolidine-2,4-dione derivatives, a number of methods for their preparation and their use as pesticides (especially pesticides and acaricides) and herbicides.

It is already known that 3-acyl-pyrrolidine-2,4-dione has pharmaceutical properties (S. Suzuki et al. Chem. Pharm. Bull 15 1120 (1967)). N-phenyl-pyrrolidine-2,4-dione is also known. R. Schmierer and H. It was synthesized by H. Midenberger (Liebigs Ann. Chem. 1985 1095). However, the biological activity of these compounds is unknown.

EP-A-0,262,399 describes compounds 3-arylpyrrolidine-2,4-dione with similar structure, but does not mention whether they have herbicidal, pesticidal or acaricide activity. Unsubstituted bicyclic 3-arylpyrrolidine-2,4-dione derivatives (see EP-A 355 599 and EP 415,211) and substituted monocyclic 3-arylpyrrolidine-2,4-dione derivatives (Cf. EP-A 377,893, EP 442,077 and EP 497 127) are already known and they have herbicidal, insecticidal or acaricide activity.

Polycyclic 3-arylpyrrolidine-2,4-dione derivatives (see EP 442 073), substituted bicyclic 3-arylpyrrolidine-2,4-dione as well as 1-H-3-aryl Pyrrolidine-2,4-dione derivatives (see also EP 456 063, EP 521 334, EP 501 129) are also known.

It has now been found that the novel substituted spirocyclic 1-H-3-arylpyrrolidine-2,4-dione derivatives of general formula (I)

In the above formula,

A and B represent cycles in which the carbon atoms to which they are attached are substituted together,

X represents alkyl, halogen or alkoxy,

Y represents hydrogen, alkyl, halogen, alkoxy or halogenoalkyl,

Z represents alkyl, halogen or alkoxy,

n represents 0, 1, 2 or 3,

G is hydrogen (a) or a group

,

E represents a metal ion equivalent or ammonium ion,

L and M represent oxygen and / or sulfur,

R ¹ may be interrupted by a heteroatom and in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or cycloalkyl, or optionally substituted phenyl, optionally substituted phenylalkyl, Substituted hetaryl, substituted phenoxyalkyl or substituted hetaryloxyalkyl,

R ² represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, or in each case optionally substituted phenyl or benzyl,

R ³ , R ⁴ and R ⁵ independently of one another in each case are optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio, or in each case optionally substituted phenyl , Phenoxy or phenylthio,

R ⁶ and R ⁷ independently of one another represent hydrogen, in each case optionally halogen-substituted alkyl, alkenyl, alkoxy or alkoxyalkyl, or optionally substituted phenyl or optionally substituted benzyl, or with adjacent N-atoms Or cycles which are optionally blocked by sulfur.

Considering the various meanings (a), (b), (c), (d), (e) and (f) of the G group of general formula (I), the following main structures (Ia) to (Ig) Result.

Wherein A, B, E, L, M, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and n have the meanings mentioned above.

Due to one or more chiral centers, the compounds of general formulas (Ia) to (Ig) are generally obtained in the form of steric mixtures which can be divided by conventional methods as required. They can be used in pure diastereomer or enantiomeric forms as well as diastereomeric mixtures thereof. Hereinafter, the present specification will always discuss the compounds of general formulas (Ia) to (Ig), even if understood to mean pure compounds as well as mixtures containing various ratios of isomers, enantiomers and stereoisomeric compounds.

It has also been found according to the invention that the novel substituted 1-H-3-arylpyrrolidine-2,4-dione derivatives of general formula (I) are obtained by one of the following methods.

(A) The following general formula (Ia) 1-H-3-arylpyrrolidine-2,4-dione derivatives or enols thereof are in the presence of a diluent and base with respect to the N-acylamino acid ester of the general formula (II) Obtained by carrying out an intramolecular condensation reaction in the presence of

(B) The compound of the following general formula (Ib) is a compound of the following general formula (Ia),

α) reacting with an acid halide of the general formula (III), if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid binder,

β) is obtained by reacting with a carboxylic anhydride of the general formula (IV) below, in the presence of a diluent if appropriate and in the presence of an acid binder, or

(C) The compound of the general formula (Ic-1) is a chloroformic acid ester of the general formula (V) wherein the compound of the general formula (Ia) is suitably in the presence of a diluent and, if appropriate, in the presence of an acid binder, or Obtained by reacting with a chloroformic acid thioester, or

(D) The compound of the following general formula (Ic-2) is a compound of the following general formula (Ia),

α) reacting with a chloromonothioformic acid ester or chlorodithioformic acid ester of the general formula (VI) in the presence of a diluent if appropriate and in the presence of an acid binder, or

β) is obtained by reacting with carbon disulfide and subsequently an alkyl halide of the general formula (iii), optionally in the presence of a diluent or in the presence of an acid binder,

(E) The compound of formula (Id) is reacted with a sulfonyl chloride of formula (VII) by reacting a compound of formula (Ia) with, in the presence of a diluent if appropriate and in the presence of an acid binder, Obtained, or

(F) The compound of the general formula (Ie) may contain 1-H-3-arylpyrrolidine-2,4-dione of the general formula (Ia) or an enol thereof, optionally in the presence of a diluent or Obtained by reacting with a phosphorus compound of the following general formula in the presence of a binder, or

(G) The compounds of the following general formula (If) are obtained by reacting the compounds of the following general formula (Ia) with the metal hydroxides or amines of the following general formulas (VII) and (XI), if appropriate in the presence of a diluent.

In the above formula,

A, B, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , L and n have the meanings mentioned above, R ⁸ represents alkyl,

Ha1 represents halogen, in particular chlorine or bromine, in formulas (III) and (iii), chlorine, bromine or iodine in formula (iii),

M represents oxygen or sulfur,

E represents a metal ion equivalent or ammonium ion,

Me represents monovalent or divalent metal ion,

s and t represent the number of 1 or 2,

R ⁵ , R ⁶ and R ⁷ in formula (XI) independently of one another represent hydrogen or alkyl.

In addition, according to the present invention

(H) The compound of the following general formula (Ig) is a compound of the following general formula (Ia),

α) reacting with a compound of the general formula (XII), if appropriate, in the presence of a diluent and, if appropriate, in the presence of a catalyst, or

β) It was further found that it is obtained by reacting with carbamoyl chloride or thiocarbamoyl chloride of the general formula (XIII) in the presence of a diluent if appropriate and in the presence of an acid binder if appropriate.

Wherein A, B, L, X, Y, Z, R ⁶ , R ⁷ and n have the meanings mentioned above.

It has also been found in accordance with the invention that the novel 1-H-3-arylpyrrolidine-2,4-dione derivatives of general formula (I) exhibit excellent pesticidal, acaricide and herbicidal activity.

The following meanings apply to the general formula of the invention:

A, B and the carbon atoms to which they are attached preferably represent a C ₃ -C ₆ -spirocycle which may be mono- or polysubstituted by alkyl, cycloalkyl, haloalkyl, alkoxy, thioalkyl, halogen or phenyl,

By alkylenediyl groups optionally interrupted by one or two oxygen and / or sulfur atoms, or by alkylenedioxyl or alkylenedithioyl groups, wherein these groups are further 5- to 5 with the carbon atoms to which they are attached Form an 8-membered spirocycle) or a C ₃ -C ₆ spirocycle,

A, B and the carbon atoms to which they are attached represent a saturated or unsaturated carbocycle in which two substituents A and B, together with the C-atom to which they are attached, are optionally substituted by alkyl, alkoxy or halogen and optionally blocked by an oxygen or sulfur atom. C ₃ -C ₆ -spirocycle).

A, B and the carbon atoms to which they are attached are particularly preferably C ₁ -C ₆ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₃ -haloalkyl, C ₁ -C ₄ -alkoxy, C _1- C ₃ -C ₆ -spirocycle which may be mono- or polysubstituted by C ₄ -thioalkyl, fluorine, chlorine or phenyl,

By alkylenediyl groups which are optionally interrupted by one or two oxygen or sulfur atoms, or by alkylenedioxyl groups or alkylenedithioxyl groups, wherein these groups together with additional 5- to 7- of the carbon atoms to which they are attached C ₃ -C ₆ -spirocycle substituted by

A, B and the carbon atom to which they are attached are substituted with two substituents A and B by alkyl (C ₁ -C ₃ ), alkoxy (C ₁ -C ₃ ) or fluorine, chlorine or bromine together with the C-atom to which they are attached And C ₃ -C ₆ -spirocycle which represents saturated or unsaturated carbocycles which are optionally blocked by oxygen or sulfur atoms.

A, B and the carbon atoms to which they are attached are very particularly preferably methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, secondary-butyl, t-butyl, cyclohexyl, trifluoromethyl, methoxy, C ₃ -C ₆ which may be at least mono- or polysubstituted by oxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary-butoxy, t-butoxy, methylthio, fluorine, chlorine or phenyl Indicates spirocycle,

By alkylenediyl groups, optionally interrupted by oxygen or sulfur atoms, or by alkylenedioxyl groups, where these groups together with the carbon atoms to which they are attached form an additional 5- to 7-membered spirocycle. Or C ₃ -C ₆ -spirocycle substituted by

A, B and the carbon atom to which they are attached The C represents a saturated or unsaturated 5-or 6-membered cycle in which optionally blocked by an oxygen or sulfur with the two substituents A and B and the carbon atom to which they are bonded ₃ -C ₆ - Spirocycle.

X preferably represents C ₁ -C ₆ -alkyl, halogen or C ₁ -C ₆ -alkoxy.

X particularly preferably represents C ₁ -C ₄ -alkyl, halogen or C ₁ -C ₄ -alkoxy.

X very particularly preferably represents methyl, ethyl, propyl, 2-propyl, fluorine, chlorine, bromine, methoxy or ethoxy.

Y preferably represents hydrogen, C ₁ -C ₆ -alkyl, halogen, C ₁ -C ₆ -alkoxy or C ₁ -C ₃ -halogenoalkyl.

Y particularly preferably represents hydrogen, C ₁ -C ₄ -alkyl, halogen, C ₁ -C ₄ -alkoxy or C ₁ -C ₂ -halogenoalkyl.

Y very particularly preferably represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl.

Z preferably represents C ₁ -C ₆ -alkyl, halogen or C ₁ -C ₆ -alkoxy.

Z particularly preferably represents C ₁ -C ₄ -alkyl, halogen or C ₁ -C ₄ -alkoxy.

Z very particularly preferably represents methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, fluorine, chlorine, bromine, methoxy or ethoxy.

n preferably represents an integer of 0 to 3.

n particularly preferably represents 0.1 or 2;

n very particularly preferably represents 0 or 1;

G is preferably hydrogen (a) or a group

,

From here,

E represents a metal ion equivalent or ammonium ion,

L and M in each case represent oxygen and / or sulfur,

R ¹ is optionally halogen-substituted C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₁ -C ₈ -alkoxy-C ₂ in each case which may be interrupted by oxygen and / or sulfur atoms -C ₈ -alkyl, C ₁ -C ₈ -alkylthio-C ₂ -C ₈ -alkyl, C ₁ -C ₈ -polyalkoxy-C ₂ -C ₈ -alkyl or cycloalkyl having 3 to 8 reducers Or

Phenyl optionally substituted by halogen, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl or C ₁ -C ₆ -halogenoalkoxy, or

Phenyl-C ₁ -C ₆ -optionally substituted by halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl or C ₁ -C ₆ -halogenoalkoxy Hetaryl, which is alkyl, optionally substituted by halogen and / or C ₁ -C ₆ -alkyl, or

Phenoxy-C ₁ -C ₆ -alkyl optionally substituted by halogen and C ₁ -C ₆ -alkyl, or

Halogen, amino and C ₁ -C ₆ - alkyl optionally substituted by a hat-aryloxy -C ₁ -C ₆ - represents alkyl,

R ² is in each case optionally halogen-substituted C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ -alkenyl, C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl or C ₁ -C ₈ -poly Alkoxy-C ₂ -C ₈ -alkyl, or in each case optionally substituted by halogen, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy or C ₁ -C ₆ -halogenoalkyl Phenyl or benzyl,

R ³ , R ⁴ and R ⁵ , independently of one another, are in each case optionally halogen-substituted C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkylamino, di (C _1- C ₈ ) -alkylamino, C ₁ -C ₈ -alkylthio, C ₂ -C ₃ -alkenylthio or C ₃ -C ₇ -cycloalkylthio, or in each case halogen, nitro, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -halogenoalkylthio, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -Phenyl, phenoxy or phenylthio optionally substituted by halogenoalkyl,

R ⁶ and R ⁷ independently represent hydrogen or, in each case, optionally halogen-substituted C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₈ -alkoxy, C _3- C ₈ -alkenyl or C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl, or

Halogen, C ₁ -C ₈ - halogenoalkyl, C ₁ -C ₈ - alkyl or C ₁ -C ₈ -, or represents a phenyl optionally substituted by alkoxy,

Benzyl optionally substituted by halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -halogenoalkyl or C ₁ -C ₈ -alkoxy, or

R ⁶ and R ⁷ together represent C ₃ -C ₆ -alkylene which is optionally interrupted by oxygen or sulfur,

G is particularly preferably hydrogen (a) or a group

,

From here,

E represents a metal ion equivalent or ammonium ion,

L and M in each case represent oxygen and / or sulfur,

R ¹ may be interrupted by 1 to 2 oxygen and / or sulfur atoms and in each case is optionally halogen-substituted C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C _6- Alkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₁₆ -alkylthio-C ₂ -C ₆ -alkyl, C ₁ -C ₆ -polyalkoxy-C ₂ -C ₆ -alkyl or 3 to 7 reducers Has cycloalkyl, or

Phenyl optionally substituted by halogen, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy, or

Phenyl-C ₁ -C ₄ -optionally substituted by halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy Alkyl or

Hetaryl optionally substituted by fluorine, chlorine, bromine and / or C ₁ -C ₄ -alkyl, or

Phenoxy-C ₁ -C ₅ -alkyl optionally substituted by fluorine, chlorine, bromine and C ₁ -C ₄ -alkyl, or optionally by fluorine, chlorine, bromine, amino and C ₁ -C ₄ -alkyl substituted het aryloxy -C ₁ -C ₅ - represents alkyl,

R ² in each case is optionally halogen-substituted C ₁ -C ₁₆ -alkyl, C ₃ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl or C ₁ -C _6- Polyalkoxy-C ₂ -C ₆ -alkyl, or

In each case phenyl or benzyl optionally substituted by halogen, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₃ -alkoxy or C ₁ -C ₃ -halogenoalkyl,

R ³ , R ⁴ and R ⁵ independently of one another in each occurrence are optionally substituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylamino, di (C _1- C ₆ ) -alkylamino, C ₁ -C ₆ -alkylthio, C ₃ -C ₄ -alkenylthio or C ₃ -C ₆ -cycloalkylthio, or

In each case fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -halogenoalkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -halogenoalkyl Phenyl, phenoxy or phenylthio optionally substituted by thio, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -halogenoalkyl,

R ⁶ and R ⁷ independently represent hydrogen or, in each case, optionally halogen-substituted C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, C _3- C ₆ -alkenyl or C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, or

Halogen, C ₁ -C ₅ - halogenoalkyl, C ₁ -C ₅ - alkyl or C ₁ -C ₅ - or represents a phenyl optionally substituted by alkoxy,

Benzyl optionally substituted by halogen, C ₁ -C ₅ -alkyl, C ₁ -C ₅ -halogenoalkyl or C ₁ -C ₅ -alkoxy, or

R ⁶ and R ⁷ together represent a C ₃ -C ₆ -alkylene ring which is optionally interrupted by oxygen or sulfur,

G is particularly preferably hydrogen (a) or a group

,

From here,

E represents a metal ion equivalent or ammonium ion,

L and M represent oxygen and / or sulfur,

R ¹ may be interrupted by 1 to 2 oxygen and / or sulfur atoms and in each case is optionally fluorine- or chlorine-substituted C ₁ -C ₁₄ -alkyl, C ₃ -C ₁₄ -alkenyl, C _1- C ₄ -alkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₄ -alkylthio-C ₂ -C ₆ -alkyl, C ₁ -C ₄ -polyalkoxy-C ₂ -C ₄ -alkyl or 3 to 6 Cycloalkyl having 3 ring atoms, or

Phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or nitro, or

Phenyl C ₁ -C ₃ -alkyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy, or

In each case represent furanoyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl optionally substituted by fluorine, chlorine, bromine, methyl or ethyl,

Phenoxy-C ₁ -C ₄ -alkyl optionally substituted by fluorine, chlorine, methyl or ethyl, or

In each case pyridyloxy-C ₁ -C ₄ -alkyl, pyrimidyloxy-C ₁ -C ₄ -alkyl or thiazolyloxy-C ₁ -C ₄ optionally substituted by fluorine, chlorine, amino, methyl or ethyl -Alkyl,

R ² in each case is optionally substituted fluorine or chlorine substituted C ₁ -C ₁₄ -alkyl, C ₃ -C ₁₄ -alkenyl, C ₁ -C ₄ -alkoxy-C ₂ -C ₆ -alkyl or C ₁ -C ₄ -polyalkoxy-C ₂ -C ₆ -alkyl, or

In each case phenyl or benzyl optionally substituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl,

R ³ , R ⁴ and R ⁵ are independently of each other C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, di-, optionally substituted with fluorine or chlorine in each case Or (C ₁ -C ₄ ) -alkylamino or C ₁ -C ₄ -alkylthio, or

In each case fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₂ -alkoxy, C ₁ -C ₄ -fluoroalkoxy, C ₁ -C ₂ -alkylthio, C ₁ -C ₂ -fluoroalkyl Phenyl, phenoxy or phenylthio optionally substituted by thio or C ₁ -C ₃ -alkyl,

R ⁶ and R ⁷ independently of one another represent hydrogen, or in each case are C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, optionally substituted by fluorine, chlorine or bromine, C ₁ -C _4- Alkoxy, C ₃ -C ₄ -alkenyl or C ₁ -C ₄ -alkoxy-C ₂ -C ₄ -alkyl, or

Phenyl optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,

Benzyl optionally substituted by fluorine, chlorine, bromine C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl or C ₁ -C ₄ -alkoxy,

R ⁶ and R ⁷ together represent a C ₄ -C ₆ -alkylene ring optionally substituted by oxygen or sulfur.

In addition to the compounds mentioned in the preparation examples, compounds of the general formula (la) may be mentioned individually:

In addition to the compounds mentioned in the preparation examples, compounds of the general formula (Ib) may be mentioned individually.

In addition to the compounds mentioned in the preparation examples, compounds of the general formula (Ic) may be mentioned individually:

According to method (A), when using ethyl N-2,4-dichlorophenylacetyl-1-amino-4-ethylcyclohexane-carboxylate, the process of the process according to the invention can be represented by the following scheme :

3- (2,4,6-trimethylphenyl) -5,5- (3-methyl) -pentamethylenepyrrolidine-2,4-dione and pivaloyl chloride according to Method (B) (Method α) When using as starting material, the process of the process according to the invention can be represented by the following scheme:

According to Method (B) (Method β), start 3- (2,4,6-trimethylphenyl) -5,5- (tetramethyl) -dimethylene-pyrrolidine-2,4-dione and acetic anhydride When used as a substance, the process of the process according to the invention can be represented by the following scheme:

According to method (C), start 3- (2,4,6-trimethylphenyl) -5,5- (3-methyl) -tetramethylenepyrrolidine-2,4-dione and ethoxyethyl chloroformate When used as a compound, the process of the process according to the invention can be represented by the following scheme:

3- (2,4,6-trimethylphenyl) -5,5- (4,4-dimethyl) -pentamethylene-pyrrolidine-2,4-dione and methyl chloromonothiophore according to method (Dα) In the case of using mate as starting material, the process of the process according to the invention can be represented by the following scheme:

3- (2,4,6-trimethylphenyl) -5,5- (4-methoxy) -pentamethylenepyrrolidine-2,4-dione, carbon disulfide and methyl iodide, according to method (Dβ) When using as starting material, the process of the process according to the invention can be represented by the following scheme:

According to method (E), 3- (2,4,6-trimethylphenyl) -5,5- (2-methyl) -pentamethylene-pyrrolidine-2,4-dione and methanesulfonyl chloride are used as starting materials. When used as, the process of the process according to the invention can be represented by the following scheme:

According to method (F), 3- (2,4-dimethylphenyl) -5,5- (3-methyl) -pentamethylenepyrrolidine-2,4-dione and 2,2,2-trifluoroethyl In the case of using methanethiochlorophosphonate as starting material, the process of the process according to the invention can be represented by the following scheme:

According to method (G), 3- (2,4,6-trimethylphenyl) -5,5- (4-t-butyl) -pentamethylene-pyrrolidine-2,4-dione and NaOH as components When used, the procedure of the process according to the invention can be represented by the following scheme:

According to method (Hα), 3- (2,4,6-trimethylphenyl) -5,5- (2-methyl) -pentamethylenepyrrolidine-2,4-dione and ethyl isocyanate are used as starting materials In the case, the procedure of the process according to the invention can be represented by the following scheme:

According to method (Hβ), 3- (2,4,6-trimethylphenyl) -5,5- (3,4-dimethyl) -pentamethylene-pyrrolidine-2,4-dione and dimethylcarbamoyl chloride When used as starting material, the process of the process according to the invention can be represented by the following scheme:

The compounds of the following general formula (II) which are required as starting materials for process (A) according to the invention are novel.

Wherein A, B, X, Y, Z, n and R ⁸ have the meanings mentioned above.

Acyl-amino acid derivatives of the general formula (II) can be used, for example, by acylating amino acid derivatives of the general formula (XIV) with phenylacetyl halides of the general formula (XV) (see Chem. Reviews 52, 237-). 416 (1953); Bhattacharya, Indien J. Chem 6, 341-5, 1968), obtained by esterifying acylamino acids of the general formula (IIa) (Chem. Ind. (London) 1568 (1968)) do.

In the above formula,

R ^a, represents hydrogen (XIVa) or alkyl (XIVb),

Hal represents chlorine or bromine,

R ⁹ represents hydrogen,

A, B, X, Y, Z and n have the meanings mentioned above.

Substituted cyclohexylaminocarboxylic acids of general formula (XIVa) can generally be obtained by Bucherer Bergs reaction or Strecker synthesis, which in each case are obtained in various isomeric forms. For example, the Bucher-Bugs reaction condition mainly provides isomers in which the R and carbamoyl groups are horizontally located (hereinafter referred to as β above), while the streaker synthesis conditions are primarily located in the R and amino groups horizontally. Isomers (hereinafter referred to as part or more) are provided.

(L. Munday, J. Chem. Soc. 4372 (1961): J. T. Eward, C. Jitrangeri, Can. J. Chem. 53, 3339 (1975).

In addition, the starting material of the following general formula (II) used in the above-mentioned method (A) was reacted with the aminonitrile of the following general formula (XVI) with the phenylacetyl halide of the following general formula (XV). ), And then the obtained compound of general formula (XVII) can be prepared by alcoholic decomposition in sulfuric acid.

In the above formula,

A, B, X, Y, Z, n and R ⁸ have the aforementioned meanings,

Hal represents chlorine or bromine.

Compounds of general formula (XVII) are also novel.

In addition to the intermediates mentioned in the preparation examples, compounds of the following general formula (II) may be mentioned by way of example, but are not limited to these.

Methyl N- (2,4-dichlorophenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylate,

Methyl N- (2,4-dichlorophenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylate,

Methyl N- (2,4-dichlorophenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylate,

Methyl N- (2,4-dichlorophenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylate,

Methyl N- (2,4-dichlorophenylacetyl) -1-amino-4-ethyl-cyclohexanecarboxylate,

Methyl N- (2,4-dichlorophenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylate,

Methyl N- (2,4-dichlorophenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylate,

Methyl N- (2,4-dichlorophenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylate,

Methyl N- (2,6-dichlorophenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylate,

Methyl N- (2,6-dichlorophenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylate,

Methyl N- (2,6-dichlorophenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylate,

Methyl N- (2,6-dichlorophenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylate,

Methyl N- (2,6-dichlorophenylacetyl) -1-amino-4-ethyl-cyclohexanecarboxylate,

Methyl N- (2,6-dichlorophenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylate,

Methyl N- (2,6-dichlorophenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylate,

Methyl N- (2,6-dichlorophenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylate,

Methyl N- (2-chloro-6-fluorophenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylate,

Methyl N- (2-chloro-6-fluorophenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylate,

Methyl N- (2-chloro-6-fluorophenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylate,

Methyl N- (2-chloro-6-fluorophenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylate,

Methyl N- (2-chloro-6-fluorophenylacetyl) -1-amino-4-ethyl-cyclohexanecarboxylate,

Methyl N- (2-chloro-6-fluorophenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylate,

Methyl N- (2-chloro-6-fluorophenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylate,

Methyl N- (2-chloro-6-fluorophenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylate,

Methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylate,

Methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylate,

Methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylate,

Methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylate,

Methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-4-ethyl-cyclohexanecarboxylate,

Methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylate,

Methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylate,

Methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylate,

Methyl N- (2,4-dimethylphenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylate,

Methyl N- (2,4-dimethylphenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylate,

Methyl N- (2,4-dimethylphenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylate,

Methyl N- (2,4-dimethylphenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylate,

Methyl N- (2,4-dimethylphenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylate,

Methyl N- (2,4-dimethylphenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylate,

Methyl N- (2,4-dimethylphenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylate,

In addition to the intermediates mentioned in the preparation examples, the following compounds of the general formula (IIa) may be mentioned by way of example, but are not limited to these.

N- (2,4-dichlorophenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylic acid,

N- (2,4-dichlorophenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylic acid,

N- (2,4-dichlorophenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylic acid,

N- (2,4-dichlorophenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylic acid,

N- (2,4-dichlorophenylacetyl) -1-amino-4-ethyl-cyclohexanecarboxylic acid,

N- (2,4-dichlorophenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylic acid,

N- (2,4-dichlorophenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylic acid,

N- (2,4-dichlorophenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylic acid,

N- (2,6-dichlorophenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylic acid,

N- (2,6-dichlorophenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylic acid,

N- (2,6-dichlorophenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylic acid,

N- (2,6-dichlorophenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylic acid,

N- (2,6-dichlorophenylacetyl) -1-amino-4-ethyl-cyclohexanecarboxylic acid,

N- (2,6-dichlorophenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylic acid,

N- (2,6-dichlorophenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylic acid,

N- (2,6-dichlorophenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylic acid,

N- (2-chloro-6-fluorophenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylic acid,

N- (2-chloro-6-fluorophenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylic acid,

N- (2-chloro-6-fluorophenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylic acid,

N- (2-chloro-6-fluorophenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylic acid,

N- (2-Chloro-6-fluorophenylacetyl) -1-amino-4-ethyl-cyclohexanecarboxylic acid,

N- (2-chloro-6-fluorophenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylic acid,

N- (2-chloro-6-fluorophenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylic acid,

N- (2-chloro-6-fluorophenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylic acid,

N- (2,4,6-trimethylphenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylic acid,

N- (2,4,6-trimethylphenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylic acid,

N- (2,4,6-trimethylphenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylic acid,

N- (2,4,6-trimethylphenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylic acid,

N- (2,4,6-trimethylphenylacetyl) -1-amino-4-ethyl-cyclohexanecarboxylic acid,

N- (2,4,6-trimethylphenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylic acid,

N- (2,4,6-trimethylphenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylic acid,

N- (2,4,6-trimethylphenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylic acid,

N- (2,4-dimethylphenylacetyl) -1-amino-2-methyl-cyclohexanecarboxylic acid,

N- (2,4-dimethylphenylacetyl) -1-amino-3-methyl-cyclohexanecarboxylic acid

N- (2,4-dimethylphenylacetyl) -1-amino-4-methyl-cyclohexanecarboxylic acid,

N- (2,4-dimethylphenylacetyl) -1-amino-3,4-dimethyl-cyclohexanecarboxylic acid,

N- (2,4-dimethylphenylacetyl) -1-amino-4-ethyl-cyclohexanecarboxylic acid,

N- (2,4-dimethylphenylacetyl) -1-amino-4-isopropyl-cyclohexanecarboxylic acid,

N- (2,4-dimethylphenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylic acid,

N- (2,4-dimethylphenylacetyl) -1-amino-4-phenyl-cyclohexanecarboxylic acid,

Compounds of formula (IIa) are formulated, for example, by the Schötten-Baumann method (see Organikum [Laboratory Practical in Organic Chemistry, 9th Edition, 446 (1970) VEB Deutscher Verlag der Wissenschaften, Berlin) From phenylacetyl halide of (XV) and amino acid of general formula (XIVa).

Acid halides of the general formula (III), which are further needed as starting materials for carrying out the processes (B), (C), (D), (E), (F), (G) and (H) according to the invention, Carboxylic anhydride of formula (IV), chloroformic acid ester or chloroformic acid thioester of formula (V), chloromonothioformic acid ester or chlorodithioformic acid ester of formula (VI), alkyl halide of formula (VII) , Sulfonyl chloride of formula (VIII), phosphorus compound of formula (IX) and metal hydroxide or amine of formula (X) and (XI) and isocyanate or carbamoyl chloride of formula (XIII) are generally organic Or inorganic chemistry.

Method (A) is carried out to conduct intermolecular condensation reactions in the presence of a base to a compound of formula II, wherein A, B, X, Y, Z, n and R ⁸ have the meanings mentioned above. It features.

Diluents which can be used in process (A) according to the invention are all inert organic solvents. These preferably include hydrocarbons such as toluene and xylene, dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and ethers such as diglycol dimethyl ether, dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl Polar solvents such as pyrrolidone and also alcohols such as methanol, ethanol, propanol, isopropanol, butanol, iso-butanol and t-butanol can be used.

Bases (deprotonating agents) that can be used to carry out process (A) according to the invention are all conventional proton acceptors. These preferably include alkali metal oxides such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides and alkaline earth metal carbonates. These may also be used, all of which are also for example triethylbenzylammonium chloride, tetrabutylammonium bromide, adogen 464 (= methyltrialkyl (C ₈ -C ₁₀ ) ammonium chloride) or TDA 1 (= tris- (methoxy Ethoxyethyl) amine). Alkali metals such as sodium or potassium can also be used. In addition, alkali metal amides such as sodium amide, sodium hydride and calcium hydride, alkali metal hydrides, alkali metal hydrides and alkali metal hydrides, and alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium t-butylate Can also be used.

In carrying out process (A) according to the invention, the reaction temperature can be varied within a wide range. In general, the reaction is carried out at a temperature of 0 to 25 ° C, preferably 50 to 150 ° C.

Process (A) according to the invention is generally carried out at atmospheric pressure.

In carrying out process (A) according to the invention, the reactants of the general formula (II) and the deprotonated base are generally used in approximately two-fold equimolar amounts. However, it is possible to use one component or other components in large amounts (up to 3 moles).

Method (Bα) is characterized by reacting a compound of formula (Ia) with a carboxylic acid halide of formula (III).

When using acid halides, the diluents which can be used in the process (Bα) according to the invention are all solvents which are inert to these compounds. These are preferably hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, halogenohydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, acetone and methyl isopropyl ketone Ethers such as ketones, diethyl ether, tetrahydrofuran and dioxane, further carboxylates such as ethyl acetate, and also strong polar solvents such as dimethyl sulfoxide and sulfolane can be used. If the acid halide is sufficiently stable against hydrolysis, the reaction can also be carried out in the presence of water.

When using the corresponding carboxylic acid halides, the acid binders suitable for the reaction of the process (Bα) according to the invention are all conventional acid acceptors. These are preferably triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig base and N, N-dimethylaniline Tertiary amines such as, alkaline earth metal oxides such as magnesium oxide and calcium oxide, alkali metal carbonates and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides such as sodium hydroxide and potassium hydroxide .

In the process (Bα) according to the invention, the reaction temperature can also be varied within a wide range when using carboxylic acid halides. In general, the reaction is carried out at a temperature of -20 to +150 ° C, preferably 0 to 100 ° C.

In carrying out the process (Bα) according to the invention, the starting materials of the general formula (Ia) and the carboxylic acid halides of the general formula (III) are generally used in approximately equivalent amounts. However, it is also possible to use carboxylic acid halides in large amounts (up to 5 moles). Post-treatment is carried out in a conventional manner.

Process (Bβ) is characterized by reacting a compound of formula (Ia) with a carboxylic anhydride of formula (IV).

In the case of using carboxylic anhydride as the reactant of general formula (IV) in the process (Bβ) according to the present invention, diluents which can be preferably used are suitable diluents when using acid halides. Apart from this, carboxylic anhydrides used in excess also act simultaneously as diluents.

In carrying out the process (Bα) according to the invention, the reaction temperature can also be varied within a wide range when using carboxylic acid anhydride. In general, the reaction is carried out at a temperature of -20 to +150 ° C, preferably 0 to 100 ° C.

In carrying out the process (Bβ) according to the invention, the starting materials of the general formula (Ia) and the carboxylic anhydrides of the general formula (IV) are generally used in approximately equivalent amounts. However, it is also possible to use carboxylic acid halides in large amounts (up to 5 moles). Post-treatment is carried out in a conventional manner.

In general, the resulting carboxylic acid as well as the diluent and excess carboxylic anhydride are removed by distillation or by washing with an organic solvent or water.

Process (C) is characterized by reacting a compound of formula (Ia) with a chloroformic ester or chloroformic thioester of formula (V).

In the case of using the corresponding chloroformic ester or chloroformic thioester, suitable acid binders for the reaction of process (C) according to the invention are all conventional acid acceptors. These are preferably triethylamine, pyridine, DABCO, DBU, DBA, Hunig base and tertiary amines such as N, N-dimethylaniline, alkaline earth metal oxides such as magnesium oxide and calcium oxide, sodium carbonate, Alkali metal carbonates and alkaline earth metal carbonates such as potassium carbonate and calcium carbonate, and also alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used.

In the case of using chloroformic acid esters or chloroformic acid thioesters, the diluents usable in the process (C) according to the invention are all solvents which are inert to these compounds. These are preferably ketones such as hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, halogenohydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, acetone and methyl isopropyl ketone Ethers such as diethylether, tetrahydrofuran and dioxane, further carboxylates such as ethyl acetate, and also strong polar solvents such as dimethyl sulfoxide and sulfolane can be used.

When chloroformic acid esters or chloroformic acid thioesters are used as carboxylic acid derivatives of the general formula (V), the reaction temperature for carrying out the process (C) according to the present invention can be varied within a wide range. When the reaction is carried out in the presence of a diluent and an acid binder, the reaction temperature is generally -20 to + 100 ° C, preferably 0 to 50 ° C.

Process (C) according to the invention is generally carried out under atmospheric pressure.

When carrying out process (C) according to the invention, the starting materials of the general formula (Ia) and the corresponding chloroformic esters or chloroformic thioesters of the general formula (V) are generally used in approximately equivalent amounts. However, it is also possible to use one component or another component in large amounts (up to 2 moles). Post-treatment is then carried out in a conventional manner. In general, the precipitated salt is removed and the remaining reaction mixture is concentrated by stripping the diluent.

In the preparation method (D), about 1 mole of chloromonothioformic acid ester or chlorodithioformic acid of about 1 mole at 0 to 120 ° C, preferably 20 to 60 ° C, per mole of the starting compound of general formula (Ia) React the ester.

Suitable diluents which are optionally added are all inert polar organic solvents such as ethers, amides, sulfones and sulfoxides.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide and dimethyl sulfide are preferably used.

In a preferred embodiment, when the strong deprotonating agent, for example sodium hydride or potassium tert-butylate, is added to prepare the enolate salt of formula (la), the acid-binder may not be added. .

When using acid binders, suitable materials are conventional inorganic or organic bases, examples of which may be mentioned sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

The reaction can be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out by conventional methods.

In the preparation method (Dβ), an equimolar amount or excess carbon disulfide per mole of starting material of the general formula (Ia) is used. This method is preferably carried out at temperatures of 0 to 50 ° C, and especially 20 to 30 ° C.

Sometimes it is advantageous to prepare the corresponding salts first from the compound of general formula (la) by adding a deprotonating agent (such as, for example, potassium tert-butylate or sodium hydride). Compound (Ia) is reacted with carbon disulphide after stirring for several hours, for example at room temperature, until the formation of the intermediate is complete.

The product is preferably further reacted with alkyl halides of the general formula (VII) at 0 to 70 ° C, in particular 20 to 50 ° C. In this method at least equimolar amounts of alkyl halides are used.

The reaction is carried out at atmospheric or elevated pressure, preferably at atmospheric pressure.

In addition, the post-treatment is carried out by conventional methods.

In the preparation method (E), about 1 mole of sulfonyl chloride of general formula (III) is reacted at -20 to 150 캜, preferably 11 to 70 캜, per mol of the starting compound of formula (Ia).

Suitable diluents which are optionally added are all inert polar organic solvents such as ethers, amides, nitriles, sulfones, sulfoxides or halogenated hydrocarbons such as methylene chloride.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethyl sulfide and methylene chloride are preferably used.

In a preferred embodiment, when the strong deprotonating agent, for example sodium hydride or potassium tert-butylate, is added to prepare the enolate salt of formula (la), the acid-binder may not be added. .

When using acid binders, suitable materials are conventional inorganic or organic bases, examples of which may be mentioned sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

The reaction can be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out by conventional methods.

In the case of obtaining the compound of formula (Ie) in the preparation method (F), 1 to 2 moles, preferably at a temperature of -40 to 150 ° C, preferably -10 to 110 ° C, per mole of the compound of general formula (Ia) Preferably, 1 to 1.3 moles of the compound of general formula (III) are reacted.

Suitable diluents optionally added are all inert polar organic solvents such as ethers, amides, nitriles, alcohols, sulfides, sulfones, sulfoxides and the like.

Acetonitrile, dimethylsulfoxide, tetrahydrofuran, dimethylformamide and methylene chloride are preferably used.

Suitable acid binders which are optionally added are conventional inorganic or organic bases such as hydroxides or carbonates. As examples thereof, sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine can be mentioned.

The reaction can be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out by conventional methods of organic chemistry.

The final product obtained is preferably purified by crystallization, chromatography purification or so-called "incipient distillation", ie removal of volatile components in vacuo.

Process (G) is characterized by reacting a compound of formula (Ia) with a metal hydroxide or an amine (XI).

Diluents which can be used in the process according to the invention are preferably ethers such as tetrahydrofuran, dioxane, diethyl ether, or alcohols such as methanol, ethanol, isopropanol and also water. Process (G) according to the invention is generally carried out under atmospheric pressure. The reaction temperature is generally -20 to 100 ° C, preferably 0 to 50 ° C.

In the production process (Hα), about 1 mole of isocyanate of the general formula (XII) is reacted at 0 to 100 ° C, preferably 20 to 50 ° C, per mole of the starting compound of the general formula (Ia).

Suitable diluents which are optionally added are all inert organic solvents such as ethers, amides, nitriles, sulfones or sulfoxides.

If appropriate, a catalyst may be added to accelerate the reaction rate. Catalysts which can be used very advantageously are organotin compounds such as, for example, dibutyltin dilaurate. The reaction is preferably carried out at atmospheric pressure.

In process (Hβ), about 1 mole of carbamoyl chloride of general formula (XIII) is reacted at 0 to 150 ° C, preferably 20 to 70 ° C, per mole of starting compound of general formula (Ia).

Suitable diluents which are optionally added are all inert polar organic solvents such as ethers, amides, sulfones or sulfoxides.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or dimethyl sulfide are preferably used.

In a preferred embodiment, when the strong deprotonating agent, for example sodium hydride or potassium tert-butylate, is added to prepare the enolate salt of formula (la), the acid-binder may not be added. .

In the case of using an acid binder, suitable materials are conventional inorganic or organic bases, examples of which may be mentioned sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.

The reaction can be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out by conventional methods.

The active compounds of the present invention are suitable for controlling animal pests, preferably arthropods and nematodes, especially insects and spider subclasses, appearing in the fields of agriculture, forestry, storage and materials, and sanitation. They are active against normally and susceptible species and all or part of the growing season. The pests mentioned above include the following.

Neck of the Isopoda, such as Oniscus asellus, Armadillidium vulgare and Porcellio scaber.

Neck of Diloplopoda, for example, Blaniulus guttulatus.

From the neck of Chilopoda, for example, Geophilus carpo-phagus and Scutigera spec.

From the order of the symphyla, for example Scutigerella immaculata.

Thysanura neck, for example Lepisma saccharina.

Neck of Collembola, for example Onychiurus armatus.

Orthoptera, for example, Blata orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Arceta Domestikus (Acheta domesticus), Gryllotalpa spp, Locusta migratoria migratorioides, Melanoplus differentialis and Systocerca gre Schistocerca gregaria.

The neck of the Dermaptera, for example Porficula auricularia.

Termites (Isoptera), for example Reticulitermes spp.

Anoplura neck, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. And Linognathus spp.

Mallophaga neck, for example Trichodectes spp. And Damalinea spp.

Thysanoptera necks, such as Hercino thrips femoralis and Tripps tabaci.

From the order of Heteroptera, eg Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rodney Rhodnius prolixus and Triatoma spp.

The cicada (Homoptera), for example Aleurodes brassi-cae, Bemisia tabaci, Trialeurodes vaporariorum, Apis gossypii , Brevicoryne brassicae, Cryptomyzus ribis, Apis fabae, Doralis pomi, Eriosoma lanigerum, hyaloptherus Arundinos (Hyalopterus arundinis), Macrosisph avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca subspecies (Empoasca) spp.), Eucelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Lao delfax stria Laodelphax striatellus, Nilapar Other Lou Regensburg (Nilaparvata lugens), sludge de-ah brother is Ella Tee (Aonidiella aurantii), ah Speedy ohtuseu Hedera (Aspidiotus hederae), pseudo nose Syracuse subspecies (Pseudococcus spp.), Silas subspecies (Psylla spp.).

The order of the Lepidoptera, such as Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euprotis chrysorrhoea, Lymantria spp. , Buculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Et al. Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prode Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo subspecies ( Chilo spp.), Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tynea pelionella Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clichy am Herma Clysia ambiguella, Homona magnanima, and Tortrix viridana.

Neck of the Coleoptera, for example, Anobium puncta-tum, Rhizopertha dominica, Bruchidius obtectus, Acanthoceles obtectus obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica subspecies Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Antonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Cethororkus assimilus hynchus assi-milis, Hypera postica, Dermestes spp., Trogoderma spp., Antrenus spp., Athenus subspecies ( Attagenus spp.), Lyctus spp., Meligthes ae-neus, Ptinus spp., Niphtus hololeucus, Ghibiium siloides (Gibbium psylloides), Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melonta Melonta melolontha, Amphimallon solstitialis and Costelitra zealandica.

The order of the Hymenopera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa subspecies ( Vespa spp.).

Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca subspecies ( Musca spp.), Pania spp., Califora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp. , Gastrophilus spp., Hippobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Taniaa spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomia hisosiami Pegomyia hyoscyami, Ceratitis capitatu, Dacus oleae, and Tipula paluosa ( Tipula paludosa).

Siphonaptera necks, such as Xenopsylla cheo-pis and Ceratophyllus spp.

Arachnida necks such as Scorpio maurus and Latrodectus mactans.

The order of Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Deermanyssus gallinae, Eriopies libis ( Eriophyes ribis, Phyllocoptruta oleivora, Bophylus spp., Ripicephalus spp., Amblyomma spp., Hyalomma spp. ), Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp. , Bryobia praetiosa, Panonicus spp. And Tetranychus spp.

The active compounds according to the invention exhibit excellent pesticidal and acaricide activity.

The active compounds according to the invention are for example mustard scarab larvae (Phaedon cochleariae), larvae of beetle larvae (Nephotettix cinctrceps) and cabbage moth caterpillars (Flutella maculipenis) (Plutella maculipennis) can be used particularly successfully in combating insects harmful to plants.

The active compounds according to the invention can be used as deciduous, drying, hardwood killing agents and, in particular, weed-killers. Weeds are, in a broad sense, understood to be all plants that grow in unwanted places. Whether the substance according to the invention acts as a total herbicide or as a selective herbicide depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants.

Dicotyledonous weeds of the genus: Sinapis, Lepidium, Gallium, Stellaria, Matricaria, Anthemis, Galinsoga, Ke Norpodium, Urtica, Senesio, Amaranthus, Portulaca, Xanthium, Con-volvulus, Ipomoea ), Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala (Rotala), Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis ), Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledonous crops of the following genus: Gossypium, Glycine, Beta, Doucus, Phaseolus, Pisum, Solanum, Linum ), Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis ) And Cucurbita.

Monocot weeds in the genus: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festus, Eleusin, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Sino Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischamum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledonous crops of the following genus: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum Panicum), Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is not at all limited in them and extends to other plants in the same way.

The compounds of the invention are suitable for the overall control of weeds, depending on concentration, for example on industrial zones and railway lines, and on sidewalks and plazas with or without trees. Likewise, the compounds of the present invention are for example found in plantations, ornamental water, orchards, vineyards, citrus fields, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, palm plantations, cocoa plantations, soft fruit plantations and hop fields. It can be used to control weeds in perennial crops growing on lawns, turf and pasture and for selective control of weeds in annual crops.

The active compounds according to the invention are particularly suitable for the selective control of monocotyledonous weeds in dicotyledonous crops by pre- and post-germination methods. The active compounds of the invention can be used particularly successfully for controlling weeds in cotton or beets.

The active compounds according to the invention can be prepared in solutions, emulsions, wetting powders, suspending agents, powders, powders, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic and polymeric materials impregnated with the active compounds. It can be converted to conventional formulations such as microcapsules.

These formulations are known methods, for example, optionally by using surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents, by mixing the active compound with a weighting agent, ie a liquid solvent and / or a solid carrier. Manufacture.

When water is used as a weighting agent, for example, an organic solvent can also be used as a cosolvent. Liquid solvents are mainly aromatic compounds such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffins such as petroleum fractions, mineral oils and vegetable oils Alcohols such as aliphatic hydrocarbons, butanol or glycol and ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethylsulfoxide, and water are suitable Do.

Solid carriers include, for example, ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetics such as highly dispersed silica, alumina and silicates. Minerals are suitable.

Solid carriers for granulation include, for example, pulverized and classified natural rocks such as calcite, marble, pumice, calcite and dolomite, and synthetic granules of inorganic and organic powders, and organic such as sawdust, coconut husks, corn cobs and tobacco stems. Granules of material are suitable. Emulsifiers and / or foam-forming agents include nonionic and anionic emulsifiers such as polyoxyethylene fatty alcohol ethers such as polyoxyethylene fatty acid esters, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and Albumen hydrolysis products are suitable. Suitable dispersants are, for example, lignin-sulfite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, gum arabic, polyvinyl alcohol and powders such as polyvinyl acetate, natural and synthetic polymers in granular or latex form, and natural phospholipids such as cephalin and lecithin can be used in the formulation. . As other additives, mineral oil and vegetable oil may be used.

Inorganic pigments such as iron oxide, titanium oxide and prussian blue, and colorants such as organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc You can also use

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of active compound.

The active compounds according to the invention can be used by themselves for weed control or in combination with known herbicides in the form of their preparations in the form of finished preparations or tank mixes.

Suitable herbicides for the mixture include known herbicides, for example 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2 for controlling weeds of cereals. , 4- (1H, 3H) -dione (ametidione) or N- (2-benzothiazolyl) -N, N'-dimethylurea (metabenzthiazuron); 4-amino-3-methyl-6-phenyl-1,2,4-triazine-5 (4H) -one (methamitron) for controlling weeds of sugar beet and 4- for controlling weeds of soybean Amino-6- (1,1-dimethylethyl) -3-methylthio-1,2,4-triazine-5 (4H) -one (methibuzin); Also 2,4-dichlorophenoxyacetic acid (2,4-D); 4- (2,4-Dichlorophenoxy) -butyric acid (2,4-DB): 2,4-dichlorophenoxypropionic acid (2,4-DP); 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (bentazone); Methyl 5- (2,4-thichlorophenoxy) -2-nitrobenzoate (biphenox); 3,5-dibromo-4-hydroxy benzonitrile (bromoxynil); 2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] -carbonyl-benzenesulfonamide (chlorosulfuron); 2- [4- (2,4-Dichlorophenoxy) -phenoxy] -propionic acid, its methyl ester or its ethyl ester (diclofo-methyl); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazine-5 (4H) -one (ethiozin); 2-4-[(6-chloro-2-benzoxazolyl) -oxy] -phenoxy-propionic acid, methyl ester thereof or ethyl ester thereof (phenoxaprop); [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl) -oxy] -acetic acid or its 1-methylheptyl ester (fluroxy pyr); Methyl 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo (1H) -imidazol-2-yl] -4 (5) -methylbenzoate (imaza) Metabenz); 3,5-diiodo-4-hydroxybenzonitrile (ioxylyl); N, N-dimethyl-N '-(4-isopropylphenyl) -urea (isoproturon); (2-methyl-4-chlorophenoxy) -acetic acid (MCPA); (4-chloro-2-methylphenoxy) -propionic acid (MCPP); N-methyl-2- (1,3-benzothiazol-2-yloxy) -acetanilide (mefenacet); 2-[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino-carbonyl] -amino] sulfonyl-benzoic acid or a salt thereof (methsulfuron); N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline (fendimethalin); 0- (6-chloro-3-phenyl-pyridazin-4-yl) S-octylthiocarbonate (pyridate); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (terbutryn); 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) -amino] -carbonyl] -amino] -sulfonyl] -thiophene-2-carboxylic acid There is something like (Tiamethuron). Surprisingly, some mixtures also show synergy.

Mixtures with other known active compounds such as fungicides, insecticides, acaricides, nematicides, algal repellents, phytonutrients and soil structure improvers are also possible.

The active compounds can be used on their own or in the form of preparations thereof, such as ready-to-use solutions, suspensions, emulsions, powders, powders, pastes and granules, or in further dilution therefrom. They are used in conventional manner, for example by conventional methods such as water supply, spraying, dispersion or dispersion.

The active compounds according to the invention can be applied at any time before or after germination of plants.

They can also be blended into the soil before sowing.

The amount of active compound can vary within a significant range. This is essentially dependent on the nature of the desired effect. Generally, the amount used is 0.01 to 10 kg, preferably 0.05 to 5 kg of active compound per hectare of soil surface.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

Production Example

Example (Ia-1)

4.14 g (0.138 mol) of sodium hydride is suspended in 70 ml of anhydrous toluene and the mixture is refluxed. To this was added dropwise 25.6 g (0.069 mol) of methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-4-t-butyl-cyclohexanecarboxylate in 140 ml of anhydrous toluene and the mixture was reacted. Reflux is continued until terminated (checked by thin layer chromatography). After cooling the mixture to room temperature, ethanol is added dropwise with ice cooling until no more hydrogen is generated. After evaporation of the solvent, the residue is dissolved in ethanol and the mixture is stirred at 0-20 ° C. in about 1% hydrochloric acid. The precipitated solid is suction filtered and dried.

After recrystallization with chloroform / hexane, 14.90 g (63% of theory) of 3- (2,4,6-trimethylphenyl) -5,5- (4-t-butyl) -pentamethylene with a melting point of> 220 ° C Pyrrolidin-2,4-dione is obtained (β-isomer).

Example (Ia-2)

37.2 g (0.331 mol) of potassium t-butylate are heated to reflux in 100 ml of anhydrous tetrahydrofuran. To this was added dropwise 52 g (0.151 mol) of methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-4,4-dimethyl-cyclohexanecarboxylate in 510 ml of anhydrous toluene and the mixture was added 90 Reflux for minutes. After the reaction is finished, the batch is brought to room temperature and 500 ml of water are added. The aqueous phase is separated and the toluene phase is extracted using 220 ml of water. The combined aqueous phases are washed with toluene and then treated with 50 ml of concentrated hydrochloric acid at room temperature. The precipitated solid is suction filtered, washed and dried. The crude product is suspended in 300 ml of methyl t-butyl ether and further purified by suction filtration.

44.9 g (95% of theory) of 3- (2,4,6-trimethylphenyl) -5,5- (4,4-dimethyl) -pentamethylene-pyrrolidine-2,4- having a melting point of 220 ° C. Obtain dione.

The final product of the following general formula (Ia) described in Table 4 was subjected to the α-isomer or β-isomer similarly to Examples (Ia-1) and (Ia-2) according to the general information in the description of the process according to the invention. Obtained in form.

Example (Ib-1)

5.12 g (0.015 mol) of 3- (2,4,6-trimethylphenyl) -5,5- (4-t-butyl) -pentamethylene-pyrrolidine-2,4-dione in 60 ml of anhydrous dichloromethane It is dissolved in and 2.1 ml of trimethylamine is added thereto. 1.13 ml of acetyl chloride in 5 ml of anhydrous dichloromethane are added at 0-10 ° C. The completion of the reaction is determined by thin layer chromatography. The mixture is washed twice successively with 100 ml of 0.5 N sodium hydroxide solution and the organic phase is dried over magnesium sulfate. The residue obtained after evaporation of the solvent is recrystallized from ethyl acetate / n-hexane.

2 g (35% of theory) of 3- (2,4,6-trimethylphenyl) -5,5- (4-t-butyl) -pentamethylene-4-acetyloxy-Δ3pyrroline having a melting point of> 220 ° C 2-one is obtained (β-isomer).

Example (Ib-2)

3- (2,4,6-trimethylphenyl) -5,5- (2-methyl) -pentamethylene-4-acetyloxy-Δ3-pyrroline-2-one having a melting point of 138 ° C. (isomer mixture) was carried out. Obtained similarly to Example (Ib-1).

The final product of the following general formula (Ib), described in Table 5, according to the general information in the description of the process according to the invention, similarly to Examples (Ib-1) and (Ib-2), α-isomers or β Obtained in the form of an isomer.

Example (Ic-1)

5.12 g (0.015 mol) of 3- (2,4,6-trimethylphenyl) -5,5- (4-t-butyl) -pentamethylene-pyrrolidine-2,4-dione in 60 ml of anhydrous dichloromethane Dissolved in and treated with 2.1 ml of triethylamine. 2.05 g of secondary-butyl chloroformate in 5 ml of anhydrous dichloromethane is added at 0-10 ° C. and the batch is continuously stirred at room temperature. The completion of the reaction is determined by thin layer chromatography. The batch is washed twice successively with 100 ml of 0.5N sodium hydroxide solution and the organic phase is dried over magnesium sulfate. After evaporation of the solvent the residue obtained is recrystallized from acetate / n-hexane.

4.4 g (66% of theory) of 0- (secondary-butyl) -0- [3- (2,4,6-trimethylphenyl) -5,5- (4-t-butyl) with melting point> 220 ° C -Pentamethylene- Δ3-pyrrolin-4-yl-2-one] carbonate is obtained (β-isomer).

Example (Ic-2)

0- (secondary-butyl) -0- [3- (2,4,6-trimethylphenyl) -5,5- (4-t-butyl) -pentamethylene-Δ3-pyrroline having a melting point of 170 ° C. 4-yl-2-one] carboxylate is obtained similarly to Example (Ic-1) (isomer mixture).

The final product of the following general formula (Ic) as described in Table 6 was subjected to the α-isomer or β-isomer similarly to Examples (Ic-1) and (Ic-2) according to the general information in the description of the process according to the invention. Obtained as

Example (Id-1)

5.99 g (0.02 mol) of 3- (2,4,6-trimethylphenyl) -5,5- (4-methyl) -pentamethylene-pyrrolidine-2,4-dione in 70 ml of anhydrous dichloromethane The solution is treated with 2.8 ml of triethylamine. Here, 2.29 g of methanesulfonylchloride in 5 ml of anhydrous dichloromethane are added dropwise at 0? 10 占 폚. The completion of the reaction is determined by thin layer chromatography. The mixture is washed twice successively with 200 ml of 0.5N sodium hydroxide solution and the organic phase is dried over magnesium sulfate. After removing the solvent and suspending the residue in ethyl acetate, 3.1 g (41% of theory) of 3- (2,4,6-trimethylphenyl) -5,5- (4-methyl having a melting point of 205-206 ° C. ) -Pentamethylene-4-methylsulfonyloxy-Δ3-pyrroline-2-one is obtained (α-isomer).

Example (Ie-1) (α-isomer)

2 g (6.2 mmol) of 3- (2,4-dichlorophenyl) -5,5- (3-methyl) -pentamethylene-pyrrolidine-2,4-dione are suspended in 20 ml of anhydrous tetrahydrofuran and This suspension is treated with 1 ml of triethylamine. After 1.5 g (7 mmol) of methyl-tert-butylthiophosphonic acid chloride is added, the mixture is stirred overnight. The solvent is evaporated and the residue is chromatographically separated using cyclohexane / ethylacetate (2: 1) on silica gel. 1.7 g (37% of theory) of the above-mentioned compound (α-isomer, melting point 69 DEG C) are obtained.

Example (If-1)

2.99 g (10 mmol) of 3- (2,4,6-trimethylphenyl) -5,5- (4-methyl) -pentamethylene-pyrrolidine-2,4-dione is suspended in 40 ml of anhydrous methylene chloride. Let's do it. 6.24 g of tetrabutylammonium hydroxide (40% aqueous solution) is added and the mixture is stirred for 15 minutes, then the solvent is evaporated and the residue is crystallized from diisopropyl ether. 5.1 g (94% of theory) of the above-mentioned compound (melting point 125 DEG C, β-isomer) are obtained.

Example (If-2)

Similarly, compound (If-2) having a melting point of 110 ° C. is obtained.

Example (Ig-1)

5.99 g (0.02 mol) of 3- (2,4,6-trimethylphenyl) -5,5- (4-methyl) -pentamethylene-pyrrolidine-2,4-dione in 70 ml of anhydrous dichloromethane The solution is treated with 2.8 ml of triethylamine. 2.34 ml of morpholinecarbamoyl chloride in 5 ml of dichloromethane are added at 0-10 ° C. and the batch is kept stirring at room temperature until it is checked by thin layer chromatography to confirm that the reaction is complete. The mixture is then washed twice with 200 ml of 0.5N sodium hydroxide solution and the organic phase is dried over magnesium sulfate. After evaporating the solvent and suspending the residue in ethyl acetate, 2.3 g (28% of theory) of 3- (2,4,6-trimethylphenyl) -5,5- (4-methyl having a melting point of 197-198 ° C. ) -Pentamethylene-4- (morpholine carbamoyl) -Δ3-pyrroline-2-one is obtained (α-isomer).

Example (Ig-2)

Similarly 3- (2,4,6-trimethylphenyl) -5,5- (4-methyl) pentamethylene-4- (morpholincarbamoyl) -Δ3-pyrrolin-2-one (melting point: 189 to 189) 193 ° C.) is obtained (β-isomer).

Similarly the compounds listed in the following table are obtained.

[Production of Starting Compound]

Example (I1-1)

29.1 g (0.117 mole) of 4- (t-butyl) -methyl-1-amino-1-cyclohexanecarboxylate hydrochloride is dissolved in 300 ml of tetrahydrofuran and the solution is 34.4 ml (0.246 moles) of triethyl Treat with amine. To this was added dropwise 23 g of mesityleneacetyl chloride in 20 ml of anhydrous tetrahydrofuran at 0 to 10 ° C. and the batch was kept stirring at room temperature. The completion of the reaction is determined by thin layer chromatography. The batch is stirred with 100 ml of 1N hydrochloric acid in 0.5 L of water and the mixture is extracted with dichloromethane. The mixture is washed with sodium bicarbonate solution, the organic phase is dried and the solution is stripped off. The crude product is recrystallized from toluene / n-hexane. Obtain 25.6 g (59% of theory) of methyl N- (2,4,6-trimethylphenylacetyl) -1-amino-4-t-butyl cyclohexanecarboxylate having a melting point of 153 to 154 ° C. (β-isomer). (Β-isomer).

Example (I1-2)

148 g (1.52 mole) of concentrated sulfuric acid at 90.9 g (0.30 mole) N- (2,4,6-trimethylphenylacetyl) -4-methyl-1-amino in 600 ml of methylene chloride at a temperature of 30 to 40 ° C. -A solution of cyclohexanenitrile is added dropwise. After 2 hours 212 ml of dry methanol are added dropwise at 40 ° C. and the mixture is stirred at 40 to 70 ° C. for 6 hours.

The reaction mixture is then poured into ice water and extracted with methylene chloride. The organic phase is washed with aqueous NaHCO ₃ , dried and evaporated. The product is purified by recrystallization from toluene / n-hexane.

73.9 g (73% of theory) of methyl N- (2,4,6-trimethylphenyl-acetyl) -4-methyl-1-amino-cyclohexanecarboxylate are obtained with a melting point of 146 ° C.

The compounds of the following general formula (II) as described in Table 8 are obtained in the form of isomeric mixtures similarly to examples (II-1) according to the general information in the description of the process according to the invention.

[Production Example of Starting Compound of Formula (XVII)]

Example XVII-1

40 ml of anhydrous tetrahydrofuran while stirring at 0-10 degreeC to 28 ml (0.2 mol) triethylamine and 40 g (0.2 mol) 1-amino- 4-phenyl- cyclohexanecarboxylic acid nitrile in 450 ml of anhydrous tetrahydrofuran. 39.3 g (0.2 mole) of mesityleneacetyl chloride (see, eg, Tetrahedron 31, 2691-2694 [1975]) was added dropwise and at the end of the reaction until the starting compound was no longer detected by thin layer chromatography. The mixture is stirred at room temperature. For workup, the reaction mixture is added to a mixture of 1000 ml of ice water and 200 ml of 1N hydrochloric acid with stirring, the precipitated solid is suction filtered, the residue is dissolved in dichloromethane, the aqueous phase is separated and the organic phase is sulfuric acid After drying over magnesium, the solvent is removed in vacuo.

65 g (91% of theory) of N- (2,4,6-trimethylphenyl-acetyl) -4-phenylcyclohexanecarboxylic acid nitrile are obtained having a melting point of 235 to 238 ° C.

The following compounds (XVII) are obtained analogously to the above according to the general description for the preparation examples:

Example A

Phaedon larvae test

Solvent: Dimethylformamide 7 parts by weight

Emulsifier: alkylaryl polyglycol ether 1 part by weight

1 part by weight of the active compound is mixed with a specified amount of solvent and an emulsifier and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Cabbage leaves (Brassica oleracea) are treated by dipping into active compound preparations of the desired concentration and infected with mustard scarab larvae (Phaedon cochleariae) while the leaves are damp.

After a certain period of time, the percentage of relief is determined. 100% means that all mustard beetle larvae have been killed, and 0% means that no mustard beetle larvae have been killed.

In this test, for example, the compounds of Preparation Examples (Ia-10), (Ia-11), (Ib-11), (Ib-12), (Ig-1) are superior to the prior art. Activity.

Example B

Flutella test

Solvent: Dimethylformamide 7 parts by weight

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with a specified amount of solvent and an emulsifier and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Cabbage leaves (Brassica oleracea) are treated by dipping into active compound preparations of the desired concentration, and the cabbage moth caterpillar (Plutella maculipennis) is infected while the leaves are damp.

After a certain period of time, the percentage of relief is determined. 100% means that all cabbage moth caterpillars have been killed, and 0% means that no one cabbage moth caterpillar has been killed.

In this test, for example, the compounds of Preparation Examples (Ia-10), (Ia-11), (Ib-12), (Ig-1) show superior activity compared to the prior art.

Example C

Nephotettix test

Solvent: Dimethylformamide 7 parts by weight

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with a specified amount of solvent and an emulsifier and the resulting concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

The mother (Oriza sativa) is treated by dipping in the preparation of the active compound of the desired concentration and infecting the larvae of Green Rice Kicada (Nephotettix cincticeps) while the hair is moist.

After a certain period of time, the percentage of relief is determined. 100% means that all the kicada larvae have been killed, and 0% means that none of the kicada larvae have been killed.

In this test, for example, the compounds of Preparation Examples (Ia-10), (Ia-11), (Ib-11), (Ib-12), (Ig-1) are superior to the prior art. Activity.

Example D

Germination test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 weight part of alkylaryl polyglycol ether

One part by weight of the active compound is mixed with the above amount of solvent, the above amount of emulsifier is added, and the concentrate is then diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Seeds of the test plants are sown in standard soil and after 24 hours, the active compound preparations are irrigated. It is advantageous to maintain a constant amount of water per unit area. The concentration of active compound in the formulation is not critical, only the amount of active compound applied per unit area is an important factor. After 3 weeks, the degree of damage of the plants is graded in% damage compared to the development of the untreated control.

The figures represent the following:

0% = no effect (same as untreated control)

100% = Complete Exam

In this test, for example, the compounds of Preparation Examples (Ia-10), (Ia-11), (Ib-12), (Ib-11), (Ic-6) are clearly superior to the prior art. One activity and crop selectivity.

Example E

Post Germination Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 weight part of alkylaryl polyglycol ether

One part by weight of the active compound is mixed with the above amount of solvent and emulsifier and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Test plants of 5 to 15 cm in height are sprayed with a formulation of the active compound so that a specific amount of the desired active compound per unit area is applied. After 3 weeks, the degree of damage of the plants is graded in% damage compared to the development of the untreated control. The figures represent the following:

0% = no effect (same as untreated control)

100% = Complete Exam

In this test, for example, the compounds of Preparation Examples (Ia-10), (Ia-11), (Ib-11), (Ib-12) have clearly superior activity and crop selectivity compared to the prior art. Indicates.

Claims (16)

Substituted 1-H-3-arylpyrrolidine-2,4-dione derivatives of general formula (I). In the above formula, A and B represent cycles substituted with the carbon atoms to which they are attached, X represents alkyl, halogen or alkoxy, Y represents hydrogen, alkyl, halogen, alkoxy or halogenoalkyl, Z represents alkyl, halogen or alkoxy, n represents 0, 1, 2 or 3, G is hydrogen (a) or a group , From here, E represents a metal ion equivalent or ammonium ion, L and M represent oxygen or sulfur, R ¹ may be interrupted by a heteroatom and in each case halogen-substituted or unsubstituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or cycloalkyl, or substituted or unsubstituted phenyl, substituted or Unsubstituted phenylalkyl, substituted hetaryl, substituted phenoxyalkyl or substituted hetaryloxyalkyl, R ² represents in each case halogen-substituted or unsubstituted alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, or in each case substituted or unsubstituted phenyl or benzyl, R ³ , R ⁴ and R ⁵ independently of one another in each occurrence are halogen-substituted or unsubstituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio, or in each case substituted or Unsubstituted phenyl, phenoxy or phenylthio, R ⁶ and R ⁷ independently of one another represent hydrogen, in each case halogen-substituted or unsubstituted alkyl, alkenyl, alkoxy or alkoxyalkyl, substituted or unsubstituted phenyl or substituted or unsubstituted benzyl, or Together with the N-atom, it represents a cycle blocked or unblocked by oxygen or sulfur. A compound according to claim 1 having any one of the following structural formulas (Ia) to (Ig) Wherein A, B, E, L, M, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and n have the meanings defined in claim 1 Have The C ₃ -C ₆ -spirocycle according to claim 1, wherein A, B and the carbon atoms to which they are attached are mono- or polysubstituted by alkyl, cycloalkyl, haloalkyl, alkoxy, thioalkyl, halogen or phenyl. By alkylenediyl groups represented or interrupted or unblocked by one or two atoms selected from oxygen and sulfur or an alkylenedioxyl or alkylenedithioyl group, wherein these groups are added together with the carbon atoms to which they are attached Form a 5- to 8-membered spirocycle of C ₃ -C ₆ -spirocycle, or A, B and the carbon atoms to which they are attached are saturated or unsaturated in which two substituents A and B are substituted or unsubstituted by alkyl, alkoxy or halogen together with the C- atoms to which they are attached and are blocked or unblocked by oxygen or sulfur atoms. C ₃ -C ₆ spirocycle, which represents a carbocycle, X represents C ₁ -C ₆ -alkyl, halogen or C ₁ -C ₆ -alkoxy, Y represents hydrogen, C ₁ -C ₆ -alkyl, halogen, C ₁ -C ₆ -alkoxy or C ₁ -C ₃ -halogenoalkyl, Z represents C ₁ -C ₆ -alkyl, halogen or C ₁ -C ₆ -alkoxy, n represents 0, 1, 2 or 3, G is hydrogen (a) or a group , From here, E represents a metal ion equivalent or ammonium ion, L and M in each case represent oxygen or sulfur, R ¹ may be interrupted by oxygen or sulfur atoms, or by both oxygen and sulfur atoms, in each case halogen-substituted or unsubstituted C ₁ -C ₂₀ -alkyl, C ₃ -C ₂₀ -alkenyl, C _1- C ₈ -alkoxy-C ₂ -C ₈ -alkyl, C ₁ -C ₈ -alkylthio-C ₂ -C ₈ -alkyl, C ₁ -C ₈ -polyalkoxy-C ₂ -C ₈ -alkyl or 3 to 8 Cycloalkyl having two reducing groups, or Or represents phenyl unsubstituted or substituted by halogen, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl or C ₁ -C ₆ -halogenoalkoxy , Phenyl-C ₁ -C unsubstituted or substituted by halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl or C ₁ -C ₆ -halogenoalkoxy ₆ -alkyl, or Hetaryl unsubstituted or substituted by halogen or C ₁ -C ₆ -alkyl, or both halogen and C ₁ -C ₆ -alkyl, or Phenoxy-C ₁ -C ₆ -alkyl unsubstituted or substituted by halogen or C ₁ -C ₆ -alkyl, or Halogen, amino and C ₁ -C ₆ - alkyl substituted by Het or unsubstituted aryloxy -C ₁ -C ₆ - represents alkyl, R ² in each case is halogen-substituted or unsubstituted C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ -alkenyl, C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl or C ₁ -C ₈ -Polyalkoxy-C ₂ -C ₈ -alkyl, or in each case substituted by halogen, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy or C ₁ -C ₆ -halogenoalkyl Or unsubstituted phenyl or benzyl, R ³ , R ⁴ and R ⁵ independently of one another in each occurrence are halogen-substituted or unsubstituted C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkylamino, di (C ₁ -C ₈ ) -alkylamino, C ₂ -C ₃ -alkenylthio or C ₃ -C ₇ -cycloalkylthio, or in each case halogen, nitro, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ - halogenoalkyl alkoxy, C ₁ -C ₄ - alkylthio, C ₁ -C ₄ - halogenoalkyl alkylthio, C ₁ -C ₄ - alkyl or C ₁ -C ₄ - substituted by halogenoalkyl Or unsubstituted phenyl, phenoxy or phenylthio, R ⁶ and R ⁷ independently represent hydrogen or, in each case, halogen-substituted or unsubstituted C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₈ -alkoxy, C ₃ -C ₈ -alkenyl or C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl, or Halogen, C ₁ -C ₈ - halogenoalkyl, C ₁ -C ₈ - alkyl or C ₁ -C ₈ - or substituted by alkoxy, or represents a phenyl ring Beach, Benzyl substituted or unsubstituted by halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -halogenoalkyl or C ₁ -C ₈ -alkoxy, or R ⁶ and R ⁷ together represent a C ₃ -C ₆ -alkylene ring which is blocked or unblocked by oxygen or sulfur. The compound of claim 1, wherein A, B and the carbon atom to which they are attached are C ₁ -C ₆ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₃ -haloalkyl, C ₁ -C ₄ -alkoxy, C C ₃ -C ₆ -spirocycle which may be mono- or polysubstituted by _1- C ₄ -thioalkyl, fluorine, chlorine or phenyl, By alkylenediyl groups interrupted or unsubstituted by one or two oxygen or sulfur atoms, or by alkylenedioxyl groups or alkylenediothioxyl groups, wherein these groups are in addition to the carbon atoms to which they are attached Or-to form a 7-membered spirocycle) or a C ₃ -C ₆ -spirocycle, or A, B and the carbon atom to which they are attached are substituted by two substituents A and B with C-atom to which they are attached by C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy or fluorine, chlorine or bromine Or C ₃ -C ₆ -spirocycle which represents a saturated or unsaturated carbocycle blocked or unblocked by sulfur atoms, X represents C ₁ -C ₄ -alkyl, halogen or C ₁ -C ₄ -alkoxy, Y represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl, Z represents methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, fluorine, chlorine, bromine, methoxy or ethoxy, n represents 0, 1 or 2, G is hydrogen (a) or a group , From here, E represents a metal ion equivalent or ammonium ion, L and M represent oxygen or sulfur, R ¹ may be interrupted by one or two atoms selected from oxygen and sulfur and in each case halogen-substituted or unsubstituted C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C ₁₆ -alkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₆ -alkylthio-C ₂ -C ₆ -alkyl, C ₁ -C ₆ -polyalkoxy-C ₂ -C ₆ -alkyl or 3 to 7 Or cycloalkyl having a reducing group, Or represents phenyl unsubstituted or substituted by halogen, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy , Phenyl-C ₁ -C unsubstituted or substituted by halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy ₄ -alkyl, or Hetaryl unsubstituted or substituted by one or more substituents selected from the group consisting of fluorine, chlorine, bromine and / or C ₁ -C ₄ -alkyl, or Phenoxy-C ₁ -C ₅ -alkyl unsubstituted or substituted by fluorine, chlorine, bromine and C ₁ -C ₄ -alkyl, or Hetaryloxy-C ₁ -C ₅ -alkyl unsubstituted or substituted by fluorine, chlorine, bromine, amino and C ₁ -C ₄ -alkyl, R ² is in each case halogen-substituted or unsubstituted C ₁ -C ₁₆ -alkyl, C ₃ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl or C ₁ -C ₆ -polyalkoxy-C ₂ -C ₆ -alkyl, or In each case phenyl or benzyl unsubstituted or substituted by halogen, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₃ -alkoxy or C ₁ -C ₃ -halogenoalkyl, R ³ , R ⁴ and R ⁵ independently of one another in each occurrence are halogen-substituted or unsubstituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylamino, di (C _1- C ₆ ) -alkylamino, C ₁ -C ₆ -alkylthio, C ₃ -C ₄ -alkenylthio or C ₃ -C ₆ -cycloalkylthio, or In each case fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -halogenoalkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -halogenoalkyl Phenyl, phenoxy or phenylthio unsubstituted or substituted by thio, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -halogenoalkyl, R ⁶ and R ⁷ independently represent hydrogen or, in each case, halogen-substituted or unsubstituted C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, C ₃ -C ₆ -alkenyl or C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, or Halogen, C ₁ -C ₅ - halogenoalkyl, C ₁ -C ₅ - alkyl or C ₁ -C ₅ - or substituted by alkoxy, or represents a phenyl ring Beach, Benzyl substituted or unsubstituted by halogen, C ₁ -C ₅ -alkyl, C ₁ -C ₅ -halogenoalkyl or C ₁ -C ₅ -alkoxy, or R ⁶ and R ⁷ together represent C ₃ -C ₆ -alkylene blocked or unblocked by oxygen or sulfur; A compound according to claim 1, wherein A, B and the carbon atoms to which they are attached are methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, secondary-butyl, t-butyl, cyclohexyl, trifluoromethyl, methoxy, C ₃ -C ₈ -spirocycle which may be mono- or polysubstituted by methylthio, fluorine, chlorine or phenyl, By alkylenediyl groups blocked or unblocked by oxygen or sulfur atoms or by alkylenedioxyl groups, where these groups together with the carbon atoms to which they are attached form an additional 5- to 7-membered spirocycle C ₃ -C ₆ -spirocycle substituted by A, B and the carbon atoms to which they are attached are C ₃ -C wherein two substituents A and B represent a saturated or unsaturated 5- or 6-membered cycle in which they are blocked or unblocked by oxygen or sulfur together with the carbon atoms to which they are attached ₆ -represents a spirocycle, X represents methyl, ethyl, propyl, 2-propyl, fluorine, chlorine, bromine, methoxy or ethoxy, Y represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl, Z represents methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, fluorine, chlorine, bromine, methoxy or ethoxy, n represents 0 or 1, G is hydrogen (a) or a group Indicates, E represents a metal ion equivalent or ammonium ion, L and M represent oxygen or sulfur, R ¹ may be interrupted by one or two atoms selected from oxygen and sulfur and in each case fluorine- or chlorine-substituted or unsubstituted C ₁ -C ₁₄ -alkyl, C ₃ -C ₁₄ -alkenyl, C _1- C ₄ -alkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₄ -alkylthio-C ₂ -C ₆ -alkyl, C ₁ -C ₄ -polyalkoxy-C ₂ -C ₄ -alkyl or 3 To cycloalkyl having from 6 to 6 ring atoms, or Phenyl substituted or unsubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or nitro, or Phenyl C ₁ -C ₃ -alkyl unsubstituted or substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy, In each case represent furanoyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl unsubstituted or substituted by fluorine, chlorine, bromine, methyl or ethyl, Phenoxy-C ₁ -C ₄ -alkyl unsubstituted or substituted by fluorine, chlorine, methyl or ethyl, or Substituted by fluorine, chlorine, amino, methyl or ethyl in each case or unsubstituted pyridyloxy -C ₁ -C ₄ - alkyl, pyrimidyl-oxy -C ₁ -C ₄ - alkyl or thiazolyl oxy -C ₁ -C ₄ -alkyl, R ² in each case is fluorine- or chlorine substituted or unsubstituted C ₁ -C ₁₄ -alkyl, C ₃ -C ₁₄ -alkenyl, C ₁ -C ₄ -alkoxy-C ₂ -C ₆ -alkyl or C ₁ -C ₄ -polyalkoxy-C ₂ -C ₆ -alkyl, or In each case phenyl or benzyl unsubstituted or substituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl, R ³ , R ⁴ and R ⁵ independently of one another are in each occurrence substituted or unsubstituted C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, Di- (C ₁ -C ₄ ) -alkylamino or C ₁ -C ₄ -alkylthio, or In each case fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₂ -alkoxy, C ₁ -C ₄ -fluoroalkoxy, C ₁ -C ₂ -alkylthio, C ₁ -C ₂ -fluoroalkyl Phenyl, phenoxy or phenylthio unsubstituted or substituted by thio or C ₁ -C ₃ -alkyl, R ⁶ and R ⁷ independently of one another represent hydrogen or in each occurrence are unsubstituted or substituted by fluorine, chlorine or bromine C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkoxy, C ₃ -C ₄ -alkenyl or C ₁ -C ₄ -alkoxy-C ₂ -C ₄ -alkyl, or Phenyl substituted or unsubstituted by fluorine, chlorine, bromine, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, Benzyl substituted or unsubstituted by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl or C ₁ -C ₄ -alkoxy, R ⁶ and R ⁷ together represent a C ₄ -C ₆ -alkylene ring unsubstituted or substituted by oxygen or sulfur. (A) Intramolecular condensation reaction was carried out on the N-acylamino acid ester of the general formula (II) in the presence of a diluent and in the presence of a base, thereby yielding 1-H-3-arylpyrrolidine-2 To obtain a 4-dione derivative or an enol thereof; (B) a compound of formula (Ia), α) reacts with an acid halide of formula (III), in the presence or absence of a diluent and in the presence or absence of an acid binder, β) reacting with a carboxylic anhydride of formula (IV) in the presence or absence of a diluent and in the presence or absence of an acid binder to give a compound of formula (Ib), (C) The compound of general formula (Ia) is reacted with chloroformic acid ester or chloroformic acid thioester of general formula (V) in the presence or absence of a diluent and in the presence or absence of an acid binder to give a general formula (Ic-1). To obtain a compound of (D) the compound of general formula (Ia), α) react with a chloromonothioformic ester or chlorodithioformic ester of general formula (VI), in the presence or absence of a diluent and in the presence or absence of an acid binder, β) in the presence or absence of a diluent and in the presence or absence of an acid binder, reacting with carbon disulfide and subsequently an alkyl halide of general formula to yield a compound of formula (Ic-2), (E) reacting a compound of formula (Ia) with sulfonyl chloride of formula (VII) in the presence or absence of a diluent and in the presence or absence of an acid binder to obtain a compound of formula (Id), (F) 1-H-3-arylpyrrolidine-2,4-dione of the general formula (Ia) or an enol thereof, in the presence or absence of a diluent and in the presence or absence of an acid binder, React with a phosphorus compound of to obtain a compound of formula (Ie), (G) reacting a compound of formula (Ia) with a metal hydroxide or amine of formula (VIII) or (XI) in the presence or absence of a diluent to give a compound of formula (If), or (H) a compound of formula (Ia), α) reacts with a compound of formula (XII) in the presence or absence of a diluent and in the presence or absence of an acid binder, (beta)) in the presence or absence of a diluent and in the presence or absence of an acid binder, reaction with carbamoyl chloride or thiocarbamoyl chloride of formula A process for preparing the substituted 1-H-3-arylpyrrolidine-2,4-dione derivative of formula (I) according to claim 1. Wherein A, B, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , L and n have the meanings defined in claim 1, R ⁸ represents alkyl, Hal represents halogen in formulas (III) and (iii), and in formula (iii) represents chlorine, bromine or iodine, M represents oxygen or sulfur, E represents a metal ion equivalent or ammonium ion, Me represents monovalent or divalent metal ion, s and t represent the number of 1 or 2, In formula (XI), R ⁵ , R ⁶ and R ⁷ independently represent hydrogen or alkyl. Compound of formula (II) Wherein A, B, X, Y, Z, n and R ⁸ have the meanings defined in claims 1 and 6. Acylating amino acid derivatives of formula (XIV) with phenylacetyl halides of formula (XV), esterifying acylamine acids of formula (IIa), or aminonitrile of formula (XVI) Reacting with phenylacetyl halide of (XV) to give a compound of general formula (XVII), and then the obtained compound is subsequently subjected to alcoholic decomposition in sulfuric acid. Method for preparing the compound. In the above formula, R ^{9 ′} represents hydrogen (XIVa) or alkyl (XIVb), A, B, X, Y, Z and n have the meanings defined in claim 1, Hal represents chlorine or bromine, R ⁹ represents hydrogen. Compound of general formula (XVII) Wherein A, B, X, Y, Z and n have the meanings defined in claim 1. A process for preparing a compound of formula (XVII) according to claim 9, characterized by reacting an aminonitrile of formula (XVI) with a phenylacetyl halide of formula (XV). Wherein A, B, X, Y and Z have the meaning as defined in claim 9, Hal represents chlorine or bromine. An arthropod killer comprising at least one compound of general formula (I). A method of controlling pests in plant protection, homes, sanitation and storage, characterized in that the compounds of formula (I) according to claim 1 act on pests or their environment. A method for producing a pesticide, characterized in that the compound of formula (I) according to claim 1 is mixed with at least one component selected from the group consisting of a weighting agent and a surfactant. A method of controlling external and internal parasites in an animal by applying the compound of formula (I) according to claim 1. An nematicide comprising at least one compound of the general formula (I). Herbicides characterized by containing at least one compound of general formula (I).