KR100346163B1 - Substituted Arylketo-Enolicheterocycles - Google Patents

Abstract

The aryl-keno-enolic heterocycle according to the present invention is represented by the following general formula (I), wherein Het represents a heterocycle group in the following (a), (b) or (c), X, Y, Z, n, A, B, E, L and M have the same meaning as in the specification. Compounds of general formula (I) are pesticides, in particular acaricides, insecticides, fungicides and herbicides. Its manufacture is also described in the specification.

Description

Substituted Aryl Keto-Enolic Heterocycle

The present invention relates to novel aryl keto-enolic heterocycles, various preparations thereof and their use as pesticides.

Any substituted Δ ³ -dihydrofuran-2-one derivatives are known to have the properties of herbicides (DE-A 4 014 420). Tetronic acid derivatives used as starting compounds (such as 3- (2-methyl-phenyl) -hydroxy-5- (4-fluoro-phenyl) Δ ³ -dihydrofuran-2-one) Is similar to that described in DE-A 4 014 420. Campbell et al., J. Chem., Et al., Which have published compounds of similar structure for which no pesticide and / or acaricide action has been described. Soc., Perkin Trans. 1. 1985 , (8) 1567-76.

The chemical properties of 3-aryl-pyrrolidine-2,4-dions have already been described (S. Suzuki et al. Chem. Pharm. Bull. 15 1120 (1967)). In addition, N-phenyl-pyrrolidine-2,4-diones were synthesized by R. Schmirrer and H. Mildenberger (Liebigs Ann. Chem. 1985 1095). The biological action of these compounds is not yet shown.

EP-A 0 262 399 discloses compounds of similar structure (3-aryl-pyrrolidine-7,4-diones), but the action of herbicides, pesticides or acaricides is not known at all. Those known to have herbicide, insecticide or acaricide action are unsubstituted bicyclic 3-aryl-pyrrolidin-2,4-dione derivatives (see EP-A 355 599 and EP 415 211), substituted bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP 501 129) and substituted mono-cyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A 377 893 , EP 442 077 and 497 127.

Polycyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A 442 073), 1H-3-aryl-pyrrolidine-dione derivatives (EP 456 063 and EP 521 334) And substituted bicyclic 3-aryl-pyrrolidine-dione derivatives (see EP 501 129) are also known.

Tetronic acid derivatives with the properties of fungicides, herbicides, acaricides and insecticides are also known (see EP 528 156).

4-arylpyrazolidine-dione derivatives having the properties of herbicides, acaricides and pesticides are described in WO 92/16510 and EP 508 126.

Now, the novel enantiomers of the novel substituted aryl keto-enolic heterocycles of the general formula (I) and the general formula (I) compounds have been found:

In the above formula

X represents alkyl, halogen or alkoxy,

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

Z represents alkyl, halogen or alkoxy,

n represents a number of 0, 1, 2 or 3,

Het represents a heterocyclic group of the following series,

A and B may be the same or different and are hydrogen, in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl optionally interrupted by at least one heteroatom, or in each case Aryl, aralkyl or hetaryl optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy or nitro, or

A and B together with the carbon atom to which they are attached form a saturated or unsaturated ring which is optionally interrupted and optionally substituted by at least one heteroatom,

E is hydrogen, in each case optionally substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl optionally interrupted by at least one heteroatom, or in each case halogen, alkyl, halogenoalkyl, alkoxy Aryl, aralkyl, or hetaryl optionally substituted by halogenoalkoxy or nitro,

A and E together with the atoms to which they are attached form a saturated or unsaturated monocyclic, bicyclic or tricyclic ring system, optionally interrupted by at least one heteroatom, and optionally substituted;

L represents an alkanediyl group,

M represents one of the following groups,

From here

R ¹ represents hydrogen or alkyl,

R ² represents in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkylthioalkyl, aryl or aralkyl,

R ³ represents optionally substituted alkyl, aryl or aralkyl,

R ⁴ represents hydrogen, halogen, in each case optionally substituted alkyl or pentyl,

R ⁵ represents hydrogen, halogen or optionally substituted alkyl,

Q represents halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, CN or nitro.

m represents 0, 1, 2, or 3.

Depending on the substituents, the compounds of general formula (I) exist as geometric isomers and / or optical isomers or as isomer mixtures of various compositions. Pure isomers and isomer mixtures, their preparation and use, and the components that make up them are included in the claims. However, what is meant below is a mixture of pure compounds and optionally various ratios of isomeric compounds, but is always referred to as compounds of the general formula (I) for convenience.

The novel compounds of general formula (I) have also been found to have very good activity as pesticides, preferably arthropod remedies, fungicides and herbicides.

Furthermore, in the presence of (A) a diluent and a base, a new substituted aryl-keto- of the general formula (Ia) when reacting a compound of the general formula (IIa) with a compound of the general formula (III) When a novel heterocycle is obtained, or (B) a compound of the following general formula (IIb) is subjected to a wave reaction of a compound of the following general formula (IIb) in the presence of a diluent and a base, a compound of the following general formula (Ib) is obtained or (C) In the presence of a diluent and a base, it was found that the compound of formula (Ic) is obtained when the compound of formula (IIc) is reacted with a compound of formula (III):

In the above general formula

A, B, E, L, M, X, Y, Z and n are the same as the above meanings,

L and M are the same as the above meaning,

G represents a leaving group such as halogen, sulfonylalkyl or sulfonylaryl.

Surprisingly, the novel substituted aryl keto-enolic heterocycles (Ia), (Ib), and (Ic) exhibited excellent properties of acaricides, insecticides and herbicides.

The compounds according to the invention are generally defined by general formula (I).

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

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

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

n preferably represents a number from 0 to 3.

Het preferably represents a heterocyclic group of the following series.

A and B are the same or different and are hydrogen, in each case optionally halogen-substituted straight or branched C ₁ -C ₁₂ -alkyl, C ₃ -C ₈ -alkenyl, C ₁ -C ₁₀ -alkoxy-C _2- May be blocked by C ₈ -alkyl, C ₁ -C ₈ -polyalkoxy-C ₂ -C ₈ -alkyl, C ₁ -C ₁₀ -alkylthio-C ₂ -C ₈ -alkyl, oxygen and / or sulfur and Cycloalkyl having 3 to 8 ring atoms, or in each case halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogeno Phenyl, pyrimidyl, imidazyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C ₁ -C ₆ -alkyl optionally substituted by alkoxy or nitro, or

A and B, together with the carbon atoms to which they are attached, are optionally interrupted by oxygen and / or sulfur, optionally halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogeno Saturated substituted by alkyl, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, or phenyl optionally substituted by halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy Or unsaturated 3- to 8-membered rings,

E is hydrogen or in each case optionally halogen-substituted straight or branched C ₁ -C ₁₂ -alkyl, C ₃ -C ₈ -alkenyl, C ₁ -C ₁₀ -alkoxy-C ₂ -C ₈ -alkyl, C ₁ -C ₈ -polyalkoxy-C ₂ -C ₈ -alkyl, C ₁ -C ₁₀ -alkylthio-C ₂ -C ₈ -alkyl, having 3 to 8 reducers, which can be interrupted by oxygen and / or sulfur Optionally substituted by cycloalkyl, or in each case halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkoxy or nitro Phenyl, pyrimidyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C ₁ -C ₆ -alkyl, or

A and E, together with the atoms to which they are attached, are optionally interrupted by oxygen and / or sulfur, optionally halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogeno Saturated substituted by alkyl, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, or phenyl optionally substituted by halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy Or unsaturated 3- to 8-membered rings,

In the formula (I), when Het represents a pyrazolinone ring

A and E with a pyrazoline ring two nitrogen atoms, C ₁ -C ₆ - alkyl, C ₁ -C ₆ - halogenoalkyl, or to be by identical or different substituents consisting of halogen, optionally mono- or polysubstituted formula Group of 1 to 4 is shown.

L preferably represents an alkanediyl group having 1 to 6 carbon atoms.

M preferably represents one of the following groups.

R ¹ preferably denotes hydrogen or C ₁ -C ₁₂ -alkyl.

R ² is preferably at each occurrence an optionally substituted C ₁ -C ₁₂ -alkyl, C ₃ -C ₈ -alkenyl, C ₃ -C ₈ -alkynyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl, C ₁ -C ₈ -alkylthio-C ₂ -C ₈ -alkyl, or in each case halogen, nitro cyano, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ - haloalkyl thio, C ₁ -C ₆ - alkyl or C ₁ -C ₆ - halogenoalkyl represents the optionally substituted phenyl or benzyl by alkyl.

R ³ preferably denotes optionally substituted halogen substituted C ₁ -C ₁₂ -alkyl, or in each case phenyl or benzyl substituted by halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy.

R ⁴ is preferably hydrogen, halogen, optionally halogen substituted C ₁ -C ₆ -alkyl or halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -haloalkyl, C Phenyl substituted by _1- C ₄ -haloalkoxy, cyano or nitro.

R ⁵ preferably denotes hydrogen, halogen or optionally halogen substituted C ₁ -C ₆ -alkyl,

Q preferably represents halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -haloalkoxy, cyano or nitro.

m preferably represents 0, 1, 2, or 3.

X particularly preferably represents C ₁ -C ₆ -alkyl, fluorine, chlorine, bromine or C ₁ -C ₄ -alkoxy,

Y particularly preferably represents halogen, C ₁ -C ₆ -alkyl, fluorine, chlorine, bromine, C ₁ -C ₆ -alkoxy or C ₁ -C ₆ -halogenoalkyl.

Z particularly preferably represents C ₁ -C ₄ -alkyl, fluorine, chlorine, bromine or C ₁ -C ₄ -alkoxy,

n particularly preferably represents a number from 0 to 2.

Het is particularly preferably a heterocyclic group of the following series,

A and B are the same or different and are hydrogen, in each case optionally halogen-substituted straight or branched C ₁ -C ₁₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₁ -C ₈ -alkoxy-C _2- C ₆ -alkyl, C ₁ -C ₆ -polyalkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₈ -alkylthio-C ₂ -C ₆ -alkyl, at 1 to 2 oxygen and / or sulfur atoms Cycloalkyl having 3 to 7 ring atoms, or in each case halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy or nitro Optionally substituted phenyl, pyridinyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolal or phenyl-C ₁ -C ₄ -alkyl, or

A and B, together with the carbon atoms to which they are attached, are optionally interrupted by oxygen and / or sulfur, optionally halogen, C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₃ -halogeno alkyl, C ₁ -C ₄ - halogenoalkyl alkoxy, C ₁ -C ₃ - alkylthio, or halogen, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - substituted by a saturated by alkoxy optionally substituted phenyl Or unsaturated 3- to 8-membered rings,

E is hydrogen or, in each case, optionally substituted straight or branched C ₁ -C ₁₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₁ -C ₈ -alkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₆ -polyalkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₈ -alkylthio-C ₂ -C ₆ -alkyl, which may be interrupted by 1 to 2 oxygen and / or sulfur atoms, 3 Cycloalkyl having from 7 to 7 ring atoms, or in each case phenyl optionally substituted by halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkoxy or nitro, Pyridinyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C ₁ -C ₄ -alkyl, or

A and E, together with the atoms to which they are attached, are optionally interrupted by oxygen and / or sulfur, optionally halogen, C ₁ -C ₅ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₃ -halogenoalkyl , C ₁ -C ₄ - halogenoalkyl alkoxy, C ₁ -C ₃ - alkylthio, or halogen, C ₁ -C ₄ - alkyl or C ₁ -C ₄ - substituted saturated by alkoxy by optionally substituted phenyl or To form an unsaturated 3- to 8-membered ring,

In the formula (I), when Het represents a pyrazolinone ring

A and E are pyrazoline ring with two nitrogen atoms, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - halogenoalkyl, by identical or different substituents consisting of fluorine or chlorine, optionally monosubstituted or multi-substituted The group of following structural formula (1) or (2) is shown.

L particularly preferably represents an alkanediyl group having from 1 to 4 carbon atoms.

M particularly preferably represents one of the following groups,

R ¹ is particularly preferably hydrogen or C ₁ -C ₁₀ -alkyl,

R ² is particularly preferably in each case fluorine-, chlorine-, bromine substituted C ₁ -C ₁₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₆ -alkylthio-C ₂ -C ₆ -alkyl, or in each case fluorine, chlorine, bromine, nitro, Cyano, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -halogenoalkylthio, C ₁ -C ₄ -alkyl or C Phenyl or benzyl optionally substituted by _1- C ₄ -halogenoalkyl.

R ³ is particularly preferably optionally substituted with fluorine, chlorine, bromine-substituted C ₁ -C ₁₀ -alkyl, or in each case fluorine, chlorine, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy Substituted phenyl or benzyl.

R ⁴ is particularly preferably hydrogen, fluorine, chlorine, bromine, optionally fluorine- or chlorine-substituted C ₁ -C ₅ -alkyl, or fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C Phenyl substituted by ₄ -alkoxy, C ₁ -C ₂ -haloalkyl, C ₁ -C ₂ -haloalkoxy, saano or nitro.

R ⁵ particularly preferably represents hydrogen, fluorine, chlorine, bromine or optionally fluorine- or chlorine-substituted C ₁ -C ₄ -alkyl.

Q is particularly preferably fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -haloalkyl, C ₁ -C ₂ -haloalkoxy, saano or nitro Indicates.

m especially preferably represents 0, 1, or 2.

X very particularly preferably represents methyl, ethyl, propyl, isopropyl, fluorine, chlorine, bromine or methoxy.

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

Z very particularly preferably represents methyl, ethyl, propofyl, isopropyl, butyl, isobutyl, t-butyl, fluorine, chlorine, bromine, methoxy or ethoxy.

n very particularly preferably represents 1;

Het very particularly preferably represents a heterocyclic group of the following series;

A and B are the same or different and are hydrogen, in each case optionally fluorine- or chlorine-substituted straight or branched C ₁ -C ₈ -alkyl, C ₃ -C ₄ -alkenyl, C ₁ -C ₆ -alkoxy- C ₂ -C ₄ -alkyl, C ₁ -C ₄ -polyalkoxy-C ₂ -C ₄ -alkyl, C ₁ -C ₆ -alkylthio-C ₂ -C ₆ -alkyl, 1 to 2 oxygen and / or Optionally blocked by sulfur atoms, cycloalkyl having 3 to 6 reducing groups, or in each case fluorine, chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or nitro Substituted phenyl, pyridinyl, imidazolyl, indolyl or phenyl-C ₁ -C ₃ -alkyl, or

A and B, together with the carbon atoms to which they are attached, are optionally interrupted by oxygen and / or sulfur, optionally fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, trifluoromethyl, C To form a saturated or unsaturated 3- to 8-membered ring substituted by _1- C ₂ -alkylthio or phenyl optionally substituted by fluorine, chlorine, methyl, methoxy,

E is hydrogen or in each case optionally fluorine- or chlorine-substituted straight or branched C ₁ -C ₈ -alkyl, C ₃ -C ₄ -alkenyl, C ₁ -C ₆ -alkoxy-C ₂ -C _4- Alkyl, C ₁ -C ₄ -polyalkoxy-C ₂ -C ₄ -alkyl, C ₁ -C ₆ -alkylthio-C ₂ -C ₄ -alkyl, which may be interrupted by 1 to 2 oxygen and / or sulfur atoms Cycloalkyl having 3 to 6 reducing groups, or phenyl, pyridinyl, optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or nitro in each case , Imidazolyl, indolyl or phenyl-C ₁ -C ₃ -alkyl, or

A and E, together with the atoms to which they are attached, are optionally interrupted by oxygen and / or sulfur, optionally fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, trifluoromethyl, C To form a saturated or unsaturated 3- to 8-membered ring substituted by _1- C ₂ -alkylthio or phenyl optionally substituted by fluorine, chlorine, methyl or methoxy,

Or when Het represents a pyrazolinone ring in general formula (I),

A and E represent the groups of the following structural formulas 1 or 2 optionally substituted mono- to trisubstituted by the same or different substituents consisting of methyl, fluorine or chlorine together with the two nitrogen atoms of the pyrazoline ring;

L represents one of the following groups,

M represents one of the following groups,

R ¹ very particularly preferably represents hydrogen or C ₁ -C ₈ -alkyl.

R ² is very particularly preferably in each case optionally fluorine-, chlorine-, bromine- substituted C ₁ -C ₈ -alkyl, C ₃ -C ₄ -alkenyl, C ₃ -C ₄ -alkynyl, cyclopropyl , Cyclopentyl, cyclohexyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₄ -alkyl, C ₁ -C ₆ -alkylthio-C ₂ -C ₄ -alkyl, or in each case fluorine, chlorine, bromine, Phenyl or benzyl optionally substituted by nitro, cyano, methylthio, ethylthio, methoxy, ethoxy, trifluoromethylthio, trifluoromethoxy, methyl, ethyl or trifluoromethyl.

R ³ is very particularly preferably optionally fluorine-, chlorine-, bromine-substituted C ₁ -C ₈ -alkyl, or in each case fluorine, chlorine, C ₁ -C ₂ -alkyl or C ₁ -C ₂ -alkoxy Phenyl or benzyl substituted by

R ⁴ is very particularly preferably hydrogen, fluorine, chlorine, optionally fluorine-, chlorine-substituted C ₁ -C ₄ -alkyl, or fluorine, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl , Phenyl substituted by difluoromethoxy, trifluoromethoxy, cyano or nitro.

R ⁵ very particularly preferably represents hydrogen, fluorine, chlorine, or optionally fluorine- or chlorine-substituted methyl, ethyl, propyl or isopropyl.

Q is very particularly preferably fluorine, chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy, trifluoromethyl, difluoromethoxy, trifluoro methoxy, cya No or nitro.

m very particularly preferably represents 0-2.

In each of these definitions, the pure enantiomeric forms of the compounds of formula (I) are included.

The definitions and descriptions of the radicals described above, whether general or in the preferred range, may be combined with one another as desired. For example, it can combine with each range and a preferable range. This applies to the resulting product, initial reactants and intermediates.

Preferred are compounds of formula (I) which are a combination of the definitions described above as being preferred in the present invention.

Particularly preferred are compounds of general formula (I) which are particularly preferred combinations of the definitions described above in the present invention.

Very particular preference is given to compounds of the formula (I) which are combinations of the definitions described above which are very particularly preferred in the present invention.

The process of the method according to the invention using 3- (2,4-dichlorophenyl) -4-hydroxy-5-methyl-Δ ³ -furan-2-one and chloromethyl ethyl ether by method (A) It can be represented by the following structural formula:

3- (2,6-dichlorophenyl) -4-hydroxy-1-isopropyl-Δ3-pyrroline-2-one and ethyl N-chloromethyl-N-methyl-carbamate by method (B) The process of the method according to the invention using can be represented by the following structural formula:

Bones using 3- (2,4,6-trichlorophenyl) -5-hydroxy-1,2-tetramethylene-Δ ⁴ -pyrazolin-3-one and chloromethyl phenyl ether by method (C) The process of the method according to the invention can be represented by the following structural formula:

The compounds of the general formula (IIa) which are required as starting materials in process (A) are known (see EP 528 156).

In the above formula

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

Compounds of the following general formula (IIb) which are required as starting materials in process (B) are known (see for example EP 355 999, EP 377 893, EP 415 211, EP 442 073, EP 456 063, EP 497 127). , EP 501 129)

In the above formula

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

Compounds of the following general formula (IIc) which are required as starting materials in process (C) are known (see eg WO 92/16510 and EP 508 126).

In the above formula

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

Compounds of the general formula (III) which are additionally required as starting compounds for carrying out the processes (A), (B) and (C) according to the invention are commonly known as compounds of organic chemistry.

Diluents which can be used to carry out the methods (A), (B) and (C) according to the invention are all solvents which are inert to these compounds. Preferred diluents are hydrocarbons such as benzine, benzene, toluene, xylene and tetralin; Halogenated hydrocarbons such as methylene chlorite, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Nitriles such as acetonitrile or propionitrile; It is also a polar solvent which is inert to the compound of general formula (III), such as dimethyl sulfoxide, dimethylformamide, sulfolane or N-methylpyrrolidone.

Salts that can be used to carry out the processes (A), (B) and (C) according to the invention are all customary acid-linkers. Preferred acid-binding agents for use are, for example, triethylbenzyl ammonium chloride, tetrabutylammonium bromide, adogen 464 (= methyltrialkyl (C ₈ , C ₁₀ ) ammonium chloride) or TDA 1 (tris- (methoxyethoxyethyl Alkali metals and alkaline earth metals, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which can be used in the presence of a phase transfer catalyst). In addition, alkali metal and alkaline earth metal hydrates such as sodium amide, sodium hydride and talsium hydride, as well as alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium t-butylate can be used. In addition, tertiary amines such as triethylamine, pyritin, DABCO, DBU, DBA, Hunig salt and N, N-dimethylaniline can be used.

When carrying out the processes (A), (B) and (C) according to the invention, the reaction temperature can be varied in a relatively wide range. The process is generally carried out at temperatures between -20 ° C and 180 ° C, preferably between 0 ° C and 130 ° C.

When carrying out the processes (A), (B) and (C) according to the invention, the reaction components (IIa) and (III) or (IIb) and (III) or (IIc) and (III) and salts are generally It is suitably used in equimolar amounts. However, it is also possible to use one component or another component in excess (up to 3 moles).

Processes (A), (B) and (C) according to the invention are usually carried out under atmospheric pressure. The reaction product is worked up in a conventional manner.

The active compounds of the present invention are suitable for controlling animal pests, preferably arthropods and nematodes, especially insects and ticks, which appear in the fields of agriculture, forestry, storage and materials, and hygiene. They are active against normally sensitive and resistant species and all or part of the growing season. The pests mentioned above include the following.

Isopoda neck, for example Oniscus asellus, Armadillidium vulgare and Porcellio scaber.

From the order of Diloplopoda, for example Blaniulus guttulatus.

From the neck of Chilopoda, for example, Geophilus carp-ophagus and Scutigera spec.

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

From the order of Thysanura, for example, Lepisma saccharina.

The neck of Collembola, for example Onychiurus armatus.

From the order of Orthoptera, for example, Blata orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Ah Keta Domestikus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Systoser Schistocerca gregaria.

From the order of the dermaptera, for example Porficula auricularia.

Termite Isoptera, for example Reticulitermes spp.

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

Allophaga, for example Trichodectes spp. And Damalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralis and Tripps tabaci.

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

The cicada (Homoptera), for example Aleurodes bra-ssicae, Bemisia tabaci, Trialeurodes vaporariorum, Apis gossypii ), Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, hyal Hyptopterus arundinis, Macrorosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca Empoasca spp., Eucelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Lao Laodelphax striatellus, Nilaparvata lagens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. And Psylla spp. )

The order of the Lepidoptera, for example, 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., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo subspecies spp.), Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bissellie-lla, Tynea pelionella (Tinea pellionella), Hofmann-ophila pseudospretella, Cacoacia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana.

Trees of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Hilotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Antonomus spp., Cytophilus subspecies ( Sitophilus spp.), Otiorrhynchus sulcatus, Cosmopolites sordidus, Cethorthornchnch assimilis, Hypera postaica a), Demestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lycusus spp. ), Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp. ), Tenebrio molitor, Agriotes spp., Conoderus spp., Melonta melolontha, Amphimalon soltitialis and Costelitra zealandica.

The order of the Hymenopera, for example Diprion spp., Hoplocampa spp., Lasius spp., Mon-omorium pharaonis and Vespa Subspecies (Vespa spp.).

Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca subspecies ( musca spp., Fannia spp., Califora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp. , Gastrophilus spp., Hippobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Porbia spp., Pegomia hisosiami (Pegomyia hyoscyami), Ceratitis capitata, Dacus oleae, and Tifula Falludosa ( Tipula paludosa).

From the tree of Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp.

Arachnida, for example Scorpio maurus and Latrodectus mactans.

From the order of Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriopies libis ( Eriophyes ribis, Phyllocoptruta oleivora, Bophylus spp., Ripicephalus spp., Ambriomma 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 are characterized by the good activity of insecticides and acaricides.

The active compounds according to the invention are harmful to plants, for example common spider mites or two-spotted spider mites (Tetranychus urticae) or red orchard spider mites (Panonychus ulmi). It can be used particularly successfully to rescue mites.

In addition, the active compound according to the present invention shows activity as a fungicide and activity against Pyridularia o-ryzae, for example, Phytoph-tora and Plasparapara. It is active against the same Oomycetes.

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: Sinapis, Lepidium, Gallium, Stellaria, Matricaria, Anthemis, Galinsoga, Kenopho Chenopodium, Urtica, Senesio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea , Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solumum, Solanum, Rorippa, Low Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis ), Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum,

Dicotyledonous plants : Gossypium, Glycine, Beta, Doucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopercicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledonous weeds : Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Ele Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischamum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Cultivated monocotyledonous plants : Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum ), Saccharum, Ananas, Asparagus and Allium.

However, the active compound use according to the invention is in no way limited to these genera and extends to other plants in the same way.

The compounds are suitable for total control of weeds in sidewalks and plazas, depending on their concentration, for example, with or without industrial areas and railways and trees. Likewise, these compounds are perennial crops on lawns, grasses and pastures, such as afforestation, ornamental tree cultivation, fruit trees, vineyards, citrus forests, nut fruit trees, banana plantations, coffee plantations, tea plantations, rubber planters, palm oil plantations. It can be used for weeding in vineyards, cocoa plantations, soft fruit planters and hop plantations, and for selectively controlling weeds in annual crops.

The compounds of formula (I) according to the invention are suitable for the selective control of monocotyledonous weeds prior to their appearance in dicotyledonous crops. These can be used, for example, in soybeans to very successfully control grass weeds.

The active compounds are conventional formulations such as solutions, emulsions, wettable powders, suspensions,

Very fine capsules can be converted from powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with the active compounds, and polymeric materials.

These formulations are prepared by known methods such as mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, and optionally using surfactants, ie emulsifiers and / or dispersion media and / or blowing agents.

When water is used as the extender, the organic solvent can also be used as an auxiliary solvent, for example. Liquid solvents are mainly aromatics such as xylene, toluene or alkylnaphthalene, chlorinated aromatics such as chlorobenzene, chloroethylene or methylene chloride and chlorinated aliphatic hydrocarbons, cyclohexane or paraffins such as petroleum fractionation, mineral oil and vegetable oils. Alcohols such as aliphatic hydrocarbons, butanol or glycols, as well as ethers and esters thereof, ketones such as acetone, methylethyl ketone, methylisobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water proper.

Suitable solid carriers are:

For example, ammonium salts and underground natural minerals such as kaolin, clay, talc, chalk, quartz, attapugite, montmorillonite, diatomaceous earth, and underground synthesis such as highly-dispersed silica, alumina, silicates Minerals are suitable, and solid carriers for granules include, for example, synthetic granules of inorganic and organic meals as well as crushed and granular natural rocks such as calcite, marble, pumice, calcite and dolomite, and sawdust, coconut shell, corn And granules of organic material such as tobacco stems are suitable; Emulsions and / or blowing agents include, for example, albumin hydrolysis products as well as polyoxyethylene fatty acid esters, polyoxyethylene aliphatic alcohol ethers, i.e. non-ions such as alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates Positive and anionic emulsifiers are suitable; As the dispersion medium, for example, lignin-sulfite waste liquid and methylcellulose are suitable.

The formulation can be used in natural and synthetic polymers in the form of natural phospholipids and synthetic phospholipids such as cephalin and lecithin, as well as adhesives such as carboxymethylcellulose, gum arabic, polyvinyl alcohol and polyvinylacetate, and in the form of latex, granules or powders. There is. Other additives include mineral and vegetable oils.

Inorganic dyes such as iron oxide, titanium oxide, and Prussian blue, and colorants such as alizarin dyes, azo dyes, and organic dyes such as metal phthalocyanine dyes, and salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc; The same micronutrients can be used.

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

The form of use of the active compounds according to the invention for controlling weeds, in their own or in the form of their preparations, can also be used as mixtures with known herbicides, also as final preparations or tank mixtures.

Suitable herbicides for the mixtures include known herbicides such as anilides such as diflufenican, propanyl; Arylcarboxylic acids such as dichloropicolinic acid, dicamba, picloram; Aryloxyalkanoic acids such as 2,4-D, 2,4-DB, 2,4-DP, fluoroxypyr, MCPA, MCPP, triclopyr; Aryloxy-phenoxy-alkanoic acid esters such as diclofo-methyl, phenoxaprop-ethyl, fluazifop-butyl, halooxyphor-methyl, quinacofop-ethyl; Azinones such as chloridazone, norflurazone; Carbamate, such as chlorprofam, desmedapem, penmedipam, profam; Chloroacetanilides such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor, propachlor; Dinitroanilines such as oryzaline, pendimethalin, trituralin; Diphenyl ethers such as acifluorophene, biphenox, fluoroglycopene, pomesafen, halosafen, lactofen, oxyfluorfen; Ureas such as chlortoluron, diuron, fluoromethuron, isoproturon, linuron, metabenzthiazuron; Hydroxylamines such as alkoxydim, cletodim, cyclooxydim, cetoxydim, trakoxydim; Imidazolinones such as imazetapyr, imazamethabenz, imazapyr, imazaquin; Nitriles such as bromoxynil, diclobenyl, oxynyl; Oxacetamides such as mefenacet; Amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cynosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, tria Sulfonylureas such as sulfuron, tribenuron-methyl; Thiocarbamates such as butyrate, cycloate, di-acrylate, EPTC, esprocap, molinate, prosulfocap, thiobencap, tri-acrylate; Triazines such as atrazine, cyanazine, simazine, cymetrine, terbutryn, terbutylazine; Triazinones such as hexazinone, metamitrone, and metrizine; Others, ie aminotriazoles, benfuresate, bentazone, synmethyline, clomazone, clopyralide, dipfencuart, dityropyr, etofumesate, fluorochloridone, glufosinate, glyphosate , Isoxaben, pyridate, quinclolac, quinmerak, sulfosate and tridiphane.

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

Pesticides include, for example, phosphates, carbamates, carboxyl esters, chlorinated hydrocarbons, phenylurea, substances produced by microorganisms, and the like.

The following compounds may be mentioned:

Acrinatrin, alphamethrin, betacyfluthrin, bifenthrin, bromofenprox, cis-resmethrin, clositerin, cycloprotrin, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin , Esfenvalerate, etofenprox, phenpropatrine, penvalerate, flucitalinate, fluvalinate, lambda-cyhalothrin, permethrin, pyresmethrin, pyrethrum, silafluorene, tralome Trine, Zetamethrin,

Alanikab, Bendiocarb, Benpracab, Buppencarb, Butokecarbsim, Carbaryl, Cartop, Ethiophenecarb, Phenobucarb, Phenoxycarb, Isoprocarb, Methiocarb, Methoxyl, Metolcarb, Oxa Wheat, pyrimikab, promecarb, propoxur, terbam, thiodicarb, thiophanox, trimetacarb, XMC, xylylcarb,

Acetate, azine force A, azine force M, bromophos A, kadusafos, carbophenothione, chlorfenbinfos, chlormephos, chlorpyrifoss, chlorpyrifoss M, cyanophos, demethone M, Demethone-S-methyl, demethone S, diazinone, dichlorboth, diclifoss, dichlorpention, dicrotophos, dimethatoate, dimethylbinforce, dioxatione, disulfotone, edifeneforce, Ethion, erythrite, phenythrothione, pention, phonophos, formotene, heptenophos, iprobenfos, isosafos, isoxation, forate, malathion, mechabam, merbin force, Mesulfenfos, methacryfoss, metamidose, nared, ometoate, oxydemethone M, oxydepropos, parathion A, parathion M, pentoate, forate, posalon, phosmet, phosphamdone, Depths, Pyrimiforce A, Pyrimiforce M, Propaphos, Prothiophos, Protoate, Blood Greater force, flutes are pentynyl on, kwinal force, salicylate thione, details phosphonic, sulfonic potep, sulfonic Pro phosphonium, tetra-chlor empty force teme phosphine, thio meton, thio Rajin, trees chlor phone, triazole crude force bar shown thione,

Buprofezin, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, pyriproxyfen, tebufenozide, tflubenzuron, triflumuron,

Imidacloprid, nitenpyram, N-[(6-chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethaneimide-amide (NI-25),

Abamectin, Amitrazine, Avermectin, Azadiractin, Bensultap, Bacillus, Turingiensis, Cyromazine, Diafenthiuron, Emamectin, Etopenprox, Penpyrad, Fipronil, Flufenprox, Loupe Nuron, Metaldehyde, Milvemectin, Pimetrozine, Tebufenpyrad, Triazuron,

Aldicarb, Bendiocarb, Benfuracarb, Cabofuran, Carbosulphan, Chloethoxyphos, Cloetocarb, Disulfotone, Etoprophos, Etrimphos, Phenamiphos, Fipronil, Phonophos, Postia Jade, furathiocarb, HCH, isazofoss, isofenfoss, methiocarb, monocrotophos, nitenpyram, oxamyl, forate, bombardment, prothiophos, pyraclophos, cebufoss, silafluorophene , Tebupyrimphos, tefluthrin, terbufoss, thiodicarb, thiaphenox,

Azocyclotin, butylpyridaben, clofentezin, cyhexatin, dipenturon, diethion, emamectin, phenazaquine, fenbutatin oxide, phenothiocarb, phenpropatrine, fenpyrad, fenpyroximate, Fluazinam, Fluazuron, Flucyclolowon, Flufenoxuron, Fluvalinate, Pufenfenx, Hexiaxans, Ivemectin, Methidation, Monoclotophosphate, Moxidextin, Naled, Posalon, Pro Phenophos, pyraclophos, pyridaben, pyrimidipene, tebufenpyrad, turingiencin, triarathene, and also 4-bromo-2- (4-chlorophenyl) -2- (ethoxymethyl)- 5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (AC 303630).

The active compounds can be used on their own or in the form of their preparations, or in the forms of use prepared from them, such as ready-to-use solutions, suspensions, wetting agents, soluble powders, pastes and granules. It is used by conventional methods such as watering, spraying, misting, spraying and the like.

The active compounds according to the invention can be applied before or after the emergence of plants. They can also be included in the soil before seeding.

The amount of active compound used can vary within a significant range. This depends substantially on the nature of the desired effect. Generally, the amount used per hectare of soil surface is from 10 g to 10 kg of active compound, preferably from 50 g to 5 kg.

The preparation and use of the active compounds according to the invention are shown in the following examples.

Manufacturing Example

Example Ia-1

1.47 g (15.5 mmol) of chloromethyl ethyl ether in 15 ml of pure dichloromethane is added to 3- (2,4,6-trimethylphenyl) -4-hydroxy-5 in 60 ml of pure dichloromethane under nitrogen at 0 ° C to 10 ° C. 4.3 g (15 mmol) of 5-pentamethylene-Δ ³ -dihydrofuran-2-one, 1.67 g (16.5 mmol) of triethylamine, and a small amount of DMAP were added dropwise. The reaction mixture was stirred at room temperature for 20 hours, washed successively with 10% citric acid, sodium bicarbonate solution and sodium chloride solution, the organic phase was dried over sodium sulfate and the solvent was removed. The crude product was then purified on silica gel column (eluent: chloroform / ethyl acetate (3: 1).

2.47 g of 3- (2,4,6-trimethylphenyl) -4-ethoxymethyl-oxy) -5,5-pentamethylene-Δ ³ -dihydrofuran-2-one having a melting point of 102 ° C. (theoretical 53 %) Was obtained.

Similar to Example I, the compounds of the following Preparation Examples of Formula (Ita) were synthesized.

Table 1

Similar to Example Ia-1, Preparation Example Ib-1 was also obtained:

¹ H-NMR (200 MHz, CDCl ₃ ): 2.12, 2.2, 2.26 (3s, 9H, Ar- CH ₃ ), 3.88 (s, 3H, SO ₂ , CH ₃ ), 3.92 (s, 3H, N- CH ₃ ), 3.25, 3.62 (m, 2H, N- CH ₂ ), 4.21 (dd, 1H, C H -N) 4.72 (ABq, 2H, O- CH ₂ N), 6.89 (s, 2H, Ar-H ).

Similar to Example Ia-1, an example of preparation of general formula (Ic-1) having a melting point of 207 ° C was also obtained.

Example Ic-1

Example of use

In the Examples used below, the compound 4-methoxy-3- (3-trifluoromethylphenyl) -5-methyl-5H-furan-2-one (known in German Patent No. 31 31 773, Example 6) This control was used.

Example A

Panonicus Exam

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

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

Active compound formulations of the desired concentration for young oak trees (Prunus do-mestica), about 30 cm tall, heavily infected with red fruit orchard mites (Panonychus ulmi) at all stages of growth. Sprayed on.

After a certain period of time, the percent rescued was determined. 100% means that all spider mites have been killed and 0% means that no spider mite has been killed.

In this test, for example, the compounds of Preparation Examples (Ia-1), (Ia-2), (Ia-5) and (Ia-7) are 100 after 7 days at an exemplary active compound concentration of 0.02% A rescue rate of% is shown.

Example B:

Tetranychus test (OP-resistant)

Solvent: Dimethylformamide 3 parts by weight

Emulsion: 1 part by weight of alkylaryl polyglycol ether

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

Soybean plants (Phaseolus vulgaris) heavily infected with common spider mites or two-spotted spider mites (Tetranychus urticae) at all stages of growth were immersed in the active compound preparation at the desired concentration. .

After a certain period of time, the relief rate was determined in%. 100% means that all mites have been killed; 0% means that none of the mites have been killed.

In this test, for example, the compounds of Preparation Examples Ia-1, Ia-2, Ia-5 and Ia-7 exhibited a rescue rate of at least 98% after 7 days at an exemplary active compound concentration of 0.02%.

Example C

Germination test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

One part by weight of the active compound is mixed with the specified amount of solvent, the indicated 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 test plants are planted in normal soil and after 24 hours, preparations of the active compounds are sprayed. Constant amounts of water per unit area were taken. The concentration of active compound in the formulation is not critical but the amount of active compound per unit area is set. After 3 weeks, the degree of damage of the plants is graded in percent of 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-1) and (Ia-2) show very good effects on weeds, while in some cases very good for crops such as wheat and soybeans, for example. Resistance was shown. At an application rate of 1000 g / ha, for example, Alopecurus, Cynodon, Digitaria, Lolium and Setaria are at least 90% infected. .

Example D:

Phaedon Larva Test

Solvent: Dimethylformamide 7 parts by weight

Emulsion: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent and the specified amount of 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 immersion in the active compound formulation of the desired concentration and infected with mustard beetle larvae (Phaedon cochleariae) while the leaves are damp. I was.

After a period of time, the percent rescued was determined. 100% means that all the scarab larvae have been killed; 0% means that none of the scarab larvae have been killed.

In this test, for example, the compounds of Preparation Examples Ia-9, Ia-12, Ia-13, Ia-14, Ia-15 Ib-1 and Ic-1 after 7 days at an exemplary active compound concentration of 0.01% , 100% of the rescue rate, while the prior art compound (A) did not rescue at all.

Example E

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 was mixed with a specified amount of solvent and a specified amount of emulsifier, and the concentrate was diluted with water to a desired concentration to prepare a suitable formulation of the active compound.

The cabbage leaves (Brasica oleracea) are treated by immersion in the active compound preparation of the desired concentration, and infected with cabbage moth caterpillar (Plutella maculipennis) while the leaves are moist. I was.

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

In this test, the compounds of Preparation Examples Ia-14 and Ia-27, for example, at a concentration of 0.01% of the exemplary active compounds, exhibited a 100% remission rate after 3 days, whereas Compound (A) of the prior art Did not rescue at all.

Example F

Nepotetics 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 the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water containing the emulsifier to the desired concentration to prepare a suitable formulation of the active compound.

The mother (Oryza sativa) was treated by immersion in the active compound formulation at the desired concentration and infected with the larvae of the cicada cicada layer (Nepotetics sinctifs) while the leaves were damp.

After a certain period of time, the percent mortality was determined. 100% means that all the larvae have been killed, and 0% means that none of the larvae have been killed.

In this test, for example, Production Examples Ia-1, Ia-3, Ia-9, Ia-12, Ia-13, Ia-15, Ia-25, Ia-26, Ia-27, Ia-28 Compounds of Ia-31, Ib-1 and Ic-1 showed 100% rescue after 6 days at an exemplary active compound concentration of 0.01%, while Compound (A) of the prior art did not rescue at all.

Example G

Miss Juice 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 the specified amount of solvent and the specified amount of 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) heavily infected with peach aphids were treated by immersion in the active compound formulation at the desired concentration.

After a certain period of time, the percent rescued was determined. 100% means that all aphids have been killed, and 0% means that none of the aphids have been killed.

In this test, for example, the compounds of Preparation Examples Ia-1 and Ia-28 showed a 100% rescue after 6 days at an exemplary active compound concentration of 0.1%, whereas Compound (A) of the prior art Did not rescue at all.

Claims (9)

Substituted aryl keto-enolic heterocycles of formula (I) Where 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 a number from 0 to 3, Het represents a heterocyclic group of the following series, A and B are the same or different and are hydrogen, in each case optionally halogen-substituted straight or branched C ₁ -C ₁₂ -alkyl, C ₃ -C ₈ -alkenyl, C ₁ -C ₁₀ -alkoxy-C _2- May be blocked by C ₈ -alkyl, C ₁ -C ₈ -polyalkoxy-C ₂ -C ₈ -alkyl, C ₁ -C ₁₀ -alkylthio-C ₂ -C ₈ -alkyl, oxygen and / or sulfur and Cycloalkyl having 3 to 8 ring atoms, or in each case halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogeno Phenyl, pyrimidyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C ₁ -C ₆ -alkyl optionally substituted by alkoxy or nitro, or A and B are optionally interrupted by oxygen and / or sulfur with the carbon atoms to which they are attached, optionally halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl Saturation substituted by phenyl optionally substituted by C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, or halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, or To form an unsaturated 3- to 8-membered ring, E is hydrogen or in each case optionally halogen-substituted straight or branched C ₁ -C ₁₂ -alkyl, C ₃ -C ₈ -alkenyl, C ₁ -C ₁₀ -alkoxy-C ₂ -C ₈ -alkyl, C ₁ -C ₈ -polyalkoxy-C ₂ -C ₈ -alkyl, C ₁ -C ₁₀ -alkylthio-C ₂ -C ₈ -alkyl, having 3 to 8 reducers, which can be interrupted by oxygen and / or sulfur Optionally substituted by cycloalkyl, or in each case halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkoxy or nitro Phenyl, pyrimidyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C ₁ -C ₆ -alkyl, or A and E, together with the atoms to which they are attached, are optionally interrupted by oxygen and / or sulfur, optionally halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl Saturated substituted by C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, or phenyl optionally substituted by halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy, or To form an unsaturated 3- to 8-membered ring, In the formula (I), when Het represents a pyrazolinone ring A and E with a pyrazoline ring two nitrogen atoms, C ₁ -C ₆ - alkyl, C ₁ -C ₆ - halogenoalkyl, or to be by identical or different substituents consisting of halogen, optionally mono- or polysubstituted formula Group of 1 to 4, L represents an alkanediyl group having 1 to 6 carbon atoms, M represents one of the following groups, R ¹ represents hydrogen or C ₁ -C ₁₂ -alkyl, R ² in each occurrence is optionally substituted C ₁ -C ₁₂ -alkyl, C ₃ -C ₈ -alkenyl, C ₃ -C ₈ -alkynyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₈ -Alkoxy-C ₂ -C ₈ -alkyl, C ₁ -C ₈ -alkylthio-C ₂ -C ₈ -alkyl, or in each case halogen, nitro, cyano, C ₁ -C ₆ -alkoxy, C _1- Phenyl or benzyl optionally substituted by C ₆ -haloalkoxy, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -haloalkylthio, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -halogenoalkyl Indicates R ³ represents optionally substituted halogen substituted C ₁ -C ₁₂ -alkyl, or in each case phenyl or benzyl substituted by halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy, R ⁴ is hydrogen, halogen, optionally halogen substituted C ₁ -C ₆ -alkyl or halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -haloalkyl, C _1- Phenyl substituted by C ₄ -haloalkoxy, cyano or nitro, R ⁵ represents hydrogen, halogen or optionally halogen substituted C ₁ -C ₆ -alkyl, Q represents halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -haloalkoxy, cyano or nitro, m represents 0, 1, 2, or 3. The method of claim 1, X represents C ₁ -C ₆ -alkyl, fluorine, chlorine, bromine or C ₁ -C ₄ -alkoxy, Y represents halogen, C ₁ -C ₆ -alkyl, fluorine, chlorine, bromine, C ₁ -C ₆ -alkoxy or C ₁ -C ₆ -halogenoalkyl, Z represents C ₁ -C ₄ -alkyl, fluorine, chlorine, bromine or C ₁ -C ₄ -alkoxy, n represents a number from 0 to 2, Het represents a heterocyclic group of the following series, From here, A and B are the same or different and are hydrogen, in each case optionally halogen-substituted straight or branched C ₁ -C ₁₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₁ -C ₈ -alkoxy-C _2- C ₆ -alkyl, C ₁ -C ₆ -polyalkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₈ -alkylthio-C ₂ -C ₆ -alkyl, at 1 to 2 oxygen and / or sulfur atoms Cycloalkyl having 3 to 7 ring atoms, or in each case halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy or nitro Optionally substituted phenyl, pyridinyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C ₁ -C ₄ -alkyl, or A and B are optionally interrupted by oxygen and / or sulfur with the carbon atoms to which they are attached, optionally halogen, C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₃ -halogenoalkyl , C ₁ -C ₄ - halogenoalkyl alkoxy, C ₁ -C ₃ - alkylthio, or halogen, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - substituted saturated by alkoxy by optionally substituted phenyl or To form an unsaturated 3- to 8-membered ring, E is hydrogen or, in each case, optionally substituted straight or branched C ₁ -C ₁₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₁ -C ₈ -alkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₆ -polyalkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₈ -alkylthio-C ₂ -C ₆ -alkyl, which may be interrupted by 1 to 2 oxygen and / or sulfur atoms, 3 Cycloalkyl having from 7 to 7 ring atoms, or in each case phenyl optionally substituted by halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkoxy or nitro, Pyridinyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C ₁ -C ₄ -alkyl, or A and E, together with the atoms to which they are attached, are optionally interrupted by oxygen and / or sulfur, optionally halogen, C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₃ -halogenoalkyl, C ₁ -C ₄ - halogenoalkyl alkoxy, C ₁ -C ₃ - alkylthio, or halogen, C ₁ -C ₄ - alkyl or C ₁ -C ₄ -, saturated or unsaturated substituted by a phenyl optionally substituted by alkoxy To form 3- to 8-membered rings, In the formula (I), when Het represents a pyrazolinone ring A and E are pyrazoline ring with two nitrogen atoms, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - halogenoalkyl, by identical or different substituents consisting of fluorine or chlorine, optionally monosubstituted or multi-substituted Group represented by the following structural formula 1 or 2, L represents an alkanediyl group having 1 to 4 carbon atoms, M represents one of the following groups, R ¹ represents hydrogen or C ₁ -C ₁₀ -alkyl, R ² is in each case optionally fluorine, chlorine, bromine substituted C ₁ -C ₁₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C ₃ -C ₈ -cycloalkyl , C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, C ₁ -C ₆ -alkylthio-C ₂ -C ₆ -alkyl, or in each case fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -halogenoalkylthio, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -Phenyl or benzyl optionally substituted by halogenoalkyl, R ³ is optionally fluorine-, chlorine-, bromine-substituted C ₁ -C ₁₀ -alkyl, or in each case phenyl substituted by fluorine, chlorine, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy Or benzyl, R ⁴ is hydrogen, fluorine, chlorine, bromine, optionally fluorine- or chlorine-substituted C ₁ -C ₅ -alkyl, or fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, Phenyl substituted by C ₁ -C ₂ -haloalkyl, C ₁ -C ₂ -haloalkoxy, cyano or nitro, R ⁵ represents hydrogen, fluorine, chlorine, bromine or optionally fluorine- or chlorine-substituted C ₁ -C ₄ -alkyl, Q represents fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -haloalkyl, C ₁ -C ₂ -haloalkoxy, cyano or nitro, m is a compound of the general formula (I) which represents 0, 1, or 2. The method of claim 1, X represents methyl, ethyl, propyl, isopropyl, fluorine, chlorine, bromine or methoxy, Y represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl, Z represents methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, fluorine, chlorine, bromine, methoxy or ethoxy, n represents 1, Het represents a heterocyclic group of the following series; A and B are the same or different and are hydrogen, in each case optionally fluorine- or chlorine-substituted straight or branched C ₁ -C ₈ -alkyl, C ₃ -C ₄ -alkenyl, C ₁ -C ₆ -alkoxy- C ₂ -C ₄ -alkyl, C ₁ -C ₄ -polyalkoxy-C ₂ -C ₄ -alkyl, C ₁ -C ₆ -alkylthio-C ₂ -C ₆ -alkyl, 1 to 2 oxygen and / or Blocked by sulfur atoms, cycloalkyl having 3 to 6 reducing groups, or in each case by fluorine, chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or nitro Optionally substituted phenyl, pyridinyl, imidazolyl, pyrazolyl, indolyl or phenyl-C ₁ -C ₃ -alkyl, or A and B are optionally interrupted by oxygen and / or sulfur with the carbon atoms to which they are attached, optionally fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, trifluoromethyl, C ₁ Forms a saturated or unsaturated 3- to 8-membered ring substituted by -C ₂ -alkylthio or phenyl optionally substituted by fluorine, chlorine, methyl, methoxy, E is hydrogen or in each case optionally fluorine- or chlorine-substituted straight or branched C ₁ -C ₈ -alkyl, C ₃ -C ₄ -alkenyl, C ₁ -C ₆ -alkoxy-C ₂ -C _4- Alkyl, C ₁ -C ₄ -polyalkoxy-C ₂ -C ₄ -alkyl, C ₁ -C ₆ -alkylthio-C ₂ -C ₄ -alkyl, which may be interrupted by 1 to 2 oxygen and / or sulfur atoms Cycloalkyl having 3 to 6 reducing groups, or phenyl, pyridinyl, optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or nitro in each case , Imidazolyl, indolyl or phenyl-C ₁ -C ₃ -alkyl, or A and E, together with the atoms to which they are attached, are optionally blocked by oxygen and / or sulfur, optionally fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, trifluoromethyl, C ₁ Or form a saturated or unsaturated 3- to 8-membered ring substituted by -C ₂ -alkylthio or phenyl optionally substituted by fluorine, chlorine, methyl or methoxy, In the formula (I), when Het represents a pyrazolinone ring, A and E represent groups of the following structural formulas 1 or 2 optionally substituted mono- to trisubstituted by the same or different substituents of methyl, fluorine or chlorine with the two nitrogen atoms of the pyrazoline ring; L represents one of the following groups, M represents one of the following groups, R ¹ represents hydrogen or C ₁ -C ₈ -alkyl, R ² in each case is optionally fluorine-, chlorine-, bromine- substituted C ₁ -C ₈ -alkyl, C ₃ -C ₄ -alkenyl, C ₃ -C ₄ -alkynyl, cyclopropyl, cyclopentyl, cyclo Hexyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₄ -alkyl, C ₁ -C ₆ -alkylthio-C ₂ -C ₄ -alkyl, or in each case fluorine, chlorine, bromine, nitro, cyano, Phenyl or benzyl optionally substituted by methylthio, ethylthio, methoxy, ethoxy, trifluoromethylthio, trifluoromethoxy, methyl, ethyl or trifluoromethyl, R ³ is optionally fluorine-, chlorine-, bromine-substituted C ₁ -C ₈ -alkyl, or in each case phenyl substituted by fluorine, chlorine, C ₁ -C ₂ -alkyl or C ₁ -C ₂ -alkoxy Or benzyl, R ⁴ is hydrogen, fluorine, chlorine, optionally fluorine-, chlorine-substituted C ₁ -C ₄ -alkyl, or fluorine, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy, Phenyl substituted by trifluoromethoxy, cyano or nitro, R ⁵ represents hydrogen, fluorine, chlorine or optionally fluorine- or chlorine-substituted methyl, ethyl, propyl or isopropyl, Q represents fluorine, chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy, trifluoromethyl, difluoromethoxy, trifluoro methoxy, cyano or nitro , m is a compound of general formula (I) which represents 0-2. (A) in the presence of a diluent and a base, a compound of formula (IIa) is reacted with a compound of formula (III) to shrink the compound of formula (Ia), or (B) the presence of a diluent and a base Under the following reaction of a compound of formula (IIb) with a compound of formula (III) to give a compound of formula (Ib), or (C) in the presence of a diluent and a base, The substituted arylketo-enoloxy heterocycle of formula (I) according to claim 1, characterized in that the compound of formula (III) is reacted with a compound of formula (III) to obtain a compound of formula (Ic) To prepare a method; In the above formula A, B, E, L, M, X, Y, Z and n have the same meanings as defined in claim 1, G is a leaving group. A pesticide composition, characterized in that it contains at least one compound of general formula (I) according to claim 1. Arthropod control, fungicide or herbicide composition, characterized in that it contains at least one compound of general formula (I) according to claim 1. Arthropods, plant hospitals in the field of plant protection, homes, hygiene and storage supplies protection, characterized in that the compounds of formula (I) according to claim 1 act on arthropods, plant hospital fungi, unwanted plants or their habitats How to control the growth of fungi or unnecessary plants. A method for controlling pests in the field of plant protection, house, sanitation and storage protection, characterized in that the compound of formula (I) according to claim 1 is acted on the pest or the habitat of the pest. A process for preparing a pesticide composition, characterized in that the compound of formula (I) according to claim 1 is mixed with at least one substance selected from the group consisting of extenders and surfactants.