DE4413669A1 - Substituted aryl ketoenol heterocycles - Google Patents

Description

The present invention relates to new substituted aryl-ketoenol heterocycles, several processes for their preparation and their use as pests pesticides.

It is known that certain substituted Δ³-dihydrofuran-2-one derivatives have herbicidal properties (cf. DE-A 40 14 420). The synthesis of the as Starting compounds used tetronic acid derivatives (such as 3- (2-methyl phenyl) -4-hydroxy-5- (4-fluorophenyl) Δ³-dihydrofuranon- (2)) is also in DE-A 40 14 420 described. Similar structured connections without specifying one insecticidal and / or acaricidal activity are from the Campbell publication et al. J. Chem. Soc., Perkin Trans. 1 1985, (8) 1567-76.

Pharmaceutical properties of 3-acyl-pyrrolidine-2,4-diones are over (S. Suzuki et al. Chem. Pharm. Bull. 15 1120 (1967)). Furthermore, were N-phenylpyrrolidine-2,4-dione by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem. 1985 1095). A biological effectiveness of these ver bindings were not described.

In EP-A 0 262 399 similarly structured compounds (3-aryl-pyrrolidine 2,4-dione) disclosed, of which, however, no herbicidal, insecticidal or acaricidal Effect has become known. Known with herbicidal, insecticidal or akari Unsubstituted, bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives have a cidative effect (EP-A 355 599 and EP 415 211), substituted bicyclic 3-aryl-pyrrolidine-2,4- dione derivatives (EP 501 129) and substituted monocyclic 3-aryl-pyrrolidine 2,4-dione derivatives (EP-A 377 893, EP 442 077 and EP 497 127).  

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

Tetronic acid derivatives with fungicidal, herbicidal, acaricidal are also known and insecticidal properties (EP 528 156).

4-arylpyrazolidinedione derivatives with herbicidal, acaricidal and insecticidal properties Shafts are described in WO 92/16510 and EP 508 126.

New substituted aryl-ketoenol heterocycles of the formula (I)

found,
in which
X represents alkyl, halogen or alkoxy,
Y represents hydrogen, alkyl, halogen, alkoxy or haloalkyl,
Z represents alkyl, halogen or alkoxy,
n stands for a number 0, 1, 2 or 3,
Het for a heterocyclic group in the series

stands,
A and B may be the same or different and are each hydrogen, optionally substituted by halogen substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, optionally interrupted by at least one heteroatom cycloalkyl or in each case optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or nitro Aryl, aralkyl or hetaryl,
or in what
A and B together with the carbon atom to which they are attached form a saturated or unsaturated, optionally interrupted by at least one heteroatom and optionally substituted cycle,
E represents hydrogen, in each case optionally substituted by halogen substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, optionally cycloalkyl interrupted by at least one heteroatom or in each case optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or nitro aryl, aralkyl or hetaryl,
or in what
A and E together with the atoms to which they are attached form a saturated or unsaturated, optionally interrupted by at least one heteroatom and optionally substituted cycle, bicyclic or tricyclic,
L represents an alkanediyl group,
M represents one of the following groupings:

in which
R¹ represents hydrogen or alkyl,
R² represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkylthioalkyl, aryl or aralkyl,
R³ represents optionally substituted alkyl, aryl or aralkyl,
R⁴ represents hydrogen, halogen, in each case optionally substituted alkyl or phenyl,
R⁵ represents hydrogen, halogen or optionally substituted alkyl,
Q represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, CN or nitro and
m represents a number 0, 1, 2 or 3,
as well as the enantiomerically pure forms of compounds of the formula (I).

Depending on the substituents, the compounds of the formula (I) can be used as geometric and / or optical isomers or isomer mixtures of different Composition. Both the pure isomers and the  Mixtures of isomers, their preparation and use and those containing them Agents are part of the claimed invention. In the following the However, for the sake of simplicity, always spoken of compounds of the formula (I) although both the pure compounds and optionally also mixtures with different proportions of isomeric compounds are meant.

Furthermore, it was found that the new compounds of formula (I) are very good effectiveness as a pesticide, preferably as an arthropo have dicides, fungicides and herbicides.

Furthermore, it was found that the new substituted aryl ketoenol heterocycles of the formula (Ia)

in which
A, B, L, M, X, Y, Z and n have the meaning given above,
receives,
if

• (A) compounds of the formula (IIa) in which
  A, B, X, Y, Z and n have the meaning given above, with compounds of the formula (III) GLM (III) in which
  L and M have the meaning given above
  and
  G represents a leaving group, such as halogen, sulfonylalkyl or sulfonylaryl,
  in the presence of a diluent and in the presence of a base.
• (B) Compounds of the formula (Ib) are also obtained in which
  A, B, E, L, M, X, Y, Z and n have the meaning given above,
  if compounds of the formula (IIb) in which
  A, B, E, X, Y, Z and n have the meaning given above,
  with compounds of the formula (III) GLM (III) in which
  L and M have the meaning given above
  and
  G represents a leaving group, such as halogen, sulfonylalkyl or sulfonylaryl,
  in the presence of a diluent and in the presence of a base.
• (C) In addition, compounds of the formula (Ic) in which
  A, E, L, M, X, Y, Z and n have the meaning given above,
  if compounds of the formula (IIc) in which
  B, E, X, Y, Z and n have the meaning given above,
  with compounds of the formula (III) GLM (III) in which
  L and M have the meaning given above
  and
  G represents a leaving group, such as halogen, sulfonylalkyl or sulfonylaryl,
  in the presence of a diluent and in the presence of a base.

Surprisingly, the new substituted aryl-ketoenol heterocycles show (Ia), (Ib) and (Ic) good acaricidal, insecticidal and herbicidal properties.

The compounds according to the invention are generally defined by the formula (I).
X preferably represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy.
Y preferably represents hydrogen, C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy or C₁-C₃-haloalkyl.
Z preferably represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy.
n is preferably a number from 0 to 3.
Het preferably represents a heterocyclic group from the series

wherein
A and B are the same or different and are hydrogen or straight-chain or branched C₁-C₁₂-alkyl optionally substituted by halogen, C₃-C₈-alkenyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl, C₁-C₈-poly alkoxy- C₂-C₈-alkyl, C₁-C₁₀-alkylthio-C₂-C₈-alkyl, cycloalkyl with 3 to 8 ring atoms, which can be interrupted by oxygen and / or sulfur or in each case optionally by halogen, C₁-C₆-alkyl, C₁-C₆ - Haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy or nitro-substituted phenyl, pyriniidyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁-C₆-alkyl,
or in what
A and B together with the carbon atom to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy substituted phenyl 3- to 8-membered ring,
E for hydrogen or in each case optionally substituted or substituted by halogen, straight-chain or branched C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₁-C₁₀- alkoxy-C₂-C₈-alkyl, C₁-C₈-polyalkoxy-C₂-C₈-alkyl, C₁- C₁₀-alkylthio-C₂- C₈-alkyl, cycloalkyl having 3 to 8 ring atoms, which can be interrupted by oxygen and / or sulfur or in each case optionally by halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy , C₁-C₆- haloalkoxy or nitro substituted phenyl, pyrimidyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁-C₆-alkyl,
or in what
A and E together with the atoms to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy substituted phenyl substituted 3- to 8-membered ring,
or if Het in formula (I) represents a pyrazolinone ring
A and E together with the two nitrogen atoms of the pyrazoline ring represent a group of the formulas 1 to 4 below which may be mono- or polysubstituted, identically or differently, by C₁-C₆-alkyl, C₁-C₆-haloalkyl or halogen

L preferably represents an alkanediyl group having 1 to 6 carbon atoms.
M preferably represents one of the following groups:

R¹ is preferably hydrogen or C₁-C₁₂ alkyl.
R² preferably represents in each case optionally substituted by halogen C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl, C₃-C₈-cycloalkyl, C₁-C₈-alk oxy-C₂-C₈-alkyl, C₁-C₈- Alkylthio-C₂-C₈-alkyl, for each optionally by halogen, nitro, cyano, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆- alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-alkyl or C₁- C₆-haloalkyl substituted phenyl or benzyl.
R³ preferably represents C₁-C₁₂- alkyl which is optionally substituted by halogen or phenyl or benzyl which is each substituted by halogen, C₁-C₆alkyl or C₁-C₆alkoxy.
R⁴ preferably represents hydrogen, halogen, optionally substituted by halogen substituted C₁-C₆-alkyl or in each case by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, cyano or nitro Phenyl.
R⁵ preferably represents hydrogen, halogen or C₁-C₆-alkyl optionally substituted by halogen.
Q preferably represents halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, cyano or nitro.
m preferably represents a number 0, 1, 2 or 3.
X particularly preferably represents C₁-C₆-alkyl, fluorine, chlorine, bromine or C₁-C₆-alkoxy.
Y particularly preferably represents hydrogen, C₁-C₆-alkyl, fluorine, chlorine, bromine, C₁-C₆-alkoxy or C₁-C₂-haloalkyl.
Z particularly preferably represents C₁-C₄-alkyl, fluorine, chlorine, bromine or C₁-C₄-alkoxy.
n particularly preferably represents a number from 0 to 2.
Het particularly preferably represents a heterocyclic group in the series

wherein
A and B are the same or different and represent hydrogen, each optionally substituted by halogen, straight-chain or branched C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₁-C₈-alkoxy-C₂-C₆-alkyl, C₁-C₆-polyalkoxy-C₂ -C₆-alkyl, C₁-C₈-alkylthio-C₂-C₆-alkyl, cycloalkyl having 3 to 7 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms or in each case optionally by halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or nitro-substituted phenyl, pyridinyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁-C₄-alkyl,
or in what
A and B together with the carbon atom to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by halogen, C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₃-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₃-alkylthio or optionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy-substituted phenyl-substituted 3- to 8-membered ring,
E for hydrogen or straight-chain or branched C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₁-C₈-alkoxy-C₂-C₆-alkyl, C₁-C₆-polyalkoxy-C₂-C₆-alkyl, C₁-, C₁-C C-alkyl C₈-Alkylthio-C₂- C₆-alkyl, cycloalkyl with 3 to 7 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms or in each case optionally by halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁ -C₄- alkoxy or nitro substituted phenyl, pyridinyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁-C₄-alkyl,
or in what
A and E together with the atoms to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by halogen, C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₃-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₃-alkylthio or optionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy substituted phenyl substituted 3- to 8-membered ring,
or in the case that in formula (I) Het represents a pyrazolinone ring
A and E together with the two nitrogen atoms of the pyrazoline ring represent a group of the formulas 1 or 2 listed below which may be mono- or polysubstituted, identically or differently, by C₁-C₄-alkyl, C₁-C₄-haloalkyl, fluorine or chlorine,

L particularly preferably represents an alkanediyl group having 1 to 4 carbon atoms.
M particularly preferably stands for one of the following groupings:

R¹ particularly preferably represents hydrogen or C₁-C₁₀ alkyl.
R² particularly preferably represents C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₃-C₈-cycloalkyl, C₃-C₈-alkoxy-C₂-C₆-alkyl, each optionally substituted by fluorine, chlorine, bromine, C₁-C₆-alkylthio-C₂-C₆-alkyl, each optionally with fluorine, chlorine, bromine, nitro, cyano, C₁-C₄-alkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, C₁-C₄ alkyl or C₁-C₄ haloalkyl substituted phenyl or benzyl.
R³ particularly preferably represents C₁-C₁₀-alkyl optionally substituted by fluorine, chlorine, bromine or phenyl or benzyl substituted by fluorine, chlorine, C₁-C₁-alkyl or C₁-C₄-alkoxy.
R⁴ particularly preferably represents hydrogen, fluorine, chlorine, bromine, C₁-C₅-alkyl optionally substituted by fluorine or chlorine or by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂ haloalkoxy, cyano or nitro substituted phenyl.
R⁵ particularly preferably represents hydrogen, fluorine, chlorine, bromine or C₁-C₄-alkyl optionally substituted by fluorine or chlorine.
Q particularly preferably represents fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, cyano or nitro.
m particularly preferably represents a number 0, 1 or 2.
X very particularly preferably represents methyl, ethyl, propyl, i-propyl, fluorine, chlorine, bromine or methoxy.
Y very particularly preferably represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy, ethoxy and trifluoromethyl.
Z very particularly preferably represents methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy and ethoxy.
n very particularly preferably stands for 1.
Het very particularly preferably represents a heterocyclic group from the series

wherein
A and B are the same or different and represent hydrogen, in each case optionally substituted by fluorine or chlorine, straight-chain or branched C₁-C₈-alkyl, C₃-Cyl-alkenyl, C₁-C₆-alkoxy-C₂-C₄-alkyl, C₁-C₄-polyalkoxy -C₂-C₄- alkyl, C₁-C₆-alkylthio-C₂-C₄-alkyl, cycloalkyl with 3 to 6 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms or each optionally by fluorine, chlorine, methyl, Ethyl, propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or nitro-substituted phenyl, pyridinyl, imidazolyl, indolyl or phenyl-C₁-C₃-alkyl,
or in what
A and B together with the carbon atom to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by fluorine, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, trifluoromethyl, C₁- Form C₂-alkylthio or a phenyl substituted 3- to 8-membered ring optionally substituted by fluorine, chlorine, methyl, methoxy,
E for hydrogen or in each case optionally substituted by fluorine or chlorine, straight-chain or branched C₁-C₈-alkyl, C₃-C₄-alkenyl, C₁-C₆-alkoxy-C₂-C₄-alkyl, C₁-C₄-polyalkoxy-C₂-C₄-alkyl , C₁-C₆-alkylthio-C₂- C₄-alkyl, cycloalkyl with 3 to 6 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms or optionally by fluorine, chlorine, methyl, ethyl, propyl, isopropyl , Methoxy, ethoxy, trifluoromethyl or nitro substituted phenyl, pyridinyl, imidazolyl, indolyl or phenyl-C₁-C₃-alkyl,
or in what
A and E together with the atoms to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by fluorine, chlorine, C₁-C₄-alkyl, C₁- C₄-alkoxy, trifluoromethyl, C₁- C₂-alkylthio or optionally substituted by fluorine, chlorine, methyl, methoxy-substituted phenyl substituted 3- to 8-membered ring,
or in the case that in formula (I) Het represents a pyrazolinone ring
A and E together with the two nitrogen atoms of the pyrazoline ring represent a group of the formulas 1 or 2 below which may be monosubstituted to trisubstituted identically or differently by methyl, fluorine or chlorine

L very particularly preferably represents one of the following groupings.

M very particularly preferably represents one of the following groupings.

R¹ very particularly preferably represents hydrogen or C₁-C₈-alkyl.
R² very particularly preferably represents C₁-C₈-alkyl, C₃-C₄-alkenyl, C₃-C₄-alkynyl, cyclopropyl, cyclopentyl, cyclohexyl, C₁-C₆-alkoxy-C₂-C₄-alkyl, each optionally substituted by fluorine, chlorine, bromine , C₁-C₆- alkylthio-C₂-C₄-alkyl, each optionally substituted by fluorine, chlorine, bromine, nitro, cyano, methylthio, ethylthio, methoxy, ethoxy, trifluoromethylthio, trifluoromethoxy, methyl, ethyl, trifluoromethyl-substituted phenyl or benzyl.
R³ very particularly preferably represents in each case optionally substituted by fluorine, chlorine, bromine C₁-C₈-alkyl or by fluorine, chlorine, C₁-C₂-alkyl or C₁-C₂-alkoxy substituted phenyl or benzyl.
R⁴ very particularly preferably represents hydrogen, fluorine, chlorine, optionally substituted by fluorine or chlorine-substituted C₁-C₄-alkyl or by fluorine, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro substituted phenyl.
R⁵ very particularly preferably represents hydrogen, fluorine, chlorine or methyl, ethyl, propyl or isopropyl optionally substituted by fluorine or chlorine.
Q very particularly preferably represents fluorine, chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro.
m very particularly preferably represents a number from 0 to 2.

The enantiomerically pure forms of compounds of the formula (I) included each.

The general or preferred areas listed above Residual definitions or explanations can be among themselves, that is, between the respective areas and preferred areas can be combined as desired. she apply to the end products as well as for the preliminary and intermediate products.  

According to the invention, preference is given to the compounds of the general formula (I) in which a combination of the above as preferred (preferred) listed meanings is present.

According to the invention, particular preference is given to the compounds of the general Formula (I) in which a combination of the above is particularly preferred listed meanings is present.

According to the invention, the compounds of general formula (I) used, in which a combination of these above is present as very particularly preferred meanings.

Using 3- (2,4-dichlorophenyl) -4-hydroxy-5-methyl- according to process (A) Δ³-furan-2-one and (chloromethyl) ethyl ether, the course of the process according to the invention represented by the following reaction scheme become:

If 3- (2,6-dichlorophenyl) -4-hydroxy-1- is used according to process (B) isopropyl-Δ³-pyrrolin-2-one and N-chloromethyl-N-methyl-carbamic acid ethyl ester, the course of the method according to the invention can be as follows Reaction scheme are reproduced.

If 3- (2,4,6-trimethylphenyl) -5-hydroxy-1,2- is used according to process (C) tetramethylene-Δ⁴-pyrazolin-3-one and (chloromethyl) phenyl ether, this can be done Process according to the invention represented by the following reaction scheme:

The compounds required as starting materials in process (A) Formula (IIa)

in which
A, X, Y, Z and n have the meaning given above are known (EP 528 156).

The compounds of the process (B) required as starting materials Formula (IIb)

in which
A, B, E, X, Y, Z and n have the meaning given above are known (cf. for example EP 355 999, EP 377 893, EP 415 211, EP 442 073, EP 456 063, EP 497 127, EP 501 129).

The compounds required as starting materials in process (C) Formula (IIc)

in which
E, B, X, Y, Z and n have the meaning given above,
are known (cf. for example WO 92/16510 and EP 508 126).

The processes (A), (B) and (C) Compounds of the formula (III) which are furthermore required as starting compounds are well known compounds of organic chemistry.

As diluents for the implementation of the invention Processes (A), (B) and (C) all solvents inert to these compounds be used. Hydrocarbons such as Gasoline, benzene, toluene, xylene and tetralin; halogenated hydrocarbons, such as Methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o- Dichlorobenzene; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Nitriles, like Acetonitrile or propionitrile; also polar, compared to the connections of the Formula (III) inert solvents, such as dimethyl sulfoxide, dimethylformamide, Sulfolan or N-methylpyrrolidone.

The bases which can be used when carrying out process (A) according to the invention are (B) and (C) all customary acid acceptors are used. Preferably Alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide,  Sodium carbonate, potassium carbonate and calcium carbonate, which are also present of phase transfer catalysts such. B. triethylbenzylammonium chloride, tetra butylammonium bromide, Adogen 464 (Adogen 464 = methyltrialkyl (C₈-C₁₀) ammonium chloride) or TDA 1 (TDA 1 = tris (methoxyethoxyethyl) amine) can be used. Furthermore, alkali metal and alkaline earth metal hydrides, such as sodium amide, Sodium hydride and calcium hydride, and also alkali metal alcoholates, such as Sodium methylate, sodium ethylate and potassium tert-butoxide can be used. Farther tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBA, Hünig base and N, N-dimethylaniline.

The reaction temperatures can be carried out when carrying out the inventive Processes (A), (B) and (C) can be varied within a relatively wide range. in the generally one works at temperatures between -20 ° C and 180 ° C, preferably between 0 ° C and 130 ° C.

When carrying out processes (A), (B) and (C) according to the invention the reaction components (IIa) and (III) or (IIb) and (III) or (IIc) and (III) and the base generally in approximately equimolar amounts. However, it is also possible that one or the other component in a larger excess (up to 3 moles) to use.

The processes (A), (B) and (C) according to the invention are generally described under Normal pressure carried out. The processing takes place according to usual methods.  

With good plant tolerance, the active ingredients are suitable for combating animal pests, preferably arthropods and nematodes; especially Insects and arachnids, which are used in agriculture, in forests, in stock and Material protection and in the hygiene sector. You are against normal sensitive and resistant species as well as against all or individual stages of development effective. The pests mentioned above include:

From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda z. B. Blaniulus guttulatus.

From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola z. B. Onychiurus armatus.

From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera z. B. Auricular Forficula.

From the order of the Isoptera z. B. Reticulitermes spp.

From the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.

From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.  

Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopdites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

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

The active compounds according to the invention are notable for high insecticidal and acaricidal effectiveness.  

They can be used to control plants with particularly good success harmful mites, such as against the common spider mite or the Bean spider mite (Tetranychus urticae) or against the fruit tree mite (Panonychus ulmi).

The active compounds according to the invention also have a fungicidal activity ability, activity against Pyricularia oryzae and activity against Oomycetes such as Phythophtora and Plasmopara).

The active compounds according to the invention can also be used as defoliants, desiccants, Herbicides and especially used as weed killers become. Weeds in the broadest sense are understood to mean all plants that are on Growing up in places where they are undesirable. Whether the substances according to the invention as total or selective herbicides act depends essentially on the turned amount.

The active compounds according to the invention can, for. B. in the following plants be used:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicot cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, lactuca, cucumis, cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, apera.  

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, sorghum, panicum, saccharum, pineapple, asparagus, allium.

However, the use of the active compounds according to the invention is by no means limited to limited to these genera, but also extends in the same way other plants.

Depending on the concentration, the compounds are suitable for the total weed control z. B. on industrial and track systems and on paths and Places with and without tree cover. Likewise, the connections to Weed control in permanent crops, e.g. B. forest, ornamental trees, fruit, wine, Citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and Hop plants, on ornamental and sports turf and pastures and for selective Weed control can be used in annual crops.

The compounds of formula (I) according to the invention are very suitable for se selective control of monocotyledon weeds in dicotyledonous crops Pre-emergence procedure. For example, you can use soy with very good results Control of harmful grass can be used.

The active ingredients can be converted into the usual formulations, such as Lö solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient impregnated natural and synthetic materials as well as very fine encapsulation in polymeric fabrics.

These formulations are prepared in a known manner, e.g. B. by Vermi the active ingredients with extenders, i.e. liquid solvents and / or fe Most carriers, optionally using surface-active agents agents, i.e. emulsifiers and / or dispersants and / or foam-producing agents Means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkylnaph  thalines, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons substances such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and esters, Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and Water.

The following are suitable as solid carriers:
e.g. B. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

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

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc can be used.  

The formulations generally contain between 0.1 and 95 Weight percent active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their Formulations also in a mixture with known herbicides Weed control are used, with ready formulations or Tank mixes are possible.

Known herbicides are suitable for the mixtures, for example anilides, such as B. Diflufenican and Propanil; Arylcarboxylic acids, such as. B. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2.4 D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy alkanoic acid esters, such as. B. diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, Haloxyfop-methyl and quizalofop-ethyl; Azinones, such as B. Chloridazon and Norflurazon; Carbamates, e.g. B. chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as e.g. B. alachlor, acetochlor, butachlor, Metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines such as e.g. B. Oryzalin, pendimethalin and trifluralin; Diphenyl ether, such as. B. Acifluorfen, Bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as B. chlorotoluron, diuron, fluometuron, isoproturon, linuron and Methabenzthiazuron; Hydroxylamines, such as. B. Alloxydim, Clethodim, Cyclo xydim, sethoxydim and tralkoxydim; Imidazolinones, e.g. B. Imazethapyr, Imazamethabenz, imazapyr and imazaquin; Nitriles such as B. bromoxynil, Dichlobenil and ioxynil; Oxyacetamides such as e.g. B. Mefenacet; Sulfonylureas, such as B. amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, Cinosulfuron, Metsulfuron-methyl, Nicosulfuron, Primisulfuron, Pyrazosulfuron ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, such as B. butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, Thiobencarb and triallates; Triazines, e.g. B. atrazine, cyanazine, simazine, Simetryne, Terbutryne and Terbutylazin; Triazinones such as e.g. B. hexazinone, Metamitron and metribuzin; Others, such as B. aminotriazole, benfuresate, Bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, Ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.  

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plants nutrients and soil structure improvers are possible.

Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and others
The following connections are mentioned:
Acrinathrin, Alphamethrin, Betacyfluthrin, Bifenthrin, Brofenprox, Cis-Resmethrin, Clocythrin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Deltamethrin, Esfenvalerin, Pyrenolhrin, Pyrenolhrin, Pyrenolhrin, Fluvalhrin, Pyrenolate Tralomethrin, Zeta-methrin, Alanycarb, Bendiocarb, Benfuracarb, Bufencarb, Butocarboxim, Carbaryl, Cartap, Ethiofencarb, Fenobucarb, Fenoxycarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propicuran, Trimoxarban, Trimoxarbiod, Tarbox XMC, Xylylcarb, Acephate, Azinphos A, Azinphos M, Bromophos A, Cadusafos, Carbophenothion, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cyanophos. Demeton M, Demeton-S-methyl, Demeton S, Diazinon, Dichlorvos, Dicliphos, Dichlorfenthion, Dicrotophos, Dimethoate, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Ethion, Etrimphos, Fenitrothion, Fenthion, Fonophos, Isothophophos, Hepthosphate, Hepten Isoxathion, Phorate, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Methacrifos, Methamidophos, Naled, Omethoate, Oxydemeton M, Oxydeprofos, Parathion A, Parathion M, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamdon, Moxim, Pirimhos, Pirimos, Pirimos , Prothiophos, Prothoate, Pyraclophos, Pyridaphenthion, Quinalphos, Salithion, Sebufos, Sulfotep, Sulprofos, Tetrachlorvinphos, Temephos, Thiomethon, Thionazin, Trichlorfon, Triazophos, Vamidothion, Buprofezin, Chlorfluazubononifonuron, Fluofluuronuronuron, Fluofluuronuron, Fluorofluoriduron, Fluofluoridifuron, Fluofluoridifonone , Triflumuron, imidacloprid, niten pyram, N - [(6-chloro-3-pyridinyl) methyl] -N'-cyano-N-methyl-ethanimidamide (NI-25), abamectin, amitrazine , Avermectin, azadirachtin, bensultap, bacillus thuringiensis, cyromazine, diafenthiuron, emamectin, ethofenprox, fenpyrad, fipronil, flufenprox, lufenuron, metaldehyde, milbemectin, pymetrozine, tebufenpyrad, triazarbofanocarbon, carbobarbon, carbohydrate, alfarbarbox, carbiazole, carbarbon, carbarbon, carbohydrate, alfalfa Disulfoton, Ethophrophos, Etrimphos, Fenamiphos, Fipronil, Fonofos, Fosthiazate, Furathiocarb, HCH, Isazophos, Isofenphos, Methiocarb, Monocrotophos, Nitenpyram, Oxamyl, Phorate, Phoxim, Prothiofos, Tyrachlofosarbin, Tof Thiafenox, Azocyclotin, Butylpyridaben, Clofentezine, Cyhexatin, Diafenthiuron, Diethion, Emamectin, Fenazaquin, Fenbutatin Oxide, Fenothiocarb, Fenpropathrin, Fenpyrad, Fenpyroximate, Fluazinam, Fluazuron, Flucycloxuron, Fluoxoxinoxython, Fluoxoxinoxin, Fluoxoxinoxin, Floxinoxin , Naled, Phosalone, Profenofos, Pyraclofos, Pyridaben, Pyrimidifen, Tebufenpyrad, Th uringiensin, triarathenes and 4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carb-ornitrile (AC 303630).

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used become. The application is done in the usual way, e.g. B. by pouring, spraying, Spray, sprinkle.

The active compounds according to the invention can be used both before and after Emergence of the plants can be applied. You can also sow before sowing Be incorporated into the floor.

The amount of active ingredient used can vary over a wide range. she depends essentially on the type of effect desired. In general the application rates are between 10 g and 10 kg of active ingredient per hectare of soil area, preferably between 50 g and 5 kg per ha.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples Example Ia-1

To 4.3 g (15 mmol) of 3- (2,4,6-trimethylphenyl) -4-hydroxy-5,5-pentamethylene-Δ³- dihydrofuran-2-one in 60 ml absolute dichloromethane, 1.67 g (16.5 mmol) Triethylamine and a spatula tip of DMAP are added under a nitrogen atmosphere 0 ° C to 10 ° C 1.47 (15.5 mmol) chloromethyl ethyl ether in 15 ml absolute Added dropwise dichloromethane. The reaction mixture becomes about 20 at room temperature Stirred for hours, then successively with 10% citric acid, Washed sodium bicarbonate and sodium chloride solution, the organic Phase dried with sodium sulfate and the solvent removed. The Crude product is on a silica gel column (mobile phase: chloroform / ethyl acetate 3: 1) further cleaned.

2.47 g (53% of theory) of 3- (2,4,6-trimethylphenyl) -4- (ethoxy) are obtained methyloxy) -5,5-pentamethylene-Δ³-dihydrofuran-2-one with melting point mp. 102 ° C.

Analogous to Example Ia-1, Preparation Example Ib-1 is also obtained:
1 H-NMR (200 MHz, CDCl₃): 2.12, 2.2, 2.26 (3s, 9H, Ar-CH₃), 3.88 (s, 3H, SO₂, CH₃), 3.92 (s, 3H, N-CH₃), 3.25, 3.62 (m, 2H, N-CH₂), 4.21 (dd, 1H, CH-N), 4.72 (ABq, 2H, O-CH₂N), 6.89 (s, 2H, Ar-H).

Analogously to example Ia-1, the preparation example of the formula (Ic-1) is also Melting point mp. 207 ° C obtained.

Example Ic-1 Examples of use

In the following application examples, the following was listed Compound used as reference substance:

A4-methoxy-3- (3-trifluoromethylphenyl) -5-methyl-5H-furan-2-one (known from DE 39 31 773, Example 6).  

Example A

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

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

Approx. 30 cm high plum trees (Prunus domestica), which are strong from all Ent development stages of the fruit tree spider mite (Panonychus ulmi) are infected, are injected with an active ingredient preparation of the desired concentration.

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

In this test z. B. the connections according to the manufacturing examples Ia-1, Ia-2, Ia-5 and Ia-7 at an exemplary active ingredient concentration of 0.02% kills 100% after 7 days.  

Example B

Tetranychus test (OP-resistant)
Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

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

Bean plants (Phaseolus vulgaris), strongly affected by all stages of development common spider mite or bean spider mite (Tetranychus urticae) are infected, by dipping into the active ingredient preparation of the desired concentration treated.

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

In this test z. B. the connections according to the manufacturing examples Ia-1, Ia-2, Ia-5 and Ia-7 at an exemplary active ingredient concentration of 0.02% kills at least 98% after 7 days.  

Example C

Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

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

Seeds of the test plants are sown in normal soil and watered with the active compound preparation after 24 hours. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
0% = no effect (like untreated control)
100% = total annihilation.

In this test, for example, show the connections according to the manufacturing process example (Ia-1) and (Ia-2) with sometimes very good tolerance to culture plants, such as B. wheat and soybeans, very potent against weeds. At an exemplary application rate of 1000 g / ha. B. Alopecurus, Cynodon, Digitaria, Lolium and Setaria recorded at least 90%.  

Example D

Phaedon larval test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

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

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with horseradish leaf beetle larvae (Phaedon cochleariae) occupied while the leaves are still moist.

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

In this test, e.g. B. the compounds according to the preparation examples Ia-9, Ia-12, Ia-13, Ia-14, Ia-15, Ib-1 and Ic-1 in an exemplary active ingredient concentration of 0.01% kills 100% after 7 days while the known compound (A) caused no killing.  

Example E

Plutella test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

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

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars (Plutella maculipennis) occupied while the leaves are still moist.

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

In this test, e.g. B. the compounds according to the preparation examples Ia-14 and Ia-27 at an exemplary active ingredient concentration of 0.01% 100% kill after 3 days, while known compound (A) did not Killing.  

Example F

Nephotettix test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

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

Rice seedlings (Oryza sativa) are dipped into the active ingredient preparation the desired concentration and treated with the green rice leafhopper (Nephotettix cincticeps) occupied while the seedlings are still moist.

In this test, e.g. B. the compounds according to the preparation examples Ia-1, Ia-3, Ia-9, Ia-12, Ia-13, Ia-15, Ia-25, Ia-26, Ia-27, Ia-28, Ia-31, Ib-1 and Ic- 1 at an exemplary active ingredient concentration of 0.01%, a kill of 100% after 6 days, while the known compound (A) does not kill caused.  

Example G

Myzus test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

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

Cabbage leaves (Brassica oleracea), heavily from the peach aphid (Myzus persicae) are infested by dipping into the active ingredient preparation desired concentration treated.

After the desired time, the effect is determined in%. Here means 100% that all aphids have been killed; 0% means that there are no aphids were killed.

In this test, e.g. B. the compounds according to the preparation examples Ia-1, Ia-28 and Ia-31 at an exemplary active ingredient concentration of 0.1% 100% kill after 6 days, while known compound (A) caused no kill.

Claims (11)

1. Substituted aryl-ketoenol heterocycles of the formula (I) in which
X represents alkyl, halogen or alkoxy,
Y represents hydrogen, alkyl, halogen, alkoxy or haloalkyl,
Z represents alkyl, halogen or alkoxy,
n stands for a number 0, 1, 2 or 3,
Het for a heterocyclic group in the series stands,
A and B may be the same or different and for hydrogen, in each case optionally substituted by halogen substituted alkyl, alkenyl, alkoxy alkyl, alkylthioalkyl, optionally interrupted by at least one hetero atom cycloalkyl or in each case optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or nitro Aryl, aralkyl or hetaryl,
or in what
A and B together with the carbon atom to which they are attached form a saturated or unsaturated, optionally interrupted by at least one heteroatom and optionally substituted cycle,
E represents hydrogen, in each case optionally substituted by halogen substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, optionally cycloalkyl interrupted by at least one heteroatom or in each case optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or nitro aryl, aralkyl or hetaryl,
or in what
A and E together with the atoms to which they are attached form a saturated or unsaturated, optionally interrupted by at least one heteroatom and optionally substituted cycle, bicyclic or tricyclic,
L represents an alkanediyl group,
M represents one of the following groupings: in which
R¹ represents hydrogen or alkyl,
R² stands for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkylthioalkyl, aryl or aralkyl,
R³ represents optionally substituted alkyl, aryl or aralkyl,
R⁴ represents hydrogen, halogen, in each case optionally substituted alkyl or phenyl,
R⁵ represents hydrogen-halogen or optionally substituted alkyl,
Q represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, CN or nitro and
m represents a number 0, 1, 2 or 3,
as well as the enantiomerically pure forms of compounds of the formula (I). 2. Compounds of formula (I) according to claim 1, in which
X represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy,
Y represents hydrogen, C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy or C₁-C₃- haloalkyl,
Z represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy,
n stands for a number from 0 to 3,
Het for a heterocyclic group in the series stands in what
A and B are the same or different and are hydrogen or straight-chain or branched C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₁-C₁ Alk-alkoxy-C₂-C₈-alkyl, C₁-C₈-polyalkoxy-C₂ which are optionally substituted by halogen -C₈-alkyl, C₁-C₁₀-alkylthio-C₂-C₈-alkyl, cycloalkyl with 3 to 8 ring atoms, which can be interrupted by oxygen and / or sulfur or in each case optionally by halogen, C₁-C₆-alkyl, C₁-C₆- Haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy or nitro substituted phenyl, pyrimidyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁- C₆-alkyl,
or in what
A and B together with the carbon atom to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halogen alkoxy, C₁-C₄-alkylthio or optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy-substituted phenyl-substituted 3- to 8-ring ring,
E for hydrogen or in each case optionally substituted or substituted by halogen, straight-chain or branched C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl, C₁-C₈-polyalkoxy-C₂-C jeweils-alkyl, C₁- C₁₀-alkylthio-C₂-C₈-alkyl, cycloalkyl with 3 to 8 ring atoms, which can be interrupted by oxygen and / or sulfur or in each case optionally by halogen, C₁-C₆-alkyl, C₁-C₆-halogen alkyl, C₁-C₆- Alkoxy, C₁-C₆-haloalkoxy or nitro-substituted phenyl, pyrimidyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁-C₆-alkyl,
or in what
A and E together with the atoms to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy-substituted phenyl substituted 3- to 8-ring ring,
or if Het in formula (I) represents a pyrazolinone ring
A and E together with the two nitrogen atoms of the pyrazoline ring represent an optionally mono- or polysubstituted, identically or differently, C₁-C₆-alkyl, C₁-C₆-haloalkyl or halogen-substituted grouping of the formulas 1 to 4 listed below L represents an alkanediyl group with 1 to 6 carbon atoms,
M represents one of the following groupings: R¹ represents hydrogen or C₁-C₁₂ alkyl,
R² for each optionally substituted by halogen C₁-C₁₂-alkyl, C₃-C C-alkenyl, C₃-C₈-alkynyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy-C₂- C₈-alkyl, C₁-C₈-alkylthio-C₂ -C₈-alkyl, each optionally by halogen, nitro, cyano, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₁-C₆-halogenoalkylthio, C₁-C₆-alkyl or C₁-C₆- haloalkyl substituted phenyl or benzyl,
R³ represents C₁-C₁₂-alkyl optionally substituted by halogen or phenyl or benzyl substituted in each case by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy,
R⁴ for hydrogen, halogen, optionally substituted by halogen C₁-C₆-alkyl or in each case by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, cyano- or nitro-substituted phenyl stands,
R⁵ represents hydrogen, halogen or C₁-C₆alkyl optionally substituted by halogen,
Q represents halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, cyano or nitro and
m represents a number 0, 1, 2 or 3,
as well as the enantiomerically pure forms of compounds of the formula (I). 3. Compounds of formula (I) according to claim 1, in which
X represents C₁-C₆-alkyl, fluorine, chlorine, bromine or C₁-C₆-alkoxy,
Y represents hydrogen C₁-C₆-alkyl, fluorine, chlorine, bromine, C₁-C₆-alkoxy or C₁-C₂-haloalkyl,
Z represents C₁-C₄-alkyl, fluorine, chlorine, bromine or C₁-C₄-alkoxy,
n stands for a number from 0 to 2,
Het for a heterocyclic group in the series stands in what
A and B are the same or different and represent hydrogen, each optionally substituted by halogen, straight-chain or branched C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₁-C₈-alkoxy-C₂-C₆-alkyl, C₁-C₆-polyalkoxy-C₂ -C₆-alkyl, C₁-C₈-alkylthio-C₂-C₆-alkyl, cyclo alkyl having 3 to 7 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms or in each case optionally by halogen, C₁-C₄-alkyl , C₁-C₄-haloalkyl, C₁-C₄-alkoxy or nitro-substituted phenyl, pyridinyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁-C₄-alkyl,
or in what
A and B together with the carbon atom to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by halogen, C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₃-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₃-alkylthio or optionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy substituted phenyl. Form a 3- to 8-membered ring,
E for hydrogen or in each case optionally substituted by halogen straight-chain or branched C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₁-C₈-alkoxy-C₂-C₆-alkyl, C₁-C₆-polyalkoxy-C₂-C₆-alkyl, C₁ -C₈- alkylthio-C₂-C₆-alkyl, cycloalkyl with 3 to 7 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms or in each case optionally by halogen, C₁-C₄-alkyl, C₁-C₄-halogen alkyl , C₁-C₄-alkoxy or nitro-substituted phenyl, pyridinyl, imi dazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁-C₄- alkyl,
or in what
A and E together with the atoms to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by halogen, C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₃-haloalkyl, C₁-C₄-halogen alkoxy, C₁-C₃-alkylthio or optionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy-substituted phenyl-substituted 3- to 8-ring ring,
or in the case that in formula (I) Het represents a pyrazolinone ring
A and E together with the two nitrogen atoms of the pyrazoline ring represent a group of the formulas 1 or 2 listed below which may be mono- or polysubstituted identically or differently by C₁-C₄-alkyl, C₁-C₄-haloalkyl, fluorine or chlorine, L represents an alkanediyl group with 1 to 4 carbon atoms,
M represents one of the following groupings: R¹ represents hydrogen or C₁-C₁₀ alkyl,
R² for C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₃-C₈-cycloalkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl, C₁-C₆, each optionally substituted by fluorine, chlorine, bromine -Alkylthio-C₂-C₆-alkyl, if necessary by fluorine, chlorine, bromine, nitro, cyano, C₁-C₄-alkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, C₁- C₄- alkyl or C₁-C₄-haloalkyl substituted phenyl or benzyl,
R³ represents C₁-C₁₀ alkyl optionally substituted by fluorine, chlorine, bromine or phenyl or benzyl substituted in each case by fluorine, chlorine, C₁-C₄ alkyl or C₁-C₄ alkoxy,
R⁴ represents hydrogen, fluorine, chlorine, bromine, optionally substituted by fluorine or chlorine, C₁-C Alkyl-alkyl or by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂ Haloalkoxy, cyano or nitro substituted phenyl,
R⁵ represents hydrogen, fluorine, chlorine, bromine or C₁-C₄alkyl optionally substituted by fluorine or chlorine,
Q represents fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, cyano or nitro and
m represents a number 0, 1 or 2,
as well as the enantiomerically pure forms of compounds of the formula (I). 4. Compounds of formula (I) according to claim 1, in which
X represents methyl, ethyl, propyl, i-propyl, fluorine, chlorine, bromine or methoxy,
Y represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy, ethoxy and trifluoromethyl,
Z represents methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy and ethoxy,
n stands for 1,
Het for a heterocyclic group in the series stands in what
A and B are the same or different and represent hydrogen, each optionally substituted by fluorine or chlorine, straight-chain or branched C₁-C₈-alkyl, C₃-C₄-alkenyl, C₁-C₆-alkoxy-C₂-C₄-alkyl, C₁-C₄-polyalkoxy -C₂-C₄-alkyl, C₁-C₆-alkylthio-C₂-C₄-alkyl, cycloalkyl with 3 to 6 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms or in each case optionally by fluorine, chlorine, methyl, Are ethyl, propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or nitro-substituted phenyl, pyridinyl, imidazolyl, indolyl or phenyl-C₁-C₃-alkyl,
or in what
A and B together with the carbon atom to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by fluorine, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, trifluoromethyl, C₁- C₂-alkylthio or optionally substituted by fluorine, chlorine, methyl, methoxy-substituted phenyl substituted 3- to 8-membered ring,
E for hydrogen or in each case optionally substituted by fluorine or chlorine, straight-chain or branched C₁-C₈-alkyl, C₃-C₄-alkene yl, C₁-C₆-alkoxy-C₂-C₄-alkyl, C₁-C₄-polyalkoxy-C₂-C₄- alkyl, C₁-C₆- alkylthio-C₂-C₄-alkyl, cycloalkyl with 3 to 6 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms or optionally by fluorine, chlorine, methyl, ethyl, propyl, iso- Propyl, methoxy, ethoxy, trifluoromethyl or nitro substituted phenyl, pyridinyl, imidazolyl, indolyl or phenyl-C₁-C₃-alkyl,
or in what
A and E together with the atoms to which they are attached, a saturated or unsaturated, optionally interrupted by oxygen and / or sulfur and optionally by fluorine, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, trifluoromethyl, C₁- C₂-alkylthio or optionally substituted by fluorine, chlorine, methyl, methoxy-substituted phenyl-substituted 3- to 8-membered ring,
or in the case that in formula (I) Het represents a pyrazolinone ring
A and E together with the two nitrogen atoms of the pyrazoline ring represent an optionally single to triple, identically or differently substituted by methyl, fluorine or chlorine grouping of the formulas 1 or 2 listed below L stands for one of the following groupings M stands for one of the following groupings R¹ represents hydrogen or C₁-C₈-alkyl,
R² for each optionally substituted by fluorine, chlorine, bromine, C₁-C₈-alkyl, C₃-C₄-alkenyl, C₃-C₄-alkynyl, cyclopropyl, cyclopentyl, cyclohexyl, C₁-C₆-alkoxy-C₂-C₄-alkyl, C₁-C₆ -Alkylthio-C₂-C₄-alkyl, each represents optionally substituted by fluorine, chlorine, bromine, nitro, cyano, methylthio, ethylthio, methoxy, ethoxy, trifluoromethylthio, trifluoromethoxy, methyl, ethyl, trifluoromethyl, phenyl or benzyl,
R³ represents in each case optionally substituted by fluorine, chlorine, bromine C₁-C₈-alkyl or by phenyl or benzyl substituted by fluorine, chlorine, C₁-C₂-alkyl or C₁-C₂-alkoxy,
R⁴ represents hydrogen, fluorine, chlorine, C₁-C₄alkyl optionally substituted by fluorine or chlorine or phenyl substituted by fluorine, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro,
R⁵ represents hydrogen, fluorine, chlorine or methyl, ethyl, propyl or isopropyl optionally substituted by fluorine or chlorine,
Q represents fluorine, chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro and
m represents a number from 0 to 2,
as well as the enantiomerically pure forms of compounds of the formula (I). 5. A process for the preparation of the substituted aryl-ketoenol heterocycles of the formula (I) according to claim 1, characterized in that (A) for obtaining compounds of the formula (Ia) in which
A, B, L, M, X, Y, Z and n have the meaning given in claim 1,
Compounds of formula (IIa) in which
A, B, X, Y, Z and n have the meaning given above, with compounds of the formula (III) GLM (III) in which
L and M have the meaning given above
and
G represents a leaving group,
in the presence of a diluent and in the presence of a base,

• (B) to obtain compounds of the formula (Ib) in which
  A, B, E, L, M, X, Y, Z and n have the meaning given above,
  Compounds of formula (IIb) in which
  A, B, E, X, Y, Z and n have the meaning given above,
  with compounds of the formula (III) GLM (III) in which
  L and M have the meaning given above
  and
  G represents a leaving group,
  in the presence of a diluent and in the presence of a base or
• (C) to obtain compounds of the formula (Ic) in which
  A, E, L, M, X, Y, Z and n have the meaning given above,
  Compounds of formula (IIc) in which
  B, E, X, Y, Z and n have the meaning given above,
  with compounds of the formula (III) GLM (III) in which
  L and M have the meaning given above
  and
  G represents a leaving group,
  in the presence of a diluent and in the presence of a base.

6. pesticides, characterized by a content of minde at least one compound of formula (I) according to claim 1. 7. arthropodicides, fungicidal and herbicidal compositions, characterized by a Content of at least one compound of formula (I). 8. Use of compounds of formula (I) according to claim 1, for Control of pests in crop protection, household, hygiene area and storage protection. 9. Use of compounds of formula (I) according to claim 1, for Control of arthropods, phytopatogenic fungi and unwanted Plant growth in crop protection, household, hygiene and Storage protection. 10. Procedures for controlling pests in crop protection, household area, hygiene area and storage protection, characterized in that compounds of formula (I) according to claim 1 on the pests and / or let their living space take effect. 11. Process for the preparation of pesticides, thereby characterized in that compounds of the formula (I) according to Claim 1, mixed with extenders and / or surfactants.