2,4,5-trisubstituted phenylketoenol useful as insecticide and herbicide

专利摘要:
The present invention relates to novel phenyl substituted cyclic ketoenols of the general formula (I), a plurality of methods for their preparation, intermediates for their preparation, pest control agents and their use as herbicides: Where Hal represents one of the following groups, From here, A, B, D, G, X, Y and Z have the meanings mentioned in the detailed description.
公开号:KR19990028452A
申请号:KR1019970709768
申请日:1996-06-17
公开日:1999-04-15
发明作者:폴커 리프；헤르만 하게만；아노 비디히；미카엘 루터；라이너 피셔；토마스 브레트슈나이더；크리스토프 에르델렌；울리케 바헨도르프-노이만；한스-조아힘 잔텔；마르쿠스 돌링거；알란 그라프；노버트 멘케；안드레아스 투르베르그；피터 다멘
申请人:볼프강 에렌스타인, 크누트 샤우에르테；바이엘 악티엔게젤샤프트；
IPC主号:

专利说明:

2, 4, 5-trisubstituted phenylketoenols useful as insecticides and herbicides
The present invention relates to novel phenyl-substituted cyclic ketoenols, several preparation methods and intermediates for their preparation, and their use as marine remedies and herbicides.
Certain phenyl-substituted cyclic ketoenols are already disclosed to be active as insecticides, acaricides and / or herbicides.
Pharmaceutical properties have already been described for 3-acyl-pyrrolidine-2, 4-dione. S. Suzuki et al., Chem. Pharm. Bull. 15 1120 (1967) .N-phenylpyrrolidine-2,4-dione is also known as R. Schmierer and H. Mildenver. Synthesized by H. Mildenberger (Liebigs Ann. Chem. 1985, 1095) The biological activity of these compounds is not described.
Compounds of similar structure (3-aryl-pyrrolidine-2,4-dione) are disclosed in EP-AO 262 399 and GB-A-266 888, but no herbicides, pesticides or acaricides are disclosed. not. Known compounds with herbicide, insecticide or acaricide action are unsubstituted, bicyclic 3-acyl-pyrrolidine-2, 4-dione derivatives (EP-A-355 599 and EP-A-415 211) and substituted Monocyclic 3-acyl-pyrrolidine-2, 4-dione derivatives (EP-A-377 893 and EP-A-442 077).
Also known compounds are polycyclic 3-aryl-pyrrolidine-2, 4-dione derivatives (EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives (EP-A-456 063, EP- A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, De 44 40 594, WO 94/01 997 and WO 95/01 358).
It is known that certain substituted Δ ³ -dihydrofuran-2-one derivatives have herbicide properties (see DE-4-A 014 420). Tetraic acid derivatives (eg 3- (2-methyl-phenyl) -4-hydroxy-5 (4-fluorophenyl) -Δ ³ -dihydrofuran-2-one) used as starting compounds Synthesis is also described in DE-A-4 014 420. Compounds of similar structure that do not have insecticidal and / or acaricides are described in Campbell et al. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76. 3-aryl-Δ ³ -dihydrofuranone derivatives having herbicide, acaricide and insecticide properties are also known from EP-A-528 156, EP-A 0 647 637 and WO 95/26345.
Certain phenyl-pyrone derivatives unsubstituted in the phenyl ring have already been described (see, for example, AM Chirazi, T. Kappe and E. Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K. Heidenbluth (Chem. Ber. 91, 2849). The possible utility of these compounds as pest control is not mentioned. Phenyl-pyrone derivatives substituted in the phenyl ring and having herbicide, acaricide and insecticide properties are described in EP-A-588 137.
Certain 5-phenyl-1,3-thiazine derivatives unsubstituted in the phenyl ring have already been described (see, E. Ziegler and E. Steiner, Monatsh. 95, 147 (1964)), R. Ketcham , T. Kappe and E. Ziegler (J. Heterocycl. Chem. 10 223 (1973)), the possible use of these compounds as pest control agents is not mentioned. 5-phenyl-1,3-thiazine derivatives substituted in the phenyl ring and having herbicidal, acaricide and pesticidal action are described in WO 94/14 785.
However, the acaricide and pesticidal activity and / or range of action of these compounds and resistance in plants, especially crops, are not always adequate.
New compounds of formula (I) have been found:

In the above formula,
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, halogenoalkyl, halogenoalkoxy, cyano or nitro,
Y represents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, cyano or nitro,
Z is halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, hydroxyl, cyano, nitro or optionally substituted phenoxy, phenylthio, 5- to 6-membered hetaryloxy, 5- to 6 -Represents original hetarylthio, phenylacyloxy or phenylacylthio,
Y and Z represent cyclic radicals optionally substituted with the carbon atom to which they are attached and optionally interrupted by a heteroatom, wherein X represents one of the meanings mentioned above,
Het represents one of the following groups,

From here,
A represents hydrogen, in each case alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or alkylthioalkyl optionally substituted by halogen, or in each case saturated or unsaturated, optionally substituted cycloalkyl or heterocycle Aryl, or in each case aryl, arylalkyl or hetaryl optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, cyano or nitro,
B represents hydrogen, alkyl or alkoxyalkyl, or
A and B represent carbocyclic or heterocyclic radicals which are saturated or unsaturated and optionally substituted with the carbon atoms to which they are attached,
D represents hydrogen or alkyl, alkenyl, alkynyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl, saturated or unsaturated heterocyclyl, arylalkyl, aryl, hetarylalkyl and hetaryl Represents an optionally substituted radical selected from the group consisting of
A and D together with the carbon atom to which they are attached represent in each case an optionally substituted carbocyclic or heterocycle radical,
G is hydrogen (a), or

Represents one of
From here,
E represents 1 equivalent of metal ion or ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R ¹ represents, in each case, alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl optionally substituted by halogen or in each case cycloalkyl or heterocyclyl optionally substituted by halogen, alkyl or alkoxy Or in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R ² represents in each case alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl optionally substituted by halogen, or in each case cycloalkyl, phenyl or benzyl optionally substituted,
R ³ , R ⁴ and R ⁵ independently of one another represent, in each case, alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio optionally substituted by halogen, or in each case optionally Substituted phenyl, phenoxy or phenylthio,
R ⁶ and R ⁷ independently of one another represent hydrogen, in each case alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl optionally substituted by halogen, or in each case phenyl or benzyl optionally substituted Or an optionally substituted cyclic radical optionally containing oxygen or sulfur together with the N atom to which they are attached.
Also depending on the nature of the substituents, the compounds of general formula (I) may be in the form of geometric and / or optical isomers or mixtures of isomers of various compositions, which may be separated by conventional methods. The present invention relates to pure isomers and isomer mixtures, their preparation and their use, and compositions containing them. However, for the sake of simplicity, always refer to the compounds of general formula (I) below, but this means a mixture of pure compounds and, if appropriate, of different amounts of isomer compounds.
Given the meaning of (1) to (5) of the group Het, the following main structures (I-1) to (I-5) emerge:

Where
A, B, D, G, X, Y and Z have the meanings mentioned above.
Considering the various meanings of (a), (b), (c), (d), (e), (f) and (g) of group G, the following note when Het represents group (1) The structures (I-1-a) to (I-1-g) are shown:

Where
A, B, E, L, M, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the meanings mentioned above.
Considering the various meanings of (a), (b), (c), (d), (e), (f) and (g) of group G, the following note when Het represents group (2) The structures (I-2-a) to (I-2-g) come out:


Where
A, B, E, L, M, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the meanings mentioned above.
Considering the various meanings of (a), (b), (c), (d), (e), (f) and (g) of group G, the following note when Het represents group (3) The structures (I-3-a) to (I-3-g) are shown:

Where
A, B, E, L, M, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the meanings mentioned above.
Depending on the position of substituent G, the compound of general formula (I-4) is present in two isomeric forms of general formula (I-4) _a and (I-4) _b represented by dashed lines in general formula (I-4). Can be.

The compounds of the general formulas (I-4) _a and (I-4) _b may exist as mixtures and also in their pure isomeric form. Where appropriate, mixtures of compounds of the general formulas (I-4) _a and (I-4) _b can be separated by physical methods known per se, for example by chromatographic methods.
For clarity, only one of the possible isomers in each case will be mentioned in the description below. This does not mean that the compounds cannot be present in the form of isomeric mixtures or in the form of other special isomers if necessary.
Considering the various meanings of (b), (c), (d), (e), (f) and (g) of the group G, the following main structure (I-) when Het represents the group (4) 4-a) to (I-4-g) are shown:


Where
A, D, E, L, M, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the meanings mentioned above.
Considering the various meanings of (a), (b), (c), (d), (e), (f) and (g) of group G, the following note when Het represents group (5) Structures (I-5-a) to (I-5-g) are obtained:


Where
A, E, L, M, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the meanings mentioned above.
In addition, the novel compounds of general formula (I) are obtained by one of the methods described below:
(A) A compound of the general formula (I-1-a) is obtained when the compound of the general formula (II) undergoes an intramolecular condensation reaction in the presence of a diluent and in the presence of a base.

Where
A, B, X, Y and Z have the meanings mentioned above,
R ⁸ represents alkyl (preferably C ₁ -C ₆ -alkyl),
(B) It has also been found that the compound of formula (I-2-a) is obtained when the compound of formula (III) is subjected to an intramolecular condensation reaction in the presence of a diluent and in the presence of a base.

Where
A, B, X, Y, Z and R ⁸ have the meanings mentioned above.
(C) It has also been found that the compound of the general formula (I-3-a) is obtained by intramolecular ring closure of the compound of the general formula (IV), if necessary, in the presence of a diluent and in the presence of an acid.

Where
A, B, X, Y, Z and R ⁸ have the meanings mentioned above,
W represents hydrogen, halogen, alkyl (preferably C ₁ -C ₆ -alkyl) or alkoxy (preferably C ₁ -C ₈ -alkoxy).
(D) Furthermore, the compound of general formula (I-4-a) may contain a compound of general formula (V) or a silylenol ether of general formula (Va), if necessary, in the presence of a diluent and, if necessary, an acid acceptor. It was found that it is obtained by reacting with a compound of formula (VI) in the presence of.


Where
A, D, X, Y and Z have the meanings mentioned above,
R8 'represents alkyl (preferably methyl),
Hal represents halogen (preferably chlorine or bromine).
(E) In addition, the compound of general formula (I-5-a) may be substituted with the compound of general formula (VII) with the compound of general formula (VI) in the presence of a diluent if necessary and in the presence of an acid acceptor if necessary. It was found that it is obtained by reacting.


Where
Hal, A, X, Y and Z have the meanings mentioned above.
(F) Furthermore, the compounds of the general formulas (I-1-b) to (I-5-b) shown above, wherein
A, B, D, R ¹ , X, Y and Z have the above-mentioned meanings. The compounds of (I-1-a) to (I-5-a) shown above, wherein A, B, D, X, Y and Z have the meanings mentioned above) in the presence of a diluent if necessary and in the presence of an acid binder if necessary,
α) reacts with an acid halide of formula (VIII), or
β) obtained by reaction with anhydrous carboxylic acid of formula (IX);

(Wherein
A, B, D, X, Y, Z and R ¹ have the aforementioned meanings,
Hal represents halogen (especially chlorine or bromine).
(G) compounds of the general formulas (I-1-c) to (I-5-c) shown above, wherein A, B, D, R ² , M, X, Y and Z have the meanings mentioned above And L stands for oxygen) is a compound of the general formulas (I-1-c) to (I-5-c) shown above, wherein A, B, D, X, Y and Z have the meanings mentioned above In each case, if necessary, in the presence of a diluent and, if necessary, in the presence of an acid binder to react with a chloroformic acid ester or a chloroformic acid thioester of the general formula (X);

(Wherein
R ² and M have the meanings mentioned above)
(H) compounds of the general formulas (I-1-c) to (I-5-c) shown above, wherein A, B, D, R ² , M, X, Y and Z have the meanings mentioned above And L represents sulfur, wherein the compounds of formulas (I-1-a) to (I-5-a) shown above, wherein A, B, D, X, Y and Z have the meanings mentioned above Have
α) reacting with a chloromonothioformic acid ester or chlorodithioformic acid ester of the general formula (XI) in the presence of a diluent if necessary and an acid binder if necessary, or
β) obtained by reacting with carbon disulfide if necessary in the presence of a diluent and, if necessary, in the presence of a base, followed by reaction with a compound of formula (XII);

(Wherein
M and R ² have the meanings mentioned above
Hal stands for chlorine, bromine or iodine)
(I) compounds of the general formulas (I-1-d) to (I-5-d) shown above, wherein A, B, D, R ³ , X, Y and Z have the meanings mentioned above Is required in each case to the compounds of the general formulas (I-1-a) to (I-5-a) shown above, wherein A, B, D, X, Y and Z have the meanings mentioned above Obtained by reaction with sulfonic acid chlorides of the general formula (XIII) in the presence of a diluent and, if desired, in the presence of an acid binder;

(Wherein
R ³ has the meanings mentioned above)
(J) compounds of the general formulas (I-1-e) to (I-5-e) shown above, wherein A, B, D, L, R ⁴ , R ⁵ , X, Y and Z are mentioned above Are compounds of the general formulas (I-1-a) to (I-4-a) shown above, wherein A, B, D, X, Y and Z have the meanings mentioned above Is obtained in each case by reacting with a phosphorus compound of formula (XIV) in the presence of a diluent if necessary and in the presence of an acid binder if necessary;

(Wherein
L, R ⁴ and R ⁵ have the meanings mentioned above,
Hal stands for halogen (especially chlorine or bromine)
(K) the compounds of the general formulas (I-1-f) to (I-5-f) shown above, wherein A, B, D, E, X, Y and Z have the meanings mentioned above Compounds of formulas (I-1-a) to (I-5-a), wherein A, B, D, X, Y and Z have the meanings mentioned above in each case as necessary Obtained by reaction with a metal compound or amine of the general formula (XV) or (XVI) in the presence of a diluent;

(Wherein
Me represents a monovalent or divalent metal (preferably an alkali or alkyl earth metal, for example lithium, sodium, potassium, magnesium or calcium),
t represents 1 or 2,
R ¹⁰ , R ¹¹ and R ¹² independently of one another represent hydrogen or alkyl (preferably C ₁ -C ₈ -alkyl)
(L) compounds of the general formulas (I-1-g) to (I-5-g) shown above, wherein A, B, D, L, R ⁶ , R ⁷ , X, Y and Z are mentioned above Is a compound of the general formulas (I-1-a) to (I-5-a) (wherein A, B, D, X, Y and Z have the meanings mentioned above) In each case
α) reacting with isocyanate or isothiocyanate of general formula (XVII) in the presence of a diluent if necessary and in the presence of a catalyst if necessary, or
β) It was found to be obtained by reaction with carbamic acid chloride or thiocabamic acid chloride of the general formula (XVIII) in the presence of a diluent if necessary and in the presence of an acid binder if necessary:

(Wherein
L, R ⁶ and R ⁷ have the meanings mentioned above).
In addition, the novel compounds of general formula (I) have very good activity as pesticides, preferably insecticides, acaricides and also herbicides, and also very good plant resistance, especially to crop plants.
Formula (I) provides a general definition of a compound according to the invention. The range of preferred substituents or radicals listed in the general formulas mentioned above and below is illustrated below:
X is preferably halogen, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl , C ₁ -C ₄ -halogenoalkoxy, cyano or nitro,
Y preferably represents hydrogen, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, cyano or nitro Indicates,
Z is preferably halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, hydroxyl, cyano or nitro Or optionally substituted with halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, nitro or cyano in each case Phenoxy, phenylthio, thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy, phenyl-C ₁ -C ₄ -alkyloxy or phenyl-C ₁ -C ₄ -alkylthio
Y and Z together are preferably optionally substituted with halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy or C ₁ -C ₄ -halogenoalkyl and one to three members are independently of each other oxygen, C ₃ -C ₄ -alkanediyl or C ₃ -C ₄ -alkenediyl which may be optionally substituted by sulfur, nitrogen or carbonyl groups, and X represents one of the meanings mentioned above.
Het is preferably a group

Represents one of
A preferably represents C ₁ -C ₁₂ -alkyl, C ₂ -C ₈ -alkenyl, C ₁ -C ₁₀ -alkoxy-C ₁ -C _8- , which represents hydrogen or, in each case, optionally substituted by halogen; Alkyl, poly-C ₁ -C ₈ -alkoxy-C ₁ -C ₈ -alkyl or C ₁ -C ₁₀ -alkylthio-C ₁ -C ₆ -alkyl, or halogen, C ₁ -C ₆ -alkyl or C ₃ -C ₈ -cycloalkyl optionally substituted by C ₁ -C ₆ -alkoxy and one or two methylene groups optionally substituted by oxygen and / or sulfur, or in each case halogen, C ₁ -C Phenyl, naphthyl, phenyl-C, optionally substituted by ₆ -alkyl, C ₁ -C ₆ -halogenoalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkoxy, cyano or nitro _1- C ₆ -alkyl, naphthyl-C ₁ -C ₆ -alkyl, or hetaryl having 5 or 6 reducing atoms and having 1 to 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen,
B preferably represents hydrogen C ₁ -C ₁₂ -alkyl or C ₁ -C ₈ -alkoxy-C ₁ -C ₆ -alkyl,
A, B and the carbon atoms to which they are attached are preferably one methylene group optionally substituted by oxygen or sulfur, C ₁ -C ₈ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₁ -C ₈ -halo Genoalkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkylthio, C ₃ -C ₁₀ -cycloalkyl or C ₅ -C ₁₀ -cycloalkenyl optionally substituted by halogen or phenyl,
A, B and the carbon atoms to which they are bonded are preferably alkylenediyl groups or alkylenedithioyl groups, optionally substituted with alkylenediyl groups having one or two oxygen and / or sulfur atoms (the substituents being the carbons to which they are attached). Together with the atoms to form an additional 5- to 8-membered ring) or C ₅ -C ₆ -cycloalkyl,
A, B and the carbon atom to which they are attached preferably represent C ₃ -C ₈ -cycloalkyl or C ₅ -C ₈ -cycloalkenyl, wherein the two substituents are in each case together with the carbon atom to which they are attached a C ₁ -C ₆ - alkyl, C ₁ -C ₆ - alkoxy or by halogen, and optionally substituted with one of the methylene groups is optionally replaced by oxygen or sulfur, C ₃ -C ₆ at each occurrence-alkanediyl, C ₃ -C ₆ -alkenediyl or C ₄ -C ₆ -alkanediendiyl,
D preferably represents C ₁ -C ₁₂ -alkyl, C ₃ -C ₈ -alkenyl, C ₃ -C ₈ -alkynyl, C ₁ -C ₁₀ which represents a channel or is optionally substituted by halogen in each case -Alkoxy-C ₂ -C ₈ -alkyl, poly-C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl or C ₁ -C ₁₀ -alkylthio-C ₂ -C ₈ -alkyl, or halogen , C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy or C ₁ -C ₄ - is optionally substituted by a halogenoalkyl one that is not directly adjacent to each other or two methylene group by oxygen and / or sulfur Optionally substituted C ₃ -C ₈ -cycloalkyl, or in each case optionally halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -halogenoalkyl, C ₁ -C ₆ -alkoxy, C _1- Phenyl substituted by C ₆ -halogenoalkoxy, cyano or nitro, hetaryl having 5 to 6 ring atoms and having 1 or 2 hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen, phenyl- C ₁ -C ₆ - alkyl 5 to have cut six oxygen reduction, het aryl group having one or two heteroatoms selected from the consisting of oxygen, sulfur and nitrogen -C ₁ -C ₆ - or represent alkyl,
A and D together preferably are C ₁ -C ₁₀ -alkyl, C ₁ optionally substituted in each case by one methylene group by oxygen or sulfur, and in each case optionally substituted by halogen, or in each case by halogen -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio, C ₃ -C ₇ -cycloalkyl, phenyl or benzyloxy, or form a fused ring and in each case one methylene group is bonded to oxygen or sulfur By an additional C ₃ -C ₆ -alkanediyl, C ₃ -C ₆ -alkenediyl or C ₄ -C ₆ -alkanediendiyl group optionally substituted by C ₁ -C ₆ -alkyl Optionally substituted C ₃ -C ₆ -alkanediyl, C ₃ -C ₆ -alkenediyl, or C ₄ -C ₆ -alkanediendiyl group,
A and D together in each case the following groups

C ₃ -C ₆ -alkanediyl or C ₃ -C ₆ -alkenediyl groups optionally containing either
G preferably represents hydrogen (a) or

Represents one of
From here,
E represents one equivalent of a metal ion or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or oxygen or sulfur.
R ¹ is preferably in each case optionally substituted by halogen C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₁ -C ₈ -alkoxy-C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkylthio-C ₁ -C ₈ -alkyl or poly-C ₁ -C ₈ -alkoxy-C ₁ -C ₈ -alkyl or represent halogen, C ₁ -C ₆ -alkyl or C ₁ -C C ₃ -C ₈ -cycloalkyl optionally substituted by ₆ -alkoxy and one or two methylene groups optionally substituted by oxygen and / or sulfur, or
Halogen, cyano, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl, C ₁ -C ₆ -halogenoalkoxy, C ₁ -C ₆ -alkyl Phenyl optionally substituted by thio or C ₁ -C ₆ -alkylsulfonyl, or
Halogen, nitro, cyano, C ₁ -C ₆ - alkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - halogenoalkyl or C ₁ -C ₆ - by a halogeno alkoxy optionally substituted phenyl C ₁ -C ₆ -alkyl or
Or represents a 5- or 6-membered hetaryl having one or two heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, optionally substituted by halogen or C ₁ -C ₆ -alkyl,
Optionally halogen or C ₁ -C ₆ - when the phenoxy substituted by alkyl -C ₁ -C ₆ - or represent alkyl,
5- or 6-membered hetaryloxy-C ₁ -C having one or two hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen and optionally substituted by halogen, amino or C ₁ -C ₆ -alkyl ₆ -alkyl.
R ² is preferably C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ -alkenyl, C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl or poly-C, which in each case is optionally substituted by halogen _1- C ₈ -alkoxy-C ₂ -C ₈ -alkyl, or
C ₃ -C ₈ -cycloalkyl optionally substituted by halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy, or
Phenyl or benzyl optionally substituted by halogen, cyano, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl or C ₁ -C ₆ -halogenoalkoxy Indicates.
R ³ preferably represents C ₁ -C ₈ -alkyl optionally substituted by halogen, or in each case halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -Halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, cyano or nitro optionally substituted with phenyl or benzyl.
R ⁴ and R ⁵ are preferably, independently of one another, in each occurrence C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkylamino, di- (C ₁ -C ₈ -alkyl) amino, C ₁ -C ₈ -alkylthio or C ₃ -C ₈ -alkenylthio, or in each case halogen, nitro, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ - halogenoalkyl alkoxy, C ₁ -C ₄ - alkylthio, C ₁ -C ₄ - halogenoalkyl alkylthio, C ₁ -C ₄ - alkyl or C ₁ -C ₄ - optionally substituted by a halogenoalkyl Phenyl, phenoxy or phenylthio.
R ⁶ and R ⁷ preferably represent, independently of one another, hydrogen or in each case optionally substituted by C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₈ -alkoxy , C ₃ -C ₈ -alkenyl or C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl, or in each case halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -halogeno alkyl, or C ₁ -C ₈ -, or represent optionally substituted phenyl or benzyl, with an alkoxy, with the C ₁ -C ₆ - alkyl which is substituted by optionally being replaced by one methylene group is optionally substituted by oxygen or sulfur, C ₃ -C ₆ -alkylene radical.
R ¹³ preferably represents hydrogen, or in each case represents C ₁ -C ₈ -alkyl or C ₁ -C ₈ -alkoxy, halogen, C ₁ -C ₄ -alkyl or C Represents C ₃ -C ₈ -cycloalkyl optionally substituted by _1- C ₄ -alkoxy and one methylene group is optionally substituted by oxygen or sulfur, or in each case halogen, C ₁ -C ₆ -alkyl, Phenyl optionally substituted by C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, nitro or cyano, phenyl-C ₁ -C ₄ -alkyl or phenyl -C ₁ -C ₄ -alkoxy,
R ¹⁴ preferably represents hydrogen or C ₁ -C ₈ -alkyl, or
R ¹³ and R ¹⁴ preferably together represent C ₄ -C ₆ -alkanediyl.
R ¹⁵ and R ¹⁶ are the same or different and preferably represent C ₁ -C ₆ -alkyl, or
R ¹⁵ and R ¹⁶ together preferably are C ₁ -C ₆ -alkyl or phenyl (which is halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ - halogenoalkyl alkoxy, nitro or cyano the by optionally substituted) by an optionally substituted C ₂ -C ₄ - shows the alkanediyl.
R ¹⁷ and R ¹⁸ independently of one another preferably represent hydrogen or C ₁ -C ₈ -alkyl optionally substituted by halogen, or halogen, C ₁ -C ₆ -alkyl, C ₁ -C _6- Phenyl optionally substituted by alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, nitro or cyano, or
R ¹⁷ and R ¹⁸ together with the carbon atom to which they are attached represent C ₅ -C ₇ -cycloalkyl optionally substituted by C ₁ -C ₄ -alkyl and one methylene group is optionally substituted by oxygen or sulfur.
R ¹⁹ and R ²⁰ are independently of each other preferably C ₁ -C ₁₀ -alkyl, C ₂ -C ₁₀ -alkenyl, C ₁ -C ₁₀ -alkoxy, C ₁ -C ₁₀ -alkylamino, C ₃ -C ₁₀ -alkenylamino, di- (C ₁ -C ₁₀ -alkyl) amino or di- (C ₃ -C ₁₀ -alkenyl) amino.
X is particularly preferably fluorine, chlorine or bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, cyano Or nitro,
Y is particularly preferably hydrogen, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, Represents cyano or nitro,
Z is particularly preferably fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, hydroxy , Cyano or nitro, or in each case fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogeno Phenoxy or benzyloxy optionally substituted by alkoxy, nitro or cyano, or
Y and Z together are particularly preferably _one optionally substituted with fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₂ -halogenoalkyl and not directly adjacent or alkanediyl or C ₃ -C ₄ - - two circles are each independently oxygen, sulfur, or C ₃ -C _4, which may be optionally replaced by a nitrogen represents Al canned yl, X is one of the above-mentioned meaning Indicates.
Het is particularly preferably a group

One of them is shown.
A particularly preferably represents hydrogen or in each case is optionally substituted with C ₁ -C ₁₀ -alkyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₈ -alkoxy-C _1- C ₆ -alkyl, poly-C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl or C ₁ -C ₈ -alkylthio-C ₁ -C ₆ -alkyl, or optionally fluorine, chlorine, C ₁ -C ₄ - alkyl or C ₁ -C ₄ - alkoxy substituted by one or two methylene groups are oxygen and / or sulfur by an alternate optionally C ₃ -C ₇ - cycloalkyl, or represent, in each case, Optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkoxy, cyano or nitro Phenyl, furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, indolyl, thiazolyl, thienyl or phenyl-C ₁ -C ₄ -alkyl,
B particularly preferably represents hydrogen C ₁ -C ₁₀ -alkyl or C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl,
A, B and the carbon atoms to which they are bonded are preferably in each case one methylene group optionally substituted by oxygen or sulfur, C ₁ -C ₆ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₃ -halogenoalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio, C ₃ -C ₈ -cycloalkyl or C ₅ -C ₈ -cycloal, optionally substituted by fluorine, chlorine or phenyl Represent kenyl,
A, B and the carbon atoms to which they are attached are particularly preferably by alkylenediyl groups optionally containing one or two oxygen or sulfur atoms, by alkylenedioxy groups or by alkylenedithiol groups (these substituents are attached to them) C ₅ -C ₆ -cycloalkyl substituted with a carbon atom to form an additional 5 to 7 membered ring, or
A, B and the carbon atom to which they are attached preferably represent C ₃ -C ₆ -cycloalkyl or C ₅ -C ₆ -cycloalkenyl, wherein the two substituents are in each case C together with the carbon to which they are attached ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, fluorine, chlorine, bromine or by optionally substituted single methylene group, the C ₃ -C ₅ optionally replaced by oxygen or sulfur, in each case, - alkanediyl 1, C ₃ -C ₅ -alkenediyl or butadienediyl.
D particularly preferably represents hydrogen or in each case is optionally substituted by C ₁ -C ₁₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C ₁ -C ₈ -alkoxy-C ₂ -C ₆ -alkyl, poly-C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl or C ₁ -C ₈ -alkylthio-C ₂ -C ₆ -alkyl Or one or two methylene groups optionally substituted by fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₂ -halogenoalkyl and not directly adjacent to oxygen and // Or C ₃ -C ₇ -cycloalkyl optionally substituted by sulfur, or in each case optionally fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C _1- Phenyl, furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl, substituted by C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkoxy, cyano or nitro, triazolyl or phenyl -C ₁ -C ₄ - represents an alkyl ,
A and D together are particularly preferably C ₁ -C optionally substituted in each case by one carbon atom by oxygen or sulfur and in each case optionally substituted by fluorine or chlorine or in each case by fluorine or chlorine Optionally substituted by ₆ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₃ -C ₆ -cycloalkyl, phenyl or benzyloxy, in each case

C ₃ -C ₅ -alkanediyl or C ₃ -C ₅ -alkenediyl group optionally containing one of them.
G particularly preferably represents hydrogen (a) or

Represents one of
From here,
E represents one equivalent of a metal ion or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur.
R ¹ is particularly preferably in each case C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl optionally substituted by fluorine or chlorine , C ₁ -C ₆ -alkylthio-C ₁ -C ₆ -alkyl or poly-C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, or represent fluorine, chlorine, C ₁ -C ₅ -alkyl Or C ₃ -C ₇ -cycloalkyl optionally substituted by C ₁ -C ₅ -alkoxy and one or two methylene groups optionally substituted by oxygen and / or sulfur, or
Fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl, C ₁ -C ₃ -halogenoalkoxy, C _1- C ₄ - alkylthio or C ₁ -C ₄ - or represents a phenyl optionally substituted by alkyl sulfonyl,
Phenyl-C ₁ optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy -C ₄ -alkyl or
In each case represent pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl, optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl,
Phenoxy-C ₁ -C ₅ -alkyl optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl, or
In each case pyridyloxy-C ₁ -C ₅ -alkyl, pyrimidyloxy-C ₁ -C ₅ -alkyl or thiazolyloxy optionally substituted by fluorine, chlorine, bromine, amino or C ₁ -C ₄ -alkyl -C ₁ -C ₅ -alkyl.
R ² is particularly preferably in each case C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, optionally substituted by fluorine or chlorine or Poly-C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, or
C ₃ -C ₇ -cycloalkyl optionally substituted by fluorine, chlorine, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, or
In each case fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy Phenyl or benzyl optionally substituted by.
R ³ particularly preferably represents C ₁ -C ₆ -alkyl optionally substituted by fluorine or chlorine, or in each case fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy , C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, cyano or nitro optionally substituted by phenyl or benzyl.
R ⁴ and R ⁵ are particularly preferably independently of each other C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylamino, di optionally substituted with fluorine or chlorine in each case -(C ₁ -C ₆ -alkyl) amino, C ₁ -C ₆ -alkylthio or C ₃ -C ₄ -alkenylthio, or in each case fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -halogenoalkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -halogenoalkylthio, C ₁ -C ₃ -alkyl or C ₁ -C _3- Phenyl, phenoxy or phenylthio optionally substituted by halogenoalkyl.
R ⁶ and R ⁷ particularly preferably independently of one another represent hydrogen or in each case are optionally substituted C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, C ₃ -C ₆ -alkenyl or C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, or in each case fluorine, chlorine, bromine, C ₁ -C ₅ -halogenoalkyl , C ₁ -C ₅ - alkyl or C ₁ -C ₅ - represents a phenyl or benzyl optionally substituted by alkoxy, or together are C ₁ -C ₄ - substituted by alkyl and optionally one methylene group is oxygen or sulfur Denotes a C ₃ -C ₆ -alkylene radical optionally substituted by.
R ¹³ particularly preferably represents hydrogen, in each case represents C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy optionally substituted by fluorine or chlorine, or fluorine, C ₁ -C _2- C ₃ -C ₇ -cycloalkyl optionally substituted by alkyl or C ₁ -C ₂ -alkoxy and one methylene group optionally substituted by oxygen or sulfur, or in each case fluorine, chlorine, bromine, C Phenyl, phenyl-C ₁ optionally substituted with _1- C ₅ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, nitro or cyano -C ₃ -alkyl or phenyl-C ₁ -C ₂ -alkoxy,
R ¹⁴ particularly preferably represents hydrogen or C ₁ -C ₆ -alkyl, or
R ¹³ and R ¹⁴ particularly preferably together represent C ₄ -C ₆ -alkanediyl.
R ¹⁵ and R ¹⁶ are the same or different and particularly preferably represent C ₁ -C ₄ -alkyl,
R ¹⁵ and R ¹⁶ are particularly preferably together preferably C ₁ -C ₄ -alkyl or phenyl (which is fluorine, chlorine, bromine, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -alkoxy, C ₁ -C ₂ - shows the alkanediyl radical-halogeno alkoxy group, a C ₂ -C ₃ optionally substituted with optionally substituted) by a nitro or cyano.
X is very particularly preferably fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tertiary butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoro Methyl, trifluoromethoxy, difluoromethoxy, cyano or nitro,
Y is very particularly preferably hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl methoxy, ethoxy, propoxy, iso-propoxy, tri Fluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro,
Z is very particularly preferably fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tertiary butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoro Methyl, trifluoromethoxy, difluoromethoxy, cyano or nitro, or
Y and Z together are particularly preferably optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy, propoxy, iso-propoxy or trifluoromethyl and directly adjacent Two unsubstituted groups represent C ₃ -C ₄ -alkanediyl optionally substituted by oxygen, and X represents one of the meanings mentioned above.
Het is very particularly preferably a group

Represents one of
A very particularly preferably represents C ₁ -C ₈ -alkyl, C ₂ -C ₄ -alkenyl, C ₁ -C ₆ -alkoxy-C ₁ which represents hydrogen, or in each case optionally substituted by fluorine or chlorine -C ₄ -alkyl, poly-C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl or C ₁ -C ₆ -alkylthio-C ₁ -C ₄ -alkyl, or optionally fluorine, chlorine, methyl Or C ₃ -C ₆ -cycloalkyl substituted by methoxy and one or two methylene groups optionally substituted by oxygen and / or sulfur, or in each case optionally fluorine, chlorine, bromine, methyl, ethyl, phenyl, pyridyl or benzyl substituted by n-propyl, iso-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
B very particularly preferably represents hydrogen, C ₁ -C ₈ -alkyl or C ₁ -C ₄ -alkoxy-C ₁ -C ₂ -alkyl,
Very particular preference is given to A, B and the carbon atoms to which they are attached, in which case one methylene group is optionally replaced by oxygen or sulfur, methyl, ethyl, n-propyl, iso-propyl, butyl, iso-butyl, s-butyl, tert-butyl, cyclohexyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, iso-butoxy, s-butoxy, tert-part C ₃ -C ₈ -cycloalkyl or C ₅ -C ₈ -cycloalkenyl optionally substituted by oxy, methylthio, ethylthio, fluorine, chlorine or phenyl,
A, B and the carbon atoms to which they are attached are very particularly preferably by means of alkylenediyl groups optionally containing oxygen or sulfur atoms or by alkylenedioxy groups (the substituents together with additional carbon atoms to which they are attached Form a ring) or C ₅ -C ₆ -cycloalkyl substituted by
A, B and the carbon atoms to which they are attached very particularly preferably represent C ₃ -C ₆ -cycloalkyl or C ₅ -C ₆ -cycloalkenyl, wherein the two substituents in each case together with the carbon to which they are attached In which one methylene group represents C ₃ -C ₄ -alkanediyl, C ₃ -C ₄ -alkenediyl or butadienediyl, optionally substituted by oxygen or sulfur,
D very particularly preferably represents hydrogen or in each case is substituted one or two methylene groups which are optionally substituted by fluorine or chlorine and are not directly adjacent to C ₁ -C _8- Alkyl, C ₃ -C ₄ -alkenyl, C ₃ -C ₄ -alkynyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₄ -alkyl, poly-C ₁ -C ₄ -alkoxy-C ₂ -C ₄ -alkyl, C ₁ -C ₄ -alkylthio-C ₂ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl, in each case fluorine, chlorine, bromine, methyl, ethyl, n-propyl, Phenyl, furanyl, pyridyl, thienyl, or benzyl optionally substituted by iso-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, or
A and D together very particularly preferably are C ₁ -C _6- , in each case one methylene group optionally substituted by oxygen or sulfur and optionally substituted by fluorine or chlorine, or in each case by fluorine or chlorine; C ₃ -C ₅ -alkanediyl or C ₃ -optionally substituted by alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₃ -C ₆ -cycloalkyl, phenyl or benzyloxy C ₅ -alkenediyl group.
G very particularly preferably represents hydrogen (a), or

Represents one of
From here,
E represents one equivalent of a metal ion or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur.
R ¹ is very particularly preferably in each case C ₁ -C ₁₄ -alkyl, C ₂ -C ₁₄ -alkenyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₆ -optionally substituted by fluorine or chlorine Alkyl, C ₁ -C ₄ -alkylthio-C ₁ -C ₆ -alkyl or poly-C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, or represent fluorine, chlorine, methyl, ethyl, n- Optionally substituted by propyl, i-propyl, n-butyl, i-butyl, t-butyl, methoxy, ethoxy, n-propoxy or iso-propoxy, one or two methylene groups being oxygen and / or C ₃ -C ₆ -cycloalkyl optionally substituted by sulfur, or
Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl or ethyl Phenyl optionally substituted by sulfonyl, or
Benzyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy, or
In each case represent furanyl, thienyl or pyridyl optionally substituted by fluorine, chlorine, bromine, methyl or ethyl,
Phenoxy-C ₁ -C ₄ -alkyl optionally substituted by fluorine, chlorine, methyl or ethyl, or
In each case pyridyloxy-C ₁ -C ₄ -alkyl, pyrimidyloxy-C ₁ -C ₄ -alkyl or thiazolyloxy-C ₁ -C ₄ optionally substituted by fluorine, chlorine, amino, methyl or ethyl -Represents alkyl.
R ² is very particularly preferably in each case substituted with C ₁ -C ₁₄ -alkyl, C ₂ -C ₁₄ -alkenyl, C ₁ -C ₄ -alkoxy-C ₂ -C _6- Alkyl or poly-C ₁ -C ₄ -alkoxy-C ₂ -C ₆ -alkyl, or
C ₃ -C ₆ -cycloalkyl optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, iso-propyl or methoxy, or
In each case phenyl or benzyl optionally substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy.
R ³ very particularly preferably represents methyl, ethyl, propyl, iso-propyl, butyl or tertiary butyl optionally substituted in each case by fluorine or chlorine, or in each case fluorine, chlorine, bromine, methyl, ethyl , Iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro optionally substituted with phenyl or benzyl.
R ⁴ and R ⁵ are very particularly preferably independently from each other C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, optionally substituted with each other by fluorine or chlorine in each case, Di- (C ₁ -C ₄ -alkyl) amino, C ₁ -C ₄ -alkylthio, or in each case fluorine, chlorine, bromine, nitro, cyano, methyl, methoxy, trifluoromethyl or tri Phenyl, phenoxy or phenylthio optionally substituted by fluoromethoxy.
R ⁶ and R ⁷ very particularly preferably independently represent hydrogen, or in each case are optionally substituted C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C _1- C ₄ -alkoxy, C ₃ -C ₄ -alkenyl or C ₁ -C ₄ -alkoxy-C ₂ -C ₄ -alkyl, in each case fluorine, chlorine, bromine, methyl, methoxy, or trifluor Phenyl or benzyl optionally substituted by romethyl or together represent a C ₅ -C ₆ -alkylene radical optionally substituted by methyl or ethyl and one methylene group optionally substituted by oxygen or sulfur.
The definitions and descriptions of the radicals mentioned in the general or preferred ranges may be combined with one another as necessary. That is, a combination between a particular range and a preferred range is possible. This applies to the final product and similarly applies to precursors and intermediates.
Preferred according to the invention are compounds of formula (I) in which a combination of the meanings given above as preferred is present.
Particularly preferred according to the invention are compounds of the formula (I) in which a combination of the meanings given above as being particularly preferred is present.
Very particular preference according to the invention is given to compounds of the formula (I) in which a combination of the meanings given above is very particularly preferred.
Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl, and those having a hetero atom, for example alkoxy, are in each case as straight or branched as possible.
The optionally substituted radical may be monosubstituted or polysubstituted, in which case the substituents may be the same or different.
Particular mention may be made of the following compounds of the general formula (I-1-a) other than the compounds mentioned in the preparation examples.

Table 1
X = CH ₃ ; Y = CH ₃ ; Z = CH ₃



Table 2: A and B have the same meaning as in Table 1, X = CH ₃ ; Y = CH ₃ ; Z = CH ₃
Table 3: A and B have the same meaning as in Table 1, X = Cl; Y = Cl; Z = Cl
Particular mention may be made of the following compounds of the general formula (I-1-a) other than the compounds mentioned in the preparation examples.

Table 4
X = CH ₃ ; Y = CH ₃ ; Z = CH ₃



Table 5: A and B have the same meaning as in Table 4, X = CH ₃ ; Y = Cl; Z = CH ₃
Table 6: A and B have the same meaning as in Table 4, X = Cl; Y = Cl; Z = Cl
Particular mention may be made of the following compounds of the general formula (I-3-a) other than the compounds mentioned in the preparation examples:

TABLE 7
X = CH ₃ ; Y = CH ₃ ; Z = CH ₃



Table 8: A and B have the same meaning as in Table 7, X = CH ₃ ; Y = Cl; Z = CH ₃
Table 9: A and B have the same meaning as in Table 7, X = Cl; Y = Cl; Z = Cl
In addition to the compounds mentioned in the preparation examples, the following compounds of general formula (I-4-a) may be mentioned:

Table 10
X = CH ₃ ; Y = CH ₃ ; Z = CH ₃



Table 11: A and D have the same meaning as in Table 10, Ⅹ = CH ₃ ; Y = Cl; Z = CH ₃
Table 12: A and D have the same meaning as in Table 10, Ⅹ = Cl; Y = Cl; Z = Cl
In addition to the compounds mentioned in the preparation examples, compounds of the general formula (I-5-a) may be mentioned:
Table 13
Ⅹ = CH ₃ ; Y = CH ₃ ; Z = CH ₃


Table 14: A has the same meaning as in Table 13, Ⅹ = CH ₃ ; Y = Cl; Z = CH ₃
Table 15: A has the same meaning as in Table 13, Ⅹ = Cl; Y = Cl; Z = Cl
According to the invention when ethyl N- [4,5-dichloro-2-methyl) -phenylacetyl] -1-amino-4-ethyl-cyclohexane-carboxylate is used as starting material according to process (A) The process of the method can be represented by the following scheme:

When using ethyl O-[(2,5-dichloro-4-methyl) -phenylacetyl] -hydroxyacetate according to method (B), the process of the method according to the invention can be represented by the following scheme have :

Use of ethyl 2-[(2-chloro-4, 5-dimethyl) -phenyl] -4- (4-methoxy) -benzylmercapto-4-methyl-3-oxo-valerate according to method (C) If so, the process of the process according to the invention can be represented by the following scheme:

According to the method (D), for example, when (chlorocarbonyl) -2-[(4,5-dichloro-2-methyl) -phenyl] -ketene and acetone are used as starting compounds, according to the invention The process of the method can be represented by the following scheme.

According to process (E), for example, when (chlorocarbonyl) -2-[(2, 4, 5-trimethyl) -phenyl] -ketene and thiobenzamide are used as starting compounds, according to the invention The process of the method can be represented by the following scheme:

According to the method (Fα) using 3-[(2, 5-dichloro-4-methyl) -phenyl] -5, 5-dimethyl-pyrrolidine-2, 4-dione and pivaloyl chloride as starting materials In the case, the process of the process according to the invention can be represented by the following scheme:

3-[(2, 4, 5-trichloro) -phenyl] -4-hydroxy-5-phenyl-Δ ³ -dihydrofuran-2-one and acetic anhydride according to method (F) (modification method β) When using as a starting compound, the process of the method according to the invention can be represented by the following scheme.

According to method (G), start 8-[(2,4-dichloro-5-methyl) -phenyl] -5, 5-pentamethylene-pyrrolidine-2, 4-dione and ethoxyethyl chloroformate When used as a compound, the process of the process according to the invention can be represented by the following scheme:

3-[(2-bromo-4, 5-dimethyl) -phenyl] -4-hydroxy-6- (3-pyridyl) -pyrone and methyl chloromono according to method (H), (modification method α) When thioformates are used as starting materials, the process of the process according to the invention can be represented by the following scheme:

5-[(5-chloro-2-fluoro-4-methyl) -phenyl] -6-hydroxy-2- (4-chlorophenyl) -thiazine- according to method (H), (modification method β) In the case of using 4-one, carbon disulfide and methyl iodide as starting components, the process of the process according to the invention can be represented by the following scheme. :

2-[(2, 4, 5-trimethyl) -phenyl] -5, 5-[(3-methyl) -pentamethylene-pyrrolidine-2, 4-dione and methanesulfonyl chloride according to method (I) When using as starting material, the process of the method according to the invention can be represented by the following scheme:

2-[(2-chloro-4-dimethyl) -phenyl] -4-hydroxy-5-methyl-6- (2-pyridyl) -pyrone and methanethio-phosphonic acid chloride 2 according to method (J), When 2, 2-trifluoroethyl ester is used as starting material, the process of the process according to the present invention can be represented by the following scheme.

When using 3-[(2, 4, 5-trichloro-phenyl] -5-cyclopropyl-5-methyl-pyrrolidine-2, 4-dione and NaOH as components according to method (K), The process of the method according to the invention can be represented by the following scheme.

3-[(2-chloro-4-bromo-5-methyl) -phenyl] -4-hydroxy-5, 5-tetramethylene-Δ ³ -dihydro- according to Method (L) (modification method α) When using furan-2-one and ethyl isocyanate as starting materials, the process of the process according to the invention can be represented by the following scheme:

Starting material 3-[(2-chloro-4, 5-dimethyl) -phenyl] -5-methyl-pyrrolidine-2, 4-dione and dimethylcarbamoyl chloride according to method (L) (modification method β) When used in the process of the process according to the invention can be represented by the following scheme "

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

Where
A, B, X, Y, Z and R ⁸ have the meanings mentioned above.
For example, acylamino acid esters of general formula (II) can be acylated with amino acid derivatives of general formula (VII) to substituted phenylacetic acid halides of general formula (III) (see Chem. Review 52, 237-416). (1953); Bhattacharya, Indian J. Chem. 6, 341-5, 1968), obtained by esterifying acylamino acids of general formula (XI) (Chem. Ind. (London) 1568 (1968)). .

Where
Hal represents chlorine or bromine,
A, B, X, Y, Z and R ⁸ have the meanings mentioned above.
Compounds of formula (VII) are novel:

Where
A, B, X, Y and Z have the meanings mentioned above.
Compounds of general formula (VII) are obtained by acylating amino acids of general formula (XI) with substituted phenylacetyl halides of general formula (Schotten-Baumann) (see Organikum, VEB Deutcher). Verlang der Wissenschaften, Berlin 1977, p. 505):

Where
Hal represents chlorine or bromine,
A, B, X, Y and Z have the meanings mentioned above.
Compounds of formula VIII are in some cases novel and can be prepared by known methods.
For example, a compound of formula (VIII) may be substituted with a substituted phenylacetic acid of formula (XIII) with a halogenating agent (eg, thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride, phosph) The porous tribromide or phosphorus pentachloride) is optionally diluted at a temperature of -20 to 150 ° C, preferably -10 to 100 ° C (eg optionally chlorinated alicyclic or aromatic hydrocarbons such as toluene or methylene chloride). Obtained by reaction in the presence of

Where
Ⅹ, Y and Z have the meanings mentioned above.
Compounds of general formula (XIII) are novel in some cases and can be prepared by methods known from Organanicum 15th edition, page 533, VEB Deutscher Verlag der Wissenschafen, Berlin 1977. For example, a compound of formula (XIII) may be substituted with a substituted phenylacetic acid ester of formula (XIV), an acid (e.g., an inorganic acid such as hydrochloric acid) or a base (alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide). By hydrolysis at a temperature between 0 and 150 ° C., preferably between 20 and 100 ° C., in the presence of) and optionally in the presence of a diluent (for example an aqueous alcohol such as methanol or ethanol):

Where
Ⅹ, Y, Z and R ⁸ have the meanings mentioned above.
Compounds of general formula (XIV) may in some cases be prepared by new and in principle known methods.
Compounds of general formula (VII) may be prepared by, for example, first replacing the substituted 1, 1, 1-trichloro-2-phenylethane of general formula (XV) with alcoholates (e.g. alkalis such as sodium methylate or sodium ethylate). Metal alcoholate) and a diluent (for example alcohol derived from an alcoholate) at a temperature of 0 ° C. to 150 ° C., preferably 20 ° C. to 120 ° C., followed by acid (preferably inorganic acid, eg Sulfuric acid), for example, from -20 ° C to 150 ° C, preferably 0 ° C to 100 ° C (see DE 3 314 249).

Compounds of general formula (XV) may in some cases be prepared by new and in principle known methods.
The compound of formula (XV) may be, for example, aniline of formula (XVI) in the presence of vinylidene chloride (CH ₂ = CCl ₂ ) and alkyl nitrile of Obtained by reaction at -20 ° C to 80 ° C, preferably 0 ° C to 60 ° C, under and in the presence of a diluent (for example an aliphatic nitrile such as acetonitrile) if necessary.

Where
Ⅹ, Y and Z have the meanings mentioned above,
R ²¹ represents alkyl, preferably C ₁ -C ₆ -alkyl.
Compounds of formulas (VI) and (IX) are known compounds of organic chemistry. Copper (II) chloride and vinylidene chloride have been known for a long time and are commercially available.
Compounds of formulas (VII) and (XI) are known in some cases and / or known methods (see, eg, Compagnon, Miocque Ann. Chim (Paris) [14] 5, p. 11-22, 23- 27 (1970).
Substituted cyclic amino carboxylic acids of general formula (XIIa) in which A and B form a ring can generally be obtained by Bucherer-Bergs synthesis or by Strecker synthesis, each of which is In these synthesis, in various isomeric forms. Thus, the conditions of the bouqueter-bergs synthesis provide mainly the isomers in which the radicals R and the carboxyl groups are in the horizontal position (hereinafter simply referred to as β) and the conditions of the flexure synthesis are the amino groups and radicals R in the horizontal position. Predominantly isomers (hereinafter referred to simply as α) (L. Munday, J. Chem. Soc. 4372 (1961); JT Eward, C. Jitrangeri, Can. J. Chem. 53, 3339 (1975). )):

Bucharer-Berg's Synthesis (β Isomers) Stacker Synthesis (α Isomers)
In addition, the starting material of formula (II) used in the above method (A) may react the compound of formula (VIII) by reacting aminonitrile of formula (VIII) with substituted phenylacetic acid halide of formula (VIII). It can be prepared by obtaining and then decomposing the acid alcohol:


Where
A, B, X, Y, Z, R ⁸ and Hal have the meanings mentioned above.
The compound of general formula is similarly novel.
The compounds of formula (III) which are required as starting materials for process (B) according to the invention are novel:

Where
A, B, X, Y, Z and R ⁸ have the meanings mentioned above.
They can in principle be produced in a simple manner according to known methods.
Thus, for example, compounds of general formula (III) are obtained by acylating the 2-hydroxy carboxylic acid esters of general formula with substituted phenylacetic acid halides of general formula (Chem. 52, 237-416 (1953)):

Where
A, B, X, Y, Z, R ⁸ and Hal have the meanings mentioned above.
In addition, compounds of formula (III) are obtained by alkylation of substituted phenylacetic acid of formula (XIII) with α-halogeno carboxylic acid esters of formula (XIII):

Where
Hal represents chlorine or bromine,
A, B, X, Y, Z and R ⁸ have the meanings mentioned above.
Compounds of formula (VII) are commercially available.
The compounds of formula (IV) which are required as starting materials for process (C) according to the invention are novel:

Where
A, B, W, X, Y, Z and R ⁸ have the meanings mentioned above.
They can in principle be prepared according to known methods.
For example, a compound of formula (IV) is obtained by acylating a substituted phenylacetic acid ester of formula (XIV) with 2-benzylthio-carbonyl halide of formula (XII) in the presence of a strong base ( Reference: MS Chambers, EJ Thomas, DJ Williams, J. Chem. Soc.Chem.Commun., (1987), 1228):


Where
Hal represents halogen (especially chlorine or bromine),
A, B, W, X, Y, Z and R ⁸ have the meanings mentioned above.
Some of the benzylthio-carboxylic acid halides of formula (XII) can be prepared by known and / or known methods (J. Antibiotics (1983), 26, 1589).
The halogenocarbonyl ketene of the general formula (VI) required as starting material of the method (D) is novel. They can in principle be prepared by simple methods according to known methods (Org. Prep. Proced. Int. 7, (4), 155-158, 1975 and DE 1,945,703). For example, the compound of formula (VI) may be substituted with an acid halide of substituted phenylmalonic acid of formula (XIII), for example thionyl chloride, phosphorus (V) chloride, phosphorus (III) chloride, jade. In the presence and optionally a base, such as pyridine or triphenyl, with salyl chloride, phosgene or thionyl bromide and optionally a catalyst such as diethyl formamide, methyl-sterylformamide or triphenylphosphine Obtained by reacting in the presence of ethylamine at a temperature of −20 to 200 ° C., preferably 0 ° C. to 150 ° C .:

Where
Hal represents chlorine or bromine,
X, Y and Z have the meanings mentioned above.
Substituted phenylmalonic acid of formula (XIII) is novel. However, they can be prepared by simple methods according to known methods (see Organikum, VEB Deutcher Verlag der Wissenschaften, Berlin 1977, p. 517 and below). For example, it may be prepared by hydrolysis from substituted phenylmalonic acid ester of the general formula (XIV).

Where
X, Y, Z and R ⁸ have the meanings mentioned above.
Carbonyl compounds of formula (V) or silyl enol ethers thereof (formula (Va) are commercially available compounds, generally known or known processes), which are required as starting materials for process (E) according to the invention It can be prepared by:

Where
A, D and R ⁸ have the meanings mentioned above.
The preparation of ketenoic acid chlorides of the general formula (VI) which is necessary as starting material for carrying out process (E) according to the invention has already been described in process (D) according to the invention. Thioamides of the general formula necessary for carrying out process (E) according to the invention are compounds generally known in the field of organic chemistry:

Where
A has the meaning mentioned above.
The malonic esters of formula (XIV) are novel:

In the above formula
R ⁸ , X, Y and Z have the meanings mentioned above.
They can be synthesized by methods generally known in organic chemistry (see Tetrahedron Lett. 27, 2763 (1986) and Organikum, VEB Deutcher Verlag der Wissenschaften, Berlin 1977, p. 587).
Acids of the general formula (VII) which are further required as starting materials for carrying out the processes (F), (G), (H), (I), (J), (K) and (L) according to the invention. Halides, carboxylic anhydrides of the general formula (VII), chloroformic acid esters or chloroformic acid thioesters of the general formula (X), chloromonothioformic acid esters of the general formula (XI) Alkyl halides, sulfonic acid chlorides of general formula (XIII), phosphorus compounds of general formula (XIV), metal hydroxides of general formulas (XV) and (XVI), metal alkoxides or amines, isocyanates of general formula (XV) and general Carbamic acid chlorides of formula (IV) are compounds commonly known in the organic or inorganic chemistry arts.
In addition, the compounds of formulas (V), (IX) to (XI), (XIV), (XIII), (XI), (XI), (XI), (XIII), and (XIIII) to (XIV) It may be prepared according to the methods described in and / or described in the patent applications cited above.
Method (A) is characterized in that A, B, X, Y, Z and R ⁸ condensate intramolecularly a compound of formula (II) having the above-mentioned meaning in the presence of a diluent and in the presence of a base. .
Diluents which can be used in process (A) according to the invention are all organic solvents which are inert to the reactants. Hydrocarbons such as toluene and xylene, further ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, further polar solvents such as dimethyl sulfoxide , Sulfolane, dimethylformamide and N-methylpyrrolidone, and alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and t-butanol may be preferably used.
Bases which can be used when carrying out method (A) according to the invention are all conventional proton acceptors. Proton acceptors that can preferably be used are alkali 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, all of which are phase Transition catalysts such as triethylbenzylammonium chloride, tetrabutylammonium bromide, adogen 464 (= methyltrialkyl (C ₈ -C ₁₀ ) ammonium chloride) or TDA 1 (= tris (methoxyethoxyethyl) -amine Can be used in the presence of Alkali metals such as sodium or potassium may further be used. Other materials that can be used include alkali metal and alkaline earth metal amides, hydrides such as sodium amide, sodium hydride and calcium hydride, and further alkali metal alcoholates such as sodium methylate, sodium ethylate And potassium t-butylate.
When carrying out process (A) according to the invention, the reaction temperature can be varied within a significant range. In general, the process is carried out at temperatures between 0 and 250 ° C, preferably between 50 and 150 ° C.
Process (A) according to the invention is generally carried out under atmospheric pressure.
When carrying out process (A) according to the invention, the reactants and deprotonation bases of formula (II) are generally used in approximately equimolar amounts to twice the molar amount. However, it is also possible to use one component or the other reactant in excess (up to 3 moles).
Method (B) is characterized in that A, B, X, Y, Z and R ⁸ intramolecularly condense the compounds of the general formula (III) having the meanings mentioned above in the presence of a diluent and in the presence of a base. .
Diluents which can be used in process (B) according to the invention are all organic solvents which are inert to the reactants. Hydrocarbons such as toluene and xylene, further ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, further polar solvents such as dimethyl sulfoxide , Sulfolane, dimethylformamide and N-methylpyrrolidone may be preferably used. Other materials that can be used are alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and t-butanol.
Bases (deprotonating agents) that can be used when carrying out method (B) according to the invention are all conventional proton acceptors. Alkali and alkaline earth metal oxides, hydroxides, carbonates such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate can be preferably used, all of which are phase transfer catalysts, eg For example, in the presence of triethylbenzylammonium chloride, tetrabutylammonium bromide, adogen 464 (= methyltrialkyl (C ₈ -C ₁₀ ) ammonium chloride) or TDA 1 (= tris (methoxyethoxyethyl) -amine) Can be used. Alkali metals such as sodium or potassium may further be used. In addition, alkali metal and alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and further alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium t- Butylate can be used.
When carrying out process (B) according to the invention the reaction temperature can be varied within a significant range. Generally the reaction is carried out at a temperature between 0 and 250 ° C, preferably between 50 and 150 ° C.
Process (B) according to the invention is generally carried out under atmospheric pressure.
When carrying out process (B) according to the invention, the reaction components and deprotonation bases of general formula (III) are generally used in approximately equimolar amounts. However, it is also possible to use one reaction component or another reaction component in an excess (3 mol or less).
Method (C) is carried out to provide a compound of formula (IV) wherein A, B, W, X, Y, Z and R ⁸ have the meanings mentioned above in the presence of an acid and optionally in the presence of a diluent It is characterized by cyclization.
Diluents which can be used in process (C) according to the invention are all organic solvents which are inert to the reactants. Hydrocarbons such as toluene and xylene, further halogenated hydrocarbons such as methylene chloride, chloroform, ethylene chloride, chlorobenzene, dichlorobenzene, further polar solvents such as dimethyl sulfoxide, sulfolane, dimethyl Formamide and N-methylpyrrolidone can be preferably used. Other materials that can be used are alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and t-butanol.
In some cases, the acid used may act as a diluent.
Acids which can be used in the process (C) according to the invention are all customary inorganic and organic acids, for example, halogenated hydrochloric acid, sulfuric acid, alkyl-, aryl- and haloalkylsulfonic acids, particularly acids which can be used are halogenated alkylcarboxylic acids. For example trifluoroacetic acid.
When carrying out process (C) according to the invention the reaction temperature can vary within a significant range. In general, the invention is carried out at temperatures between 0 and 250 ° C, preferably between 50 and 150 ° C.
Process (C) according to the invention is generally carried out under atmospheric pressure.
When carrying out process (C) according to the invention, the reaction components and acids of general formula (IV) are generally used in equimolar amounts. However, it is also possible to use an acid in catalytic amounts in some cases.
Process (D) according to the invention is carried out in the presence and in the case of the presence of a carbonyl compound of formula (V) or a silylenol ether of formula (Va) with a ketenoic acid halide of formula (VI) and According to the presence of acid acceptors.
Diluents which can be used in process (D) according to the invention are all organic solvents which are inert to the reactants. Hydrocarbons such as o-dichlorobenzene, tetralin, toluene and xylene, further ethers such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, further polar solvents such as dimethyl Sulfoxide, sulfolane, dimethylformamide or N-methylpyrrolidone may be preferably used.
Acid acceptors that can be used when carrying out the method (D) according to the invention are all customary acid acceptors.
Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunich (H nig) base and N, N-dimethyl-aniline can be preferably used.
When carrying out the modification process (D) according to the invention, the reaction temperature can be varied within a significant range. In general, the present invention is conveniently carried out at temperatures between 0 and 250 ° C, preferably between 50 and 220 ° C.
Process (D) according to the invention is preferably carried out under atmospheric pressure.
When carrying out process (D) according to the invention, the acid acceptors are generally used in approximately equimolar amounts, as required, and the reaction components of formulas (V) or (VI) and (V). However, it is also possible to use an excess (up to 5 moles) of one or the other reaction component.
Process (E) is characterized in that the reaction of thioamide of formula (VII) and ketenoic acid halide of formula (VI) is optionally carried out in the presence of a diluent and optionally in the presence of an acid acceptor.
Diluents which can be used in the modification process (E) according to the invention are all inert organic solvents. Hydrocarbons such as o-dichlorobenzene, tetralin, toluene and xylene, further ethers such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, further polar solvents such as dimethyl Sulfoxide, sulfolane, dimethylformamide or N-methyl-pyrrolidone may be preferably used.
Acid acceptors that can be used when carrying out method (E) according to the invention are all conventional acid acceptors.
Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunich (H nig) base and N, N-dimethyl-aniline can be preferably used.
When carrying out process (E) according to the invention the reaction temperature can be varied within a significant range. In general, the process is conveniently carried out at temperatures between 0 and 250 ° C, preferably between 20 and 220 ° C.
Process (E) according to the invention is preferably carried out at atmospheric pressure.
When carrying out the process (E) according to the invention, the acid acceptors are generally used in approximately equimolar amounts, as required, and in accordance with the reaction components of formulas (VII) and (VI). However, it is also possible to use excess (up to 5 moles) of one or the other reactants.
Process (Fα) is carried out by the compounds of formulas (I-1-a) to (I-5-a) in each case in the presence of a carboxylic acid halide of formula It is characterized by reacting in the presence of.
Diluents which can be used in the process (Fα) according to the invention are all solvents which are inert to the acid halide. Hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, also halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, further ketones such as acetone And methyl isopropyl ketone, further ethers such as diethyl ether, tetra hydrofuran and dioxane, further carboxylic esters such as ethyl acetate, further strong polar solvents. For example, dimethylformamide, dimethyl sulfoxide and sulfolane can be preferably used. If the acid halide is stable against hydrolysis, the reaction may also be carried out in the presence of water.
Possible acid-binding agents when carrying out the reaction according to the method (Fα) according to the invention are all customary acid acceptors. Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunich (H nig) bases and N, N-dimethyl-aniline, additionally oxides of alkaline earth metals such as oxides and magnesium and calcium oxide, further alkali metals and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and Calcium carbonate and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide can be preferably used.
When carrying out the method Fα according to the invention the reaction temperature can be varied within a significant range. In general the invention is carried out at temperatures between -20 and + 150 ° C, preferably between 0 and 100 ° C.
When carrying out the process (Fα) according to the invention, the starting materials of the general formulas (I-1-a) to (I-5-a) and the carboxylic acid halides of the general formula (VII) are generally approximately the same in each case Used in molar amounts. However, it is also possible to use carboxylic acid halides in excess (5 mol or less). The reaction post-treatment is carried out in a conventional manner.
Process (Fβ) is carried out by the compounds of general formulas (I-1-a) to (I-5-a) and anhydrous carboxylic acids of general formula (VIII) in the presence of a diluent and optionally in the presence of an acid binder. Reaction.
Diluents which can be used in the process (Fβ) according to the invention are preferably those which can be used preferably when using acid halides. In addition, the anhydrous carboxylic acid used in excess may also act as a diluent at the same time.
The acid binders added as needed in the process (Fβ) are preferably possible acid binders, preferably with acid halides.
The reaction temperature of the process (Fβ) according to the invention can be varied within a significant range. In general, the process is conveniently carried out at temperatures between -20 and +150 ° C, preferably between 0 and 100 ° C.
When carrying out the process (Fβ) according to the invention, the anhydrous carboxylic acids of the general formulas (I-1-a) to (I-5-a) and of general formula (VII) which are starting materials are generally approximately the same in each case Used in molar amounts. However, it is also possible to use an excess of carboxylic acid anhydride (5 mol or less). The reaction post-treatment is carried out in a conventional manner.
Generally, after this, the diluent and excess anhydrous carboxylic acid and the resulting carboxylic acid are removed by distillation or washing with organic solvent or water.
Method (G) comprises compounds of formulas (I-1-a) to (I-5-a) and in each case chloroformic acid esters or chloroformic acid thioesters in the presence of a diluent, And optionally in the presence of an acid binder.
Possible acid-binding agents in the modification process (G) according to the invention are all customary acid acceptors. Tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBA, Hunich base and N, N-dimethyl-aniline, further oxides of alkaline earth metals such as magnesium oxide and calcium oxide, further Furnaces of alkali metals and alkaline earth metals such as sodium carbonate, potassium carbonate and calcium carbonate, and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide can be preferably used.
Diluents which can be used in process (G) according to the invention are all solvents which are inert to chloroformic acid esters or chloroformic acid thioesters. Hydrocarbons such as benzine, benzene, toluene, xylene, and tetralin, additional halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, further ketones such as , Acetone and methyl isopropyl ketone, further ethers such as diethyl ether, tetrahydrofuran and dioxane, further carboxylic esters such as ethyl acetate, and / or nitriles such as acetonitrile In addition, strong polar solvents such as dimethylformamide, dimethyl sulfoxide and sulfolane can be preferably used.
When carrying out process (G) according to the invention the reaction temperature can be varied within a significant range. Generally the reaction temperature is between -20 and +100 ° C, preferably between 0 and 50 ° C.
Process (G) according to the invention is generally carried out under atmospheric pressure.
When carrying out the method (G) according to the invention, the chloroformic acid esters and chloroformic acid thioesters of the general formulas (I-1-a) to (I-5-a) and (VII) as starting materials are Generally used in approximately equimolar amounts. However, it is also possible to use one reactant or another reactant in excess (up to 2 moles). The reaction post-treatment is carried out in a conventional manner. Thereafter, the precipitated salts are removed and the diluent is stripped to concentrate the residual reaction mixture.
The process (H) according to the invention is carried out in the presence of the compounds of the general formulas (I-1-a) to (I-5-a) in each case in the presence of the compound of the general formula (Hα), or with carbon disulfide and optionally with an alkyl halide of the general formula (Hβ) in the presence of a diluent and optionally in the presence of a base.
In the production process (Hα), approximately 1 mole of general formula is used with respect to 1 mole of starting compound of general formulas (I-1 -a) to (I-5-a) at 0 to 120 ° C, preferably 20 to 60 ° C. The chloromonothioformic acid ester or chlorodithioformic acid ester of (XI) is reacted.
Possible diluents which are optionally added are all inert polar solvents such as ethers, amides, sulfones, sulfoxides, and halogenoalkanes.
Preferably dimethylsulfoxide, terahydrofuran, dimethyl formamide or methylene chloride is used.
In a preferred embodiment, the enolate salt of the compounds of formulas (I-1-a) to (I-5-a) is prepared by adding a strong deprotonating agent, for example sodium hydride or potassium t-butylate In addition, it may not be added to the acid binder.
When using acid binders, possible materials are conventional inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned.
The reaction may be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out by conventional methods.
In the preparation method (Hβ), an equimolar amount or excess carbon disulfide is added in each case to 1 mole of the starting compound of general formulas (I-1-a) to (I-5-a). This reaction is preferably carried out at a temperature of 0 to 50 ° C, preferably 20 to 30 ° C.
Often it is convenient to first prepare the corresponding salts from the compounds of formulas (I-1-a) to (I-5-a) by adding a base (eg potassium t-butylate or sodium hydride). Do. Compounds (I-1-a) to (I-5-a) are in each case stirred until reaction between carbon disulfide and intermediates is finished, for example, at room temperature and then for a while.
In addition, bases that can be used in the method (Hβ) are conventional proton receptors. Hydrides of alkali metals, alcoholates of alkali metals, carbonates or bicarbonates or nitrogen bases of alkali metals and alkaline earth metals can be preferably used. Sodium hydride, sodium methanolate, sodium hydroxide, potassium hydroxide, calcium carbonate, sodium bicarbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclononene ( DBN) and diazabicycloundecene (DBU) may be mentioned by way of example.
Diluents that can be used in this method are all conventional solvents.
Aromatic hydrocarbons such as benzene or toluene, alcohols such as methanol, ethanol, isopropanol or ethylene glycol, nitriles such as acetonitrile, ethers such as tetrahydrofuran or dioxane, amides, For example, dimethylformamide, or other polar solvents such as dimethylsulfoxide or sulfolane can be preferably used.
Further reactions with alkyl halides of general formula (XII) are preferably carried out at 0 to 70 ° C, in particular at 20 to 50 ° C. At least equimolar amounts of alkyl halides are used in the reaction.
The reaction is carried out at atmospheric or elevated pressure, preferably at atmospheric pressure.
Post-treatment is carried out in a conventional manner.
Process (I) according to the invention comprises the compounds of formulas (I-1-a) to (I-5-a) in each case in the presence of a sulfonic acid chloride of formula (VII) and optionally a diluent and In some cases, in the presence of an acid binder.
In the preparation method (I), about 1 mole of general to 1 mole of the starting compound of general formulas (I-1-a) to (I-5-a) at -20 to 150 ° C, preferably 20 to 70 ° C. The sulfonic acid chloride of formula (XIII) is reacted.
Method (I) is preferably carried out in the presence of a diluent.
Diluents that can be used are all inert polar solvents, for example ethers, amides, ketones, carboxylic acid esters, nitriles, sulfones, sulfoxides, or halogenated hydrocarbons, for example methylene chloride.
Preferably dimethylsulfoxide, tetrahydrofuran, dimethyl formamide or methylene chloride is used.
In a preferred embodiment, the enolate salt of the compounds of formulas (I-1-a) to (I-5-a) is added a strong deprotonating agent (e.g. sodium hydride or potassium t-butylate) If prepared, the addition of an acid binder may not be added.
When using acid binders, the possible materials are conventional inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned.
The reaction may be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out by conventional methods.
Process (J) according to the invention comprises the compounds of formulas (I-1-a) to (I-5-a) in each case in the presence of a phosphorus compound of formula (XIV) and optionally a diluent and In some cases, in the presence of an acid binder.
In the preparation method (J), 1 to 2 moles per 1 mole of the compound of (I-1-a) to (I-5-a) at a temperature between -40 and 150 ° C, preferably -10 to 110 ° C. And, preferably, 1 to 1.3 moles of the phosphorus compound of the general formula (XIV) is reacted to obtain a compound of the general formulas (I-1-e) to (I-6-e).
Method (J) is preferably carried out in the presence of a diluent.
Possible diluents are all inert polar solvents such as ethers, carboxylic acid esters, halogenated hydrocarbons, ketones, amides, nitriles, sulfones, sulfoxides and the like.
Preferably acetonitrile, dimethylsulfoxide, tetrahydrofuran, dimethyl formamide or methylene chloride are used.
Possible acid binders which are optionally added are conventional inorganic or organic bases such as hydroxides, carbonates or amines, for example sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.
The reaction may be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out by conventional methods of organic chemistry. The final product is preferably purified by crystallization, chromatographic purification or so-called "incipient distillation", ie by removing volatile components under vacuum.
Process (K) comprises the compounds of formulas (I-1-a) to (I-5-a) with a metal hydroxide or metal alkoxide of formula (XV), or an amine of formula (XVI) and optionally a diluent It is characterized by reacting in the presence of.
Diluents which can be used in the process (K) according to the invention are preferably ethers such as tetrahydrofuran, dioxane or diethyl ether, or other alcohols such as methanol, ethanol, isopropanol, and water to be. Process (K) according to the invention is generally carried out at atmospheric pressure. The reaction temperature is generally between -20 and 100 ° C, preferably between 0 and 50 ° C.
The process (L) according to the invention comprises in each case the compounds of the general formulas (I-1-a) to (I-5-a) in the presence and in the case of the presence of the compounds of the general formula Either in the presence of a catalyst (Lα) or in the presence of a compound of the general formula (XVII) and optionally in the presence of a diluent and optionally in the presence of an acid binder (Lβ).
In the production process (Lα), about 1 mole of general formula per mole of starting compound of general formulas (I-1-a) to (I-5-a) at 0 to 100 ° C, preferably 20 to 50 ° C. The isocyanate of (X ') is reacted.
Method (Lα) is preferably performed in the presence of a diluent.
Possible diluents are all inert organic solvents, for example aromatic hydrocarbons, halogenated hydrocarbons, ethers, amides, nitriles, sulfones or sulfoxides.
In some cases, a catalyst may be added to accelerate the reaction. A catalyst that can be used very advantageously is an organic tin compound, for example dibutyl tin dilaurate.
The reaction is preferably carried out at atmospheric pressure.
In the production process (Lβ), about 1 mole of general formula per mole of starting compound of general formula (I-1-a) SOWL (I-5-a) at 0 to 150 ° C, preferably 20 to 70 ° C. The carbamic acid chloride of (iii) is reacted.
Possible diluents which are optionally added are all inert polar organic solvents, for example ethers, carboxylic acid esters, nitriles, ketones, amides, sulfones, sulfoxides or halogenated hydrocarbons.
Preferably dimethylsulfoxide, tetrahydrofuran, dimethyl formamide or methylene chloride is used.
In a preferred embodiment, the enolate salt of the compounds of formulas (I-1-a) to (I-5-a) is added a strong deprotonating agent (e.g. sodium hydride or potassium t-butylate) If prepared, the addition of an acid binder can be avoided.
When using an acid binder, possible materials are customary inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine may be mentioned.
The reaction may be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out by conventional methods.
The active compounds are suitable for the control of arthropods and nematodes, in particular insects and arachnids, which are encountered in the protection and sanitation zones of animal pests, in particular agriculture, forestry, storage and materials. It is active against all or some stages of moderately sensitive or resistant species and metamorphosis. The pests mentioned above include:
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 carpophagus 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 the Orthoptera, for example, Blata orientalis, Periplaneta americana, Leucophaea maderae, Blatelela germanica, Ah Keta Domestikus, Gryllotalpa spp., Locusta migratoria migratoriodes, 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 vastartix, 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 brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Apis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, hyaloftheru Hyopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca subspecies Empoasca spp.), Eucelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Lao delfax Laodelphax striatellus, Nilaparvata lugens, 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., Spodoptera exigua, Mestra brassicae, Panolis flammea, Prode Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo subspecies ( Chilo spp.), Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tynea pelionel Tinea pellionella, Hofmannophila pseudospretella, Cacoacia podana, Capua reticulana, Choristoneura fumiferana and Clistone Clysia ambigulella, Homona magnanima, and Tortrix viridana.
Trees of Coleoptera, for example, Anobium punctatum, Acanthoscelides obtectus, Hilotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilakna pilachisae varivestis, Atomaira spp., Oryzaephilus surinamensis, Antonomus spp., Sitophilus spp., Othiorincus sulcatus (Otiorrhynchus sulcatus), Cosmopolites sordidus, Cethorthornchus assimilis, Hypera postica, Dermestes spp., Tro Tromoderma spp., Antrenus spp., Atageus spp., Lyctus spp., Meligethes aeneus, Ptinus Subspecies (Ptinus spp.), Niptus holoeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes subspecies (Agriotes spp.), Conoderus spp., Melonta melolontha, Amphimallon solstitialis and Costelytra zeallandica.
The order of the Hymenopera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa subspecies ( Vespa spp.).
Diptera N, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca subspecies (Musca spp.), Pania spp., Calaphora 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, Phobia spp., Pegomia hyossi Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludo (Tipula paludosa).
From the tree of Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp.
Arachnida, for example Scorpio maurus and Latrodectus mactans.
The order of the ticks Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus spp., Eriopis libis (Eriophyes ribis), Phyllocoptruta oleivora, Bophylus spp., Ripicephalus spp., Amblyomma spp., Hyalomma spp. .), Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus subspecies. ), Bryobia praetiosa, Panonhchus spp. And Tetranychus spp.
The active compounds according to the invention are distinguished by excellent pesticidal and acaricide activity.
They are particularly used successfully for phytopathogenic insects, such as, for example, mustard beetle larvae (Phaedon cocleariae), beetle beetle (Nepotetics cactifs) or Chinese cabbage moth (Flutella maculipenis). Can be.
The active compounds according to the invention can also be used as deciduous, drying, broadleaf plant killing agents and in particular weed-removing agents. The term "weeds" broadly means all plants that grow in unwanted places. Whether the compounds according to the invention act as total or selective herbicides depends essentially on the amount used.
The dosage of the active compounds according to the invention for removing weeds is from 0.001 to 10 kg / ha, preferably from 0.005 to 5 kg / ha.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds in the following genus: Sinapis, Lepidium, Gallium, Stellaria, Matricaria, Anthemis, Galinsoga, Ke Nopodium, Urtica, Senesio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala ), Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galleosis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the following genus: Gossypium, Glycine, Beta, Doucus, Phaseolus, Pisum, Solanum, Linum ), Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis ) And Cucurbita.
Monocot weeds in the genus: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festus, Eleusin, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Sino Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Iscamum ), Sphenoclea, Dactyloctenium, Agrostis, Alpecurus and Apera.
Monocot crops of the following genus: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum Panicum), Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is not limited at all in the above, but extends to other plants in the same way.
The compounds of the invention are suitable for the overall control of weeds, depending on concentration, for example on industrial areas and railways, and on sidewalks and plazas with or without trees. Similarly, the compounds of the present invention include, for example, plantation, ornamental water, orchard, vineyard, citrus field, nut orchard, banana plantation, coffee plantation, tea plantation, rubber plantation, palm plantation, cocoa plantation, soft fruit plantation and hop field, decoration And to control weeds in perennial crops growing on sports grass and pasture, and to selectively control weeds in annual crops.
The active compounds according to the invention are suitable for the selective control of monocotyledonous weeds by both pre- and post-germination methods in dicotyledonous crops. They can be very successfully used to control forage harmful plants, for example in cotton or beets.
The active compounds are usually used as solutions, emulsions, hydrating powders, suspensions, powders, powders, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with the active compounds, and microcapsules in polymeric materials. It can be converted into the formulation of.
These formulations are prepared by known methods, for example by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally using surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents. do.
When water is used as the extender, for example an organic solvent can also be used as an auxiliary solvent. Liquid solvents are mainly aromatic compounds such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffins, for example mineral oil fractions, mineral oils and vegetable oils. Alcohols such as aliphatic hydrocarbons, butanol or glycol and ethers and esters thereof, as well as strong polar solvents such as ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, dimethylformamide and dimethyl sulfoxide, are suitable Do.
Solid carriers include, for example, ammonium salts and ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly dispersed silica, alumina and silicates. This is suitable. Solid carriers for granulation include, for example, pulverized and classified natural rocks such as calcite, marble, pumice, calcite and dolomite, and synthetic granules of inorganic and organic powders, and organic such as sawdust, coconut husk, corncobs and tobacco stems. Granules of material are suitable. Emulsifiers and / or foam-forming agents include, for example, nonionic and anionic emulsifiers, for example polyoxyethylene fatty alcohol ethers such as polyoxyethylene fatty acid esters, alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, aryls Sulfonates and albumen hydrolysis products are suitable. Suitable dispersants are, for example, lignin-sulfite waste liquors and methylcellulose.
Adhesives, for example, natural and synthetic polymers in the form of powders, granules or emulsions, such as carboxymethylcellulose, gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids may be used in the formulation. Can be. As other additives, mineral oil and vegetable oil may be used.
Inorganic pigments such as iron oxide, titanium oxide and prussian blue, and colorants such as alizarin dyes, azo dyes and organic dyes such as metal phthalocyanine dyes and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc You can also use
The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of active compound.
The active compounds according to the invention are prepared from commercially available formulations and mixtures of these with other active compounds such as insecticides, attractants, fungicides, acaricides, nematicides, fungicides, growth-modulating substances or herbicides. May exist in the form of use. Pesticides include, for example, phosphate esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and the like.
Examples of particularly advantageous components for the mixture are as follows:
2-aminobutane; 2-anilidedo-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide; (E) -2-methoxyamino-N-methyl-2- (2-phenoxyphenyl) -acetamide; 8-hydroxyquinoline sulfate; Methyl (E) -2- {2- [6- (2-cyanophenoxy) -pyrimidin-4-yloxy] -phenyl} -3-methoxyacrylate; Methyl (E) -methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), Aldimorph, Ampropyl Force, Anilazine, Azaconazole, Benalacyl, Benodanil, Benomil, Binapacryl, Biphenyl, Vitertanol, Blastisidin-S, Bromuconazole, burimate, butiobate, calcium polysulfide, captapol, captan, carbendazim, carboxycin, quinomethionate, chloroneb, chloropicrine, chlorothalonil, clozolinate, cupraneb, Cymoxanyl, cyproconazole, cyprofuram, dichlorophene, diclobutrazole, diclofloanide, diclomezin, dichloran, dietofencarb, difenokazole, dimethymolol, dimethomorph , Diconazole, dinocap, diphenylamine, dipyrithione, ditalimfoss, dithianon, dodine, drazoxolone, edifene force, epoxyconazole, etirimole, ethriazole, phenarimol, fenbuco Nazol, fenfuram, phenytropane, fenpiclonyl, fenpropidine, fenpropormoff, fentin ah Tate, Phenyl Hydroxide, Ferbam, Perimzone, Fluazinam, Fludioxonyl, Fluoride, Fluquinconazole, Flusilazole, Flusulfamid, Plutoranyl, Flutriafol, Polpet, Pocetyl -Aluminum, phthalide, fuberidazole, furlaxyl, purmecyclox, guazintin, hexachlorobenzene, hexaconazole, hymexazole, imazaryl, imbenconazole, iminooctadine, iprobenfos (IBP ), Iprodione, isoprothiolane, kasugamycin, copper preparations such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, auxin-copper and Brodeaux mixtures, mancopers, Mancozeb, maneb, mepanipyrim, mepronyl, metallaxyl, metconazole, metasulfocarb, metfuroxam, metiram, metsulfobox, michaelrobutanyl, nickel dimethyldithiocarbamate, nitro De-isopropyl, Noari Mall, Opuras, Oxadic Yarn, oxamocarb, oxycarboxycin, pepurazoate, fenconazole, penicuron, phosphodiphene, phthalide, fimaricin, piperaline, polycarbamate, polyoxin, probenazole, prochloraz, pro Simidone, propamocarb, propiconazole, propineb, pyrazophos, pyriphenox, pyrimethanyl, pyroquilon, quintogen (PCNB), sulfur and sulfur preparations, tebuconazole, teclophthalam, Tecnazen, tetraconazole, thibendazole, thiathiophene, thiophanate-methyl, thiram, tollclofos-methyl, tolylufluoride, triadimefon, triadimenol, triazoxide, trichlamide, Tricyclazole, tridemorph, triflumizol, tripolin, triticazole, validamycin A, vinclozoline, geneb, zelam.
Thread Bacteria:
Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octylinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, teclophthalam, copper sulfate and other copper agents.
Pesticides / Acaricides / Necticides:
Abamectin, AC 303 630, Acetate, Acrinatrin, Alanicab, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Ajinfoss A, Ajinfoss M, Azo Cyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultope, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Bupropezin, Butocaxin, Butylpyridaben, kadusafos, carbaryl, carbofuran, carbophenothione, carbosulphan, cartop, CGA 157 419, CGA 184 699, chloretocarb, chlorethoxyphosphate, chlorfenbinfos, chlorfluazuron, chlor Mephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocitrin, clofenthezin, cyanophosph, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, Cyromazine, deltamethrin, Demetone-M, Demetone-S, Demetone-S-methyl, Di Pentiuron, diazinon, diclopention, dichlorboth, diclifoss, dicrotophos, diethione, diflubenzuron, dimethatoate, dimethylbinfoss, dioxation, disulfotone, ediffenfoss, emma Mectin, Espenvalate, Ethiophenecarb, Ethion, Etofenprox, Etoprophos, Etrifoam, Phenamifoss, Penazaquine, Penbutatin, Phenytrothion, Phenobucarb, Phenothiocarb , Phenoxycarb, phenpropartin, fenpyrad, fenpyroximate, pention, fenvalrate, fipronil, fluazinam, flucycloxanthone, flucitalinate, flufenoxuron, flufenprox , Fluvalinate, phonophos, formitol, phosphthiazate, fufenfenx, furathiocarb, HCH, heptenophos, hexaflumuron, hexiax, imidacloprid, isprobenfos, isazofoss , Isopenfoss, isoprocarb, isoxation, ibe Tin, ramsa-cyhalothrin, lufenuron, malathion, mecarbam, mebinfos, mesulfenfos, metaldehyde, metacryphos, metamidophos, methidathione, methiocarb, methamyl, methol Carb, Milvemectin, Monoclotophos, Moxidecin, Naled, NC 184, NI 25, Nitenpyram, Ometoate, Oxamyl, Oxidemetone M, Oxidepropos, Parathion A, Parathion M, Permethrin, Pento 8, forate, posalon, posmet, phosphamdone, bombard, pyrimicab, pyrimifos M, pyrimifos A, propenophos, promecarb, propaphos, propoxur, prothiophos, Protoate, pymetrozine, paraclofos, pyridapention, pyresmethrin, pyrethrum, pyridaben, pyrimidipene, pyripropoxyphene, quinalfoss, RH 5992, salityon, cebufoss, silafluorophene , Sulfofep, sulfprophos, tebufenozide, tebufenpyrad, tebupyrimifos, te Rubenzuron, Tefluthrin, Temefos, Terbam, Terbufos, Tetrachlorbinfos, Thiaphenox, Thiodicarb, Thiopanox, Thiomethone, Tionazine, Turingiencin, Tralomethrin, Triara Ten, triazofoss, triazuron, trichlorphone, triflumuron, trimetacarb, tamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.
Herbicides:
Anilides such as, for example, diflufenican and propanyl; Arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram; Aryloxy alkanoic acids such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluoxypyr, MCPA, MCPP, and triclopyr; Aryloxy-phenoxy-alkanoic acid esters such as, for example, diclofomethyl, phenoxaprop-ethyl, fluazifop-butyl, halooxyphosph-methyl, and quinacofop-ethyl; Azinones such as, for example, chloridazone and norflurazon; Carbamate, such as chlorprofam, desmedapem, penmedipam, and profam; Chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor, and propachlor; Dinitroanilines such as, for example, oryzaline, pendimethalin and trituralin; Diphenyl ethers such as, for example, asifluorophene, biphenox, fluoroglycopene, pomesafen, halosafen, lactofen and oxyfluorfen; Ureas such as, for example, chlorotoluron, diuron, fluoromethuron, isoproturon, linuron and metabenzthiazuron; Hydroxylamines such as, for example, alkoxydim, cletodim, cyclooxydim, cetoxydim and trakoxydim; Imidazolinones such as for example imazetapyr, imazamethabenz, imazapyr and imazaquin; Nitriles such as, for example, bromoxynil, diclobenyl and oxynyl; Oxyacetamides such as for example mefenacet; For example amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfone, cynosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl Sulfonylureas such as triasulfuron and tribenuron-methyl; Thiol carbamates such as, for example, butyrate, cycloate, di-acrylate, EPTC, esprocarb, molinate, prosulfocarb, thiobenecarb and tri-acrylate; Triazines such as, for example, atrazine, cyanazine, simazine, cymetrin, terbutryn and terbutylazine; Triazinones such as, for example, hexazinone, metamitrone, and metrizine; For example aminotriazoles, benfusate, bentazone, synmethyline, clomazone, clopyralide, dipfencuart, dithiopyr, etofumesate, fluorochloridone, glufosinate, glyphosate And others such as isoxaben, pyridate, quinclolac, quinmerak, sulfosate and tridiphane.
The active compounds according to the invention may also be present in admixture with synergists in their commercially available formulations and in the use forms prepared from these formulations. Synergists are compounds that increase the action of the active compound without the need for the synergist added itself to be activated.
The active compound content of the use forms prepared from commercially available formulations can vary within considerable ranges. The concentration of the active compound of the use form is 0.0000001 to 95% by weight, preferably 0.0001 to 1% by weight.
The compound is used in a conventional manner suitable for the use form.
When used in hygienic pests and stored pests, the active compounds according to the invention show excellent residual activity against wood and clay and excellent stability against alkalis on lime surfaces.
The active compounds according to the invention are not only pests of plants, sanitary and stored agricultural products, but also animal parasites (in vitro parasites) such as hard mites, mollusk mites, scabies mites, HARVEST MITES, flies (bite or lick). It is active as a veterinary medicine for parasites, parasitic fly larvae, teeth, hairy teeth, birds teeth and fleas. These parasites include:
Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pthirus spp., Sole Norpotes subspecies (Solenopotes spp.).
Allophagida neck and Amlycerina and Ischnocerina subfamily, for example Trimenopon spp., Menopon spp., Trinoton spp. ), Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodextes spp., Felicola spp.
Diptera and Nematotosrina and Brachyycerina subs, such as Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Plebotomus spp., Lutzomyia spp., Culicoides spp., Creecoides spp. Crysops spp., Hibomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Filippomia subspecies (Philipomyia spp.), Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp. ), Morellia spp., Pannia spp., Glossina spp., Califora spp., Lucilli Lucilia spp., Chrysomyia spp., Wolfartia spp., Sarcophaga spp., Oestrus spp., Hippoderma subspecies spp.), Gasosterophilus spp., Hippobosca spp., Lipoptana spp., Melophagus spp.
From the order of the Siphonaptera, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
The order of the Heteroptera, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
Neck of Blatarida, for example, Blata orientalis, Periplaneta americana, Blata germanica, Supela spp.
Acarina (Acarida) subclass and the tree of Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otabius spp. ., Ixodes spp., Amblyomma spp., Bophylus spp., Dermacentor spp., Haemaphysalis spp. ), Hyaloma subspecies (Hyalomma spp.), Lipisphalus subspecies (Rhipicephalus spp.), Dermanis subspecies (Dermanyssus spp.), Rileytia spp., Pneumonyssus spp. , Sternostoma spp., Varoa spp.
Neck of Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheiletiella spp. .), Ornithocheyletia spp., Myobia spp., Sorergates spp., Demodex spp., Trombicula spp. ), Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp. ), Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp. ), Notoedres spp., Knemidocoptes spp., Cytodic subspecies tes spp.), Laminosioptes spp.
For example, these compounds show excellent activity against Boophilus microplus and Lucilia cuprina.
The active compounds of general formula (I) according to the invention can also be used for farming livestock such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese and bees and other pets. It is suitable for controlling arthropods that infect animals such as dogs, cats, birds in cages and fish in fish tanks and also so-called laboratory animals such as hamsters, guinea pigs, rats and mice. Controlling arthropods reduces deaths and yield reduction (for example in the production of meat, milk, wool, hides, eggs, honey), thus making the management of animals more economical and easier by using the active compounds according to the invention. Is possible.
The active compounds according to the invention can be administered parenterally in the livestock sector by intestinal administration in the form of tablets, capsules, solutions, potions, granules, pastes, antagonists, by mixing the drug into feed and by suppositories, eg For example by injection (intramuscular, subcutaneous, intravenous and intraperitoneal, etc.), in the form of insertions, by intranasal administration, for example in the form of dipping or dipping, spraying, swelling and dropping, washing and misting And in the form of shaped articles containing the active compounds, for example in the form of necklaces, ear marks, tail marks, leg bands, tethers or markings, etc., in a known manner by transdermal use.
When administered to livestock, poultry, pets and the like, the active compound of general formula (I) is directly or 100 as a preparation containing 1 to 80% by weight of the active compound (e.g. powders, emulsions, flowables). It may be used to dilute to 10,000 times, or may be used as a chemical bath.
It has also been found that the compounds of the general formula (I) according to the invention have a strong pesticidal activity against pests destroying industrial materials.
The following pests are mentioned by way of example and by way of example and are not intended to limit the invention:
Beetle neck, for example, Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum , Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Mintes rugicollis, Xyleborus species, Tryptodendron species, Apate monachus, Bostrychus capucins, Heterorobostrychus brunnes, Synoxilon ( Synoxylon species, Dinoderus minutus
From the necks of Hymenopterans, for example, Sirex jubencus, Urocerus gigas, Urocerus gigas taignus, Uroserus augur ( Urocerus augur)
Termites, for example, Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes ), Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus
Bristletails neck, for example Lepisma saccharina
Industrial materials in this regard are understood in the sense of non-biological materials, for example plastics, adhesives, sizes, paper and board, leather, wood and wood products and paints.
Materials which should be particularly preferably protected from the attack of pests are wood and wood products.
Wood and wood products which may be protected by the preparations according to the invention or by compositions containing such preparations are for example construction timbers, wooden beams, railway sleepers, bridge components, boat bridges, wooden vehicles ), Boxes, pallets, containers, telephone poles, wooden signs, windows or doors made of wood, plywood, chipboard, connectors or wood products commonly used in house construction or furniture.
The active compounds can be used, for example, in the form of concentrates or common conventional agents, for example powders, granules, solutions, suspensions, emulsions or pastes.
The formulations mentioned may be prepared by conventional methods, for example, one or more solvents or diluents, emulsifiers, dispersants and / or binders or fixatives, water repellents, optionally drying agents and UV stabilizers, and optionally colorants and pigments and It can be prepared by mixing different processing aids.
The pesticidal compositions or concentrates used for protecting wood or wood materials contain the active compounds according to the invention in concentrations of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
The amount of composition or concentrate used depends on the type and frequency of the pests and the medium. Optimal use can be determined in each case by a series of tests. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.0001 to 10% by weight, based on the material to be protected.
Solvents and / or diluents used are organic chemical solvents or low volatility and / or polar organic chemical solvent mixtures or solvent mixtures and / or water and optionally emulsifiers and / or wetting agents.
Organic chemical solvents which can preferably be used are oily or oily solvents having an evaporation number of at least 35 and a flash point of at least 30 ° C, preferably at least 45 ° C. Corresponding suitable mineral oils or their aromatic fractions or mineral oil-containing solvent compounds, such as oily or oily solvents, which have low volatility and are insoluble in water, preferably white spirit, petroleum and / or alkylbenzenes do.
Materials that can be advantageously used are mineral oils having a boiling range of 170 to 220 ° C., white spirits having a boiling range of 170 to 220 ° C., spindle oils having a boiling range of 250 to 350 ° C., boiling ranges of 160 to 280 ° C. Petroleum or aromatic fractions, terpentine oil.
In a preferred embodiment, liquid aliphatic hydrocarbons having a boiling range of 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling range of 180 to 220 ° C. and / or spindle oil and / or monochloronaphthalene, preferably Α-monochloronaphthalene is used.
Low volatility organic oil phase or oily solvents having an evaporation index of at least 35 and a flash point of at least 30 ° C., preferably at least 45 ° C., have solvent mixtures also having an evaporation index of at least 35 and at least 30 ° C., preferably at least 45 ° C. If the pesticide / fungicide mixture is flash soluble or emulsifiable in this mixed solvent, it can be partially replaced with an organic solvent of high or medium volatility.
In a preferred embodiment, some organic chemical solvents or solvent mixtures are replaced with polar cycloaliphatic organic chemical solvents or solvent compounds. Preferred materials used are cycloaliphatic organic chemical solvents with hydroxyl and / or ester and / or ether groups, for example glycol ethers, esters and the like.
Organic chemical binders are combined dry oils and / or synthetic resins which can be diluted with water and / or dissolved or dispersed or emulsified in the organic chemical solvent used, in particular acrylate resins, vinyl resins such as polyvinyl acetate, Polyester resins, polycondensation or polyaddition resins, polyurethane resins, alkyd resins or modified alkyd resins, phenolic resins, hydrocarbon resins such as indene / coumarone resins, silicone resins, dry vegetable oils and / or Dry binders and dry binders which are dried by physical means and are based on natural and / or artificial resins.
Artificial resins used as binders are used in the form of emulsions, dispersions or solutions. Up to 10% bitumen or bituminous material can also be used as the binder. In addition, dyes, pigments, waterproofing agents, fragrant substances and known inhibitors or anti-corrosive agents may also be used.
The composition or concentrate according to the invention preferably contains at least one alkyd resin or modified alkyd resin and / or dry vegetable oil as an organic chemical binder. Preferably used according to the invention are alkyd resins having an oil content of at least 45% by weight, preferably 50 to 68% by weight.
All or some of the binders mentioned above may be replaced with fixatives (mixtures) or plasticizers (mixtures). These additives are intended to prevent volatilization, crystallization or precipitation formation of the active compound. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
Plasticizers are phthalic acid esters such as dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adi Pate, stearate, for example butyl stearate or amyl stearate, oleate, for example butyl oleate, glycerol ether or high molecular weight glycol ethers, glycerol esters and p-toluenesulfonic acid esters .
The fixative is chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone or ethylbenzophenone.
Water in particular is a possible solvent or diluent, optionally mixed with the abovementioned organic chemical solvents or diluents, emulsifiers and dispersants.
Particularly effective protection of wood is achieved by large scale industrial impregnation methods, for example vacuum, double vacuum or pressurized methods.
Optionally, the ready-to-use composition may additionally contain other pesticides and optionally one or more fungicides.
Further components which can be mixed are preferably the insecticides or fungicides mentioned in WO 94/29 268. The compounds mentioned in the above documents are clearly part of the present application.
Very particularly preferred components which can be mixed are insecticides, for example chlorpyriphos, bombardment, silafluoropin, alphamethrin, cyfluthrin, cipermethrin, deltamethrin, permethrin, imidacloprid, NI-25, Flufenoxuron, hexaflumuron and triflumuron and fungicides, for example, ethoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, ciproconazole, metconazole, forehead Zaryl, diclofloanid, tolyluanide, 3-iodo-2-propynylbutyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazoline -3-one.
The preparation and use of the material according to the invention is explained with reference to the following examples.
Manufacturing Example
Example (I-1-a-1):

25.0 g (0.072 mol) of Example (II-2) compound in 150 ml of anhydrous toluene were added dropwise to 18.5 g (0.165 mol) of potassium t-butylate in 57 ml of anhydrous tetrahydrofuran (THF) at reflux temperature, and the mixture was 1.5 Stirred to reflux for hours. For workup, 220 ml of water is added, the aqueous layer is separated, the toluene phase is extracted with 110 ml of water, the aqueous phases are mixed, washed with toluene and acidified at 10-20 ° C. with approximately 26 ml of concentrated HCl. I was. The product was suction filtered, washed, dried and washed by stirring in methyl t-butyl (MTB) ethyl / n-hexane.
Yield: 18.0 g (79% of theory), Melting point: 159 占 폚.
The following compounds of formula (I-1-a) were prepared analogously to the examples or according to the general preparation instructions:
Table 1

Example (I-1-b-1):

1.13 ml (0.015 mol) of acetyl chloride in 5 ml of anhydrous methylene chloride was added to 4.5 g (0.015 mol) of the compound of Example (I-1-a-1) and 2.1 ml (15 mmol) of triethylamine in 70 ml of anhydrous methylene chloride. To 10 ° C. The mixture was stirred at room temperature until thin layer chromatography check confirmed the reaction was complete. For workup, the mixture was washed twice with 50 ml 0.5N sodium hydroxide solution, dried over magnesium sulfate and evaporated. The crude product was recrystallized from MTB ether / n-hexane.
Yield: 3.4 g (66% of theory), Melting point: 209 ° C
The following compounds of formula (I-b-1) were prepared analogously to this example or according to general preparation instructions:
TABLE 2

*) α isomers were separated from the isomer mixture as secondary components by chromatographic separation.
Example (I-1-c-1)

1.5 ml (15 mmol) of ethyl chloroformate in 5 ml of anhydrous methylene chloride were added from 0 to 10 in 4.5 g (0.015 mol) of the compound of Example (I-1-a-1) and 2.1 ml of triethylamine in 70 ml of anhydrous methylene chloride. Add dropwise at ° C and stir the mixture at room temperature until thin layer chromatography check confirms the reaction is complete. For workup, the mixture was washed twice with 50 ml 0.5N sodium hydroxide solution, dried over magnesium sulfate and evaporated.
Yield: 3.3 g (59% of theory), Melting point: 193 ° C
Compounds of formula (I-1-c) are obtained similarly to the examples or according to general preparation instructions.
TABLE 3

*) α isomers were separated from the isomer mixture as secondary products by chromatography.
Example (II-1)

17.5 g of the compound according to Example (VII-1) in 100 ml of methylene chloride were carefully added dropwise to 30.3 g (0.308 mol) of concentrated sulfuric acid at 30 to 40 ° C, and the mixture was stirred at this temperature for 2 hours. 41 ml of anhydrous methanol was then added dropwise until the internal temperature of about 40 ° C. was set, and the mixture was stirred at 40 to 70 ° C. for an additional 6 hours.
For workup, the mixture was poured into 0.29 kg of ice, extracted with methylene chloride, washed with aqueous sodium bicarbonate, dried and evaporated. The crude product was purified by column chromatography on silica gel using mobile phase methylene chloride / ethylacetate 2: 1.
Yield: 13.1 g (67% of theory), Melting point: 147 ° C
Example (II-2)

40.9 g (0.23 mol) of 2,4,5-trimethylphenylacetic acid and 33.6 ml (0.461 mol) of thionyl chloride were stirred at room temperature for 30 minutes and then at 50 ° C. until gas evolution ceased. Excess thionyl chloride was removed in vacuo at 50 ° C. Then 50 ml of anhydrous toluene were added and the mixture was evaporated again. The residue was dissolved in 100 ml of dry THF (solution 1).
Solution 1 was added to 47.9 g of methyl cis-4-methylcyclohexamine-l-carboxylate and 64.6 ml (0.460 mole) of triethylamine in 600 ml of dry THF at 0-10 ° C., and the mixture was then stirred at room temperature for 1 hour. Stirred. It was then filtered by suction, washed with anhydrous THF and evaporated. The residue was dissolved in methylene chloride and the mixture was washed with 0.5 N HCl, dried and evaporated. The crude product was purified by column chromatography on silica gel using methylene chloride / ethyl acetate 7: 1.
Yield: 32 g (32% of theory), Melting point: 158 ° C
The following compounds of formula (II) were prepared analogously to Examples (II-1) and (II-2) and according to the general instructions for preparation.
Table 4

Table 4 (continued)

Example (X-1)

Starting from 17.8 g of 2,4,5-trimethylphenylacetic acid, solution 1 was prepared as in Example (II-2).
Solution 1 was added dropwise to 16.8 ml (0.12 mol) of 1-amino-tetrahydropyran-1-carboxylic acid nitrile (70% pure) and triethylamine in 150 ml of anhydrous THF at 0-10 ° C., and the mixture was further stirred at room temperature for 1 hour. Was stirred. It was then evaporated and the residue was dissolved in methylene chloride and the mixture was washed with 0.5 N HCl, dried and evaporated. The crude product was recrystallized from MTB ether / n-hexane.
Yield: 17.5 g (61% of theory), Melting point: 156 ° C
Example (I-2-a-1)

8.42 g (75 mmol) of potassium t-butylate was introduced into 50 ml of dimethylformamide and 1-ethyloxycarbonyl-cyclohexyl 2,4,5-trimethyl according to Example (III-1) in 50 ml of dimethylformamide. A solution of 16.6 g (50 mmol) of phenylacetate was added dropwise at 0-10 ° C. and the mixture was stirred at rt overnight.
For workup, the reaction mixture was added dropwise to 500 ml of ice-cold 1N HCl, and the precipitated product was filtered off with suction, washed with water and dried in a vacuum drying cabinet. For further purification, the crude product was then boiled with n-hexane / acetone.
Yield: 9.2 g (64% of theory) at melting point 209-212 ° C
The following compounds of general formula (I-2-a) were obtained analogously to this example or according to general guidelines.
Table 5

Example (I-2-b-1)

2.86 g (10 mmol) of the compound according to Example I-2-a-1 was initially introduced into 40 ml of methylene chloride, 1.52 g (15 mmol) of triethylamine was added and 1.57 of pivaloyl chloride in 40 ml of methylene chloride g (15 mmol) of the solution was added dropwise with ice cooling, then the mixture was stirred at room temperature for 1-2 hours. The mixture was washed successively with 10% strength citric acid, 1N NaOH and NaCl solution for workup, and the organic phase was dried over MgSO ₄ and evaporated. For further purification, the crude product was then further stirred with some petroleum ether.
Yield: 3.0 g (81% of theory) at melting point 128-132 ° C
The following compounds of formula (I-2-b) are obtained analogously to this example or according to general preparation instructions.
Table 6

Example (III-1)

8.9 g (50 mmol) of 2,4,5-trimethyl-phenylacetic acid is initially introduced into 50 ml of toluene, 11.9 g (100 mmol) of thionyl chloride is added, and the mixture is stirred at 80 ° C. until hydrogen chloride release stops. And then evaporated. The crude acid chloride was boiled overnight with 8.6 g (50 mmol) ethyl 1-hydroxy-cyclohexanecarboxylate in 50 ml of toluene and then the mixture was evaporated.
Yield: 18.6 g (quantitative) of 1-ethoxycarbonyl-cyclohexyl 2,4,6-trimethylphenylacetate as a colorless oil.
The following compounds of formula (III) are obtained analogously to the examples or according to general preparation instructions.
TABLE 7

Example (I-3-a-1)

26.0 g (60.7 mmol) of the compound according to Example (IV-1) were heated under reflux with 55 ml of trifluoroacetic acid in 110 ml of toluene for 3 hours. Excess trifluoroacetic acid was removed in vacuo and 400 ml of water and 120 ml of MTB ether were added to the residue and NaOH was added until pH 14. The mixture was extracted twice using MTB ether. The aqueous phase was then acidified with concentrated HCl and extracted three times with MTB ether. The organic phase was dried and concentrated.
Yield: 8.80 g (52% of theory), Melting point: 160 to 162 ° C
Example (I-3-b-1)

Produce:
1.0 g (3.6 mmol) of the compound according to Example (I-3-b-1) was introduced into 15 ml of anhydrous methylene chloride and 0.75 ml of triethylamine were added. A solution of 0.82 g (4.68 mmol) of 6-chloronicotinyl chloride in 3 ml of anhydrous methylene chloride was added dropwise while cooling with ice. The mixture was stirred at rt for 2 h. It was washed twice with 10% strength citric acid and the mixed aqueous phase was extracted with methylene chloride. The combined organic phases were washed twice with 1N NaOH and the aqueous alkaline phase was extracted with methylene chloride. Finally the combined organic phases were dried and concentrated to stir the residue with petroleum ether.
Yield: 1.37 g (91% of theory), Melting point: 123-126 ° C.
Compounds of the general formula (I-3-b) listed in the table below were prepared similarly to Examples I-3-b-1 and according to general preparation instructions.

Example (I-3-c-1)

Produce:
1.0 g (3.6 mmol) of the compound according to Example (I-3-c-1) was initially introduced into 15 ml of anhydrous methylene chloride and 0.75 ml (1.5 equiv) of triethylamine were added. A solution of 0.61 ml (0.64 g, 4.68 mmol) of isobutyl 6-chloroformate in 3 ml of anhydrous methylene chloride was added dropwise while cooling with ice. The mixture was stirred at rt for 2 h. The combined organic phases were washed twice with 10% strength citric acid and the mixed aqueous phases were extracted with methylene chloride. The combined organic phases were washed twice with 1N NaOH and the aqueous alkaline phase was extracted with methylene chloride. Finally, the mixed organic phases were concentrated to dryness.
Post-treatment is carried out as in Example (I-3-b-1).
Yield: 1.32 g (97% of theory), oil
¹ H-NMR (400 MHz, DMSO):
δ = 0.60-0.70m, 6H, CH (CH ₃ ) ₂
1.00-1.05m, 3H, CH ₂ CH ₃
1.50-1.60 m, 1H, CH (CH ₃ ) ₂
1.70-1.76d, 3H, C (CH ₃ )
1.90-2.02m, 2H, CH ₂ CH ₃
2.05-2.20m, 9H, ArCH ₃
3.65-3.72m, 2H, OCH ₂
6.75-6.80d, 1H, Ortho Ar-H
7.01s, 1H, Meta Ar-H
Example (I-3-c-2)
Compounds of general formula (I-3-c-2) were obtained similarly to examples (I-3-c-1) as oils:

Example (IV-1)

A: 25 g (98 mmol) of Formula (XIII-1) and 1 drop of dimethylformamide were stirred together with 17.5 g (147 mmol) of thionyl chloride in 100 ml of toluene for 5 minutes at room temperature and then until gas evolution stopped Stir at 100 ° C. Volatile constituents were removed under high vacuum.

B: 72 ml (118 mmol) of butyllithium (1.6 M) were added dropwise to 18 ml (130 mmol) of diisopropylamine in 100 ml of THF while cooling with ice and the mixture was stirred at this temperature for an additional 15 minutes. 18.8 g (108 mmol) of the compound according to Example (XIV-3) dissolved in 40 ml of THF was added dropwise at 0 ° C and the mixture was stirred at this temperature for 30 minutes. The acid chloride prepared according to A dissolved in 40 ml of THF was then added dropwise at 0 ° C. and the mixture was stirred at room temperature for 1 hour. 350 ml MTB and water drop were then added and the mixture was extracted twice with 10% strength ammonium chloride solution, dried and concentrated. The crude product (40 g) was purified by column chromatography (mobile phase cyclohexane / ethyl acetate 10/1). Yield: 27.0 g (64% of theory), oil.
¹ H-NMR (CDCl ₃ , 400 MHz)
δ = 0.80-0.95m, 3H, CH ₂ CH ₃
1.42 s, 3H, C-CH ₃
1.65-2.05m, 2H, CH ₂ CH ₃
2.15-2.35m, 9H, ArCH ₃
3.10-3.45m, 2H, SCH ₂
3.70-3.80m, 6H, OCH ₃
6.70-7.30m, 6H, Ar-H
Example (I-4-a-1)

6.7 g (30 mmol) of 2- (2,4,5-trimethylphenyl) -chlorocarbonylketene were obtained from 4,5-dihydro-2,2,5,5-tetramethyl-3- (2H) -furanone. Heated at 200 ° C. for 4 hours with 4.3 g (30 mmol). After column chromatography on silica gel using toluene / ethanol 20: 1 as the mobile phase, 4.6 g ( 46% of theory).
The following compounds of general formula (I-4-a) were obtained similarly to this example and according to the general instructions for the preparation examples.
Table 8

Example (I-4-b-1)

2.5 g (7.5 mmol) of compound (I-4-a-1) were initially added to 25 ml of ethyl acetate, 0.75 g of triethylamine was added and 0.6 g of acetyl chloride in 20 ml of ethyl acetate was added dropwise at 0 ° C. The mixture was stirred at room temperature for 20 hours and the product was washed twice with 50 ml of semi-concentrated sodium chloride solution to separate the precipitate, dried over sodium sulfate and evaporated in vacuo. The residue was chromatographed on silica gel using toluene / acetone 50: 1.
Yield: 0.8 g of melting point 143-144 占 폚 (of theory 29% of theory).
The compounds of formula I-4-b, listed in the table below, were prepared similarly to examples I-4-b-1 and according to the general guidelines of the preparation examples.
Table 9

Example (I-4-c-1)

1.7 g (5 mmol) of compound (I-4-a-3) were initially introduced into 20 ml of ethyl acetate, 0.5 g (5 mmol) of triethylamine was added, and 0.5 g of methyl chloroformate in 5 ml of ethyl acetate. (5 mmol) was added dropwise at 0 ° C. The mixture was stirred at rt for 20 h, the precipitate was separated and the product was washed twice with 50 ml of a semi-concentrated sodium chloride solution, dried over sodium sulfate and evaporated in vacuo. The residue was chromatographed on silica gel using toluene / acetone 30/1. 1.0 g (51% of theory) with a melting point of 144-146 ° C.
The following compounds of general formula (I-4-c) were obtained similarly to this example and according to the general instructions for preparation.
Table 10

Example (I-5-a-1)

2.2 g (10 mmol) of 2- (2,4,5-trimethylphenyl) -chlorocarbonyl ketene were heated with 1.6 g (10 mmol) of 4-fluorothiobenzamide in 80 ml of toluene at 50 ° C. for 6 hours. . The precipitate was separated, washed with cyclohexane and dried. 2.8 g (82% of theory) with a melting point of 215-216 ° C were obtained.
Example (XIII-1)

247 g (1.162 mole) (75% pure) of the compound according to Example (XIV-1) was added dropwise to a mixture of 100 g (1.785 moles) of KOH in 130 ml of water and 260 ml of methanol at room temperature and the mixture was heated at reflux for 5 hours. . After cooling, it was diluted with 300 ml of water and extracted with ethyl acetate. The aqueous phase was acidified with semi-concentrated hydrochloric acid and the precipitate was suction filtered and dried.
Yield: 77 g (45% of theory), Melting point: 119-121 ° C
Example (XIII-2)

2,4,5-trichloro-phenylacetic acid at a melting point of 112-115 ° C. was obtained similarly to Example (XIII-1).
Preparation of 2,4,5-trimethyl-phenylacetic acid

Example (XIII-3)
286 g (1.4 mol) of 1,2,4,5-tetramethylbenzine of 66% purity was dissolved in 563 ml of carbon tetrachloride, and successively 27.5 g (0.15 mol) of N-bromosuccinimide and 0.4 g of benzyl chloride were added to room temperature. Were introduced continuously. The mixture was heated to 80 ° C. and 248 g (1.39 mol) of N-bromosuccinimide were added in portions. The mixture was then stirred for additional 30 minutes at 80 ° C. and cooled to room temperature. The solid was suction filtered and the solvent stripped at 20 millibars through the solid bridge. The residue was then distilled under high vacuum to yield 226 g (66% of theory) of 2,4,5-trimethylbenzyl having a boiling point of 95 ° C. and a purity of 86% under 0.05 millibar.
A solution of 226 g (0.91 ml) of 2,4,5-trimethyl-benzyl bromide (86% purity) in 94 ml of toluene was added dropwise to a solution of 63 ml of water and 0.6 g of Aliquat 336, and the mixture was then stirred at 80 ° C. for 4 hours. It was. After cooling to room temperature, the supernatant was separated and the organic phase was washed twice with water and twice with saturated NaCl solution, dried and concentrated. After distillation, 103 g (70%) of 2,4,5-trimethyl-benzyl cyanide having a boiling point of 120 ° C. at 99% purity and 0.2 millibar was obtained.
2118 ml of concentrated sulfuric acid were added to 2662 ml of water at room temperature and the solution was heated to 90 ° C. 355 g (2.23 mol) of 2,4,5-trimethyl-benzyl cyanide were weighed and placed in semi-concentrated sulfuric acid at this temperature, and then the mixture was stirred at 100 ° C. for 8 hours. After cooling, the reaction mixture was poured into ice water with vigorous stirring and suction filtered. The solid was washed several times with water then dried with petroleum ether. 358 g (90% of theory) of 2,4,5-trimethyl-phenylacetic acid at a melting point of 123-125 ° C were obtained.
The novel phenyl acetic acid of formula (XIII) listed in Table 11 below was prepared analogously to Examples (XIII-1) and (XIII-3) and according to general instructions for preparation.
Table 11


Compounds of general formula (XIII) are novel except for compounds in which X, Y, Z = CH ₃ and X, Y, Z = Cl.
Example (XIV-3)

35 g (0.143 mol) of methyl 2-chloro-4-bromo-5-methylphenylacetate and 31 g of CuCN were heated at reflux in 350 ml of dimethylformamide for 1 day. The solvent was stripped in vacuo, the residue was partitioned between water and tertiary butyl-methylether and the organic phase was dried and evaporated.
Yield: 18 g
The novel phenyl acetic acid esters of formula (XIV) listed in Table 12 were prepared analogously to Example (XIV).
Table 12

A compound represented by the general formula (ⅩⅩⅣ) is novel except for the X, Y, Z = CH ₃ and X, Y, Z = Cl compound.
Example (XIV-1)

700 ml of a 30% strength methanol solution of sodium methylate was added dropwise to a solution of 347 g (0.948 mol) of a compound according to Example (XV-1) (purity 74.3%) in 410 ml of methanol at room temperature, and the mixture was heated at reflux for 5 hours. After cooling to room temperature, 110 ml of concentrated sulfuric acid was added dropwise. The mixture was boiled under reflux for 1 hour, methanol was distilled off and the solid residue was dissolved in water. The organic phase was separated and the aqueous phase extracted twice with 1.5 l methylene chloride. The combined organic phases were dried over Na ₂ SO ₄ and concentrated.
Yield: 247 g black oil 92% of theory with 75% content (gas chromatography)
Example (XXIV-2)

Methyl 2,4,5-trichloro-phenylacetate was obtained as black oil as 95% of theory, 80% purity (gas chromatography) similar to Example (XXIV-1).
Example (XXV-1)

2205 g (22.7 mol) of 1,1-dichloroethane were added to a completely cooled mixture of 229.7 g (2.272 mol) tertiary butyl nitrite in 990 ml in anhydrous acetonitrile and 254.8 g (1.775 mol) anhydrous copper chloride (II). Dropwise, the mixture was kept at 30 ° C or lower. Then a mixture of 232 g (1.49 mol) of 4-chloro-2,5-dimethylaninine and 1500 ml of anhydrous acetonitrile was then added dropwise at a temperature below 30 ° C. The mixture was stirred at room temperature until gas evolution ceased, then carefully poured into 6 l of 20% strength HCl and extracted several times with a total of 6 l methyl tert-butyl ether (MTBE). The combined organic phases were washed with 20% strength HCl, dried and concentrated. The remaining oil was rectified.
Yield: 347 g of black oil 63% of theory with a content of 74% (gas chromatography)
Example (XXV-2)
2- (2,4,5-trichlorophenyl) -1,1,1-trichloroethane was obtained similarly to Example (XXV-1) in the form of a black oil in 81% yield of 78% of theory. .
1,1,1-Trichloro-2-phenyl-ethane of the general formula (XXV) listed in Table 13 was prepared analogously to Example (XXV-1):
Table 13

The oil was used without further purification when preparing a compound of formula (XXIV). Compounds of formula (XXV) are novel except for compounds where X, Y, Z = Cl.
Synthesis of 2,4,5-trimethylphenylcarbonylketene
Methyl 2,4,5-trimethylphenylacetate

100 g (0.56 mol) of 2,4,5-trimethylphenylacetic acid were dissolved in 230 ml of methanol, and 6 ml of concentrated hydrochloric acid was added to heat the mixture for 10 hours under reflux. It was then cooled to rt and the methanol was removed in vacuo. The residue was stirred in a solution of 53 g of sodium carbonate and dissolved in 260 ml of water to dissolve the organic phase in 200 ml of toluene. The organic phase was separated, dried and concentrated to distill the residue. 48.6 g of methyl 2,4,5-trimethylphenylacetate having a boiling point of 86 DEG C under 0.2 millibar was obtained.
Dimethyl 2- (2,4,5-trimethylphenyl) -malonate

18.6 g (0.62 mol, 80% pure) sodium hydride was initially introduced into 384 ml of dimethyl carbonate and the mixture was heated to about 80 ° C. 48 g (0.25 mol) of methyl 2,4,5-trimethylphenylacetate dissolved in 100 ml of dimethyl carbonate were then added dropwise and the mixture was heated at reflux for 4 hours. It was cooled to room temperature, excess sodium hydride was triturated with ethanol and the mixture was then poured into 1500 ml ice water. PH 4-5 was made with 6 N hydrochloric acid and the organic phase was dissolved in toluene. The organic phase was separated, dried and concentrated to use the residue in the next step without further purification. 51.6 g of dimethyl 2- (2,4,5-trimethylphenyl) -malonate were obtained as an oil.

2- (2,4,5-trimethylphenyl) -malonic acid

51.6 g (0.21 mol) of dimethyl 2- (2,4,5-trimethylphenyl) -malonate were added dropwise at room temperature to a mixture of 180 ml of methanol and 38.1 g (0.68 mol) of potassium hydroxide dissolved in 92 ml of water. The mixture was then heated at reflux for 5 hours, then cooled back to room temperature and concentrated.
The residue was stirred in ice water to pour fluorine and the mixture was washed with some toluene. The aqueous solution was acidified to pH 1 with concentrated hydrochloric acid while cooling with ice, and the precipitate was dried by suction filtration. 30.3 g of 2- (2,4,5-trimethylphenyl) -malonic acid were obtained.

2,4,5-trimethylphenylchlorocarbonylketen

30 g of 2- (2,4,5-trimethylphenyl) -malonic acid was suspended in 60 ml of toluene at 50-60 ° C. and 62.5 ml of thionyl chloride were added dropwise. The mixture was then heated at 90-100 ° C. for 15 hours. It was then cooled, the volatile components were driven off with an inert gas and the excess thionyl chloride was distilled off. 30.6 g of 2,4,5-trimethylphenylchlorocarbonyl ketene was isolated as residue.

Example of use
Example A
Phaedon Larva 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 (Brasica oleracea) are treated by immersion in the active compound formulation of the desired concentration, and infected with mustard beetle larvae (Paedon cocleariae) while the leaves are moist.
After a certain period of time, the percent rescued was determined. 100% means that all the beetle larvae have been killed; 0% means that the beetle larva is not killed at all.
In this test, for example, the compounds according to Preparation Examples I-4-b-1 and I-4-a-4 showed a relief rate of 100% after 7 days at an exemplary active compound concentration of 0.1%. .
Example B
Flutella test
Solvent: Dimethylformamide 7 parts by weight
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
1 part by weight of the active compound is mixed with 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.
Apricot leaves (Brasica oleracea) are treated by immersion in the active compound formulation of the desired concentration and infected with cabbage moth (Flutella maculenis) caterpillars while the leaves are moist.
After a certain period of time, the percent rescued was determined. 100% means that all caterpillars have been killed; 0% means that the caterpillar was not killed at all.
In this test, for example, Production Examples I-1-a-1, I-1-b-2, I-1-c-1, I-4-a-3, I-4-a-1, Compounds of I-4-b-1 and I-4-a-4 showed a rescue rate of 100% after 7 days at exemplary active compound concentrations of 0.1%.
Example C
Spodovterra Exam
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 (Brasica oleracea) are treated by dipping into active compound preparations of the desired concentration and infected with caterpillar (Spodoptera frugiperda) caterpillars while the leaves are moist.
After a certain period of time, the percent rescued was determined. 100% means that all caterpillars have been killed; 0% means that the caterpillar was not killed at all.
In this test, for example, Production Examples I-1-a-1, I-1-b-2, I-4-a-3, I-4-a-1, I-4-b-1 and The compound of I-4-a-4 showed a rescue rate of 100% after 7 days at an exemplary active compound concentration of 0.1%.
Example D
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 to the desired concentration to prepare a suitable formulation of the active compound.
Rice hair (Oryza sativa) is treated by immersion in the active compound formulation of the desired concentration and infected with the caterpillar of the Cicada (Nepotetics sinctifs) while the leaves are moist.
After a certain period of time, the percentage of relief is determined. 100% means that all caterpillars have been killed; 0% means that the caterpillar was not killed at all.
In this test, for example, Production Examples I-2-a-2, I-2-a-3, I-2-b-4, I-2-b-5, I-1-a-1, I-1-b-2, I-1-c-1, I-1-b-1, I-1-b-3, I-1-c-2, I-1-c-3, I- Compounds of 4-a-3 and I-4-a-4 showed a rescue rate of 100% after 6 days at an exemplary active compound concentration of 0.1%.
Example E
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 (Brasica oleracea) severely infected with peach aphid (Myzus persicae) are treated by immersion in the active compound preparation of the desired concentration.
After a certain period of time, the percentage of relief is determined. 100% means that all aphids have been killed; 0% means that the aphid has not been killed at all.
In this test, for example, Production Examples I-2-a-1, I-2-b-4, I-1-b-2, I-1-b-3 and I-1-c-2 and The compound of I-4-a-4 showed a rescue rate of 100% after 6 days at an exemplary active compound concentration of 0.1%.
Example F
Tetranicus test (OP tolerance / immersion treatment)
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.
Soybean plants (Phaseolus vulgaris) heavily infected with spotted mites (Tetranychus urticae) are treated by dipping into active compound preparations of the desired concentration.
After a certain period of time, the percentage of relief is determined. 100% means that all caterpillars have been killed; 0% means that the caterpillar was not killed at all.
In this test, for example, compounds of Preparation Examples I-2-b-2, I-2-b-1, I-1-b-2 and I-4-b-1 exhibited 0.1% exemplary activity. After 13 days at the compound concentration, a rescue rate of at least 98% was shown.
Example G
Germination test
Solvent: 5 parts by weight of acetone
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, the specified amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.
Seeds of the test plants are sown in normal soil, and after 24 hours, the active compound preparations are watered. It is important to keep the amount of water per unit area constant. The concentration of active compound in the formulation is not critical, only the amount of active compound applied per unit area is important.
After 3 weeks, the degree of plant damage is assessed at 0% damage compared to the development of the untreated control. The figures have the following meanings:
0% has no action (as in untreated controls),
100% indicates complete death.
In this test, for example, when the compound according to Preparation Example I-4-a-3 is applied in an amount of, for example, 500 g / ha while showing good resistance by Beta vulgaris, Relief rates were 90% for Alopecurus myosuroids, 96% for Avena fatua and 95% for Seratia viridis.
Example H
Fly Larva Test / Development Inhibition
Test Animals: All Larva Stages of Lucilia Cupri (OP-resistant)
[Pupae and adult (no active compound contacted)]
Solvent: 35 parts by weight of ethylene glycol monomethyl ether
Emulsifier: 35 parts by weight of nonylphenol polyglycol ether
To obtain a suitable formulation, 3 parts by weight of the active compound are mixed with 7 parts by weight of the solvent / emulsifier mixture mentioned above and the resulting emulsion concentrate is diluted in each case with water to the desired concentration.
Per concentration, 30-50 larvae are transferred to horse meat (1 cm 3) placed in a glass tube and pipette 500 μl of test dilution. Transfer the glass tube to a plastic beaker with sea sand at the bottom and keep it in a climate control room (26 ° C ± 1.5 ° C, 70% relative humidity ± 10%). The activity is checked after 24 hours and after 48 hours (flesh larvae action). After the larvae appear (about 72 hours), the glass tube is removed and a perforated plastic lid is placed on the beaker. After 1 1/2 times of developmental period (hatching of control flies). Count the flies and pupa / puparina.
The criteria for action are the killing of the larvae treated after 48 hours (the larvae effect) or the suppression of the emergence of adult from the larvae or the pupaeization. The criteria for in vitro action of a substance are the inhibition of fly development, or the politics of development before the adult phase. 100% larval activity means that all larvae die after 48 hours. 100% developmental-inhibiting activity means no adult flies.
In this test, for example, the compound of Preparation Example I-4-a-1 showed 100% activity at an exemplary active compound concentration of 1000 ppm.
Example I
Test / SP-Resistant Parkhurst Strains Using Bufilus microplus Resistant Species
Test Animals: Adult Adults Fully Suicidal
Solvent: Dimethyl Sulfoxide
20 mg of active substance is dissolved in 1 ml of dimethyl sulfoxide and diluted with the same solvent to low concentration.
Repeat this test five times. 1 μl of solution is injected into the abdomen and the animal is transferred to a dish and placed in a climate control room. Activity is determined to be scatter suppression. 100% means that not one tick was spawned.
In this test, for example, the compounds of Preparation Examples I-4-a-1 and I-4-b-1 showed 100% activity at concentrations of 20 μl / individual active compound.

权利要求:
Claims (18)
[1" claim-type="Currently amended] Compound of general formula (I):

Where
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, halogenoalkyl, halogenoalkoxy, cyano or nitro,
Y represents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, cyano or nitro,
Z is halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, hydroxyl, cyano, nitro, or optionally substituted phenoxy, phenylthio, 5- to 6-membered hetaryloxy, 5- to 6-membered hetarylthio, phenylalkyloxy or phenylalkylthio;
Y and Z represent cyclic radicals which are optionally substituted with the carbon atoms to which they are attached and are optionally interrupted by heteroatoms, wherein X represents one of the meanings mentioned above,
Het represents one of the following groups,

From here,
A represents hydrogen, in each case alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or alkylthioalkyl optionally substituted by halogen, or in each case saturated or unsaturated, optionally substituted cycloalkyl or heterocycle Aryl, or in each case aryl, arylalkyl or hetaryl optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, cyano or nitro,
B represents hydrogen, alkyl or alkoxyalkyl, or
A and B represent carbocyclic or heterocyclic radicals which are saturated or unsaturated and optionally substituted with the carbon atoms to which they are attached,
D represents hydrogen or alkyl, alkenyl, alkynyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl, saturated or unsaturated heterocyclyl, arylalkyl, aryl, hetarylalkyl and hetaryl Represents an optionally substituted radical selected from the group consisting of
A and D together with the atoms to which they are attached represent in each case an optionally substituted carbocyclic or heterocyclic radical,
G is hydrogen (a), or

Represents one of
From here,
E represents 1 equivalent of metal ion or ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R ¹ represents, in each case, alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl optionally substituted by halogen or in each case cycloalkyl or heterocyclyl optionally substituted by halogen, alkyl or alkoxy Or in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R ² represents in each case alkyl, alkenyl alkoxyalkyl or polyalkoxyalkyl optionally substituted by halogen, or in each case cycloalkyl, phenyl or benzyl optionally substituted,
R ³ , R ⁴ and R ⁵ independently of one another represent, in each case, alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio optionally substituted by halogen, or in each case optionally Substituted phenyl, phenoxy or phenylthio,
R ⁶ and R ⁷ independently of one another represent hydrogen, in each case alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl optionally substituted by halogen, or in each case phenyl or benzyl optionally substituted Or an optionally substituted cyclic radical optionally containing oxygen or sulfur together with the N atom to which they are attached.
[2" claim-type="Currently amended] The method of claim 1,
X is halogen, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, cyano or nitro,
Y represents hydrogen, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, cyino or nitro,
Z is halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, hydroxyl, cyano or nitro, or each Phenoxy optionally substituted with halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, nitro or cyano, Phenylthio, thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy, phenyl-C ₁ -C ₄ -alkyloxy or phenyl-C ₁ -C ₄ -alkylthio;
Y and Z together are optionally substituted with halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy or C ₁ -C ₄ -halogenoalkyl and one to three members independently of one another are oxygen, sulfur, nitrogen Or substituted C ₃ -C ₄ -alkanediyl or C ₃ -C ₄ -alkenediyl, which may be optionally substituted by carbonyl groups, X represents one of the meanings mentioned above,
Het the following group


Represents one of
A represents hydrogen or in each occurrence is optionally substituted by halogen C ₁ -C ₁₂ -alkyl, C ₂ -C ₈ -alkenyl, C ₁ -C ₁₀ -alkoxy-C ₁ -C ₈ -alkyl, poly -C ₁ -C ₈ -alkoxy-C ₁ -C ₈ -alkyl or C ₁ -C ₁₀ -alkylthio-C ₁ -C ₆ -alkyl, or represent halogen, C ₁ -C ₆ -alkyl or C _1- C ₃ -C ₈ -cycloalkyl optionally substituted by C ₆ -alkoxy and one or two methylene groups optionally substituted by oxygen and / or sulfur, or in each case halogen, C ₁ -C ₆ -alkyl , C ₁ -C ₆ - halogenoalkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - halogenoalkyl, cyano or by nitro, optionally substituted phenyl, naphthyl, phenyl -C ₁ -C ₆ -alkyl, naphthyl-C ₁ -C ₆ -alkyl, or hetaryl having 5 or 6 reducing atoms and having 1 to 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen,
B represents hydrogen C ₁ -C ₁₂ -alkyl or C ₁ -C ₈ -alkoxy-C ₁ -C ₆ -alkyl, or
A, B and the carbon atoms to which they are attached may be selected from one methylene group optionally substituted by oxygen or sulfur, C ₁ -C ₈ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₁ -C ₈ -halogenoalkyl, C ₁ -C ₈ - alkoxy, C ₁ -C ₈ - alkylthio, halogen or phenyl optionally substituted by a C ₃ -C ₁₀ - cycloalkyl or C ₅ -C ₁₀ - alkenyl, or represents a cycloalkyl,
A, B and the carbon atoms to which they are attached are optionally substituted by alkylenediyl groups having one or two oxygen and / or sulfur atoms, by alkylenedioxyl groups or by alkylenedithioyl groups (the substituents being C ₅ -C ₆ -cycloalkyl substituted with carbon atoms to form an additional 5- to 8-membered ring, or
A, B and the carbon atom to which they are attached represent C ₃ -C ₈ -cycloalkyl or C ₅ -C ₈ -cycloalkenyl, wherein two substituents are in each case C ₁ together with the carbon atom to which they are attached -C ₆ - alkyl, C ₁ -C ₆ - is optionally substituted by alkoxy or halogen the substituted single methylene group is optionally substituted by oxygen or sulfur, in each case, C ₃ -C ₆ - alkanediyl, C ₃ -C ₆ -alkenediyl or C ₄ -C ₆ -alkanediendiyl,
D represents hydrogen or in each case is optionally substituted by halogen C ₁ -C ₁₂ -alkyl, C ₃ -C ₈ -alkenyl, C ₃ -C ₈ -alkynyl, C ₁ -C ₁₀ -alkoxy- C ₂ -C ₈ -alkyl, poly-C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl or C ₁ -C ₁₀ -alkylthio-C ₂ -C ₈ -alkyl, or halogen, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy or C ₁ -C ₄ - haloalkyl is optionally substituted by a halogeno alkyl, one or two not directly adjacent to the methylene group is optionally replaced by oxygen and / or sulfur C ₃ -C ₈ -cycloalkyl, or in each case optionally halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -halogenoalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C _6- Phenyl substituted by halogenoalkoxy, cyano or nitro, hetaryl having 5 to 6 ring atoms and having 1 or 2 hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen, phenyl C ₁ -C ₆ -Alkyl or 5 to 6 Het having one or two heteroatoms selected from the group consisting of a reducing character having oxygen, sulfur and nitrogen, aryl -C ₁ -C ₆ - or represent alkyl,
A and D together are C ₁ -C ₁₀ -alkyl, C ₁ -C ₆ optionally substituted in each case by one methylene group by oxygen or sulfur, and in each case by halogen or in each case by halogen -Alkoxy, C ₁ -C ₆ -alkylthio, C ₃ -C ₇ -cycloalkyl, phenyl or benzyl oxy, or form a fused ring and in each case one methylene group is optionally replaced by oxygen or sulfur and C ₁ -C ₆ - by an optionally substituted alkane diendi a group-of the added alkyl optionally substituted by C ₃ -C ₆ - alkanediyl, C ₃ -C ₆ - or C ₄ -C ₆ days canned al C ₃ -C ₆ -alkanediyl, C ₃ -C ₆ -alkenediyl or C ₄ -C ₆ -alkanediendiyl group, or
A and D together in each case the following groups

A C ₃ -C ₆ -alkanediyl or C ₃ -C ₆ -alkenediyl group optionally containing one of
G represents hydrogen (a) or

Represents one of
From here,
E represents 1 equivalent of a metal ion or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R ¹ in each case is C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₁ -C ₈ -alkoxy-C ₁ -C ₈ -alkyl, C ₁ -C ₈ optionally substituted by halogen -Alkylthio-C ₁ -C ₈ -alkyl or poly-C ₁ -C ₈ -alkoxy-C ₁ -C ₈ -alkyl, or halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy C ₃ -C ₈ -cycloalkyl optionally substituted by and one or two methylene groups optionally substituted by oxygen and / or sulfur, or
Halogen, cyano, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl, C ₁ -C ₆ -halogenoalkoxy, C ₁ -C ₆ -alkyl Phenyl optionally substituted by thio or C ₁ -C ₆ -alkylsulfonyl, or
Phenyl-C optionally substituted by halogen, nitro, cyano, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl or C ₁ -C ₆ -halogenoalkoxy _1- C ₆ -alkyl, or
Or represents 5- or 6-membered hetaryl having one or two hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen and optionally substituted by halogen or C ₁ -C ₆ -alkyl,
Optionally halogen or C ₁ -C ₆ - when the phenoxy substituted by alkyl -C ₁ -C ₆ - or represent alkyl,
5- or 6-membered hetaryloxy-C ₁ -C ₆ having one or two hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen, optionally substituted by halogen, amino or C ₁ -C ₆ -alkyl -Alkyl,
R ² in each case is C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl or poly-C _1- C ₈ -alkoxy-C ₂ -C ₈ -alkyl, or
C ₃ -C ₈ -cycloalkyl optionally substituted by halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy, or
Phenyl or benzyl optionally substituted by halogen, cyano, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl or C ₁ -C ₆ -halogenoalkoxy Indicates
R ³ represents C ₁ -C ₈ -alkyl optionally substituted by halogen, or in each case halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogeno Phenyl or benzyl optionally substituted by alkyl, C ₁ -C ₄ -halogenoalkoxy, cyino or nitro,
R ⁴ and R ⁵ independently of one another are in each case substituted with C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkylamino, di- (C ₁ -C ₈ -alkyl) amino, C ₁ -C ₈ -alkylthio or C ₃ -C ₈ -alkenylthio or in each case halogen, nitro, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C _{4-halogeno-alkoxy,} C ₁ -C ₄ - alkylthio, C ₁ -C ₄ - halogenoalkyl alkylthio, C ₁ -C ₄ - alkyl or C ₁ -C ₄ - by a halogenoalkyl, optionally substituted phenyl, Phenoxy or phenylthio,
R ⁶ and R ⁷ independently of one another represent hydrogen or in each case are optionally substituted C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₈ -alkoxy, C ₃ -C ₈ -alkenyl or C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl, or in each case halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -halogenoalkyl or C ₁ -C ₈ - alkoxy exhibited by a phenyl or benzyl group optionally substituted, or together are C ₁ -C ₆ - alkyl which is substituted by optionally being replaced by one methylene group is optionally substituted by oxygen or sulfur, C ₃ -C ₆ -alkylene radical,
R ¹³ represents hydrogen or, in each case, represents C ₁ -C ₈ -alkyl or C ₁ -C ₈ -alkoxy or is halogen, C ₁ -C ₄ -alkyl or C ₁ -C C ₃ -C ₈ -cycloalkyl optionally substituted by ₄ -alkoxy and one methylene group optionally substituted by oxygen or sulfur, or in each case halogen, C ₁ -C ₆ -alkyl, C _1- Phenyl, phenyl-C ₁ -C ₄ -alkyl or phenyl-C ₁ optionally substituted by C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, nitro or cyano -C ₄ -alkoxy,
R ¹⁴ represents hydrogen or C ₁ -C ₈ -alkyl, or
R ¹³ and R ¹⁴ together represent C ₄ -C ₆ -alkanediyl,
R ¹⁵ and R ¹⁶ are the same or different and represent C ₁ -C ₆ -alkyl, or
R ¹⁵ and R ¹⁶ together represent C ₁ -C ₆ -alkyl or phenyl (which is halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C C ₂ -C ₄ -alkanediyl optionally substituted by ₄ -halogenoalkoxy, nitro or cyano),
R ¹⁷ and R ¹⁸ independently represent hydrogen or C ₁ -C ₈ -alkyl optionally substituted by halogen, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ - halogenoalkyl, C ₁ -C ₄ - halogeno-alkoxy, or represent a nitro or by cyano, optionally substituted phenyl,
R ¹⁷ and R ¹⁸ together with the carbon atom to which they are attached represent C ₅ -C ₇ -cycloalkyl optionally substituted by C ₁ -C ₄ -alkyl and one methylene group is optionally substituted by oxygen or sulfur,
R ¹⁹ and R ²⁰ independently of _one another are C ₁ -C ₁₀ -alkyl, C ₂ -C ₁₀ -alkenyl, C ₁ -C ₁₀ -alkoxy, C ₁ -C ₁₀ -alkylamino, C ₃ -C ₁₀ -al A compound of formula (I) representing kenylamino, di- (C ₁ -C ₁₀ -alkyl) amino or di- (C ₃ -C ₁₀ -alkenyl) amino.
[3" claim-type="Currently amended] The method of claim 1,
X represents fluorine, chlorine or bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, cyano or nitro ,
Y is hydrogen, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, cyano or nitro Indicates
Z is fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, hydroxy, cyano or Nitro, or in each case fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, nitro or Phenoxy or benzyloxy optionally substituted by cyano, or
Y and Z together are optionally substituted with one or two members which are optionally substituted with fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₂ -halogenoalkyl alkanediyl or _{C 3 -C 4 - - C 3} -C 4 , which may be independent of one another, optionally replaced by an oxygen, sulfur or nitrogen represent the Al canned one, X represents one of the above-mentioned meaning,
Het Group

Represents one of
A represents hydrogen or in each case is optionally substituted by C ₁ -C ₁₀ -alkyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₈ -alkoxy-C ₁ -C ₆ -alkyl , Poly-C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl or C ₁ -C ₈ -alkylthio-C ₁ -C ₆ -alkyl, or optionally fluorine, chlorine, C ₁ -C _4- Represents C ₃ -C ₇ -cycloalkyl substituted by alkyl or C ₁ -C ₄ -alkoxy and one or two methylene groups optionally substituted by oxygen and / or sulfur, or in each case optionally fluorine, chlorine , Bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkoxy, phenyl substituted by cyano or nitro, fura carbonyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, indolyl, thiazolyl, thienyl or phenyl -C ₁ -C ₄ - represents an alkyl,
B represents hydrogen, C ₁ -C ₁₀ -alkyl or C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl
A, B and the carbon atoms to which they are attached in each case are one methylene group optionally substituted by oxygen or sulfur, C ₁ -C ₆ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C _3- C ₃ -C ₈ -cycloalkyl or C ₅ -C ₈ -cycloalkenyl optionally substituted by halogenoalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio, fluorine, chlorine or phenyl Or
A, B and the carbon atoms to which they are attached are selected by alkylenediyl groups optionally containing one or two oxygen or sulfur atoms, by alkylenedioxy groups or by alkylenedithiol groups (the substituents being C ₅ -C ₆ -cycloalkyl substituted with a carbon atom to form an additional 5 to 7 membered ring, or
A, B and the carbon atom to which they are attached represent C ₃ -C ₆ -cycloalkyl or C ₅ -C ₆ -cycloalkenyl, wherein the two substituents together with the carbon to which they are attached are optionally in each case C _1- C ₃ -C ₅ -alkanediyl, C optionally substituted by C ₄ -alkyl, C ₁ -C ₄ -alkoxy, fluorine, chlorine or bromine and in each case one methylene group is optionally substituted by oxygen or sulfur ₃ -C ₅ -alkenediyl or butadienediyl,
D represents hydrogen or in each case is optionally substituted by C ₁ -C ₁₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C ₁ -C _8- Alkoxy-C ₂ -C ₆ -alkyl, poly-C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl or C ₁ -C ₈ -alkylthio-C ₂ -C ₆ -alkyl, or optionally fluorine One or two methylene groups, substituted by chlorine, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy or C ₁ -C ₂ -halogenoalkyl and not directly adjacent to each other, are replaced by oxygen and / or sulfur. Optionally substituted C ₃ -C ₇ -cycloalkyl, or in each case optionally fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkoxy Phenyl substituted by C ₁ -C ₄ -halogenoalkoxy, cyano or nitro, furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl, triazolyl or phenyl -C ₁ -C ₄ -alkyl, or
A and D together are C ₁ -C ₆ -alkyl, in each case one carbon atom optionally substituted by oxygen or sulfur, in each case optionally substituted by fluorine or chlorine, or in each case by fluorine or chlorine, Optionally substituted by C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₃ -C ₆ -cycloalkyl, phenyl or benzyloxy, in each case

C ₃ -C ₅ -alkanediyl or C ₃ -C ₅ -alkenediyl group optionally containing one of
G represents hydrogen (a) or

Represents one of
From here,
E represents one equivalent of a metal ion or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R ¹ is in each case optionally substituted with C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C _1- C ₆ -alkylthio-C ₁ -C ₆ -alkyl or poly-C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, or represent fluorine, chlorine, C ₁ -C ₅ -alkyl or C _1- C ₃ -C ₇ -cycloalkyl optionally substituted by C ₅ -alkoxy and one or two methylene groups optionally substituted by oxygen and / or sulfur, or
Fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl, C ₁ -C ₃ -halogenoalkoxy, C _1- C ₄ - alkylthio or C ₁ -C ₄ - or represents a phenyl optionally substituted by alkyl sulfonyl,
Phenyl-C ₁ optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy -C ₄ -alkyl or
In each case represent pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl, optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl,
Phenoxy-C ₁ -C ₅ -alkyl optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl, or
In each case pyridyloxy-C ₁ -C ₅ -alkyl, pyrimidyloxy-C ₁ -C ₅ -alkyl or thiazolyloxy optionally substituted by fluorine, chlorine, bromine, amino or C ₁ -C ₄ -alkyl -C ₁ -C ₅ -alkyl,
R ² is C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl or poly-C _1- , each optionally substituted by fluorine or chlorine; C ₆ -alkoxy-C ₂ -C ₆ -alkyl, or
C ₃ -C ₇ -cycloalkyl optionally substituted by fluorine, chlorine, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, or
In each case fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy Phenyl or benzyl optionally substituted by
R ³ represents C ₁ -C ₆ -alkyl optionally substituted by fluorine or chlorine, or in each case fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C _1- Phenyl or benzyl optionally substituted by C ₂ -halogenoalkoxy, C ₁ -C ₂ -halogenoalkyl, cyano or nitro,
R ⁴ and R ⁵ independently of each other are C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylamino, di- (C ₁ optionally substituted in each case by fluorine or chlorine; -C ₆ -alkyl) amino, C ₁ -C ₆ -alkylthio or C ₃ -C ₄ -alkenylthio, or in each case fluorine, chlorine, bromine, nitro, cyano, C ₁ -C _3- Alkoxy, C ₁ -C ₃ -halogenoalkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -halogenoalkylthio, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -halogenoalkyl Phenyl, phenoxy or phenylthio optionally substituted by
R ⁶ and R ⁷ independently of one another represent hydrogen or in each case are C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, optionally substituted by fluorine or chlorine, C ₃ -C ₆ -alkenyl or C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, or in each case fluorine, chlorine, bromine, C ₁ -C ₅ -halogenoalkyl, C _1- Phenyl or benzyl optionally substituted by C ₅ -alkyl or C ₁ -C ₅ -alkoxy, together optionally substituted by C ₁ -C ₄ -alkyl and one methylene group optionally substituted by oxygen or sulfur Represents a C ₃ -C ₆ -alkylene radical,
R ¹³ represents hydrogen or in each case represents C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy optionally substituted by fluorine or chlorine, or fluorine, C ₁ -C ₂ -alkyl or C ₁ -C ₂ - is optionally substituted by alkoxy, one of the methylene groups is optionally replaced by oxygen or sulfur, C ₃ -C ₇ - cycloalkyl, or represent fluorine, chlorine, bromine, C ₁ -C ₅ at each occurrence -Phenyl, phenyl-C ₁ -C ₃ -optionally substituted by -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, nitro or cyano Alkyl or phenyl-C ₁ -C ₂ -alkyloxy,
R ¹⁴ represents hydrogen or C ₁ -C ₆ -alkyl, or
R ¹³ and R ¹⁴ together represent C ₄ -C ₆ -alkanediyl,
R ¹⁵ and R ¹⁶ are the same or different and represent C ₁ -C ₄ -alkyl, or
R ¹⁵ and R ¹⁶ together represent C ₁ -C ₄ -alkyl or phenyl (which is fluorine, chlorine, bromine, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -alkoxy, Compound of formula (I) which represents a C ₂ -C ₃ -alkanediyl radical optionally substituted by C ₁ -C ₂ -halogenoalkoxy, nitro or cyano).
[4" claim-type="Currently amended] The method of claim 1,
X is fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tertiary butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, trifluorome Methoxy, difluoromethoxy, cyano or nitro,
Y is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, tri Fluoromethoxy, difluoromethoxy, cyano or nitro,
Z is fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, trifluor Methoxy, difluoromethoxy, cyano or nitro, or
Y and Z together are two members that are optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy, propoxy, iso-propoxy or trifluoromethyl and are not directly adjacent C ₃ -C ₄ -alkanediyl optionally substituted by this oxygen, X represents one of the aforementioned meanings,
Het Group


Represents one of
A represents hydrogen or in each occurrence is optionally substituted by C ₁ -C ₈ -alkyl, C ₂ -C ₄ -alkenyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl , Poly-C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl or C ₁ -C ₆ -alkylthio-C ₁ -C ₄ -alkyl, or optionally by fluorine, chlorine, methyl or methoxy C ₃ -C ₆ -cycloalkyl substituted and one or two methylene groups optionally substituted by oxygen and / or sulfur, or in each case optionally fluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso -Phenyl, pyridyl or benzyl substituted by propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
B represents hydrogen, C ₁ -C ₈ -alkyl or C ₁ -C ₄ -alkoxy-C ₁ -C ₂ -alkyl, or
A, B and the carbon atoms to which they are attached in each case one methylene group is optionally replaced by oxygen or sulfur, methyl, ethyl, n-propyl, iso-propyl, butyl, iso-butyl, s-butyl, 3 Tert-butyl, cyclohexyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, iso-butoxy, s-butoxy, tert-butoxy, methylthio, C ₃ -C ₈ -cycloalkyl or C ₅ -C ₈ -cycloalkenyl optionally substituted by ethylthio, fluorine, chlorine or phenyl,
A, B and the carbon atom to which they are attached are either by an alkylenediyl group optionally containing oxygen or a sulfur atom or by an alkylenedioxy group (the substituents together with the carbon atom to which they are attached form an additional 5-6 membered ring) C ₅ -C ₆ -cycloalkyl substituted by
A, B and the carbon atom to which they are attached represent C ₃ -C ₆ -cycloalkyl or C ₅ -C ₆ -cycloalkenyl, wherein two substituents together with the carbon atom to which they are attached are in each case one methylene Group represents C ₃ -C ₄ -alkanediyl, C ₃ -C ₄ -alkenediyl or butadienediyl, optionally substituted by oxygen or sulfur,
D represents C ₁ -C ₈ -alkyl, C _3- , which in each case is substituted by oxygen and / or sulfur by one or two methylene groups optionally substituted by fluorine or chlorine and not directly adjacent C ₄ -alkenyl, C ₃ -C ₄ -alkynyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₄ -alkyl, poly-C ₁ -C ₄ -alkoxy-C ₂ -C ₄ -alkyl, C _1- C ₄ -alkylthio-C ₂ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl, or in each case fluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl, meso Phenyl, furanyl, pyridyl, thienyl or benzyl optionally substituted by oxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, or
A and D together are C ₁ -C ₆ -alkyl, C _1- , in each case one methylene group optionally substituted by oxygen or sulfur and optionally substituted by fluorine or chlorine, or in each case by fluorine or chlorine C ₃ -C ₅ -alkanediyl or C ₃ -C ₅ -alkendi optionally substituted by C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₃ -C ₆ -cycloalkyl, phenyl or benzyloxy Represents a group,
G represents hydrogen (a) or

Represents one of
From here,
E represents one equivalent of a metal ion or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R ¹ is in each case optionally substituted with C ₁ -C ₁₄ -alkyl, C ₂ -C ₁₄ -alkenyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₆ -alkyl, C _1- C ₄ -alkylthio-C ₁ -C ₆ -alkyl or poly-C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, or represent fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl , n-butyl, i-butyl, t-butyl, methoxy, ethoxy, n-propoxy or isopropoxy, optionally substituted by one or two methylene groups by oxygen and / or sulfur C ₃ -C ₆ -cycloalkyl, or
Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl or ethyl Phenyl optionally substituted by sulfonyl, or
Benzyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy, or
In each case represent furanyl, thienyl or pyridyl optionally substituted by fluorine, chlorine, bromine, methyl or ethyl,
Phenoxy-C ₁ -C ₄ -alkyl optionally substituted by fluorine, chlorine, methyl or ethyl, or
In each case pyridyloxy-C ₁ -C ₄ -alkyl, pyrimidyloxy-C ₁ -C ₄ -alkyl or thiazolyloxy-C ₁ -C ₄ optionally substituted by fluorine, chlorine, amino, methyl or ethyl -Alkyl,
R ² in each case is C ₁ -C ₁₄ -alkyl, C ₂ -C ₁₄ -alkenyl, C ₁ -C ₄ -alkoxy-C ₂ -C ₆ -alkyl or poly-C optionally substituted by fluorine or chlorine _1- C ₄ -alkoxy-C ₂ -C ₆ -alkyl, or
C ₃ -C ₆ -cycloalkyl optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, iso-propyl or methoxy, or
In each case phenyl or benzyl optionally substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
R ³ in each case represents methyl, ethyl, propyl, iso-propyl, butyl or tert-butyl optionally substituted by fluorine or chlorine, or in each case fluorine, chlorine, bromine, methyl, ethyl, iso-propyl , Phenyl or benzyl optionally substituted by tert-butyl, methoxy, ethoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
R ⁴ and R ⁵ independently of one another are in each occurrence substituted with C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, di- (C ₁ -C ₄ -alkyl) amino or C ₁ -C ₄ -alkylthio or in each case by fluorine, chlorine, bromine, nitro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy Optionally substituted phenyl, phenoxy or phenylthio,
R ⁶ and R ⁷ independently represent hydrogen or, in each case, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkoxy, optionally substituted by fluorine or chlorine, C ₃ -C ₄ -alkenyl or C ₁ -C ₄ -alkoxy-C ₂ -C ₄ -alkyl, or in each case optionally substituted by fluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl Or a C ₅ -C ₆ -alkylene radical optionally substituted by methyl or ethyl together with one methylene group optionally substituted by oxygen or sulfur.
[5" claim-type="Currently amended] (A) intramolecular condensation of the compound of formula (II) in the presence of a diluent and in the presence of a base to obtain a compound of formula (I-1-a), or
(B) intramolecular condensation of the compound of formula (III) in the presence of a diluent and in the presence of a base to give a compound of formula (I-2-a), or
(C) the compound of formula (IV) is closed intramolecularly in the presence of a diluent and in the presence of an acid as necessary to give a compound of formula (I-3-a), or
(D) Reacting a compound of formula (V) or silylenol, ether of formula (Va) with a compound of formula (VI) in the presence of a diluent if necessary and in the presence of an acid acceptor if necessary To give the compound of formula (I-4-a),
(E) The compound of formula (VII) is reacted with a compound of formula (VI) in the presence of a diluent if necessary and in the presence of an acid acceptor if necessary to form a compound of formula (I-5-a). To obtain,
Obtained compounds of (I-1-a) to (I-5-a),
(F) in each case, if necessary, in the presence of a diluent and, if necessary, in the presence of an acid binder, a) reacting with an acid halide of the general formula (VIII), or
β) reacted with the anhydrous carboxylic acid of formula (IX);
(G) reacting with chloroformic acid ester or chloroformic thioester of general formula (X) if necessary in the presence of a diluent and, if desired, in the presence of an acid binder;
(H) α) reacting with chloromonothioformic acid ester or chlorodithioformic acid ester of general formula (XI) in the presence of diluent if necessary and in the presence of acid binder if necessary,
β) reacting with this carbon sulfide in the presence of a diluent if necessary and in the presence of a base if necessary, followed by reaction with a compound of formula (XII);
(I) reacting with sulfonic acid chlorides of the general formula (XIII) in the presence of a diluent if necessary and in the presence of an acid binder if necessary;
(J) if necessary react with a phosphorus compound of formula (XIV) in the presence of a diluent and, if necessary, in the presence of an acid binder;
(K) optionally reacting with a metal compound or amine of the general formula (XV) or (XVI) in the presence of a diluent;
(L) α) reacting with an isocyanate or isothiocyanate of the general formula (XVII) in the presence of a diluent if necessary and in the presence of a catalyst if necessary,
β) reacting with carbamic acid chloride or thiocabamic acid chloride of the general formula (XVIII) in the presence of a diluent if necessary and in the presence of an acid binder if necessary, How to prepare the compound:



R ¹ -CO-O-CO-R ¹ (IX)
R ² -M-CO-Cl (X)

R ² -Hal (XII)
R ³ -SO ₂ -Cl (XIII)

Me (OR ¹⁰ ) _t (XV)

R ⁶ -N = C = L (XVII)

Where
A, B, D, X, Y, Z, L, M, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings mentioned in claim 1,
R ⁸ represents alkyl,
W represents hydrogen, halogen, alkyl or alkoxy,
R ^{8 '} represents alkyl,
Hal in formulas (VI), (VIII) and (XIV) represents halogen,
Hal in formula (XII) represents chlorine, bromine or solvent
Me represents a monovalent or divalent metal,
t represents a number of 1 or 2,
R ¹⁰ , R ¹¹ and R ¹² independently of one another represent hydrogen or alkyl.
[6" claim-type="Currently amended] Compound of formula (II):

Where
A, B, X, Y and Z have the meanings referred to in claim 1,
R ⁸ represents alkyl.
[7" claim-type="Currently amended] Compound of general formula (III):

Where
A, B, X, Y and Z have the meanings referred to in claim 1,
R ⁸ represents alkyl.
[8" claim-type="Currently amended] Compound of general formula (XXI):

Where
A, B, X, Y and Z have the meanings mentioned in claim 1.
[9" claim-type="Currently amended] Compound of general formula (XXIX):

Where
A, B, X, Y and Z have the meanings mentioned in claim 1.
[10" claim-type="Currently amended] Compound of formula (IV):

Where
A, B, X, Y and Z have the meanings referred to in claim 1,
R ⁸ represents alkyl,
W represents hydrogen, halogen, alkyl or alkoxy.
[11" claim-type="Currently amended] Compound of general formula (VI):

Where
X, Y and Z have the meanings mentioned in claim 1,
Hal represents chlorine or bromine.
[12" claim-type="Currently amended] Compound of formula (XXXIII):

Where
X, Y and Z have the meanings mentioned in claim 1.
[13" claim-type="Currently amended] Compound of formula (XXXIV):

Where
X, Y and Z have the meanings mentioned in claim 1,
R ⁸ represents alkyl.
[14" claim-type="Currently amended] A pest control composition and a herbicide comprising at least one compound of the general formula (I) according to claim 1.
[15" claim-type="Currently amended] Use of a compound of formula (I) according to claim 1 for controlling pests and for controlling unwanted plant growth.
[16" claim-type="Currently amended] A method for controlling pests, characterized in that the compound of formula (I) according to claim 1 acts on pests, unwanted plants and / or their environment.
[17" claim-type="Currently amended] A process for preparing a pest control composition or herbicide, characterized in that the compound of formula (I) according to claim 1 is mixed with an extender and / or a surfactant.
[18" claim-type="Currently amended] Use of a compound of formula (I) according to claim 1 for the preparation of pest control compositions and herbicides.

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CN1931827B|2012-05-16|2- and 2,5-substituted phenylketo-enols

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ES2248846T3|2006-03-16|Cyclic cetoenols substituted by phenyl.

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US6569810B1|2003-05-27|Cyclopentane-1,3-dione derivatives

同族专利:

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公开号 | 公开日

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ZA9605465B|1997-01-24|

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DE19602524A1|1997-01-02|

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KR100438145B1|2004-10-14|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1995-06-28|Priority to DE19523471.5

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1995-06-28|Priority to DE19523471

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1996-01-25|Priority to DE19602524.9

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1996-01-25|Priority to DE1996102524

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1996-06-17|Application filed by 볼프강 에렌스타인, 크누트 샤우에르테, 바이엘 악티엔게젤샤프트

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1999-04-15|Publication of KR19990028452A

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2004-10-14|Application granted

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2004-10-14|Publication of KR100438145B1

优先权:

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申请号 | 申请日 | 专利标题

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DE19523471.5|1995-06-28|

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DE19523471|1995-06-28|

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DE19602524.9|1996-01-25|

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DE1996102524|DE19602524A1|1995-06-28|1996-01-25|2,4,5-trisubstituted phenylketoenols|