DE19602524A1 - 2,4,5-trisubstituted phenylketoenols - Google Patents

Abstract

The invention concerns novel phenyl-substituted cyclic keto-enols of formula (I) in which Het stands for one of the groups shown in which A, B, D, G, X, Y and Z have the meanings indicated in the description. Also disclosed are several processes and intermediate products for producing these compounds and their use as pest-control agents and herbicides.

Description

The invention relates to new phenyl-substituted cyclic ketoenols, several ver drive and intermediates for their manufacture and their use as Pesticides and herbicides.

It has already been known that certain phenyl-substituted cyclic keto enols are effective as insecticides, acaricides and / or herbicides.

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

EP-A-0 262 399 and GB-A-2 266 888 disclose similarly structured compounds gene (3-aryl-pyrrolidine-2,4-diones) disclosed, of which, however, no herbicidal, in secticidal or acaricidal activity has become known. Known with herbicidal, insecticidal or acaricidal activity are unsubstituted, bicyclic 3-aryl-pyr rolidin-2,4-dione derivatives (EP-A-355 599 and EP-A-415 211) and substituted ones monocyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A- 442 077).

Polycyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A- 442 073) and 1H-arylpyrrolidinedione 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 Δ³-dihydrofuran-2-one derivatives herbizi have properties (cf. DE-A-40 14 420). The synthesis of the starting compounds used tetronic acid derivatives (such as 3- (2-methylphenyl) -4- Hydroxy-5- (4-fluorophenyl) -Δ³-dihydrofuranon- (2)) is also in DE-A-40 14 420 described. Similar structured compounds without specifying an insecticide and / or acaricidal activity are from the publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76. Furthermore, 3-aryl Δ³-dihydrofuranone derivatives with herbicidal, acaricidal and insecticidal properties known from EP-A-528 156, EP-A 0 647 637 and WO 95/26345.  

Certain phenyl pyrone derivatives that are unsubstituted in the phenyl ring are already present became known (see A.M. Chirazi, T. Kap and E. Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K. Heidenbluth, Chem. Ber. 91, 2849) where a possible usability as a pest control for these compounds means is not specified. Phenyl-pyrone-Deri substituted in the phenyl ring vate with herbicidal, acaricidal and insecticidal properties are in EP-A- 588 137.

Certain 5-phenyl-1,3-thiazine derivatives unsubstituted in the phenyl ring are be already known (see E. Ziegler and E. Steiner, monthly 95, 147 (1964), R. Ketcham, T. Kap and E. Ziegler, J. Heterocycl. Chem 10, 223 (1973)) where a possible application as pest control for these compounds means is not specified. 5-phenyl-1,3-thiazine substituted in the phenyl ring Derivatives with herbicidal, acaricidal and insecticidal activity are described in WO 94 / 14,785.

The acaricidal and insecticidal activity and / or range of activity, and the Plant compatibility of these compounds, especially with regard to crop zen, but is not always sufficient.

New compounds of the formula (I)

found,
in which
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, cyano or nitro,
Y represents hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cyano or nitro,
Z represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, hydroxy, cyano, nitro or in each case optionally substituted phenoxy, phenylthio, 5- to 6-membered hetaryloxy, 5- to 6-membered hetarylthio, phenylalkyloxy or phenylalkylthio,
Y and Z together with the carbon atoms to which they are attached represent an optionally substituted and optionally interrupted by heteroatoms, where X has one of the abovementioned meanings,
Het for one of the groups

wherein
A for hydrogen, for in each case optionally substituted by halogen alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or alkyl thioalkyl, for in each case saturated or unsaturated and optionally substituted cycloalkyl or heterocyclyl or for in each case optionally by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano or nitro-substituted aryl, arylalkyl or hetaryl,
B represents hydrogen, alkyl or alkoxyalkyl, or
A and B together with the carbon atom to which they are attached represent a saturated or unsaturated, optionally substituted carbocycle or heterocycle,
D represents hydrogen or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl, saturated or unsaturated heterocyclyl, arylalkyl, aryl, hetarylalkyl or hetaryl or
A and D together with the atoms to which they are attached represent an optionally substituted carbocycle or heterocycle,
G for hydrogen (a) or for one of the groups

stands,
wherein
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R¹ stands for alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl, optionally substituted by halogen, or for cycloalkyl or heterocyclyl, optionally substituted by halogen, alkyl or alkoxy, or for optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or heterooxyoxyalkyl,
R² represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl optionally substituted by halogen, or cycloalkyl, phenyl or benzyl optionally substituted,
R³, R⁴ and R⁵ independently of one another each represent optionally substituted by halogen substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio or each optionally substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another are hydrogen, each optionally substituted by halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, each optionally substituted phenyl or benzyl, or together with the N atom to which they are attached, one optionally form oxygen or sulfur-containing optionally substituted cycle.

The compounds of formula (I) can, depending on the type of Substituents, as geometric and / or optical isomers or isomer mixtures, are present in different compositions, possibly in the usual Way can be separated. Both the pure isomers and the Mixtures of isomers, their preparation and use and those containing them Agents are the subject of the present invention. The following is the one for the sake of simplicity, however, always spoken of compounds of the formula (I), although both the pure compounds and optionally mixtures with under different proportions of isomeric compounds are meant.

Including the meanings (1) to (5) of the Het group The following main structures (I-1) to (I-5):

wherein
A, B, D, G, X, Y and Z have the meaning given above.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (I-1-a) to (I-1-g) when Het is group (1),

wherein
A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the meanings given above.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (I-2-a) to (I-2-g) when Het represents group (2),

wherein
A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the meaning given above.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (I-3-a) to (I-3-g) when Het is group (3),

wherein
A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the meaning given above.

Depending on the position of the substituent G, the compounds of the formula (I-4) can be present in the two isomeric forms of the formulas (I-4) _a and (I-4) _b ,

which is expressed by the dashed line in formula (I-4) that should.

The compounds of the formulas (I-4) _a and (I-4) _b can be present both as mixtures and in the form of their pure isomers. Mixtures of the compounds of the formulas (I-4) _a and (I-4) _b can optionally be separated in a manner known per se by physical methods, for example by chromatographic methods.

For reasons of better clarity, only one will be used in the following of the possible isomers listed. That doesn't rule out the connections optionally in the form of the isomer mixtures or in the other iso mer form.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (I-4-a) bis result (I-4-g) when Het represents group (4),

wherein
A, D, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the meanings given above.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures result (I-5-a) to (I-5-g) when Het is group (5),

(I-5-g):

wherein
A, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the meanings given above.

Furthermore, it was found that the new compounds of the formula (I) are used one of the methods described below:

• (A) Compounds of the formula (I-1-a) are obtained in which
  A, B, X, Y and Z have the meanings given above,
  if
  Compounds of formula (II) in which
  A, B, X, Y and Z have the meanings given above,
  and
  R⁸ represents alkyl (preferably C₁-C₆ alkyl),
  condensed intra-molecularly in the presence of a diluent and in the presence of a base.
• (B) It has also been found that compounds of the formula (I-2-a) in which
  A, B, X, Y and Z have the meanings given above,
  get when one
  Compounds of formula (III) in which
  A, B, X, Y, Z and R⁸ have the meanings given above,
  condensed intra-molecularly in the presence of a diluent and in the presence of a base.
• (C) It was also found that compounds of the formula (I-3-a) in which
  A, B, X, Y and Z have the meanings given above,
  get when one
  Compounds of formula (IV) in which
  A, B, X, Y, Z and R⁸ have the meanings given above and
  W represents hydrogen, halogen, alkyl (preferably C₁-C₆-alkyl) or alk oxy (preferably C₁-C₈-alkoxy),
  optionally cyclized intramolecularly in the presence of a diluent and in the presence of an acid.
• (D) It is also found that the compounds of the formula (I-4-a) in which
  A, D, X, Y and Z have the meanings given above,
  get when one
  Compounds of formula (V) in which
  A and D have the meanings given above,
  or their silylenol ethers of the formula (Va) in which
  A and D have the meaning given above and
  R⁸ represents alkyl (preferably methyl),
  with compounds of the formula (VI) in which
  X, Y and Z have the meanings given above and
  Hal represents halogen (preferably chlorine or bromine),
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor.
• (E) It was also found that the compounds of the formula (I-5-a) in which
  A, X, Y and Z have the meanings given above,
  obtained if compounds of the formula (VII) in which
  A has the meaning given above,
  with compounds of the formula (VI) in which
  Hal, X, Y and Z have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor.

It was also found

• (F) that the compounds of the formulas (I-1-b) to (I-5-b) shown above, in which A, B, D, R 1, X, Y and Z have the meanings given above, are obtained, if compounds of the formulas (I-1-a) to (I-5-a) shown above, in which A, B, D, X, Y and Z have the meanings given above,
  α) with acid halides of the formula (VIII) in which
  R¹ has the meaning given above and
  Hal stands for halogen (especially chlorine or bromine)
  or
  β) with carboxylic anhydrides of the formula (IX) R¹-CO-O-CO-R¹ (IX) in which
  R¹ has the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
• (G) that the compounds of the formulas (I-1-c) to (I-5-c) shown above, in which A, B, D, R², M, X, Y and Z have the meanings given above and L represents oxygen, is obtained if compounds of the formulas (I-1-a) to (I-5-a) shown above, in which A, B, D, X, Y and Z have the meanings given above, each
  with chloroformate or chloroformate thioester of the formula (X) R²-M-CO-Cl (X) in which
  R² and M have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
• (H) that compounds of the formulas (I-1-c) to (I-5-c) shown above, in which A, B, D, R², M, X, Y and Z have the meanings given above and L represents sulfur, is obtained when compounds of the formulas (I-1-a) to (I-5-a) shown above, in which A, B, D, X, Y and Z have the meanings given above, in each case
  α) with chloromothio formic acid esters or chlorodithio formic acid esters of the formula (XI) in which
  M and R² have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder
  or
  β) with carbon disulfide and then with compounds of the formula (XII) R²-Hal (XII) in which
  R² has the meaning given above and
  Hal represents chlorine, bromine or iodine,
  if appropriate in the presence of a diluent and if appropriate in the presence of a base,
• (I) that compounds of the formulas (I-1-d) to (I-5-d) shown above, in which A, B, D, R³, X, Y and Z have the meanings given above, are obtained if compounds of the formulas (I-1-a) to (I-5-a) shown above, in which A, B, D, X, Y and Z have the meanings given above, in each case
  with sulfonic acid chlorides of the formula (XIII) R³-SO₂-Cl (XIII) in which
  R³ has the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
• (J) that compounds of the formulas (I-1-e) to (I-5-e) shown above, in which A, B, D, L, R⁴, R⁵, X, Y and Z have the meanings given above have obtained if compounds of the formulas (I-1-a) to (I-4-a) shown above, in which A, B, D, X, Y and Z have the meanings given above, in each case
  with phosphorus compounds of the formula (XIV) in which
  L, R⁴ and R⁵ have the meanings given above and
  Hal represents halogen (especially chlorine or bromine),
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
• (K) that compounds of the formulas (I-1-f) to (I-5-f) shown above, in which A, B, D, E, X, Y and Z have the meanings given above, are obtained if compounds of the formulas (I-1-a) to (I-5-a) in which A, B, D, X, Y and Z have the meanings given above,
  each
  with metal compounds or amines of the formulas (XV) or (XVI) Me (OR¹⁰) _t (XV) in which
  Me for a mono- or divalent metal (preferably an alkali or alkaline earth metal such as lithium, sodium, potassium, magnesium or calcium),
  t for the number 1 or 2 and
  R¹⁰, R¹¹, R¹² independently of one another represent hydrogen or alkyl (preferably C₁-C₈-alkyl),
  if appropriate in the presence of a diluent,
• (L) that compounds of the formulas (I-1-g) to (I-5-g) shown above, in which A, B, D, L, R⁶, R⁷, X, Y and Z have the meanings given above have obtained if compounds of the formulas (I-1-a) to (I-5-a) shown above, in which A, B, D, X, Y and Z have the meanings given above, in each case
  α) with isocyanates or isothiocyanates of the formula (XVII) R⁶-N = C = L (XVII) in which
  R⁶ and L have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst or
  β) with carbamic acid chlorides or thiocarbamic acid chlorides of the formula (XVIII) in which
  L, R⁶ and R⁷ have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

Furthermore, it was found that the new compounds of formula (I) are very good effectiveness as pesticides, preferably as insecticides, Have acaricides and herbicides and also very good plant ver are inert, especially to crops.

The compounds of the invention are generally defined by the formula (I). Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:
X preferably represents halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, cyano or nitro,
Y preferably represents hydrogen, halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, cyano or nitro,
Z preferably represents halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogen alkyl, C₁-C₄-haloalkoxy, hydroxy, cyano, nitro or in each case optionally by halogen, C₁-C₄-alkyl, C₁- C₄-alkoxy, C₁-C₄-halo genalkyl, C₁-C₄-haloalkoxy, nitro or cyano substituted phenoxy, phenylthio, thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy, phenyl-C₁-C₄-alkyloxy or phenyl-C₁-C-alkylthio or
Y and Z are preferably, together with the carbon atoms to which they are attached, a C₃-C₅-alkanediyl or C₃- C₅- optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₄-haloalkyl Alkenediyl, in which one to three members can optionally be replaced independently of one another by oxygen, sulfur, nitrogen or a carbonyl group, where X has one of the meanings mentioned above.

Het preferably represents one of the groups

A preferably represents hydrogen, in each case optionally by halogen substituted C₁-C₁₂-alkyl, C₂-C₈-alkenyl, C₁-C₁₀-alkoxy-C₁-C₈-alkyl, Poly-C₁-C₈-alkoxy-C₁-C₈-alkyl or C₁-C₁₀-alkylthio-C₁-C₆-alkyl, each Weil optionally by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy sub substituted C₃-C₈-cycloalkyl, in which optionally one or two Methylene groups are replaced by oxygen and / or sulfur or for each optionally by halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, cyano or nitro substituted Phe nyl, naphthyl, phenyl-C₁-C₆-alkyl, naphthyl-C₁-C₆-alkyl or hetaryl with  5 or 6 ring atoms and one to three heteroatoms from the Sauer series substance, sulfur and nitrogen.

B preferably represents hydrogen-C₁-C₁₂-alkyl or C₁-C₈-alkoxy-C₁-C₆- alkyl or
A, B and the carbon atom to which they are attached are preferably C₃-C₁₀ cycloalkyl or C₅-C₁₀ cycloalkenyl, in which a methylene group is optionally replaced by oxygen or sulfur and which is optionally replaced by C₁-C₈-alkyl, C₃-C₁₀ -Cycloalkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio, halogen or phenyl are substituted or
A, B and the carbon atom to which they are attached are preferably C₅-C₆-cycloalkyl, which by an optionally containing one or two oxygen and / or sulfur atoms containing alkylenediyl, or by an alkylenedioxyl or by an alkylenedithioyl Group is substituted, which forms a further five- to eight-membered ring with the carbon atom to which it is attached or
A, B and the carbon atom to which they are attached are preferably C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, in which two substituents together with carbon atoms to which they are attached, each optionally by C₁-C₆-alkyl , C₁-C₆-alkoxy or halogen-substituted C₃-C₆-alkanediyl, C₃-C₆-alkanediyl or C₄-C₆-alkanediadiyl, where in each case one methylene group is optionally replaced by oxygen or sulfur.

D preferably represents hydrogen, in each case optionally substituted by halogen C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl, C₁-C₁₀-alkoxy- C₂-C₈-alkyl, poly-C₁-C₈-alkoxy- C₂-C₈-alkyl or C₁-C₁₀-alkylthio-C₂-C₈- alkyl, optionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, in which given if necessary, one or two not directly adjacent methylene groups are replaced by oxygen and / or sulfur or for each optionally by halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, cyano or nitro substituted phenyl, hetaryl with 5 to 6 ring atoms and one or two heteroatoms from the series oxygen, sulfur and nitrogen phenyl-C₁-C₆-alkyl or hetaryl-C₁-C₆-alkyl with 5 to 6 ring atoms and one or two heteroatoms from the series Oxygen, sulfur and nitrogen or
A and D together preferably represent a C₃-C₆-alkanediyl, C₃-C₆-alkene diyl or C₄-C₆-alkadienediyl group, in which a methylene group is optionally replaced by oxygen or sulfur and which are each optionally substituted by halogen or each optionally substituted by halogen substituted C₁-C₁₀-alkyl, C₁-C Alk-alkoxy, C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, phenyl or benzyloxy or by another, forming a fused ring C₃-C₆-alkanediyl, C₃-C₆-alkene diyl or C₄-C₆-alkadienediyl group, in which a methylene group is optionally replaced by oxygen or sulfur and which are optionally substituted by C₁-C₆-alkyl, or
A and D together represent a C₃-C₆-alkanediyl or C₃-C₆-alkendiyl group, each of which optionally includes one of the following groups

is included.  

G preferably represents hydrogen (a) or one of the groups

in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M stands for oxygen or sulfur.

R¹ preferably represents in each case optionally substituted by halogen C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl or poly-C₁-C₈ -alkoxy-C₁-C₈-alkyl or for C₃-C₈-cycloalkyl optionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy, in which one or two methylene groups are optionally replaced by oxygen and / or sulfur,
for phenyl optionally substituted by halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or C₁-C₆-alkylsulfonyl,
for phenyl-C₁-C₆-alkyl optionally substituted by halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy,
for 5- or 6-membered hetaryl optionally substituted by halogen or C₁-C₆-alkyl and having one or two heteroatoms from the series consisting of oxygen, sulfur and nitrogen,
for optionally substituted by halogen or C₁-C₆-alkyl phenoxy-C₁-C₆-alkyl or
for optionally substituted by halogen, amino or C₁-C₆-alkyl 5- or 6-membered hetaryloxy-C₁-C₆-alkyl with one or two hetero atoms from the series oxygen, sulfur and nitrogen.

R² preferably represents in each case optionally substituted by halogen C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl or poly-C₁-C₈- alkoxy-C₂-C₈-alkyl,
for C₃-C₈-cycloalkyl optionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy or
for phenyl or benzyl optionally substituted by halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy.

R³ preferably represents C₁-C₈- optionally substituted by halogen Alkyl or in each case optionally by halogen, C₁-C₆-alkyl, C₁-C₆- Alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, cyano or nitro substituted phenyl or benzyl.

R⁴ and R⁵ independently of one another are preferably each in each case halogen-substituted C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkyl amino, di- (C₁-C₈-alkyl) amino, C₁-C₈-alkylthio or C₃-C₈-alkenylthio or for each optionally by halogen, nitro, cyano, C₁-C₄- Alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkyl or C₁-C₄-haloalkyl substituted phenyl, phenoxy or Phenylthio.

R⁶ and R⁷ independently of one another preferably represent hydrogen, for each optionally substituted by halogen C₁-C₈-alkyl, C₃-C₈-cyclo alkyl, C₁-C₈-alkoxy, C₃-C₅-alkenyl or C₁-C₈-alkoxy-C₂-C₈-alkyl, for each optionally by halogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl or C₁-C₈ alkoxy substituted phenyl or benzyl or together for a C₃-C₆alkylene radical optionally substituted by C₁-C₆alkyl, in which optionally a methylene group by oxygen or Sulfur is replaced.  

R¹³ preferably represents hydrogen or in each case optionally by halogen substituted C₁-C₈ alkyl or C₁-C₈ alkoxy for optionally by Halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy substituted C₃-C₈-cycloalkyl, in which optionally a methylene group by oxygen or Sulfur is replaced, or for each optionally by halogen, C₁-C₆- Alkyl, C₁-C₆ alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, nitro or cyano substituted phenyl, phenyl-C₁-C₄-alkyl or phenyl-C₁-C₄- alkoxy.

R¹⁴ is preferably hydrogen or C₁-C₈ alkyl or
R¹³ and R¹⁴ together preferably represent C₄-C₆-alkanediyl.

R¹⁵ and R¹⁶ are the same or different and are preferably C₁-C₆ alkyl or
R¹⁵ and R¹⁶ together preferably represent a C₂-C₄-alkanediyl radical, optionally by C₁-C₆-alkyl or by optionally by halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄ -Halogenalk oxy, nitro or cyano substituted phenyl is substituted.

R¹⁷ and R¹⁸ independently of one another preferably represent hydrogen, optionally substituted by halogen C₁-C₈-alkyl or optionally by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogeno alkyl, C₁-C₄ -Halogenalkoxy, nitro or cyano substituted phenyl or
R¹⁷ and R¹⁸ together with the carbon atom to which they are attached represent C₅-C₇-cycloalkyl optionally substituted by C₁-C₄-alkyl, in which a methylene group is optionally replaced by oxygen or sulfur.

R¹⁹ and R²⁰ independently of one another preferably represent C₁-C₁₀-alkyl, C₂-C₁₀- Alkenyl, C₁-C₁₀ alkoxy, C₁-C₁₀ alkylamino, C₃-C₁₀ alkenylamino, di- (C₁-C₁₀-alkyl) amino or di- (C₃-C₁₀-alkenyl) amino.

X particularly preferably represents fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, cyano or nitro,
Y particularly preferably represents hydrogen fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, cyano or nitro,
Z particularly preferably represents fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, hydroxy, cyano, nitro or in each case optionally by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C-haloalkoxy, nitro or cyano substituted phenoxy or benzyloxy, or
Y and Z are particularly preferably together with the carbon atoms to which they are attached, optionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₂-haloalkyl C₃-C₄-alkanediyl or C₃-C₄-alkenediyl, in which one or two not directly adjacent members can optionally be replaced independently by oxygen, sulfur or nitrogen, where X has one of the meanings mentioned above.

Het is particularly preferably one of the groups

A particularly preferably represents hydrogen, in each case optionally by Fluorine or chlorine substituted C₁-C₁₀ alkyl, C₂-C₆ alkenyl, C₁-C₈-  Alkoxy-C₁-C₆-alkyl) poly-C₁-C₆-alkoxy-C₁-C₆-alkyl or C₁-C₈-alkylthio- C₁-C₆-alkyl or for optionally by fluorine, chlorine, C₁-C₄-alkyl or C₁-C₄-alkoxy substituted C₃-C₇-cycloalkyl, in which optionally one or two methylene groups by oxygen and / or sulfur are replaced or for each optionally by fluorine, chlorine, bromine, C₁- C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, Cy ano or nitro substituted phenyl, furanyl, pyridyl, imidazolyl, Triazolyl, pyrazolyl, indolyl, thiazolyl, thienyl or phenyl-C₁-C₄-alkyl.

B particularly preferably represents hydrogen, C₁-C₁₀-alkyl or C₁-C₆-alkoxy-C₁-C₄-alkyl or
A, B and the carbon atom to which they are attached are particularly preferred for C₃-C₅-cycloalkyl or C₅-C₈-cycloalkenyl, in each of which a methylene group is optionally replaced by oxygen or sulfur and which may be replaced by C₁-C₆-alkyl , C₃-C₅-cycloalkyl, C₁-C₃-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, fluorine, chlorine or phenyl are substituted or
A, B and the carbon atom to which they are attached are particularly preferably C₅-C₆-cycloalkyl, which is substituted by an alkylene diyl group which may contain one or two oxygen or sulfur atoms or by an alkylene dioxyl or by an alkylene dithiol group which forms a further five- to seven-membered ring with the carbon atom to which it is attached or
A, B and the carbon atom to which they are bonded are particularly preferred for C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl, in which two substituents together with the carbon atoms to which they are bonded, each optionally by C₁-C₄-alkyl, C₁-C₄-alkoxy, fluorine, chlorine or bromine-substituted C₃-C₅-alkanediyl, C₃-C₅-alkenediyl or butadiene diyl, where in each case one methylene group is optionally replaced by oxygen or sulfur.

D particularly preferably represents hydrogen, in each case optionally substituted by fluorine or chlorine, C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₅-alkoxy-C₂-C₆-alkyl, poly-C₁-C₆ -alkoxy-C₂-C₆-alkyl or C₁-C₅-alkylthio-C₂-C₆-alkyl, for C₃-C₇- optionally substituted by fluorine, chlorine, C₁-C₄- alkyl, C₁-C₄-alkoxy or C₁-C₂-haloalkyl Cyclo alkyl, in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and / or sulfur or for each optionally by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-Ha logenalkyl, C₁-C₄-alkoxy , C₁-C₄-haloalkoxy, cyano or nitro substituted phenyl, furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl, triazolyl or phenyl-C₁-C₄-alkyl or
A and D together are particularly preferably a C₃-C₅alkanediyl or C₃-C₅alkenediyl group, in which in each case one carbon atom is replaced by oxygen or sulfur and which are optionally substituted by fluorine, chlorine or by in each case optionally by fluorine or chlorine substituted C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, phenyl or benzyloxy or
where in each case one of the following groups:

is included;
G particularly preferably represents hydrogen (a) or one of the groups

in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M stands for oxygen or sulfur.

R¹ particularly preferably represents C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl or poly- each optionally substituted by fluorine or chlorine, C₁-C₆-alkoxy-C₁-C₆-alkyl or for C₃-C₇-cycloalkyl optionally substituted by fluorine, chlorine, C₁-C₅-alkyl or C₁-C₅-alkoxy, in which one or two methylene groups are optionally substituted by oxygen and / or sulfur are replaced,
for optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl, C₁-C₃-haloalkoxy, C₁-C₄-alkyl thio or C₁-C₄-alkylsulfonyl Phenyl,
for phenyl-C₁-C₄-alkyl optionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy,
for pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl, each optionally substituted by fluorine, chlorine, bromine or C₁-C₄alkyl,
for optionally substituted by fluorine, chlorine, bromine or C₁-C₄-alkyl phenoxy-C₁-C₅-alkyl or
for each optionally substituted by fluorine, chlorine, bromine, amino or C₁-C₄-alkyl substituted pyridyloxy-C₁-C₅-alkyl, pyrimidyloxy-C₁-C₅-alkyl or thiazolyloxy-C₁-C₅-alkyl.

R² particularly preferably represents C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl or poly-C₁-C₆-alkoxy-C₂-C₆-alkyl, each optionally substituted by fluorine or chlorine,
for C₃-C₇-cycloalkyl optionally substituted by fluorine, chlorine, C₁-C₄-alkyl or C₁-C₄-alkoxy or
for phenyl or benzyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C C-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy.

R³ is particularly preferably optionally fluorine or chlorine substituted C₁-C₆ alkyl or in each case optionally by fluorine, chlorine, Bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkoxy, C₁-C₂-halogen alkyl, cyano or nitro substituted phenyl or benzyl.

R⁴ and R⁵ independently of one another are particularly preferably each C₁-C₆-alkyl optionally substituted by fluorine or chlorine, C₁-C₆- Alkoxy, C₁-C₆-alkylamino, di- (C₁-C₆-alkyl) amino, C₁-C₆-alkylthio or C₃-C₄-alkenylthio or for each optionally by fluorine, chlorine, Bromine, nitro, cyano, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, C₁-C₃-alkyl thio, C₁-C₃-haloalkylthio, C₁-C₃-alkyl or C₁-C₃-haloalkyl substi tuated phenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another particularly preferably represent hydrogen, for each C₁-C₆- optionally substituted by fluorine or chlorine Alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl or C₁-C₆-alk oxy-C₂-C₆-alkyl, for each optionally by fluorine, chlorine, bromine, C₁- C₅-haloalkyl, C₁-C₅-alkyl or C₁-C₅-alkoxy substituted phenyl or benzyl, or together for an optionally by C₁-C₄ alkyl substituted C₃-C₆ alkylene radical, in which optionally a methyl oil group is replaced by oxygen or sulfur.

R¹³ particularly preferably represents hydrogen or in each case optionally C₁-C oder-alkyl or C₁-C₆-alkoxy substituted by fluorine or chlorine, for optionally substituted by fluorine, C₁-C₂-alkyl or C₁-C₂-alkoxy C₃-C₇-cycloalkyl, in which optionally a methylene group Oxygen or sulfur is replaced or for each if necessary by Fluorine, chlorine, bromine, C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₂-haloalkyl, C₁- C₂-haloalkoxy, nitro or cyano substituted phenyl, phenyl-C₁-C₃- alkyl or phenyl-C₁-C₂-alkyloxy.  

R¹⁴ particularly preferably represents hydrogen or C₁-C₆-alkyl or
R¹³ and R¹⁴ together are particularly preferably C₄-C₆-alkanediyl.

R¹⁵ and R¹⁶ are the same or different and are particularly preferably C₁-C₄-alkyl or
R¹⁵ and R¹⁶ together are particularly preferably a C₂-C₃-alkanediyl radical, optionally by C₁-C₄-alkyl or by optionally by fluorine, chlorine, bromine, C₁-C₂-alkyl, C₁-C₂-haloalkyl, C₁-C₂-alkoxy , C₁-C₂-haloalkoxy, nitro or cyano substituted phenyl is substituted.

X very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro,
Y very particularly preferably represents hydrogen fluorine, chlorine, bromine, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, Cyano or nitro,
Z very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro, or
Y and Z are very particularly preferably together with the carbon atoms to which they are attached, optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy, propoxy, iso-propoxy or trifluoromethyl C₃-C₄ -Alkanediyl, in which two non-directly adjacent members are optionally replaced by oxygen, where X has one of the meanings mentioned above.

Het very particularly preferably stands for one of the groups

A very particularly preferably represents hydrogen, in each case optionally C₁-C₈-alkyl, C₂-C₄-alkenyl, C₁-C₆- substituted by fluorine or chlorine Alkoxy-C₁-C₄-alkyl, poly-C₁-C₄-alkoxy-C₁-C₄-alkyl or C₁-C₆-alkylthio- C₁-C₄-alkyl, or for optionally by fluorine, chlorine, methyl or Methoxy substituted C₃-C₆-cycloalkyl, in which optionally one or two methylene groups are replaced by oxygen and / or sulfur are or for each optionally by fluorine, chlorine, bromine, methyl, Ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl, trifluor methoxy, cyano or nitro substituted phenyl, pyridyl or benzyl.

B very particularly preferably represents hydrogen, C₁-C₈-alkyl or C₁-C₄-alkoxy-C₁-C₂-alkyl or
A, B and the carbon atom to which they are attached very particularly preferably represent C₃-C₅-cycloalkyl or C₅-C₅-cycloalkenyl, in which in each case one methylene group is replaced by oxygen or sulfur and which is optionally replaced by methyl, ethyl, n- Propyl, iso-propyl, butyl, iso-butyl, sec. Butyl, tert-butyl, cyclohexyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, iso-butoxy, sec.-butoxy, tert .-Butoxy, methylthio, ethylthio, fluorine, chlorine or phenyl are substituted or
A, B and the carbon atom to which they are attached very particularly preferably represent C₅-C₆-cycloalkyl, which is substituted by an alkylene diyl group which may contain an oxygen or sulfur atom or by an alkylene dioxyl group which is substituted by the carbon atom, to which it is bound forms a further five- or six-membered ring or
A, B and the carbon atom to which they are attached are very particularly preferably C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl, in which two substituents together with the carbon atoms to which they are attached are C₃-C₄ -Alkanediyl, C₃-C Alk-alkenediyl or butadienediyl, where in each case a methylene group is optionally replaced by oxygen or sulfur.

D very particularly preferably represents hydrogen, in each case optionally substituted by fluorine or chlorine, C₁-C₅-alkyl, C₃-C₄-alkenyl, C₃-C₄-alkynyl, C₁-C₆-alkoxy-C₂-C₄-alkyl, poly-C₁- C₄-alkoxy-C₂-C₄-alkyl, C₁-C₄-alkylthio-C₂-C₄-alkyl or C₃-C₆-cycloalkyl, in which one or two non-directly adjacent methylene groups are optionally replaced by oxygen and / or sulfur or for each optionally phenyl, furanyl, pyridyl, thienyl or benzyl substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
or
A and D together are very particularly preferably a C₃-C₅-alkanediyl or C₃-C₅-alkenedyl group, in which a methylene group is optionally replaced by oxygen or sulfur and which, if appropriate, by fluorine, chlorine or by each optionally by fluorine or Chlorine substituted C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, phenyl or benzyloxy are substituted.

G very particularly preferably represents hydrogen (a) or one of the groups pen

in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M stands for oxygen or sulfur.

R¹ very particularly preferably represents C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₆-alkyl, C₁-C₄-alkylthio-C₁-C₆-alkyl, poly, each optionally substituted by fluorine or chlorine -C₁-C₄-alkoxy-C₁-C₄-alkyl or for optionally by fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, methoxy, ethoxy, n -Propoxy or iso-propoxy substituted C₃-C₆-cycloalkyl, in which one or two methylene groups are optionally replaced by oxygen and / or sulfur,
for phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl,
for benzyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
for furanyl, thienyl or pyridyl, each optionally substituted by fluorine, chlorine, bromine, methyl or ethyl,
for optionally substituted by fluorine, chlorine, methyl or ethyl phenoxy-C₁-C₄-alkyl or
for each optionally substituted by fluorine, chlorine, amino, methyl or ethyl pyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C₄-alkyl or thiazolyloxy-C₁-C₄-alkyl.

R² very particularly preferably represents C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₂-C₆-alkyl or poly-C₁-C₄-alkoxy-C₂-C₆-alkyl, each optionally substituted by fluorine or chlorine ,
for C₃-C₆-cycloalkyl optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or methoxy,
or for phenyl or benzyl optionally substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy.

R³ very particularly preferably represents optionally by fluorine or chlorine substituted methyl, ethyl, propyl, iso-propyl, butyl, tert-butyl, or each optionally by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, iso-propoxy, trifluoromethyl, trifluor methoxy, cyano or nitro substituted phenyl or benzyl.

R⁴ and R⁵ independently of one another are very particularly preferably each for C₁-C₄-alkyl optionally substituted by fluorine or chlorine, C₁-C₄- Alkoxy, C₁-C₄-alkylamino, di- (C₁-C₄-alkyl) amino or C₁-C₄-alkylthio or for each optionally by fluorine, chlorine, bromine, nitro, cyano, Methyl, methoxy, trifluoromethyl or trifluoromethoxy substituted Phenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another very particularly preferably represent water substance for C₁- optionally substituted by fluorine or chlorine C₄-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₃-C₄-alkenyl or C₁-C₄- Alkoxy-C₂-C₄-alkyl, each optionally by fluorine, chlorine, bromine, Methyl, methoxy or trifluoromethyl-substituted phenyl or benzyl, or together for one optionally by methyl or ethyl substituted C₅-C₆ alkylene radical, in which optionally a methyl oil group is replaced by oxygen or sulfur.  

The radicals listed above or listed in preferred areas Definitions or explanations can be made with each other, i.e. also between the respective areas and preferred areas can be combined as desired. they seem for the end products as well as for the preliminary and intermediate products accordingly.

According to the invention, preference is given to the compounds of the formula (I) in which a combination of those listed as preferred (preferred) above Meanings exist.

According to the invention, particular preference is given to the compounds of the formula (I), in which are a combination of those listed as particularly preferred above Meanings exist.

The compounds of the formula are very particularly preferred according to the invention (I) in which a combination of the above is particularly preferred listed meanings is present.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can NEN, also in connection with heteroatoms, such as. B. in alkoxy, if possible, each be straight or branched.

Optionally substituted radicals can be mono- or polysubstituted, in the case of multiple substitutions, the substituents are the same or different can.  

In particular, except for the verb mentioned in the manufacturing examples the following compounds of the formula (I-1-a):

Table 1

X = CH₃; Y = CH₃; Z = CH₃

Table 2

A and B have the same meaning as in Table 1 with:
X = CH₃; Y = Cl; Z = CH₃

Table 3

A and B have the same meaning as in Table 1 with:
X = Cl; Y = Cl; Z = Cl

In particular, except for the verb mentioned in the manufacturing examples the following compounds of the formula (I-2-a):

Table 4

X = CH₃; Y = CH₃; Z = CH₃

Table 5

A and B have the same meaning as in Table 4 with:
X = CH₃; Y = Cl; Z = CH₃

Table 6

A and B have the same meaning as in Table 4 with:
X = Cl; Y = Cl; Z = Cl

In particular, besides those mentioned in the production examples Compounds called the following compounds of formula (I-3-a):

Table 7

X = CH₃; Y = CH₃; Z = CH₃

Table 8

A and B have the same meaning as in Table 7 with:
X = CH₃; Y = Cl; Z = CH₃

Table 9

A and B have the same meaning as in Table 7 with:
X = Cl; Y = Cl; Z = Cl

In particular, except for the verb mentioned in the manufacturing examples the following compounds of the formula (I-4-a):

Table 10

X = CH₃; Y = CH₃; Z = CH₃

Table 11

A and B have the same meaning as in Table 10 with: <99999 00070 552 001000280000000200012000285919988800040 0002019602524 00004 99880 / DL < X = CH₃; Y = Cl; Z = CH₃

Table 12

A and B have the same meaning as in Table 10 with:
X = Cl; Y = Cl; Z = Cl

In particular, except for the verb mentioned in the manufacturing examples the following compounds of the formula (I-5-a):

Table 13

X = CH₃; Y = CH₃; Z = CH₃

Table 14

A and B have the same meaning as in Table 13 with:
X = CH₃; Y = Cl; Z = CH₃

Table 15

A and B have the same meaning as in Table 13 with:
X = Cl; Y = Cl; Z = Cl

According to process (A), N - [(4,5-dichloro-2-methyl) -phenylacetyl] -1- amino-4-ethyl-cyclohexane-carboxylic acid ethyl ester as the starting material so the Course of the method according to the following reaction scheme as are given:

According to process (B), O - [(2,5-dichloro-4-methyl) -phenylacetyl] - hydroxyacetic acid ethyl ester, the course of the process according to the invention rens can be represented by the following reaction scheme:

If 2 - [(2-chloro-4,5-dimethyl) phenyl] -4- (4-meth oxy) -benzylmercapto-4-methyl-3-oxo-valeric acid ethyl ester, so the course the process of the invention by the following reaction scheme again are given:

For example, according to process (D) (chlorocarbonyl) -2 - [(4,5- Dichloro-2-methyl) phenyl] ketene and acetone as starting compounds, so can  the course of the process according to the invention by the following reaction Scheme are reproduced:

For example, according to process (E) (chlorocarbonyl) -2 - [(2,4,5- Trimethyl) phenyl] ketene and thiobenzamide as starting compounds, so the course of the process according to the invention by the following reaction Scheme are reproduced:

According to method (Fα) 3 - [(2,5-dichloro-4-methyl) -phenyl] -5,5-di is used methyl-pyrrolidine-2,4-dione and pivaloyl chloride as starting materials, so the Course of the process according to the invention by the following reaction scheme are reproduced:

According to method (F) (variant β) 3 - [(2,4,5-trichloro) phenyl] -4- hydroxy-5-phenyl-Δ³-dihydrofuran-2-one and acetic anhydride as starting compounds  gen, so the course of the method according to the invention by the following Re action scheme are reproduced:

According to method (G), 8 - [(2,4-dichloro-5-methyl) -phenyl] -5,5-penta is used methylene-pyrrolidine-2,4-dione and ethyl chloroformate as Aus gang connections, the course of the method according to the invention the following reaction scheme can be reproduced:

Is used according to process (H), (variant α) 3 - [(2-bromo-4,5-dimethyl) -phe nyl] -4-hydroxy-6- (3-pyridyl) pyrone and chloromothio formic acid methyl ester as Starting products, the course of the reaction can be shown as follows will:

If one uses according to process (H), (variant β) 5 - [(5-chloro-2-fluoro-4-methyl) - phenyl] -6-hydroxy-2- (4-chlorophenyl) thiazin-4-one, carbon disulfide and Me  thyl iodide as starting components, the course of the reaction can be as follows are given:

According to process (I), 2 - [(2,4,5-trimethyl) phenyl] -5.5 - [- (3-methyl) - pentamethylene] -pyrrolidine-2,4-dione and methanesulfonic acid chloride as starting product, the course of the reaction can be reproduced using the following reaction scheme are given:

If, according to process (J), 2 - [(2-chloro-4,5-dimethyl) phenyl] -4-hydroxy- 5-methyl-6- (2-pyridyl) pyrone and methanthophosphonyl chloride- (2,2,2-trifluoro ethyl ester) as starting materials, the course of the reaction can be carried out by the following Reaction scheme are reproduced:

According to process (K), 3 - [(2,4,5-trichloro) phenyl] -5-cyclopropyl-5- methyl-pyrrolidine-2,4-dione and NaOH as components, so the course of the process according to the invention represented by the following reaction scheme will:

According to process (L) (variant α) 3 - [(2-chloro-4-bromo-5-methyl) - phenyl] -4-hydroxy-5,5-tetramethylene-Δ³-dihydro-furan-2-one and ethyl isocyanate as Starting products, the course of the reaction can be by the following reaction scheme are reproduced:

According to process (L) (variant β), 3 - [(2-chloro-4,5-dimethyl) -phe is used nyl] -5-methyl-pyrrolidine-2,4-dione and dimethyl carbamic acid chloride as starting products, the course of the reaction can be represented by the following scheme will:

The compound required as starting materials in process (A) according to the invention formulas (II)

in which
A, B, X, Y, Z and R⁸ have the meanings given above,
are new.

The acylamino acid esters of the formula (II) are obtained, for example, by Amino acid derivatives of the formula (XIX)

in which
A, B and R⁸ have the meanings given above,
with substituted phenylacetic acid halides of the formula (XX)

in which
X, Y and Z have the meanings given above and
Hal represents chlorine or bromine,
acylated (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem 6, 341-5, 1968)
or if you have acylamino acids of the formula (XXI)

in which
A, B, X, Y and Z have the meanings given above,
esterified (Chem. Ind. (London) 1568 (1968)).

The compounds of formula (XXI)

in which
A, B, X, Y and Z have the meanings given above,
are new.

The compounds of formula (XXI) are obtained when amino acids of Formula (XXII)

in which
A and B have the meanings given above,
with substituted phenylacetic acid halides of the formula (XX)

in which
X, Y and Z have the meanings given above and
Hal represents chlorine or bromine,
acylated according to Schotten-Baumann (Organikum, VEB German Publishing House of Sciences, Berlin 1977, p. 505).

Some of the compounds of the formula (XX) are new and can be re-used produce known methods.

The compounds of formula (XX) are obtained, for example, by substi tuated phenylacetic acids of formula (XXIII)

in which
X, Y and Z have the meaning given above,
with halogenating agents (e.g. thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride) optionally in the presence of a diluent (e.g. optionally chlorinated aliphatic or aromatic hydrocarbons such as toluene or methylene chloride) at temperatures of -20 ° C to 150 ° C, preferably from -10 ° C to 100 ° C, implemented.

Some of the compounds of the formula (XXIII) are new, they can be relieved Produce processes known from the literature (Organikum 15th edition, p. 533, VEB German Publishing House of Sciences, Berlin 1977). You get the connections of formula (XXIII), for example, by using substituted phenylacetic acid esters of the formula (XXIV)

in which
X, Y, Z and R⁸ have the meaning given above,
in the presence of an acid (e.g. an inorganic acid such as hydrochloric acid) or a base (e.g. an alkali hydroxide such as sodium or potassium hydroxide) and optionally a diluent (e.g. an aqueous alcohol such as methanol or ethanol ) hydrolyzed at temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C.

The compounds of formula (XXIV) are partly new, they can be im Establish the principle of known processes.

The compounds of formula (XXIV) are obtained, for example, by sub substituted 1,1,1-trichloro-2-phenylethanes of the formula (XXV)

in which
X, Y and Z have the meaning given above,
first with alcoholates (e.g. alkali metal alcoholates such as sodium methylate or sodium ethylate) in the presence of a diluent (e.g. alcohol derived from the alcoholate) at temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C , and then with an acid (preferably an inorganic acid such as sulfuric acid) at temperatures between -20 ° C and 150 ° C, preferably 0 ° C and 100 ° C, (see. DE 33 14 249).

The compounds of formula (XXV) are partly new, they can be im Establish the principle of known processes.

The compounds of formula (XXV) are obtained, for example, if Anilines of the formula (XXVI)

in which
X, Y and Z have the meaning given above,
in the presence of an alkyl nitrite of the formula (XXVII)

R²¹-ONO (XXVII)

in which
R²¹ represents alkyl, preferably C₁-C₆ alkyl,
in the presence of copper (II) chloride and optionally in the presence of a diluent (for example an aliphatic nitrile such as acetonitrile) at a temperature of from -20 ° C. to 80 ° C., preferably 0 ° C. to 60 ° C., with vinylidene chloride (CH₂ = CCl₂) is implemented.

The compounds of formula (XXVI) and (XXVII) are known compounds of organic chemistry. Copper (II) chloride and vinylidene chloride have long been knows and can be bought.

Some of the compounds of the formulas (XIX) and (XXII) are known and / or can be represented by known methods (see e.g. Compagnon, Miocque Ann. Chim. (Paris) [14] 5, pp. 11-22, 23-27 (1970)).

The substituted cyclic aminocarboxylic acids of the formula (XXIIa) in which A and B form a ring are generally according to the Bucherer-Bergs synthesis or available after the Strecker synthesis and each fall under different forms of isomers. So you get according to the conditions of Bucherer-Bergs synthesis predominantly the isomers (hereinafter the simplicity for the sake referred to as β), in which the radicals R and the carboxyl group are equatorial, while according to the conditions of the Strecker synthesis gend the isomers (hereinafter referred to as α for the sake of simplicity), in which the amino group and the radicals R are equatorial.

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

Furthermore, the starting used in the above method (A) can be substances of formula (II)

in which
A, B, X, Y, Z and R⁸ have the meanings given above,
produce if aminonitriles of the formula (XXVIII)

in which
A and B have the meanings given above,
with substituted phenylacetic acid halides of the formula (XX)

in which
X, Y, Z and Hal have the meanings given above,
to compounds of the formula (XXIX)

in which
A, B, X, Y and Z have the meanings given above,
implements
and then subjecting it to acidic alcoholysis.

The compounds of formula (XXIX) are also new.

Those required as starting materials in process (B) according to the invention Compounds of formula (III)

in which
A, B, X, Y, Z and R⁸ have the meanings given above,
are new.

They can be produced in a simple manner using methods which are known in principle.

The compounds of formula (III) are obtained, for example, when
2-hydroxycarboxylic acid esters of the formula (XXX)

in which
A, B and R⁸ have the meanings given above,
with substituted phenylacetic acid halides of the formula (XX)

in which
X, Y, Z and Hal have the meanings given above,
acylated (Chem. Reviews 52, 237-416 (1953)).

Furthermore, compounds of the formula (III) are obtained if
substituted phenylacetic acids of the formula (XXIII)

in which
X, Y and Z have the meanings given above,
with α-halocarboxylic acid esters of the formula (XXXI)

in which
A, B and R⁸ have the meanings given above and
Hal represents chlorine or bromine,
alkylated.

The compounds of formula (XXXI) are commercially available.

The compounds required as starting materials in the above process (C) of the formula (IV)

in which
A, B, W, X, Y, Z and R⁸ have the meanings given above,
are new.

They can be produced using methods that are known in principle.

The compounds of formula (IV) are obtained, for example, if substituted phenylacetic acid esters of the formula (XXIV)

in which
X, Y, R⁸ and Z have the meanings given above,
with 2-benzylthio-carboxylic acid halides of the formula (XXXII)

in which
A, B and W have the meanings given above and
Hal represents halogen (especially chlorine or bromine),
acylated in the presence of strong bases (see, for example, BMS Chambers, EJ Thomas, DJ Williams, J. Chem. Soc. Chem. Commun., (1987), 1228).

Some of the benzylthio-carboxylic acid halides of the formula (XXXII) are known and / or can be prepared by known processes (J. Antibiotics (1983), 26, 1589).

The halogen carbonyl ketenes required as starting materials in process (D) Formula (VI) are new. They can be created using methods that are known in principle easy to manufacture (see e.g. Org. Prep. Proced Int., 7, (4), 155-158, 1975 and DE 19 45 703). The compounds of the formula (VI) are obtained

in which
X, Y and Z have the meanings given above and
Hal represents chlorine or bromine,
if
substituted phenylmalonic acids of the formula (XXXIII)

in which
X, Y and Z have the meanings given above,
with acid halides, such as thionyl chloride, phosphorus (V) chloride, phosphorus (III) chloride, oxalyl chloride, phosgene or thionyl bromide, optionally in the presence of catalysts, such as diethylformamide, methyl sterylformamide or triphenylphosphine and optionally in the presence of bases such as, for. As pyridine or triethylamine, at a temperature between -20 ° C and 200 ° C, preferably between 0 ° C and 150 ° C.

The substituted phenylmalonic acids of the formula (XXXIII) are new. You leave but can be produced in a simple manner by known processes (cf. e.g. Orga nikum, VEB German Publishing House of Sciences, Berlin 1977, p. 517 ff.), z. B. from substituted phenylmalonic acid esters of the formula (XXXIV)

in which
X, Y, Z and R⁸ have the meaning given above,
obtained by saponification.

Those required as starting materials for process (E) according to the invention Carbonyl compounds of the formula (V) or their silylenol ethers of the formula (Va)

in which
A, D and R⁸ have the meanings given above,
are commercially available compounds which are known or which can be obtained by known processes.

The production of the process (E) according to the invention as The ketene acid chlorides of the formula (VI) required as starting materials have already been obtained described in process (D) according to the invention. The to carry out the Process (E) according to the invention required thioamides of the formula (VII)

in which
A has the meaning given above,
are generally known compounds in organic chemistry.

The malonic esters of the formula (XXXIV)

in which
R⁸, X, Y and Z have the meanings given above,
are new and can be prepared according to well-known methods of organic chemistry (see e.g. Tetrahedron Lett 27 2763 (1986) and Organikum VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. 587 ff.).

The processes (F), (G), (H), (I), (J), (K) and (L) acid halides of the formula required as starting materials (VIII), carboxylic anhydrides of the formula (IX), chloroformate or chlorine formic acid thioesters of the formula (X), chloromothio formic acid esters or Chlorodithio formic acid esters of the formula (IX), alkyl halides of the formula (XII), Sulfonic acid chlorides of the formula (XIII), phosphorus compounds of the formula (XIV) and metal hydroxides, metal alkoxides or amines of the formula (XV) and (XVI) and Isocyanates of the formula (XVII) and carbamic acid chlorides of the formula (XVIII) generally known compounds of organic or inorganic chemistry.

The compounds of the formulas (V), (VII) to (XVIII), (XIX), (XXII), (XXVIII), (XXX), (XXXI), (XXXII), (XXXIII and (XXXIV) are also from the Patent applications cited at the outset are known and / or can be identified there Manufacture specified methods.

Process (A) is characterized in that compounds of the formula (II), in which A, B, X, Y, Z and R⁸ have the meanings given above, in the presence of a diluent and in the presence of a base an intra subject to molecular condensation.  

All of them can be used as diluents in process (A) according to the invention organic solvents inert to the reactants will. Hydrocarbons such as toluene and xylene are preferably usable, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and Diglycol dimethyl ether, also polar solvents, such as dimethyl sulfoxide, Sulfolane, dimethylformamide and N-methyl-pyrrolidone, and alcohols such as Me ethanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and tert-butanol.

As a base (deprotonating agent) can be in the implementation of the Invention According to method (A) all usual proton acceptors are used. Before alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, Sodium carbonate, potassium carbonate and calcium carbonate, which are also present of phase transfer catalysts such. B. triethylbenzylammonium chloride, tetra butylammonium bromide, Adogen 464 (= methyltrialkyl (C₈-C₁₀) ammonium chloride) or TDA 1 (= tris (methoxyethoxyethyl) amine) can be used. Wei alkali metals such as sodium or potassium can also be used. Further are alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, Sodium hydride and calcium hydride, and also alkali metal alcoholates, such as Sodium methylate, sodium ethylate and potassium tert-butoxide can be used.

The reaction temperature can be carried out when carrying out the Ver driving (A) can be varied within a wide range. In general one works at temperatures between 0 ° C and 250 ° C, preferably between 50 ° C and 150 ° C.

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

When carrying out process (A) according to the invention, the reak is set tion component of formula (II) and the deprotonating base in general in equimolar to about double equimolar amounts. However, it is also possible one or the other component in a larger excess (up to 3 moles) use.

Process (B) is characterized in that compounds of the formula (III) in which A, B, X, Y, Z and R⁸ have the meanings given above,  intramole in the presence of a diluent and in the presence of a base kular condensed.

All can be used as diluents in process (B) according to the invention organic solvents inert to the reactants will. Hydrocarbons such as toluene and xylene are preferably usable, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and Diglycol dimethyl ether, also polar solvents, such as dimethyl sulfoxide, Sulfolane, dimethylformamide and N-methyl-pyrrolidone. Alko get like methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and tert-butanol can be used.

As a base (deprotonating agent) can be in the implementation of the Invention according to method (B) all usual proton acceptors are used. Alkali metal and alkaline earth metal oxides and hydroxides are preferably usable and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which are also used in counter were from phase transfer catalysts such. B. triethylbenzylammonium chloride, Tetrabutylammonium bromide, Adogen 464 (= methyltrialkyl (C₈-C₁₀) ammonium chloride) or TDA 1 (= tris (methoxyethoxyethyl) amine) can be used nen. Alkali metals such as sodium or potassium can also be used. Also alkali metal and alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcohol latex, such as sodium methylate, sodium ethylate and potassium tert-butoxide can be used.

The reaction temperature can be carried out when carrying out the Ver driving (B) can be varied within a wide range. In general one works at temperatures between 0 ° C and 250 ° C, preferably between 50 ° C and 150 ° C.

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

When carrying out process (B) according to the invention, the reak is set tion components of formula (III) and the deprotonating bases in general mean in approximately equimolar amounts. However, it is also possible to use one  or use other components in a larger excess (up to 3 moles) the.

Process (C) is characterized in that compounds of the formula (IV) in which A, B, W, X, Y, Z and R⁸ have the meaning given above, in the presence of an acid and optionally in the presence of a diluent cyclized intramolecularly.

All of them can be used as diluents in process (C) according to the invention organic solvents inert to the reactants will. Hydrocarbons such as toluene and xylene are preferably usable, halogenated hydrocarbons such as dichloromethane, chloroform, ethylene chloride, chlorobenzene, dichlorobenzene, and also polar solvents, such as dime thylsulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone. Farther can alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, iso butanol, tert-butanol can be used.

If necessary, the acid used can also serve as a diluent.

As acid, all customary anor ganic and organic acids are used, such as. B. Halogen water Substance acids, sulfuric acid, alkyl, aryl and haloalkyl sulfonic acids, in particular halogenated alkyl carboxylic acids such. B. Trifluoroacetic acid used.

The reaction temperature can be carried out when carrying out the Ver driving (C) can be varied within a wide range. In general one works at temperatures between 0 ° C and 250 ° C, preferably between 50 ° C and 150 ° C.

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

When carrying out process (C) according to the invention, the Reaction components of the formulas (IV) and the acid z. B. in equimolar men a. However, it is optionally also possible to catalyze the acid Use quantities.  

Process (D) according to the invention is characterized in that carbo nyl compounds of the formula (V) or their silylenol ethers of the formula (Va) with Ketene acid halides of the formula (VI), if appropriate in the presence of a ver diluent and optionally in the presence of an acid acceptor.

All can be used as diluents in process (D) according to the invention organic solvents inert to the reactants will. Hydrocarbons, such as o-dichlorobenzene, are preferably usable. Tetralin, toluene and xylene, furthermore ethers, such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, also polar solvents, such as dimethyl sulfoxide, Sulfolane, dimethylformamide or N-methyl-pyrrolidone.

As acid acceptors when carrying out the ver driving (D) all usual acid acceptors are used.

Tertiary amines such as triethylamine, pyridine, diaza are preferably usable bicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclonones (DBN), Hunig base or N, N-dimethyl-aniline.

The reaction temperature can be carried out when carrying out the process according to the invention Process (D) can be varied within a wide range. More appropriate wise one works at temperatures between 0 ° C and 250 ° C, preferably between 50 ° C and 220 ° C.

Process (D) according to the invention is preferably carried out under normal pressure carried out.

When carrying out process (D) according to the invention, the Reaction components of the formulas (V) and (VI) and optionally the acid acceptor generally in approximately equimolar amounts. However, it is also possible one or the other component in a larger excess (up to 5 mol) to use.

Process (E) according to the invention is characterized in that thio amides of the formula (VII) with ketene acid halides of the formula (VI) if in the presence of a diluent and optionally in the presence an acid acceptor.  

In the process variant (E) according to the invention, all inert organic solvents are used. Preferably usable are also hydrocarbons such as o-dichlorobenzene, tetralin, toluene and xylene Ethers such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, except the polar solvent, such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl pyrrolidone.

As acid acceptors when carrying out the ver driving (E) all usual acid acceptors are used.

Tertiary amines such as triethylamine, pyridine, diaza are preferably usable bicyclooctane (DABCO), diazabicycloundecane (DBU), diazabicyclonones (DBN), Hunig base and N, N-dimethyl-aniline.

The reaction temperature can be carried out when carrying out the process according to the invention Process (E) can be varied within a wide range. More appropriate wise one works at temperatures between 0 ° C and 250 ° C, preferably between 20 ° C and 220 ° C.

Process (E) according to the invention is expediently carried out under normal pressure carried out.

When carrying out process (E) according to the invention, the Reaction components of the formulas (VII) and (VI) and optionally the acid generally accept in approximately equimolar amounts. However, it is also possible one or the other component in a larger excess (up to 5 mol) to use.

The process (Fα) is characterized in that compounds of Formulas (I-1-a) to (I-5-a) each with carboxylic acid halides of the formula (VIII) optionally in the presence of a diluent and optionally in In the presence of an acid binder.

All can be used as diluents in the process (Fα) according to the invention solvents inert to the acid halides are used. Preferential hydrocarbons such as gasoline, benzene, toluene, xylene and Tetralin, also halogenated hydrocarbons, such as methylene chloride, chloroform,  Carbon tetrachloride, chlorobenzene and o-dichlorobenzene, also ketones, such as Acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetra hydrofuran and dioxane, moreover carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethylformamide, dimethyl sulfoxide and Sulfolan. If the hydrolysis stability of the acid halide allows, the Implementation can also be carried out in the presence of water.

Acid binders used in the reaction according to the invention Process (Fα) all usual acid acceptors into consideration. Preferably used are tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), Diazabicycloundecen (DBU), Diazabicyclononen (DBN), Hünig-Base and N, N-Di methyl aniline, also alkaline earth metal oxides, such as magnesium and calcium oxide, also alkali and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate as well as alkali hydroxides such as sodium hydroxide and Potassium hydroxide.

The reaction temperature in the process (Fα) according to the invention can be varied within a wide range. Generally you work at temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.

When performing the method (Fα) according to the invention, the off Starting materials of the formulas (I-1-a) to (I-5-a) and the carboxylic acid halide Use formula (VIII) in general in approximately equivalent amounts det. However, it is also possible to enlarge the carboxylic acid halide Use excess (up to 5 moles). The processing takes place according to usual Methods.

The process (Fβ) is characterized in that compounds of Formulas (I-1-a) to (I-5-a) each with carboxylic anhydrides of the formula (IX) optionally in the presence of a diluent and optionally in In the presence of an acid binder.

In the process of the invention (Fβ) can be used as diluent preferably those diluents are used that are also used in the Ver Use of acid halides are preferred. Furthermore  can also be used in excess as a carboxylic acid anhydride Thinners act.

Acid binders that may be added in process (Fβ) preferably those acid binders in question that are also in use of acid halides are preferred.

The reaction temperature can be internal in the process (Fβ) according to the invention can be varied within a larger range. Generally one works at Temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.

When carrying out the method (Fβ) according to the invention Starting materials of the formulas (I-1-a) to (I-5-a) and the carboxylic anhydride Use formula (IX) in general in approximately equivalent amounts det. However, it is also possible to use a larger excess of the carboxylic anhydride shot (up to 5 moles) to use. The processing takes place according to the usual method the.

The general procedure is to use diluents and in excess existing carboxylic acid anhydride and the resulting carboxylic acid Distillation or by washing with an organic solvent or with Water removed.

The process (G) is characterized in that compounds of the For meln (I-1-a) to (I-5-a) each with chloroformates or chlor ants acid thiol esters of formula (X) optionally in the presence of a dilution by means of and optionally in the presence of an acid binder.

All of them come as acid binders in process (G) according to the invention usual acid acceptors into consideration. Tertiary are preferably used Amines such as triethylamine, pyridine, DABCO, DBU, DBA, Hünig base and N, N- Dimethyl-aniline, also alkaline earth metal oxides, such as magnesium and calcium oxide, also alkali and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate as well as alkali hydroxides such as sodium hydroxide and Potassium hydroxide.  

All can be used as diluents in process (G) according to the invention inert to the chloroformates or chloroformates Solvents are used. Hydrocarbons are preferably usable, such as gasoline, benzene, toluene, xylene and tetralin, as well as halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, and also ketones such as acetone and methyl isopropyl ketone towards ethers such as diethyl ether, tetrahydrofuran and dioxane, and moreover carbon acid esters such as ethyl acetate, also nitriles such as acetonitrile and also strongly polar Solvents such as dimethylformamide, dimethyl sulfoxide and sulfolane.

The reaction temperature can be carried out when carrying out the Ver driving (G) can be varied within a wide range. The reaction tem temperature is generally between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° C.

Process (G) according to the invention is generally carried out under normal pressure carried out.

When carrying out the method (G) according to the invention Starting materials of the formulas (I-1-a) to (I-5-a) and the corresponding chlor ants Acid esters or chloroformic acid thiol esters of the formula (X) in general each because used in approximately equivalent amounts. However, it is also possible one or the other component in a large excess (up to 2 mol) to use. The processing takes place according to usual methods. In general the procedure is to remove precipitated salts and the remaining reak concentrated by pulling off the diluent.

Process (H) according to the invention is characterized in that Compounds of the formulas (I-1-a) to (I-5-a) each with (Hα) compounds of Formula (XI) in the presence of a diluent and optionally in counter were an acid binder or (Hβ) carbon disulfide and then with Alkyl halides of the formula (XII) optionally in the presence of a Diluent and optionally in the presence of a base.

In the production process (Hα), the per mole of starting compound Formulas (I-1-a) to (I-5-a) approx. 1 mol of chloromothio formic acid ester or chlorine  dithio formic acid ester of formula (XI) at 0 to 120 ° C, preferably at 20 to 60 ° C around.

All inert polar come as optionally added diluents organic solvents in question, such as ethers, amides, sulfones, sulfoxides, but also halogen alkanes.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or Methylene chloride used.

Is made in a preferred embodiment by adding strong Depro toning agents such as B. sodium hydride or potassium tert-butylate the enolate salt of the compounds (I-1-a) to (I-5-a), can be based on the further addition of acid be dispensed with.

If acid binders are used, common inorganic or organic compounds are used African bases in question, examples include sodium hydroxide, sodium carbonate, Potassium carbonate, pyridine and triethylamine listed.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses standard methods.

In the manufacturing process (Hβ) the per moles of starting compounds Formulas (I-1-a) to (I-5-a) each represent the equimolar amount or an excess Carbon disulfide too. One works preferably at temperatures of 0 to 50 ° C and especially at 20 to 30 ° C.

It is often expedient first of all to use the compounds of the formulas (I-1-a) to (I-5-a) by adding a base (such as potassium tert-butoxide or sodium hydride) to produce the appropriate salt. The compounds (I-1-a) to (I-5-a) always with carbon disulfide until the formation of the intermediate connection is complete, e.g. B. after stirring for several hours at room temperature maturity.

All conventional proton acceptors can be used as bases in the process (Hβ) be set. Alkali metal hydrides, alkali metal are preferably usable  alcoholates, alkali or alkaline earth metal carbonates or bicarbonates or Nitrogen bases. Examples include sodium hydride, sodium methoxide, Sodium hydroxide, calcium hydroxide, potassium carbonate, sodium hydrogen carbonate, Triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclo octane (DABCO), diazabicyclonones (DBN) and diazabicycloundecene (DBU).

All customary solvents can be used as diluents in this process be used.

Aromatic hydrocarbons such as benzene or are preferably usable Toluene, alcohols such as methanol, ethanol, isopropanol or ethylene glycol, nitriles such as acetonitrile, ethers such as tetrahydrofuran or dioxane, amides such as dimethyl formamide or other polar solvents such as dimethyl sulfoxide or sulfolane.

The further reaction with the alkyl halide of the formula (XII) takes place before preferably at 0 to 70 ° C and especially at 20 to 50 ° C. Here will at least the equimolar amount of alkyl halide used.

One works at normal pressure or under increased pressure, preferably at Normal pressure.

The processing is again carried out using customary methods.

Process (I) according to the invention is characterized in that Ver Bindings of the formulas (I-1-a) to (I-5-a) each with sulfonic acid chlorides Formula (XIII) optionally in the presence of a diluent and given if necessary in the presence of an acid binder.

In the production process (I), the per mole of starting compound Formula (I-1-a to I-5-a) about 1 mol of sulfonic acid chloride of formula (XIII) at -20 to 150 ° C, preferably at 0 to 70 ° C.

Process (I) is preferably carried out in the presence of a diluent carried out.  

All inert polar organic solvents can be used as diluents Question like ethers, amides, ketones, carboxylic acid esters, nitriles, sulfones, sulfoxides or halogenated hydrocarbons such as methylene chloride.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, Methylene chloride used.

Is made in a preferred embodiment by adding strong Deprotonating agents (such as sodium hydride or potassium tertiary butoxide) Enolate salt of the compounds (I-1-a) to (I-5-a), can be added to the further acid binders can be dispensed with.

If acid binders are used, the usual inorganic or organic compounds are used bases in question, examples include sodium hydroxide, sodium carbonate, Potassium carbonate, pyridine and triethylamine listed.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses standard methods.

Process (J) according to the invention is characterized in that Compounds of formulas (I-1-a) to (I-5-a) each with phosphorus compounds of formula (XIV) optionally in the presence of a diluent and if appropriate in the presence of an acid binder.

The manufacturing process (J) uses to obtain compounds Formulas (I-1-e) to (I-6-e) to 1 mol of the compounds (I-1-a) to (I-5-a), 1 to 2, preferably 1 to 1.3 mol of the phosphorus compound of the formula (XIV) at Tempe temperatures between -40 ° C and 150 ° C, preferably between -10 and 110 ° C.

Process (J) is preferably carried out in the presence of a diluent carried out.

All inert, polar organic solvents can be used as diluents Question like ethers, carboxylic acid esters, halogenated hydrocarbons, ketones, Amides, nitriles, sulfones, sulfoxides etc.  

Acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethyl are preferred formamide, methylene chloride used.

Conventional inorganic or organic bases in question such as hydroxides, carbonates or amines. Exemplary be sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethyl amine listed.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses the usual methods of organic chemistry. The end products who preferably by crystallization, chromatographic purification or by so-called "distillation", i.e. H. Removal of volatile components in the Va vacuum cleaned.

The process (K) is characterized in that compounds of Formulas (I-1-a) to (I-5-a) each with metal hydroxides or metal alkoxides Formula (XV) or amines of formula (XVI), optionally in the presence of a Diluent.

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

The process (L) according to the invention is characterized in that Compounds of the formulas (I-1-a) to (I-5-a) each with (Lα) compounds of Formula (XVII) optionally in the presence of a diluent and counter also in the presence of a catalyst or (Lβ) with compounds of Formula (XVIII) optionally in the presence of a diluent and counter if necessary in the presence of an acid binder.

In production process (Lα), the per mole of starting compound Formulas (I-1-a) to (I-5-a) approx. 1 mol isocyanate of the formula (XVII) at 0 to 100 ° C, preferably at 20 to 50 ° C.  

Process (Lα) is preferably carried out in the presence of a diluent carried out.

All inert organic solvents are suitable as diluents, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, Amides, nitriles, sulfones or sulfoxides.

If necessary, catalysts can be added to accelerate the reaction will. As catalysts, organotin compounds, such as B. Dibutyltin dilaurate can be used.

It is preferably carried out at normal pressure.

In the production process (Lβ), the per mole of starting compound Formulas (I-1-a) to (I-5-a) approx. 1 mol of carbamic acid chloride of the formula (XVIII) 0 to 150 ° C, preferably at 20 to 70 ° C.

All inert polar come as optionally added diluents organic solvents in question such as ethers, carboxylic acid esters, nitriles, ketones, Amides, sulfones, sulfoxides or halogenated hydrocarbons.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or Methylene chloride used.

Is made in a preferred embodiment by adding strong Depro toning agents (such as sodium hydride or potassium tert-butylate) the enolate salt of the compound (I-1-a) to (I-5-a), can on the further addition of Acid binders can be dispensed with.

If acid binders are used, common inorganic or organic compounds are used African bases in question, examples include sodium hydroxide, sodium carbonate, Potassium carbonate, triethylamine or pyridine called.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses standard methods.  

The active substances are suitable for controlling animal pests preferably arthropods and nematodes, especially insects and arachnids, those in agriculture, in forests, in the protection of stocks and materials, and on occur in the hygiene sector. They are normally sensitive and resistant Species as well as against all or individual stages of development. To the above Pests mentioned include:

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

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

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

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

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

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

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

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

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

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

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

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

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

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

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

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

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

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

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

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

From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.  

Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

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

They can be used to control plants with particularly good success harmful insects, such as against the larvae of horseradish Leaf beetle (Phaedon cochleariae) or against the larvae of the green leafhopper (Nephotettix cincticeps) against the caterpillars of the cockroach (Plutella maculipennis).

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

The dosages of the inventive weed control necessary Active substances are between 0.001 and 10 kg / ha, preferably between 0.005 and 5 kg / ha.

The active compounds according to the invention can, for. B. ver used in the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotola, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyprus, Sorghum, Agropyron, Cycnodon, Monochoria, Fimbristylis, Sagittaria, Iochasumum, Pasum , Sphenoclea, Dactyloctenium, Agrostis, Alo pecurus, Apera.
Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Sachharum, Pineapple, Asparagus, Allium.

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

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

The active compounds according to the invention are very suitable for selective control Pre-and post-treatment of monocotyledonous weeds in dicotyledon crops ren. You can, for example, in cotton or sugar beet with very good Success can be used to control harmful grass.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated nated natural and synthetic substances as well as very fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner, e.g. B. by Ver mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally using surface-active agents Agents, that is emulsifiers and / or dispersants and / or foam generators resources.  

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

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

In the formulations, adhesives such as carboxymethyl cellulose, ver natural and synthetic polymers in powder, granular or latex form be used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and na natural phospholipids such as cephalins and lecithins and synthetic phos pholipid. Other additives can be mineral and vegetable oils.

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

The formulations generally contain between 0.1 and 95% by weight Active ingredient, preferably between 0.5 and 90%.

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

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

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanide; 2,6-di chloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-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, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Foleolazyl, Fuminolafil, Fulfillazol, Futolanyl, Fumolazol, Futolanyl, Futolanyl, Futolanyl, Futolanyl, Futolanyl, Futin, Futolan, Futin, Futin, Fidium Furmecyc lox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifen thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor fluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocy thrin, Chrinophhrin, Clophin Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxatophion, Fufionophon, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufox
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,
Lamda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, M 25, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, Phosphamdon, phoxim, pirimicarb, pirimiphos M, Primiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozine, Pyrachlophos, Pyradaphenthion, Pyresmethrin, pyrethrum, Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio methon, Thionazin, Thuringiensin, Tralomichonon, Triaromenontron, Triaromenontron, Triarathenlarbon, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triaromenontrin, Triarathenltronium, Triaromenontrin, Triarathenltron, Triaromenontron
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Herbicides

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

The active ingredient according to the invention can also be in its commercially available form formulations and in the application forms prepared from these formulations in a mixture with synergists. Synergists are connections through which the effect of the active ingredients is increased without the added synergist must be actively active itself.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary widely. The drug concentration the use forms can be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms Wise.

When used against hygiene and storage pests, the stands out Active ingredient through an excellent residual effect on wood and clay as well due to good stability to alkali on limed substrates.  

The active compounds according to the invention act not only against plant and hygiene and storage pests, but also against in the veterinary sector animal parasites (ectoparasites) such as tortoise ticks, leather ticks, mite mites, Running mites, flies (stinging and licking), parasitic fly larvae, lice, Hair lice, featherlings and fleas. These parasites include:

From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the subordinates Amblycerina as well Ischnocerina e.g. B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.

From the order Diptera and the subordinates Nematocerina as well Brachycerina e.g. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the Siphonapterida z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.

From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. B. Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneu monyssus spp., Sternostoma spp., Varroa spp.  

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

For example, they show excellent effectiveness against Boophilus microplus and Lucilia cuprina.

The active compounds of the formula (I) according to the invention are also suitable for combating treatment of arthropods, the farm animals, such as. B. cattle, sheep, Goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, Geese, bees, other pets such as B. dogs, cats, house birds, aqua reindeer fish and so-called experimental animals, such as B. hamsters, guinea pigs, Infect rats and mice. By fighting these arthropods are said to Deaths and reduced performance (for meat, milk, wool, skins, eggs, Honey, etc.) can be reduced, so that by using the invention Active ingredients a more economical and easier animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, Tab Latvian, capsules, watering, drenching, granules, pastes, boluses, feed-through Method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), Implan tate, by nasal application, by dermal application in the form, for example of diving or bathing (dipping), spraying (spray), pouring on (pour-on and Spot-on), washing, powdering and with the help of active ingredients Shaped bodies, such as collars, ear tags, tail tags, limb straps, Halters, marking devices etc.

When used for cattle, poultry, pets etc. you can use the active ingredients of the formula (I) as formulations (for example powders, emulsions, flowable Agents), which contain the active ingredients in an amount of 1 to 80% by weight, directly or after 100 to 10,000-fold dilution, or as a chemical Use bath.  

It has also been found that the compounds of the formula 1 show a high insecticidal activity against insects, the technical materials to destroy.

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

Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticuliterrnes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes dar winiensis, Zootermopsis nevadensis, Coptotermes formosanus.
Bristle tails like
Lepisma saccharina.

In the present context, technical materials include non-living ones To understand materials, such as preferably plastics, adhesives, glues, Pa paper and cardboard, leather, wood and wood processing products and paints.

It is very particularly preferred to protect against insect attack material around wood and wood processing products.

Among wood and wood processing products, which by the invention Agents or mixtures containing them can be protected is exemplary to understand: timber, wooden beams, railway sleepers, bridge parts, jetties, Wooden vehicles, boxes, pallets, containers, telephone poles, wooden panels,  Wooden windows and doors, plywood, chipboard, carpentry or wood pro products that are used in general in house construction or in joinery Find.

The active ingredients can be used as such, in the form of concentrates or in general usual formulations such as powders, granules, solutions, suspensions, emul sions or pastes.

The formulations mentioned can be prepared in a manner known per se be, e.g. B. by mixing the active ingredients with at least one solution or diluent, emulsifier, dispersing and / or binding or fixing agent tels, water repellants, possibly desiccants and UV stabilizers and opp if necessary dyes and pigments and other processing aids.

The insecticidal agents used to protect wood and wood-based materials or concentrates contain the active ingredient according to the invention in a concentra tration from 0.0001 to 95 wt .-%, in particular 0.001 to 60 wt .-%.

The amount of agents or concentrates used depends on the type and type come from insects and depending on the medium. The optimal amount to use can be determined by test series in the application. Generally in my opinion, however, it is sufficient 0.0001 to 20% by weight, preferably 0.001 to 10 wt .-%, of the active ingredient, based on the material to be protected.

An organic chemical solvent serves as the solvent and / or diluent solvent or solvent mixture and / or an oily or oily heavy volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agent.

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

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

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

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partly due to slightly or medium-volatile organic chemistry cal solvents are replaced, with the proviso that the solvent mix also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide fungicide Mixture is soluble or emulsifiable in this solvent mixture.

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

As an organic chemical binder in the present Er finding the known water-dilutable and / or in the used organic chemical solvents soluble or dispersing or emul gable synthetic resins and / or binding drying oils, especially binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, Polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene Coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or Resin used.  

The synthetic resin used as a binder can be in the form of an emulsion, disper sion or solution. Bitumen or bituminous substances up to 10 wt .-%, are used. In addition, you can dyes, pigments, water-repellent agents, odor cores known per se tien and inhibitors or corrosion protection agents and the like. Be used.

According to the invention, preference is given to organic chemical binders least an alkyd resin or modified alkyd resin and / or a drying one vegetable oil contained in the medium or in the concentrate. According to the invention alkyd resins with an oil content of more than 45 wt .-%, preferably as 50 to 68 wt .-%, used.

The binder mentioned can be wholly or partly by a fixation medium (mixture) or a plasticizer (mixture) can be replaced. These additions should volatilize the active ingredients and crystallize or from prevent falling. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as Dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight Gly kolether, glycerol ester and p-toluenesulfonic acid ester.

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

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

A particularly effective wood protection is provided by industrial impregnation drive, e.g. B. vacuum, double vacuum or printing process.

The ready-to-use agents can optionally also be other insecticides and optionally contain one or more fungicides.  

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

Insecticides such as chlorine can be used as very particularly preferred mixing partners pyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, delta methrin, permethrin, imidacloprid, M-25, flufenoxuron, hexaflumuron and tri flumuron, as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, Tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N- octylisothiazolin-3-one, be.

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

Manufacturing examples Example (I-1-a-1)

To 18.5 g (0.165 mol) of potassium tert-butoxide in 57 ml of anhydrous tetrahydrofuran (THF) is added dropwise at reflux temperature 25.0 g (0.072 mol) of the compound according to Example (II-2) in 150 ml of anhydrous toluene and stirred in for 1.5 hours Reflux. For working up, 220 ml of water are added and the aqueous phase is separated , the toluene phase is extracted with 110 ml of water, the aqueous phases are combined, wash it with toluene and acidify at 10 to 20 ° C with about 26 ml conc. HCl on. The product is filtered off, washed, dried and by stirring in Washed methyl tert-butyl (MTB) ether / n-hexane.

Yield: 18.0 g (79% of theory), mp: 159 ° C.

Analogously or according to the general information on the preparation, the following compounds of formula (I-1-a):  

Table 1

Example (I-1-b-1)

4.5 g (0.015 mol) of the compound according to Example (I-1-a-1) and 2.1 ml (15 mmol) Triethylamine in 70 ml of absolute methylene chloride are at 0 to 10 ° C with 1.13 ml (0.15 mol) of acetyl chloride in 5 ml of absolute methylene chloride. At Room temperature is stirred until the reaction by thin layer chromatography control has ended. For working up, twice with 50 ml of 0.5 N sodium hydroxide washed alkali, dried over magnesium sulfate and evaporated. The Rohpro product is recrystallized from MTB ether / n-hexane.

Yield: 3.4 g (66% of theory), mp: 209 ° C.

Analogously or according to the general information on the preparation, the following compounds of formula (I-b-1):  

Table 2

Example (I-1-c-1)

To 4.5 g (0.015 mol) of the compound according to Example (I-1-a-1) and 2.1 ml of tri ethylamine in 70 ml of absolute THF is added dropwise at 0 to 10 ° C. 1.5 ml (15 mmol) Chloroformic acid ethyl ester in 5 ml of absolute methylene chloride and stirred Room temperature until the reaction after thin layer chromatography control is finished. For working up, it is washed twice with 50 ml of 0.5 N sodium hydroxide solution, dried over magnesium sulfate and evaporated.

Yield: 3.3 g (59% of theory), mp: 193 ° C.

Analogously or according to the general information on the preparation, the following compounds of formula (I-1-c):  

Table 3

Example II-1

To 30.3 g (0.308 mol) conc. Sulfuric acid is carefully added dropwise at 30 to 40 ° C 17.5 g of the compound according to Example (XXIX-1) and stirred for 2 hours Temperature. Then 41 ml of absolute methanol are added dropwise so that one Set internal temperature of about 40 ° C and stir for 6 hours at 40 to 70 ° C.

For working up, pour onto 0.29 kg of ice, extracted with methylene chloride, washes with aqueous sodium bicarbonate solution, dries and evaporates. The crude product is run by column chromatography on silica gel medium methylene chloride / ethyl acetate 2: 1 cleaned.

Yield: 13.1 g (67% of theory), mp: 147 ° C.  

Example (II-2)

40.9 g (0.23 mol) of 2,4,5-trimethylphenylacetic acid and 33.6 ml (0.461 mol) Thionyl chloride are 30 minutes at room temperature and then at 50 ° C. stirred until gas evolution is complete. Excess thionyl chloride removed at 50 ° C in a vacuum. Then you add 50 ml of absolute toluene and evaporates again. The residue is taken up in 100 ml of absolute THF (Solution 1).

To 47.9 g of cis-4-methylcyclohexylamine-1-carboxylic acid methyl ester and 64.6 ml (0.460 mol) of triethylamine in 600 ml of absolute THF is added dropwise at 0 to 10 ° C. solution Solution 1 and then stirred for 1 hour at room temperature. Then is abge sucks, washed with absolute THF and evaporated. The backlog is in Methylene chloride added, washed with 0.5 N HCl, dried and concentrated steams. The crude product is obtained by column chromatography on silica gel Methylene chloride / ethyl acetate 7: 1 cleaned.

Yield: 25 g (32% of theory), mp: 158 ° C.

Analogous to Examples (II-1) and (II-2) and according to the general information the following compounds of formula (II) are prepared for the preparation.  

Table 4

Example (XXIX-1)

Starting from 17.8 g of 2,4,5-trimethylphenylacetic acid, as in Example (II-2) Solution 1 prepared.

To 16.8 g of 1-amino-tetrahydropyran-1-carbonitrile (70%) and 16.8 ml (0.12 mol) of triethylamine in 150 ml of absolute THF is added dropwise at 0 to 10 ° C. Solution 1 and stir for 1 hour at room temperature. Then it is evaporated and the residue is taken up in methylene chloride, washed with 0.5 N HCl, dries and evaporates. The crude product is recrystallized from MTB ether / n-hexane lized.

Yield: 17.5 g (61% of theory), mp: 156 ° C.  

Example (I-2-a-1)

8.42 g (75 mmol) of potassium tert-butoxide are placed in 50 ml of DMF, at 0 to 10 ° C a solution of 16.6 g (50 mmol) of 2,4,5-trimethylphenylacetic acid (1- ethyloxycarbonyl-cyclohexyl) ester according to Example (III-1) in 50 ml of DMF drips and stirred overnight at room temperature.

For working up, the reaction mixture is dropped in 500 ml of ice-cold 1N HCl, sucks off the precipitated product, washes with water and dries in a vacuum drying cabinet. For further purification, the raw product is Boiled hexane / acetone.

Yield: 9.2 g (64% of theory) of mp: 209-212 ° C.

Analogously or according to the general information on the preparation, the following compounds of formula (I-2-a):  

Table 5

Example (I-2-b-1)

2.86 g (10 mmol) of the compound according to Example I-2-a-1 are dissolved in 40 ml Dichloromethane submitted, 1.52 g (15 mmol) of triethylamine added, under Ice cooling a solution of 1.57 g (13 mmol) of pivaloyl chloride in 40 ml of dichlor added dropwise methane and stirred for 1 to 2 h at room temperature. To work up tation is washed successively with 10% citric acid, 1N NaOH and NaCl Solution, the organic phase dries over MgSO₄ and evaporated. The raw The product is stirred with a little petroleum ether for further purification.

Yield: 3.0 g (81% of theory), mp: 128-132 ° C.

Analogously or according to the general information on the preparation, the following compounds of formula (I-2-b):  

Table 6

Example (III-1)

8.9 g (50 mmol) of 2,4,5-trimethyl-phenylacetic acid are pre-charged in 50 ml of toluene lays, 11.9 g (100 mmol) of thionyl chloride are added until the chlorine has ended Hydrogen evolution stirred at 80 ° C and evaporated. The raw acid chloride is together with 8.6 g (50 mmol) of 1-hydroxy-cyclohexanecarboxylic acid ethyl ester Boiled overnight in 50 ml of toluene, then evaporated.

Yield: 18.6 g (quant.) 2,4,6-trimethyl-phenylacetic acid- (1-ethoxycarbonyl cyclohexyl) ester as a colorless oil.

Analogously or in accordance with the general regulations for the production, the the following compounds of formula (III):  

Table 7

Example (I-3-a-1)

26.0 g (60.7 mmol) of the compound according to Example (IV-1) are mixed with 55 ml Trifluoroacetic acid in 110 ml of toluene heated under reflux for 3 hours. About trifluoroacetic acid is removed in vacuo, the residue with 400 ml Water and 120 ml of MTB ether are added, pH 14 is adjusted with NaOH. Man extracted 2 times with MTB ether, acidifies the aqueous phase with concentrated HCl and extracted 3 times with MTB ether. The organic phases are dried and constricted. Yield 8.8 g (52% of theory), mp. 160 to 162 ° C.  

Example (I-3-b-1)

Approach:
1.0 g (3.6 mmol) of the compound according to Example I-3-a-1 are abs in 15 ml. Submitted methylene chloride and mixed with 0.75 ml of triethylamine. A solution of 0.82 g (4.68 mmol) 6-chloronicotinoyl chloride in 3 ml abs. Methylene chloride are added dropwise with ice cooling. The mixture is stirred at room temperature for 2 hours. It is washed twice with 10% citric acid and the combined aqueous phases are extracted with methylene chloride. The combined organic phases are washed twice with 1 N NaOH and the aqueous alkaline phases are extracted with methylene chloride. Finally, the combined organic phases are dried, concentrated and the residue is stirred with petroleum ether. Yield 1.37 g (91% of theory), mp. 123 to 126 ° C.

Analogously to Example I-3-b-1 or according to the general description, the Compounds of the formula I-3-b listed in the table below poses.

Example (I-3-c-1)

Approach:
1.0 g (3.6 mmol) of the compound according to Example I-3-a-1 are abs in 15 ml. Submitted methylene chloride and mixed with 0.75 ml (1.5 eq) triethylamine. A solution of 0.61 ml (0.64 g; 4.68 mmol) 6-chloroformate isobutyl ester in 3 ml abs. Methylene chloride is added dropwise with ice cooling. The mixture is stirred at room temperature for 2 hours. It is washed twice with 10% citric acid and the combined aqueous phases are extracted with methylene chloride. The combined organic phases are washed twice with 1 N NaOH and the aqueous alkaline phases are extracted with methylene chloride. Finally the combined organic phases are dried and concentrated.

Yield 1.32 g (97% of theory), oil.

1 H-NMR (400 MHz, DMSO):
δ = 0.60-0.70 m, 6H, CH (C H ₃) ₂
1.00-1.05 m, 3H, CH₂C H ₃
1.50-1.60 m, 1H, CH (C H ₃) ₂
1.70-1.76 d, 3H, C (C H ₃)
1.90-2.02 m, 2H CH₂C H ₃
2.05-2.20 m, 9H, ArC H ₃
3.65-3.72 m, 2H OC H₂
6.75-6.80 d, 1H, ortho Ar- H
7.01 s, 1H, meta Ar- H

Example (I-3-c-2)

Analogously to Example (I-3-c-1), the compound of formula (I-3-c-2) was used as an oil receive:

Example (IV-1)

A: 25 g (98 mmol) of the compound of the formula (XXXII-1)

1 drop of DMF with 17.5 g (147 mmol) of thionyl chloride in 100 ml Toluene for 5 minutes at room temperature and then at 100 ° C stirred until gas evolution is complete. Become volatile removed in a high vacuum.  

B: Dropwise to 18 ml (130 mmol) of diisopropylamine in 100 ml of THF Ice cooling 72 ml (118 mmol) butyllithium (1.6 M) and stir 15 more Minutes at this temperature. Then drop 18.8 g (108 mmol) of the compound according to Example (XXIV-3) dissolved in 40 ml THF at 0 ° C and stirred for 30 minutes at this temperature. Subsequently the acid chloride prepared according to A is dissolved in 40 ml THF at 0 ° C added dropwise, the mixture is stirred at room temperature for 1 hour. Then you give 350 ml MTB ether and a few drops of water, extracted 2 times with 10% Ammonium chloride solution, dries and concentrates. The raw product (40 g) is column chromatographed (eluent cyclohexane / ethyl acetate 10/1) cleaned. Yield 27.0 g (64% of theory), oil.

1 H-NMR (CDCl₃, 400 MHz):
δ: 0.80-0.95 m, 3H CH₂C H ₃
1.42 s, 3H, CC H ₃
1.65-2.05 m, 2H C H ₂CH₃
2.15-2.35 m, 9H ArC H
3.10-3.45 m, 2H SC H₂
3.70-3.80 m, 6H OC H ₃
6.70-7.30 m, 6H Ar- H

Example (I-4-a-1)

6.7 g (30 mmol) of 2- (2,4,5-trimethylphenyl) chlorocarbonyl ketene are mixed with 4.3 g (30 mmol) 4,5-dihydro-2,2,5,5-tetramethyl-3- (2H) -furanone heated to 200 ° C for 4 h. After column chromatography on silica gel with toluene / ethanol 20: 1 as the eluent 4.6 g (46% of theory) of mp: 182-184 ° C. are obtained.

Analogously or according to the general information on the preparation, the following compounds of formula (I-4-a):  

Table 8

Example (I-4-b-1)

2.5 g (7.5 mmol) of the compound (I-4-a-1) are placed in 25 ml of ethyl acetate, mixed with 0.75 g of triethylamine and at 0 ° C 0.6 g of acetyl chloride in 20 ml of vinegar added dropwise ester. The mixture is stirred at room temperature for 20 h, the precipitate is separated off, washes twice with 50 ml semi-conc. Sodium chloride solution, dries over Na trium sulfate and evaporated in vacuo. The residue is on silica gel Chromatographed toluene / acetone 50: 1.

Yield: 0.8 g (29% of theory) of mp: 143-144 ° C.

Analogous to example I-4-b-1 or according to the general information on the preparation were the compounds of the formula listed in the table below I-4-b made:  

Table 9

Example (I-4-c-1)

1.7 g (5 mmol) of the compound (I-4-a-3) are placed in 20 ml of ethyl acetate, 0.5 g (5 mmol) of triethylamine were added and 0.5 g (5 mmol) of chlorine at 0 ° C methyl formate added dropwise in 5 ml of ethyl acetate. Stir for 20 hours Room temperature, separates the precipitate, washes twice with 50 ml concentrated sodium chloride solution, dries over sodium sulfate and evaporates in Vacuum on. The residue is chromato on silica gel with toluene / acetone 30/1 graphed. Yield 1.0 g (51% of theory) of melting point 144 to 146 ° C.

Analogously or according to the general information on the preparation, the following compounds of formula (I-4-c):  

Table 10

Example (I-5-a-1)

2.2 g (10 mmol) of 2- (2,4,5-trimethylphenyl) chlorocarbonyl ketene are mixed with 1.6 g (10 mmol) 4-fluorothiobenzamide in 80 ml of toluene heated to 50 ° C for 6 hours. Of the The precipitate is separated off, washed with cyclohexane and dried. Man receives 2.8 g (82% of theory) of melting point 215 to 216 ° C.

Example (XXIII-1)

To a mixture of 100 g (1.785 mol) KOH in 130 ml water and 260 ml Methanol is added dropwise at room temperature to 247 g (1.162 mol) of the compound according to Example (XXIV-1) (75%) and heated under reflux for 5 hours. After cooling is diluted with 300 ml of water and with ethyl acetate extracted. The aqueous phase is acidified with half-concentrated hydrochloric acid Suction filtered and dried.

Yield: 77 g (45% of theory), m.p .: 119-121 ° C.  

Example (XXIII-2)

Analogously to Example (XXIII-1), 2,4,5-trichlorophenylacetic acid, mp: 112-115 ° C.

Preparation of 2,4,5-trimethyl-phenylacetic acid

Example (XXIII-3)

286 g (1.4 mol) of 66% 1,2,4,5-tetramethylbenzene are dissolved in 563 ml of tetrachlor carbon dissolved and in succession at room temperature 27.5 g (0.15 mol) of N- Bromosuccinimide and 0.4 g benzoyl chloride entered. It is heated to 80 ° C and 248 g (1.39 mol) of N-bromosuccinimide were added in portions. After that leaves stirring for a further 30 minutes at 80 ° C. and then cooling Room temperature. The solid is suctioned off and the solvent is added Withdrawn 20 mbar over a solid bridge. Then you distill the Residue in a high vacuum and receives 226 g (66% of theory) 2,4,5-trimethyl  benzyl bromide with a bp of 95 ° C at 0.05 mbar and a purity of 86%.

To a solution of 57 g (1.16 mol) sodium cyanide in 63 ml water and 0.6 g Aliquat 336 is a solution of 226 g (0.91 mol) 2,4,5- Trimethyl benzyl bromide (86%) was added dropwise in 94 ml of toluene and then 4 hours stirred at 80 ° C. After cooling to room temperature, the Pha separated and the organic phase twice with water and twice with saturated NaCl solution washed, dried and concentrated. After 103 g (70%) of 2,4,5-trimethyl-benzyl cyanide are obtained with a distillation Purity of 99% and a boiling point of 120 ° C at 0.2 mbar.

2118 ml of concentrated sulfur become 2662 ml of water at room temperature acid dropped and the solution heated to 90 ° C. Dosed at this temperature 355 g (2.23 mol) of 2,4,5-trimethyl-benzyl cyanide were added to the semi-concentrated Sulfuric acid and stirred for 8 hours at 100 ° C. After cooling, give the reaction mixture with vigorous stirring in ice water and suction. The feast fabric is washed several times with water and then with petroleum ether and dried 16564 00070 552 001000280000000200012000285911645300040 0002019602524 00004 16445et. 358 g (90% of theory) of 2,4,5-trimethylphenylacetic acid are obtained with a melting point of 123-125 ° C.  

Example (XXIV-1)

To dissolve 347 g (0.948 mol) of the compound according to Example (XXV-1) (74.3%) in 410 ml of methanol, 700 ml of one is dropped at room temperature 30% methanolic solution of sodium methylate, heated for 5 hours Reflux, cools to room temperature and drops 110 ml conc. Sulfuric acid too. The mixture is boiled under reflux for one hour, the methanol is distilled off and the is taken solid residue in water. The organic phase is separated off and extracted the aqueous phase twice with 1.5 l of methylene chloride. The united organic Phases are dried over Na₂SO₄ and concentrated.

Yield: 247 g of a dark oil containing 92% of theory 75% (GC).

Example (XXIV-2)

Analogously to Example (XXIV-1), 2,4,5-trichlorophenylacetic acid methyl is obtained ester as a dark oil in a yield of 95% of theory and a purity of 80% (GC).  

Example (XXV-1)

To the well-cooled mixture of 229.7 g (2.272 mol) tert-butyl nitrite and 254.8 g (1.775 mol) of anhydrous copper (II) chloride in 990 ml of anhydrous acetonitrile 2205 g (22.7 mol) of 1,1-dichloroethene are added dropwise, opening the mixture keeps below 30 ° C. Then at a temperature below 30 ° C a mixture from 232 g (1.49 mol) of 4-chloro-2,5-dimethylaniline and 1500 ml of anhydrous aceto added dropwise nitrile. At room temperature until the end of gas evolution stirred, the mixture was then carefully poured into 6 l of 20% HCl and several times extracted with a total of 6 l of methyl tert-butyl ether (MTBE). The united organization African phases are washed with 20% HCl, dried and concentrated. The remaining oil was rectified.

Yield: 347 g dark oil 63% of theory with a content of 74% (GC).

Example (XXV-2)

Analogously to Example (XXV-1) 2- (2,4,5-trichlorophenyl) -1,1,1-trichlor were obtained ethane in the form of a dark oil in a yield of 81% of theory and grading 78%.  

Synthesis of 2,4,5-trimethylphenylcarbonyl ketene 2,4,5-Trimethylphenylacetic acid methyl ester

There were 100 g (0.56 mol) of 2,4,5-trimethylphenylacetic acid in 230 ml of methanol dissolved, mixed with 6 ml of concentrated sulfuric acid and 10 hours to return river heated. The mixture was then cooled to room temperature and the methanol removed in vacuum. The residue was dissolved in a solution of 53 g sodium carbonate, dissolved in 260 ml of water, stirred in and the organic phase in 200 ml Toluene added. The organic phase was separated off, dried and concentrated narrowed and distilled. 48.6 g of methyl 2,4,5-trimethylphenylacetate were obtained obtained with a boiling point of 86 ° C at 0.2 mbar.

2- (2,4,5-Trimethylphenyl) malonic acid dimethyl ester

There were 18.6 g (0.62 mol, 80%) sodium hydride in 384 ml of dimethyl carbonate submitted and heated to about 80 ° C. Then 48 g (0.25 mol) of 2,4,5- Trimethylphenylacetic acid methyl ester, dissolved in 100 ml of dimethyl carbonate, added drips and heated to reflux for 4 hours. The mixture was at room temperature temperature cooled, the excess sodium hydride destroyed with ethanol and then poured into 1500 ml of ice water. With 6 N hydrochloric acid a pH of 4 to 5 and the organic phase taken up with toluene. The orga African phase was separated, dried, concentrated and without further purification used in the next stage. 51.6 g of 2- (2,4,5-trimethylphenyl) - malonic acid dimethyl ester obtained as an oil.

1 H-NMR (CDCl₃): δ = 7.12 (s, 1H); 6.98 (s, 1H); 4.84 (s, 1H); 3.75 (s, 6H); 2.27 (s, 3H); 2.23 (s, 3H); 2.21 ppm (s, 3H).  

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

To a mixture of 180 ml of methanol and 38.1 g (0.68 mol) of potassium hydroxide, dissolved in 92 ml of water, 51.6 g (0.21 mol) of 2- (2,4,5- Trimethylphenyl) malonic acid dimethylester added dropwise. Then five Heated to reflux, then cooled back to room temperature and constricted.

The residue was stirred into ice water and washed with a little toluene. The aqueous solution was cooled down with concentrated hydrochloric acid acidified to a pH of 1, the precipitate was suction filtered and dried. It 30.3 g of 2- (2,4,5-trimethylphenyl) malonic acid were obtained.

1 H-NMR (d₆-DMSO): δ = 7.03 (s, 1H); 6.95 (s, 1H); 4.66 (s, 1H); 2.17 (s, 3H); 2.16 ppm (s, 6H).

2,4,5-trimethylphenylchlorocarbonyl ketene

There were 30 g of 2- (2,4,5-trimethylphenyl) malonic acid in 60 ml of toluene at 50 to Suspended 60 ° C and added dropwise with 62.5 ml of thionyl chloride. The Wed Schung was then heated to 90 to 100 ° C for 15 hours. After that was cooled, the volatile constituents expelled with protective gas and that over distilled off thionyl chloride. 30.6 g of 2,4,5-tri isolated methylphenylchlorocarbonyl ketene.

1 H-NMR (CDCl₃): δ = 7.07 (s, 2H); 2.27 (s, 3H); 2.22 (s, 3H); 2.21 ppm (s, 3H).  

Examples of use Example A Phaedon larval test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

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

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

In this test, e.g. B. the compounds according to the preparation examples I-4-b-1 and I-4-a-4 at an exemplary active ingredient concentration of 0.1% 100% kill after 7 days.  

Example B Plutella test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

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

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

In this test, e.g. B. the compounds according to the preparation examples I-1-a-1, I-1-b-2, I-1-c-1, I-4-a-3, I-4-a-1, I-4-b-1 and I- 4-a-4 in an exemplary active ingredient concentration of 0.1%, killing of 100% after 7 days.  

Example C Spodoptera test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the owl butterfly (Spodoptera frugiperda) occupied while the leaves are still moist.

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

In this test, e.g. B. the compounds according to the preparation examples I-1-a-1, I-1-b-2, I-4-a-3, I-4-a-1, I-4-b-1 and I-4-a-4 in an exemplary Active ingredient concentration of 0.1% and 100% killed after 7 days.  

Example D Nephotettix test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Rice seedlings (Oryza sativa) are immersed in the active ingredient preparation desired concentration and treated with the green rice leafhopper (Nephotettix cincticeps) when the seedlings are still moist.

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

In this test, e.g. B. the compounds according to the preparation 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-4-a-3 and I-4-a-4 at an exemplary drug concentration of 0.1% kills 100% after 6 days.  

Example E Myzus test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

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

After the desired time, the kill is determined in%. Here means 100% that all aphids have been killed, 0% means that no aphids ab were killed.

In this test, e.g. B. the compounds according to the preparation examples I-2-a-1, I-2-b-4, I-1-b-2, I-1-b-3, I-1-c-2 and I-4-a-4 in an exemplary Active ingredient concentration of 0.1%, killing 100% after 6 days.  

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

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

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

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

In this test, e.g. B. the compounds according to the preparation examples I-2-b-2, I-2-b-1, I-1-b-2 and I-4-b-1 at an exemplary drug concentration of 0.1% a killing of at least 98% after 13 days.  

Example G Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Seeds of the test plants are sown in normal soil and after 24 hours doused with the active ingredient preparation. You keep the amount of water per Area unit expediently constant. The drug concentration in the Preparation does not matter, the only decisive factor is the application rate of the Active ingredient per unit area.

After three weeks, the degree of damage to the plants is rated in% Damage compared to the development of the untreated control.

It means:
0% = no effect (like untreated control)
100% = total annihilation.

In this test, e.g. B. the connection according to the manufacturing example I-4-a-3 with an exemplary application rate of 500 g / ha and good Tolerability due to beta vulgaris damage of 90% in Alopecurus myosuroides, 96% in Avena fatua and 95% in Setaria viridis.  

Example H Test with fly larvae / development-inhibiting effect

Test animals: All larval stages of Lucilia cuprina (OP-resistant) [dolls and adults (without contact with the active ingredient)]
Solvent: 35 parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether

Three weights are mixed to prepare a suitable formulation parts of active ingredient with seven parts of the solvent emulsifier specified above Mix and dilute the emulsion concentrate thus obtained with water to desired concentration.

30 to 50 larvae per concentration are on horses in glass tubes deflected (1 cm³), to which 500 µl of the dilution to be tested pi be petted. The glass tubes are placed in plastic cups Floor is covered with sea sand, and in an air-conditioned room (26 ° C ± 15 ° C, 70% rel. Humidity ± 10%). The effects are checked after 24 hours and 48 hours (larvicidal activity). After the larvae migrate (approx. 72 h) the glass tubes are removed and perforated plastic lids on the beakers set. After 1 1/2 times the development time (hatching of the control flies) who which the hatched flies and the dolls / doll covers counted.

The criterion for the effect is the occurrence of death in the treated lar ven after 48 h (larvicidal effect), or the inhibition of adult hatching from the Dolls or the inhibition of doll formation. As a criterion for in vitro The effect of a substance is the inhibition of flea development or an ent development standstill before the adult stage. 100% means larvicidal Effect that all larvae have died after 48 hours. 100% development lungsinhibitory effect means that no adult flies have hatched.

In this test, e.g. B. the compound according to preparation example I-4-a-1 with an exemplary active ingredient concentration of 1000 ppm, an effect of 100%.  

Example I Test with Boophilus miicroplus resistant / SP-resistant Parkhurst strain

Test animals: adult sucked females
Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide, lower concentration ions are prepared by dilution in the same solvent.

The test is carried out in 5-fold determination. 1 µl of the solutions is added to the Abdomen injected, the animals transferred into bowls and in an air-conditioned Saved space. The effect is determined by the inhibition of egg laying. 100% means that no tick has laid.

In this test, e.g. B. the compounds according to the preparation examples I-4-a-1 and I-4-b-1 at an exemplary drug concentration of 20 ug per Animal an effect of 100%.

Claims (18)

1. Compounds of formula (I) in which
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, cyano or nitro,
Y represents hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cyano or nitro,
Z represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, hydroxy, cyano, nitro or in each case optionally substituted phenoxy, phenylthio, 5- to 6-membered hetaryloxy, 5- to 6-membered hetarylthio, phenylalkyloxy or phenylalkylthio,
Y and Z together with the carbon atoms to which they are attached represent an optionally substituted cycle which may be interrupted by heteroatoms, where X has one of the meanings mentioned above,
Het for one of the groups wherein
A for hydrogen, for in each case optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or alkylthioalkyl, for in each case saturated or unsaturated and optionally substituted cycloalkyl or heterocyclicl or for in each case optionally by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano or nitro substituted aryl, arylalkyl or hetaryl,
B represents hydrogen, alkyl or alkoxyalkyl, or
A and B together with the carbon atom to which they are attached represent a saturated or unsaturated, optionally substituted carbocycle or heterocycle,
D represents hydrogen or an optionally substituted radical from the series consisting of alkyl, alkenyl, alkynyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl, saturated or unsaturated heterocyclyl, arylalkyl, aryl, hetarylalkyl or hetaryl or
A and D together with the atoms to which they are attached represent an optionally substituted carbocycle or heterocycle,
G for hydrogen (a) or for one of the groups stands,
wherein
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R 1 represents in each case optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl or for in each case optionally substituted by halogen, alkyl or alkoxy cycloalkyl or heterocyclicl or for optionally substituted or unsubstituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R² represents in each case optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl, phenyl or benzyl,
R³, R⁴ and R⁵ independently of one another each represent optionally substituted by halogen alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio or represent optionally substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another are hydrogen, each optionally substituted by halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, each optionally substituted phenyl or benzyl, or together with the N atom to which they are attached, one optionally form oxygen or sulfur-containing optionally substituted cycle. 2. Compounds of formula (I) according to claim 1, in which
X represents halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, cyano or nitro,
Y represents hydrogen, halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, cyano or nitro,
Z represents halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, hydroxy, cyano, nitro or in each case optionally by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy , C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, nitro or cyano substituted phenoxy, phenylthio, thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy, phenyl-C₁-C₄-alkyloxy or phenyl-C₁-C₄-alkylthio, or
Y and Z together with the carbon atoms to which they are attached represent a C₃-C₅alkanediyl or C₃-C₅alkenediyl optionally substituted by halogen, C₁-C₆-alkyl, C₁-C Alkalkoxy or C₁-C₄-haloalkyl , in which one to three members can optionally be replaced independently of one another by oxygen, sulfur, nitrogen or a carbonyl group, where X has one of the meanings mentioned above.
Het for one of the groups A for hydrogen, each optionally substituted by halogen C₁-C₁₂-alkyl, C₂-C₈-alkenyl, C₁-C₁₀-alkoxy-C₁-C₈-alkyl, poly-C₁-C₈-alkoxy-C₁-C₈-alkyl or C₁ -C₁ ₀-alkylthio-C₁-C₆-alkyl, for each optionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy substituted C₃-C₈-cycloalkyl, in which optionally one or two methylene groups by oxygen and / or sulfur are replaced or for phenyl, naphthyl, phenyl-C₁-C₆-alkyl optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, cyano or nitro, Naphthyl-C₁-C₆-alkyl or hetaryl with 5 or 6 ring atoms and one to three heteroatoms from the series consisting of oxygen, sulfur and nitrogen,
B represents hydrogen, C₁-C₁₂-alkyl or C₁-C₈-alkoxy-C₁-C₆-alkyl,
A, B and the carbon atom to which they are attached represent C₃-C₁₀ cycloalkyl or C₅-C₁₀ cycloalkenyl, in which a methylene group is optionally replaced by oxygen or sulfur and which is optionally replaced by C₁-C₈-alkyl, C₃-C₁₀- Cycloalkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio, halogen or phenyl are substituted or
A, B and the carbon atom to which they are attached are C₅-C₆-cycloalkyl, which is substituted by an alkylene diyl group which may contain one or two oxygen and / or sulfur atoms, or by an alkylene dioxyl or by an alkylene dithioyl group which forms a further five- to eight-membered ring with the carbon atom to which it is attached or
A, B and the carbon atom to which they are attached are C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, in which two substituents together with carbon atoms to which they are attached, each optionally by C₁-C₆-alkyl , C₁-C₆-alkoxy or halogen-substituted C₃-C₆-alkanediyl, C₃-C₆-alkanediyl or C₄- C₆-alkanediediyl, where in each case a methyl group is optionally replaced by oxygen or sulfur,
D for hydrogen, for each optionally substituted by halogen C₁-C₁₂-alkyl, C₃-C C-alkenyl, C₃-C₈-alkynyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl, poly-C₁-C₈-alkoxy-C₂ -C₈-alkyl or C₁-C₁₀-alkylthio- C₂-C₈-alkyl, for C₃-C₈-cycloalkyl optionally substituted by halogen, C₁-Coxy-alkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkyl, in which optionally a or two not directly adjacent methylene groups are replaced by oxygen and / or sulfur or for phenyl optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, cyano or nitro , Hetaryl with 5 to 6 ring atoms and one or two heteroatoms from the series oxygen, sulfur and nitrogen, phenyl-C₁-C₆-alkyl or hetaryl-C₁-C₆-alkyl with 5 to 6 ring atoms and one or two heteroatoms from the series oxygen , Sulfur and nitrogen stands or
A and D together represent a C₃-C₆-alkanediyl, C₃-C₆-alkenediyl or C₄- C₆-alkadienediyl group, in which a methylene group is optionally replaced by oxygen or sulfur and which are each optionally substituted by halogen or in each case optionally halogen-substituted C₁-C₁₀-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, phenyl or benzyloxy or by another C₃-C₆-alkanediyl-, C₃-C₆- forming a fused ring Alkenediyl or C₄-C₆-alka diendiyl group, in which in each case one methyl group is replaced by oxygen or sulfur and which are optionally substituted by C₁-C₆-alkyl, or
A and D together represent a C₃-C₆-alkanediyl or C₃-C₆-alkendiyl group, each of which optionally includes one of the following groups is included
G for hydrogen (a) or for one of the groups in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M represents oxygen or sulfur,
R¹ for each optionally substituted by halogen C₁-C₂₀- alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl or poly-C₁-C₈-alkoxy -C₁-C₈-alkyl or C₃-C₈-cycloalkyl optionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy, in which one or two methylene groups are optionally replaced by oxygen and / or sulfur,
for phenyl optionally substituted by halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C--alkoxy, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or C₁-C₆-alkylsulfonyl,
for phenyl-C₁-C₆-alkyl optionally substituted by halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁ C₆-haloalkoxy,
for 5- or 6-membered hetaryl optionally substituted by halogen or C₁-C₆alkyl and having one or two heteroatoms from the series consisting of oxygen, sulfur and nitrogen,
for phenoxy-C₁-C₆-alkyl optionally substituted by halogen or C₁-C₆-alkyl or
represents 5- or 6-membered hetaryloxy-C₁-C₆-alkyl with one or two heteroatoms from the series consisting of oxygen, sulfur and nitrogen, optionally substituted by halogen, amino or C₁-C₆-alkyl,
R² is in each case optionally substituted by halogen C₁-C₂₀- alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl or poly-C₁-C₈- alkoxy-C₂-C₈-alkyl,
for C₃-C₈-cycloalkyl optionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy or
represents phenyl or benzyl optionally substituted by halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy,
R³ represents C₁-C₈-alkyl optionally substituted by halogen or in each case optionally substituted by halogen, C₁-C gegebenenfalls-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, cyano or nitro, phenyl or benzyl,
R⁴ and R⁵ independently of one another each optionally substituted by halogen C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkyl amino, di- (C₁-C₈-alkyl) amino, C₁-C₈-alkylthio or C₃-C₈ -Alkenyl thio or for each optionally halogen, nitro, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-halo genalkylthio, C₁-C₄-alkyl or C₁-C₄-haloalkyl substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another for hydrogen, for in each case optionally substituted by halogen C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyl or C₁-C₈-alkoxy-C₂- C₈-alkyl, are each optionally substituted by halogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl or C₁-C₈-alkoxy or phenyl or benzyl or together represent a C₃-C₆-alkylene radical optionally substituted by C₁-C₆-alkyl, in which optionally one Methylene group is replaced by oxygen or sulfur,
R¹³ for hydrogen or in each case optionally substituted by halogen C₁-C₈-alkyl or C₁-C₈-alkoxy, for optionally substituted by halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy C₃-C₈-cycloalkyl, in which optionally a methylene group by Oxygen or sulfur is replaced, or for each optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, nitro or cyano, phenyl-C₁-C₄- is alkyl or phenyl-C₁-C₄-alkoxy,
R¹⁴ represents hydrogen or C₁-C₈ alkyl or
R¹³ and R¹⁴ together represent C₄-C₆-alkanediyl,
R¹⁵ and R¹⁶ are the same or different and are C₁-C₆ alkyl or
R¹⁵ and R¹⁶ together represent a C₂-C₄-alkanediyl radical, optionally by C₁-C₆-alkyl or by optionally by halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄ Haloalkoxy, nitro or cyano substituted phenyl is substituted,
R¹⁷ and R¹⁸ independently of one another for hydrogen, for optionally substituted by halogen C₁-C₈-alkyl or for optionally by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, nitro or Cyano substituted phenyl or
R¹⁷ and R¹⁸ together with the carbon atom to which they are attached represent C₅-C₇-cycloalkyl optionally substituted by C₁-C₄-alkyl, in which a methylene group is optionally replaced by oxygen or sulfur,
R¹⁹ and R²⁰ independently of one another for C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₁₀-alkoxy, C₁-C₁₀-alkylamino, C₃-C₁₀-alkenylamino, di- (C₁- C₁₀-alkyl) amino or di- ( C₃-C₁₀-alkenyl) amino. 3. Compounds of formula (I) according to claim 1, in which
X represents fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, cyano or nitro,
Y represents hydrogen, fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, cyano or nitro,
Z for fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂- haloalkyl, C₁-C₂-haloalkoxy, hydroxy, cyano, nitro or in each case optionally by fluorine, chlorine, bromine, C₁-C₄ -Alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, nitro or cyano substituted phenoxy or benzyloxy or
Y and Z together with the carbon atoms to which they are bonded for C₃-C₄alkanediyl or C₃-C₄ optionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄alkoxy or C₁-C₂-haloalkyl -Alkenediyl, in which one or two non-directly adjacent members can optionally be replaced independently by oxygen, sulfur or nitrogen, where X has one of the meanings mentioned above,
Het for one of the groups A for hydrogen, for each optionally substituted by fluorine or chlorine C₁-C₁₀ alkyl, C₂-C₆ alkenyl, C₁-C₈-alkoxy-C₁-C₆-al kyl, poly-C₁-C₆-alkoxy-C₁-C₆-alkyl or C₁-C₈-alkylthio-C₁-C₆- alkyl or for C₃-C₇-cycloalkyl optionally substituted by fluorine, chlorine, C₁-C₄-alkyl or C₁-C₄-alkoxy, in which optionally one or two methylene groups are substituted by oxygen and / or sulfur are replaced or for phenyl, furanyl, pyridyl, imidazolyl, each substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, cyano or nitro , Triazolyl, pyrazolyl, indolyl, thiazolyl, thienyl or phenyl-C₁-C₄-alkyl,
B represents hydrogen, C₁-C₁₀-alkyl or C₁-C₆-alkoxy-C₁-C₄-alkyl or
A, B and the carbon atom to which they are attached represent C₃-C₈- cycloalkyl or C₅-C₈-cycloalkenyl, in which case a methylene group is optionally replaced by oxygen or sulfur and which is optionally replaced by C₁-C₆-alkyl, C₃- C₈- cycloalkyl, C₁-C₃-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, fluorine, chlorine or phenyl are substituted or
A, B and the carbon atom to which they are attached represent C₅-C₆-cycloalkyl which is substituted by an alkylene diyl group which may contain one or two oxygen or sulfur atoms, or by an alkylene dioxyl or by an alkylene dithiol group, which forms a further five- to seven-membered ring with the carbon atom to which it is attached or
A, B and the carbon atom to which they are attached are C₃-C₆- cycloalkyl or C₅-C₆-cycloalkenyl, in which two substituents together with the carbon atoms to which they are attached, each optionally by C₁-C₄ -Alkyl, C₁-C₄-alkoxy, fluorine, chlorine or bromine-substituted C₃-C₅-alkanediyl, C₃-C oder-alkenediyl or butadiene diyl, where in each case one methylene group is optionally replaced by oxygen or sulfur,
D for hydrogen, for C₁-C₁₀-alkyl, C₃-C₁-alkenyl, C₃-C₆-alkynyl, C₁-C₈-alkoxy-C₂-C₆-alkyl, poly-C₁-C₆-alkoxy- each optionally substituted by fluorine or chlorine C₂-C₆-alkyl or C₁-C₈- alkylthio-C₂-C₆-alkyl, optionally substituted by fluorine, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₂-haloalkyl, C₃-C₇-cycloalkyl, in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and / or sulfur or for each optionally by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁- C₄- Halogenalkoxy, cyano or nitro substituted phenyl, furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl, triazolyl or phenyl-C₁-C₄-alkyl or
A and D together represent a C₃-C₅-alkanediyl or C₃-C₅-alkene diyl group, in which in each case one carbon atom is optionally replaced by oxygen or sulfur and which are optionally substituted by fluorine, chlorine or by each optionally by fluorine or Chlorine substituted C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, phenyl or benzyloxy or
where in each case one of the following groups: is included;
G for hydrogen (a) or for one of the groups in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M represents oxygen or sulfur,
R¹ for C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl or poly-C₁-C₆ each optionally substituted by fluorine or chlorine -alkoxy-C₁-C₆-alkyl or for C₃-C₇-cycloalkyl optionally substituted by fluorine, chlorine, C₁-C₅-alkyl or C₁-C₅-alkoxy, in which one or two methylene groups are optionally replaced by oxygen and / or sulfur,
for phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl, C₁-C₃-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-alkylsulfonyl ,
for phenyl-C₁-C,-alkyl optionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy,
for each pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl optionally substituted by fluorine, chlorine, bromine or C₁-C₄ alkyl,
for optionally substituted by fluorine, chlorine, bromine or C₁-C₄-alkyl phenoxy-C₁-C₅-alkyl or
represents in each case optionally substituted by fluorine, chlorine, bromine, amino or C₁-C₄-alkyl pyridyloxy-C₁-C₅-alkyl, pyrimidyloxy-C₁-C₅-alkyl or thiazolyloxy-C₁-C₅-alkyl,
R² is in each case optionally substituted by fluorine or chlorine, C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl or poly-C₁-C₆-alkoxy-C₂-C₆-alkyl,
for C₃-C₇-cycloalkyl optionally substituted by fluorine, chlorine, C₁-C₄-alkyl or C₁-C₄-alkoxy or
represents phenyl or benzyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkyl or C₁-C₃- haloalkoxy,
R³ for optionally substituted by fluorine or chlorine C₁-C₆-alkyl or in each case optionally by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkoxy, C₁-C₂-haloalkyl, cyano or nitro substituted phenyl or benzyl,
R⁴ and R⁵ independently of one another, each optionally substituted by fluorine or chlorine, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkyl amino, di- (C₁-C₆-alkyl) amino, C₁-C₆-alkylthio or C₃ -C₄-alkenyl thio or for each optionally by fluorine, chlorine, bromine, nitro, cyano, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, C₁-C₃-alkyl thio, C₁-C₃-haloalkylthio, C₁-C₃-alkyl or C₁-C₃-haloalkyl substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another for hydrogen, each optionally substituted by fluorine or chlorine C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl or C₁-C₆-alk oxy-C₂-C₆ -alkyl, optionally substituted by fluorine, chlorine, bromine, C₁-C₅-haloalkyl, C₁-C₅-alkyl or C₁-C₅-alkoxy-substituted phenyl or benzyl, or together for a C₃ optionally substituted by C₁-C₄-alkyl -C₆-alkylene radical, in which a methylene group is optionally replaced by oxygen or sulfur,
R¹³ for hydrogen or in each case optionally substituted by fluorine or chlorine C₁-C₆-alkyl or C₁-C₆-alkoxy, for optionally substituted by fluorine, C₁-C₂-alkyl or C₁-C₂-alkoxy C₃-C₇-cycloalkyl, in which optionally a Methylene group is replaced by oxygen or sulfur or phenyl, phenyl, substituted by fluorine, chlorine, bromine, C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₂- haloalkyl, C₁-C₂-haloalkoxy, nitro or cyano Is C₁-C₃-alkyl or phenyl-C₁-C₂-alkyloxy,
R¹⁴ represents hydrogen or C₁-C₆-alkyl or
R¹³ and R¹⁴ together represent C₄-C₆-alkanediyl,
R¹⁵ and R¹⁶ are the same or different and are C₁-C₄ alkyl or
R¹⁵ and R¹⁶ together represent a C₂-C₃-alkanediyl radical, which may be by C₁-C₄-alkyl or optionally by fluorine, chlorine, bromine, C₁-C₂-alkyl, C₁-C₂-haloalkyl, C₁-C₂-alkoxy, C₁-C₂-haloalkoxy, nitro or cyano substituted phenyl is substituted. 4. Compounds of formula (I) according to claim 1, in which
X represents fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, isobutyl, isopropyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro,
Y for hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro stands,
Z represents fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, isobutyl, isopropyl, tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro, or
Y and Z together with the carbon atoms to which they are attached represent C₃-C₄alkanediyl optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, iso-propoxy or trifluoromethyl, in which two non-directly adjacent members are optionally replaced by oxygen, where X has one of the meanings mentioned above,
Het for one of the groups A for hydrogen, for in each case optionally substituted by fluorine or chlorine C₁-C₈-alkyl, C₂-C₄-alkenyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, poly-C₁-C₄-alkoxy-C₁-C₄-alkyl or C₁-C₆-alkylthio-C₁-C₄- alkyl, or for C₃-C₆-cycloalkyl optionally substituted by fluorine, chlorine, methyl or methoxy, in which case one or two methylene groups are replaced by oxygen and / or sulfur or for each optionally phenyl, pyridyl or benzyl substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
B represents hydrogen, C₁-C₈-alkyl or C₁-C₄-alkoxy-C₁-C₂-alkyl or
A, B and the carbon atom to which they are attached represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, in which case a methylene group is optionally replaced by oxygen or sulfur and which is optionally replaced by methyl, ethyl, n-propyl, iso-propyl, butyl, iso-butyl, sec.-butyl, tert.-butyl, cyclohexyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, iso-butoxy, sec.-butoxy, tert.- Butoxy, methylthio, ethylthio, fluorine, chlorine or phenyl are substituted or
A, B and the carbon atom to which they are attached are C₅-C₆-cycloalkyl, which is substituted by an alkylene diyl group which may contain an oxygen or sulfur atom or by an alkylenedioxyl group which is linked to the carbon atom to which it is bound, forms a further five- or six-membered ring or
A, B and the carbon atom to which they are attached represent C₃-C₆- cycloalkyl or C₅-C₆-cycloalkenyl, in which two substituents together with the carbon atoms to which they are attached represent C₃-C₄alkanediyl, C₃-C₄-alkenediyl or butadienediyl, in each of which a methylene group is optionally replaced by oxygen or sulfur,
D for hydrogen, for in each case optionally substituted by fluorine or chlorine, C₁-C Alkyl-alkyl, C₃-C₄-alkenyl, C₃-C₄-alkynyl, C₁-C,-alkoxy-C₂-C₄-alkyl, poly-C₁-C₄-alkoxy- C₂-C₄-alkyl, C₁-C₄-alkyl thio-C₂-C₄-alkyl or C₃-C₆-cycloalkyl, in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and / or sulfur or, if appropriate, by fluorine , Chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro substituted phenyl, furanyl, pyridyl, thienyl or benzyl,
or
A and D together represent a C₃-C₅-alkanediyl or C₃-C₅-alkenediyl group, in which a methylene group is optionally replaced by oxygen or sulfur and which is optionally substituted by fluorine, chlorine or by C₁ optionally substituted by fluorine or chlorine -C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄- alkylthio, C₃-C₆-cycloalkyl, phenyl or benzyloxy are substituted,
G for hydrogen (a) or for one of the groups in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M represents oxygen or sulfur,
R¹ for each optionally substituted by fluorine or chlorine C₁-C₁₄ alkyl, C₂-C₁₄ alkenyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₆-alkyl, poly-C₁-C₄ -alkoxy-C₁-C₄-alkyl or optionally by fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, methoxy, ethoxy, n-propoxy or iso -Propoxy-substituted C₃-C₆-cycloalkyl in which one or two methylene groups are optionally replaced by oxygen and / or sulfur,
for phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl,
for benzyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
for furanyl, thienyl or pyridyl, each optionally substituted by fluorine, chlorine, bromine, methyl or ethyl,
for optionally substituted by fluorine, chlorine, methyl or ethyl phenoxy-C₁-C₄-alkyl or
represents in each case optionally substituted by fluorine, chlorine, amino, methyl or ethyl pyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C₄-alkyl or thiazolyloxy-C₁-C₄-alkyl,
R² is in each case optionally substituted by fluorine or chlorine, C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₂-C₆-alkyl or poly-C₁-C₄-alkoxy-C₂-C₆-alkyl,
for C₃-C₆-cycloalkyl optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or methoxy,
or represents phenyl or benzyl optionally substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
R³ for methyl, ethyl, propyl, isopropyl, butyl, tert-butyl which is optionally substituted by fluorine or chlorine, or in each case optionally by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, Ethoxy, iso-propoxy, trifluoromethyl, trifluoromoxy, cyano or nitro substituted phenyl or benzyl,
R⁴ and R⁵ independently of one another, each optionally substituted by fluorine or chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkyl amino, di- (C₁-C₄-alkyl) amino or C₁-C₄-alkylthio or for are each optionally substituted by fluorine, chlorine, bromine, nitro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy, phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another for hydrogen, each optionally substituted by fluorine or chlorine, C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₃-C₄-alkenyl or C₁-C₄-alkoxy-C₂-C₄ -alkyl, each for phenyl or benzyl optionally substituted by fluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl, or together for an optionally substituted by methyl or ethyl C₅-C₆-alkylene radical, in which, if appropriate, a methylene group by oxygen or sulfur he is is. 5. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that to obtain

• (A) compounds of the formula (I-1-a) in which
  A, B, X, Y and Z have the meanings given in claim 1,
  Compounds of formula (II) in which
  A, B, X, Y and Z have the meanings given in claim 1,
  and
  R⁸ represents alkyl,
  intramolecularly condensed in the presence of a diluent and in the presence of a base,
• (B) compounds of the formula (I-2-a) in which
  A, B, X, Y and Z have the meanings given above,
  Compounds of formula (III) in which
  A, B, X, Y, Z and R⁸ have the meanings given above,
  intramolecularly condensed in the presence of a diluent and in the presence of a base,
• (C) compounds of the formula (I-3-a) in which
  A, B, X, Y and Z have the meanings given above,
  Compounds of formula (IV) in which
  A, B, X, Y, Z and R⁸ have the meanings given above and
  W represents hydrogen, halogen, alkyl or alkoxy,
  optionally cyclized intramolecularly in the presence of a diluent and in the presence of an acid,
• (D) compounds of the formula (I-4-a) in which
  A, D, X, Y and Z have the meanings given in claim 1,
  Compounds of formula (V) in which
  A and D have the meanings given above,
  or their silylenol ethers of the formula (Va) in which A and D have the meaning given above and
  R ^{8 ′ represents} alkyl,
  with compounds of the formula (VI) in which
  X, Y and Z have the meanings given above and
  Hal stands for halogen,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor,
• (E) compounds of the formula (I-5-a) in which
  A, X, Y and Z have the meanings given above,
  Compounds of formula (VII) in which
  A has the meaning given above,
  with compounds of the formula (VI) in which
  Hal, X, Y and Z have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor, and if appropriate subsequently subsequently the compounds of the formulas (I-1-b) to (I-5-b) shown above
• (F) α) with acid halides of the formula (VIII) in which
  R¹ has the meaning given in claim 1 and
  Hal stands for halogen
  or
• β) with carboxylic anhydrides of the formula (IX) R¹-CO-O-CO-R¹ (IX) in which
  R¹ has the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
  or
• (G) with chloroformate or chloroformate thioester of the formula (X) R²-M-CO-Cl (X) in which
  R² and M have the meanings given in claim 1,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
  or
• (H) α) with chloromothio formic acid esters or chlorodithio formic acid esters of the formula (XI) in which
  M and R² have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder
  or
• β) with carbon disulfide and then with compounds of the formula (XII) R²-Hal (XII) in which
  R² has the meaning given above and
  Hal represents chlorine, bromine or iodine,
  if appropriate in the presence of a diluent and if appropriate in the presence of a base,
  or
• (I) with sulfonic acid chlorides of the formula (XIII) R³-SO₂-Cl (XIII) in which
  R³ has the meaning given in claim 1,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
  or
• (J) with phosphorus compounds of the formula (XIV) in which
  L, R⁴ and R⁵ have the meanings given above and
  Hal stands for halogen,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
  or
• (K) with metal compounds or amines of the formulas (XV) or (XVI) Me (OR¹⁰) _t (XV) in which
  Me for a monovalent or divalent metal
  t for the number 1 or 2 and
  R¹⁰, R¹¹, R¹² independently of one another represent hydrogen or alkyl,
  if appropriate in the presence of a diluent,
  or
• (L) α) with isocyanates or isothiocyanates of the formula (XVII) R⁶-N = C = L (XVII) in which
  R⁶ and L have the meanings given in claim 1,
  if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst or
• β) with carbamic acid chlorides or thiocarbamic acid chlorides of the formula (XVIII) in which
  L, R⁶ and R⁷ have the meanings given above,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder.

6. Compounds of formula (II) in which
A, B, X, Y and Z have the meanings given in claim 1 and
R⁸ represents alkyl. 7. Compounds of formula (III) in which
A, B, X, Y and Z have the meanings given in claim 1 and
R⁸ represents alkyl. 8. Compounds of the formula (XXI) in which
A, B, X, Y and Z have the meanings given in claim 1. 9. Compounds of the formula (XXIX) in which
A, B, X, Y and Z have the meanings given in claim 1. 10. Compounds of the formula (IV) in which
A, B, X, Y and Z have the meanings given in claim 1,
R⁸ represents alkyl and
W represents hydrogen, halogen, alkyl or alkoxy. 11. Compounds of the formula (VI) in which
X, Y and Z have the meanings given in claim 1 and
Hal stands for chlorine or bromine. 12. Compounds of the formula (XXXIII) in which
X, Y and Z have the meanings given in claim 1. 13. Compounds of the formula (XXXIV) in which
X, Y and Z have the meanings given in claim 1 and
R⁸ represents alkyl. 14. pesticides and herbicides, characterized by a Content of at least one compound of formula (I) according to claim 1. 15. Use of compounds of formula (I) according to claim 1 for Control of pests and unwanted vegetation. 16. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are applied to pests, unwanted vegetation and / or their habitat leaves. 17. Process for the preparation of pesticides and Herbicides, characterized in that compounds of the formula (I) according to claim 1 with extenders and / or surface-active agents mixed. 18. Use of compounds of formula (I) according to claim 1 for Manufacture of pesticides and herbicides.