DE4415334A1 - Substituted spirocyclic 1H-3-aryl-pyrrolidine-2,4-dione derivatives - Google Patents

Description

The invention relates to new substituted spirocyclic 1H-3-aryl-pyrrolidine-2,4-dione Derivatives, several processes for their preparation and their use as Pesticides and herbicides.

Pharmaceutical properties of 3-acyl-pyrrolidine-2,4-diones have been previously described (S. Suzuki et al. Chem. Pharm. Bull. 15 1120 (1967)). Furthermore, N-phenyl pyrrolidin-2,4-dione by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem. 1985 1095). A biological activity of these compounds has been established not described. Furthermore, 5-vinyl tetramic acids with pharmaceutical Properties described (GB-A 22 66 888).

EP-A 0 262 399 discloses 3-aryl-pyrrolidine-2,4-diones, but of which no herbicidal, insecticidal or acaricidal activity has become known. The herbicidal, insecticidal or acaricidal activity is known from unsubstituted, bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A 355 599) and (EP 415 211) as well as substituted monocyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A 377 893), (EP 442 077), (EP 497 127) and substituted bicyclic 3-aryl pyrrolidone derivatives (EP 501 129).

Polycyclic 3-arylpyrrolidine-2,4-dione derivatives (EP 442 073) and 1H-3-arylpyrrolidinedione derivatives (EP 456 063) and (EP 521 334).  

There have now been new substituted spirocyclic 1H-3-aryl-pyrrolidine-2,4-dione derivatives of formula (I)

found in which
A and B together with the carbon atom to which they are attached represent an unsubstituted or substituted 5-6-membered cycle interrupted by at least one heteroatom,
X represents alkyl, halogen or alkoxy,
Y represents hydrogen, alkyl, halogen, alkoxy or haloalkyl,
Z represents alkyl, halogen or alkoxy,
n stands for a number 0, 1, 2 or 3,
G for hydrogen (a) or for the groups

stands,
E represents a metal ion equivalent or an ammonium ion,
L and M each represent oxygen or sulfur,
R 1 represents in each case optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or cycloalkyl, which can be interrupted by heteroatoms, in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R² represents in each case optionally substituted by halogen, alkyl, cycloalkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or in each case optionally substituted phenyl or benzyl,
R³, R⁴ and R⁵ independently of one another each represent alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio optionally substituted by halo and optionally substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently represent hydrogen, in each case optionally substituted by halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, optionally substituted phenyl, optionally substituted benzyl, or together with the N atom to which they are attached, for one optionally interrupted by oxygen or sulfur cycle.

Including the different meanings (a), (b), (c), (d), (e) and (f) the Group G of the general formula (I) results in the following main structure doors (Ia) to (Ig):

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

Due to one or more centers of chirality, the compounds of the formula fall (Ia) - (Ig) generally as a mixture of stereoisomers. They can be both in shape their diastereomer mixtures as well as pure diastereomers or enantiomers be used.

Furthermore, it was found that the new substituted 1H-3-aryl-pyrrolidine 2,4-dione derivatives of the formula (I) according to one of those described below Procedure receives.

• (A) 1H-3-aryl-pyrrolidine-2,4-diones or their enols of the formula (Ia) are obtained in which
  A, B, X, Y, Z and n have the meaning given above if one
  N-acylamino acid esters of the formula (II) in which
  A, B, X, Y, Z and n have the meaning given above, and
  R⁸ represents alkyl,
  intramolecularly condensed in the presence of a diluent and in the presence of a base; or
• (B) compounds of the formula (Ib) are obtained in which
  A, B, X, Y, Z, R¹ and n have the meaning given above,
  if compounds of the formula (Ia), in which
  A, B, X, Y, Z and n have the meaning given above, α) with acid halides of the formula (III) in which
  R¹ has the meaning given above and
  Hal represents halogen, especially chlorine and bromine,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder or
  β) with carboxylic anhydrides of the formula (IV) R¹-CO-O-CO-R¹ (IV) 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
• (C) compounds of the formula (Ic-1) are obtained in which
  A, B, X, Y, Z, R² and n have the meaning given above, and
  M represents oxygen or sulfur,
  if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with chloroformate or chloroformate thiol ester of the formula (V) R²-M-CO-Cl (V) in which
  R² and M have the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder; or
• (D) compounds of the formula (Ic-2) are obtained in which
  A, B, R², X, Y, Z and n have the meaning given above and
  M represents oxygen or sulfur,
  if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above, α) with chloromothio formic acid esters or chlorodithio formic acid esters of the formula (VI) in which
  M and R² have the meaning 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 alkyl halides of the general formula (VII) R²-Hal (VII) 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 an auxiliary base; or
• (E) compounds of the formula (Id) are obtained in which
  A, B, X, Y, Z, R³ and n have the meaning given above,
  if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with sulfonic acid chlorides of the formula (VIII) R³-SO₂-Cl (VIII) 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; or
• (F) 3-aryl-pyrrolidine-2,4-diones of the formula (Ie) are obtained in which
  A, B, L, X, Y, Z, R⁴, R⁵ and n have the meaning given above if one
  1-H-3-aryl-pyrrolidine-2,4-diones of the formula (Ia) or their enols in which
  A, B, X, Y, Z and n have the meaning given above, with phosphorus compounds of the formula (IX) in which
  L, R⁴ and R⁵ have the meaning given above and
  Hal represents halogen, especially chlorine and bromine,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder; or
• (G) compounds of the formula (If) are obtained in which
  A, B, X, Y, Z and n have the meaning given above, and
  E represents a metal ion equivalent or an ammonium ion if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above, with metal compounds or amines of the formulas (X) and (XI) in which
  Me for mono- or divalent metal ions,
  t for the number 1 or 2,
  R¹⁰, R¹¹ and R¹² independently represent hydrogen or alkyl and
  R¹³ represents hydrogen, hydroxy or C₁-C₄ alkoxy,
  if appropriate in the presence of a diluent.
• H) It was also found that compounds of the formula (Ig) in which
  A, B, L, X, Y, Z, R⁶, R⁷ and n have the meaning given above, is obtained if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above, α) with compounds of the formula (XII) R⁶-N = C = L (XII) in which
  L and R⁶ have the meaning given above
  optionally 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 (XIII) in which
  L, R⁶ and R⁷ have the meaning 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 1H-3-arylpyrrolidine-2,4-dione derivatives of formula (I) through excellent insecticidal, acaricidal and herbicidal effects award.

The following applies to the general formulas of the present application:
A, B and the carbon atom to which they are attached preferably represent a 5-6-membered spirocycle which is the group

and / or contains oxygen and / or sulfur which is unsubstituted or simple or several times by alkyl, cycloalkyl, haloalkyl, alkoxy, thioalkyl, halogen or phenyl may be substituted.

A, B and the carbon atom to which they are attached are particularly preferred for a 5-6-membered spirocycle, which is the group

and / or contains oxygen and / or sulfur which is unsubstituted or simple or several times by C₁-C₆-alkyl, C₁-C₈-cycloalkyl, C₁-C₃-haloalkyl, C₁- C₄-alkoxy, C₁-C₄-thioalkyl, fluorine, chlorine or phenyl may be substituted.

A, B and the carbon atom to which they are attached are very special preferred for a 5-6-membered spirocycle, the group

and / or contains oxygen and / or sulfur which is unsubstituted or singly or multiply by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, trifluoromethyl, methoxy, methylthio, fluorine , Chlorine or phenyl may be substituted.
X preferably represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy.
X particularly preferably represents C₁-C₄-alkyl, halogen or C₁-C₄-alkoxy.
X very particularly preferably represents methyl, ethyl, propyl, 2-propyl, fluorine, chlorine, bromine, methoxy or ethoxy.
Y preferably represents hydrogen, C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy or C₁-C₃-haloalkyl.
Y particularly preferably represents hydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy or C₁-C₂-haloalkyl.
Y very particularly preferably represents hydrogen methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl.
Z preferably represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy.
Z particularly preferably represents C₁-C₄-alkyl, halogen or C₁-C₄-alkoxy.
Z very particularly preferably represents methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy or ethoxy.
G preferably represents hydrogen (a) or the groups

in which
E represents a metal ion equivalent or an ammonium ion and
L and M each represent oxygen or sulfur.

R¹ preferably represents in each case optionally substituted by halogen C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl, C₁-C₈-polyalkoxy -C₁-C₈-alkyl or cycloalkyl with 3 to 8 ring atoms, which can be interrupted by oxygen and / or sulfur atoms and substituted by C₁-C₆-alkyl,
for phenyl optionally substituted by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy,
for phenyl-C₁-C₆-alkyl optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy
for hetaryl optionally substituted by halogen and / or C₁-C₆alkyl,
for optionally substituted by halogen and / or C₁-C₆-alkyl phenoxy-C₁-C₆-alkyl or
for optionally substituted by halogen, amino and / or C₁-C₆-alkyl hetaryloxy-C₁-C₆-alkyl.

R² preferably represents in each case optionally substituted by halogen C₁-C₂₀-alkyl, C₃-C₁₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl, C₁-C₈-polyalkoxy-C₂-C₈-alkyl
for C₃-C₆-cycloalkyl optionally substituted by halogen or C₁-C₆-alkyl or
for phenyl or benzyl optionally substituted by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkyl.

R³, R⁴ and R⁵ independently of one another are preferably each in each case halogen substituted C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino, Di- (C₁-C₈) alkylamino, C₁-C₈-alkylthio, C₃-C ₅-alkenylthio, C₃-C₇-Cyc loalkylthio, for each optionally by halogen, nitro, cyano, C₁-C₄- Alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁- C₄-alkyl, C₁-C₄-haloalkyl substituted phenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another preferably represent hydrogen, in each case optionally substituted by halogen C₁-C₁₀ alkyl, C₃-C₁₀ cycloalkyl, C₁-C₁₀-alkoxy, C₃-C₈-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl, for given otherwise by halogen, C₁-C₈-haloalkyl, C₁-C₈-alkyl or C₁-C₈-alkoxy substituted phenyl, optionally with halogen, C₁-C₈-alkyl, C₁-C₈- Haloalkyl or C₁-C₈-alkoxy substituted benzyl or together with the N atom to which they are attached, for one if necessary Oxygen or sulfur interrupted 3- to 7-membered ring.

R⁹ preferably represents hydrogen, R¹, COR¹ or CO₂R², where R¹ or R² can assume the meanings given above as preferred for R¹ or R².

n is preferably a number from 0 to 3.  

G particularly preferably represents hydrogen (a) or the groups

in which
E represents a metal ion equivalent or an ammonium ion and
L and M each represent oxygen or sulfur,
R¹ particularly preferably represents in each case optionally substituted by halogen C₁-C₁₆-alkyl, C₂-C₈-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl, C₁-C₆ Polyalkoxy-C₁-C₆-alkyl or cycloalkyl having 3 to 7 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms and substituted by C₁-C--alkyl,
for phenyl optionally substituted by halogen, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy,
for phenyl-C₁-C₄-alkyl optionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy,
for furanyl, thienyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl optionally substituted by fluorine, chlorine, bromine and / or C₁-C₄alkyl,
for optionally substituted by fluorine, chlorine, bromine and / or C₁-C₄-alkyl phenoxy-C₁-C₅-alkyl or
for each optionally substituted by fluorine, chlorine, bromine, amino and / or C₁-C₄-alkyl substituted pyridyloxy-C₁-C₆-alkyl, pyrimidinyloxy-C₁-C₆-alkyl or thiazolyloxy-C₁-C₆-alkyl.

R² particularly preferably represents in each case optionally substituted by halogen C₁-C₁₆-alkyl, C₃-C₈-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl, C₁-C₆- polyalkoxy-C₂-C₆-alkyl,
for optionally substituted by fluorine, chlorine or C₁-C₄-alkyl C₃-C₆-cycloalkyl or
for phenyl or benzyl optionally substituted by halogen, nitro, C₁-C₄-alkyl, C₁-C₃-alkoxy or C₁-C₃-haloalkyl.

R³, R⁴ and R⁵ independently of one another are particularly preferred for C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆- optionally substituted by halogen Alkylamino, di- (C₁-C₆) alkylamino, C₁-C₆-alkylthio, C₃-C₄-alkenylthio, C₃- C₆-cycloalkylthio, each optionally by fluorine, chlorine, bromine, nitro, Cyano, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, C₁-C₃-alkylthio, C₁-C₃-Ha logenalkylthio, C₁-C₃-alkyl, C₁-C₃-haloalkyl substituted phenyl, phen oxy or phenylthio.

R⁶ and R⁷ independently of one another particularly preferably represent hydrogen, each optionally substituted by halogen C₁-C₈-alkyl, C₃-C₈- Cycloalkyl, C₁-C₈-alkoxy, C₃-C₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, for optionally by halogen, C₁-C₅-haloalkyl, C₁-C₅-alkyl or C₁-C₅- Alkoxy substituted phenyl, optionally substituted by halogen, C₁-C₅-alkyl, C₁- C₅-haloalkyl or C₁-C₅-alkoxy substituted benzyl or together with the N atom to which they are attached, for one if necessary Oxygen or sulfur interrupted 4- to 7-membered ring.

R⁹ particularly preferably represents hydrogen-COR¹ 'or CO₂R¹', where R¹ 'is C₁-C₆ alkyl, phenyl or benzyl.

n particularly preferably represents a number from 0 to 2.

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

in which
E represents a metal ion equivalent or an ammonium ion and
L and M each represent oxygen or sulfur.

R¹ very particularly preferably represents C₁-C₁₄-alkyl, C₂-C₆-alkenyl, C₁-C₄-alkoxy-C₁-C₆-alkyl, C₁-C₄-alkylthio-C₁-C₆-alkyl, C₁, each optionally substituted by fluorine or chlorine -C₄-polyalkoxy-C₁-C₄-alkyl or cycloalkyl with 3 to 6 ring atoms, which can be interrupted by 1 to 2 oxygen and / or sulfur atoms and can be substituted by methyl or ethyl,
for phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or nitro,
for phenyl-C₁-C₃-alkyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,
for thienyl, furanyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl,
for optionally substituted by fluorine, chlorine, methyl, ethyl phenoxy-C₁-C₄-alkyl or
for optionally substituted by fluorine, chlorine, amino, methyl, ethyl, substituted pyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C₄-alkyl or thiazolyloxy-C₁-C₄- alkyl.

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

R³, R⁴ and R⁵ independently of one another very particularly preferably stand for each C₁-C₄-alkyl optionally substituted by fluorine or chlorine, C₁-C₄- Alkoxy, C₁-C₄-alkylamino, di- (C₁-C₄) -alkylamino, C₁-C₄-alkylthio, for each optionally by fluorine, chlorine, bromine, nitro, cyano, C₁-C₂ alkoxy, C₁-C₂-fluoroalkoxy, C₁-C₂-alkylthio, C₁-C₂-fluoroalkylthio, C₁-C₃-alkyl substituted phenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another very particularly preferably represent hydrogen, in each case optionally substituted by fluorine, chlorine, bromine C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₁-C₄-alkyl, for optionally by fluorine, chlorine, bromine, C₁-C₄-haloalkyl, C₁-C₄-alkyl or C₁-C₄-alkoxy substituted phenyl, optionally for fluorine, Chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-alkoxy substituted benzyl or together with the N atom to which they are attached are, for a possibly interrupted by oxygen or sulfur 5- to 7-membered ring.

R⁹ very particularly preferably represents hydrogen COR¹ 'or CO₂R¹', wherein R¹ 'represents C₁-C₄ alkyl, phenyl or benzyl.

n very particularly preferably represents 0 or 1.

The compounds of the formula fall because of one or more centers of chirality (Ia) - (Ig) generally as mixtures of stereoisomers. They can be both in shape ver their mixtures of diastereomers as well as pure diastereomers or enantiomers be applied.  

According to process (A), 4- (2,4-dichlorophenylacetyl-amino-1-acetyl) is used piperidine-4-carboxylic acid ethyl ester, the course of the ver driving can be represented by the following reaction scheme:

If 3- (2,4,6-trimethylphenyl) -5,5- is used according to process (B) (variant a) (ethylene thioethylene) pyrrolidine-2,4-dione and pivaloyl chloride as starting materials, see above can the course of the method according to the invention by the following reac are reproduced:

If 3- (2,4,6-trimethylphenyl) -5,5- is used according to method B (variant β) ethylenethiomethylene-pyrrolidine-2,4-dione and acetic anhydride as starting compounds, the course of the method according to the invention can be as follows Reaction scheme are reproduced:

Is used according to process (C) 3- (2,4,6-trimethylphenyl) -5,5-ethylene thio methylene-pyrrolidine-2,4-dione and ethyl chloroformate as starting connections, so the course of the method according to the invention following reaction scheme can be reproduced.

If, according to process (D _a ), 3- (2,4,6-trimethylphenyl) -5,5-ethylenoxa, ethylene-pyrrolidine-2,4-dione and methyl chloromothio formate are used as starting products, the course of the reaction can be represented as follows:

If 3- (2,4,6-trimethylphenyl) -5,5-ethylenethio-pyrrolidine-2,4-dione, carbon disulfide and methyl iodide are used as starting components in accordance with process (D _β ), the course of the reaction can be represented as follows :

Is used according to method (E) 3- (2,4,6-trimethylphenyl) -5,5-methylene-thio propylene-pyrrolidine-2,4-dione and methanesulfonic acid chloride as the starting product, see above the course of the reaction can be represented by the following reaction scheme:

Is used according to method (F) 3- (2,4-dimethylphenyl) -5,5-ethylene-thio ethylene-pyrrolidine-2,4-dione 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:

Is used according to method (G) 3- (2,4,6-trimethylphenyl) -5,5-ethylene-thio methylene-pyrrolidine-2,4-dione and NaOH as components, so the course of the process according to the invention represented by the following reaction scheme become:

If 3- (2,4,6-trimethylphenyl) -5,5-ethylene-oxaethylene-pyrrolidine-2,4-dione and ethyl isocyanate are used as starting products in process (H _α ), the course of the reaction can be represented by the following scheme :

If 3- (2,4,6-trimethylphenyl) -5,5- (ethylene-benzylamino-ethylene-pyrrolidine-2,4-dione and dimethylcarbamoyl chloride) are used as starting products in process (H _b ), the course of the reaction can be determined by the following scheme are reproduced:

The cyclic aminocarboxylic acids of the formula interrupted by heteroatoms (XIVa), in which A and B have the meaning given above, are in generally after the Bucherer-Bergs reaction or after the Strecker synthesis available.

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

The starting materials used in process (A) above can also be used of the formula (II)

in which
A, B, X, Y, Z, n and R⁸ have the meaning given above, if aminonitriles of the formula (XVI)

in which
A and B have the meaning given above, with phenylacetic acid halides of the formula (XV)

in which
X, Y, Z and n have the meaning given above and
Hal represents chlorine or bromine,
to compounds of the formula (XVII)

in which
A, B, X, Y, Z and n have the meaning given above, which are then subjected to sulfuric acid alcoholysis.

The compounds of formula (XVII) are also new and are the subject of general claim of a previously filed application, including the procedures includes.

The compounds of which are required as starting materials in process (A) above Formula (II)

in which
A, B, X, Y, Z, n and R⁸ have the meaning given above,
are new and the subject of the general claim of a previously filed application.

You get z. B. also acyl amino acid esters of the formula (II), if one  Amino acid derivatives of the formula (XIV),

in which
R⁸ 'represents hydrogen (XIVa) or alkyl (XIVb) and
A and B have the meaning given above
with phenylacetic acid halides of the formula (XV)

in which
X, Y, Z and n have the meaning given above and
Hal represents chlorine or bromine,
acylated (Chem. Reviews 52, 237-416 (1953); Bhattacharya, India J. Chem. 6 341-5 1968) and the acylamino acids of the formula (IIa) formed for R⁸ ′ = hydrogen,

in which
A, B, X, Y, Z and n have the meaning given above, esterified.

In addition to the intermediates mentioned in the preparation examples, the following compounds of the formula (II) may be mentioned as examples, but not by way of limitation:
N- (2,4-dichlorophenylacetyl) -1-aminothiolanecarboxylic acid methyl ester,
N- (2,4-dichlorophenylacetyl) -1-amino-tetrahydrothiopyran-carboxylic acid, ethyl ester,
N- (2,4-dichlorophenylacetyl) -1-amino-tetrahydropyran-carboxylic acid methyl ester,
4- (2,4-dichlorophenylacetylamino) -N-methyl-piperidine-4-carboxylic acid methyl ester,
4- (2,4-dichlorophenylacetylamino) -N-acetyl-piperidine-4-carboxylic acid methyl ester,
4- (2,4-dichlorophenylacetylamino) -N-carboxyethyl-piperidine-4-carboxylic acid methyl ester,
N- (2,6-dichlorophenylacetyl) -1-aminothiolanecarboxylic acid methyl ester,
N- (2,6-dichlorophenylacetyl) -1-amino-tetrahydrothiopyran-carboxylic acid, ethyl ester,
N- (2,6-dichlorophenylacetyl) -1-amino-tetrahydropyran-carboxylic acid methyl ester,
4- (2,6-dichlorophenylacetylamino) -N-methyl-piperidine-4-carboxylic acid methyl ester,
4- (2,6-dichlorophenylacetylamino) -N-acetyl-piperidine-4-carboxylic acid methyl ester,
4- (2,6-dichlorophenylacetylamino) -N-carboxyethyl-piperidine-4-carboxylic acid methyl ester,
N- (2-chloro-6-fluoro-phenyl-acetyl) -1-amino-3-thiolanecarboxylic acid methyl ester,
N- (2-chloro-6-fluoro-phenyl-acetyl) -1-amino-4-tetrahydro-thiopyranecarboxylic acid, methyl ester,
N- (2-chloro-6-fluoro-phenyl-acetyl) -1-amino-tetrahydropyran-carboxylic acid, methyl ester,
4- (2-chloro-6-fluoro-phenyl-acetylamino) -N-methyl-piperidine-4-carboxylic acid, theme ester,
4- (2-chloro-6-fluoro-phenyl-acetylamino) -N-acetyl-piperidine-4-carboxylic acid, methyl ester,
4- (2-chloro-6-fluoro-phenyl-acetylamino) -N-carboxyethyl-piperidine-4-ca-rbonic acid, methyl ester,
N- (2,4,6-trimethylphenyl-acetyl) -1-aminothiolanecarboxylic acid methyl ester,
N- (2,4,6-trimethylphenyl-acetyl) -1-amino-tetrahydrothiopyranecarboxylic acid, methyl ester,
N- (2,4,6-trimethylphenyl-acetyl) -1-amino-tetrahydropyranecarboxylic acid, ethyl ester,
4- (2,4,6-trimethylphenyl-acetylamino) -N-methyl-piperidine-4-carboxylic acid remethyl ester,
(2,4,6-trimethylphenyl-acetylamino) -N-acetyl-piperidine-4-carboxylic acid methyl ester,
(2,4,6-trimethylphenyl-acetylamino) -N-carboxyethyl-piperidine-4-carbonic acid methyl ester,
N- (2,4-dimethylphenyl-acetyl) -1-aminothiolanecarboxylic acid methyl ester,
N- (2,4-dimethylphenyl-acetyl) -1-amino-tetrahydrothiopyran-carboxylic acid, methyl ester,
N- (2,4-dimethylphenyl-acetyl) -1-amino-tetrahydropyran-carboxylic acid methyl ester,
4- (2,4-Dimethylphenyl-acetylamino) -N-methyl-piperidine-4-carboxylic acid, ethyl ester,
(2,4-Dimethylphenyl-acetylamino) -N-acetyl-piperidine-4-carboxylic acid, methyl ester,
Methyl 4- (2,4-dimethylphenyl-acetylamino) -4-carboxyethyl-piperidine-4-carbonate,
N- (2,4-Dimethylphenyl-acetyl) -1-amino-4-phenyl-cyclohexane carboxylic acid - methyl ester.

In addition to the intermediates mentioned in the preparation examples, the following compounds of the formula (IIa) may be mentioned as examples, but not by way of limitation:
N- (2,4-dichlorophenylacetyl) -1-aminothiolanecarboxylic acid,
N- (2,4-dichlorophenylacetyl) -1-amino-tetrahydrothiopyran-carboxylic acid, -
N- (2,4-dichlorophenylacetyl) -1-aminotetrahydropyranecarboxylic acid,
4- (2,4-dichlorophenylacetylamino) -N-methyl-piperidine-4-carboxylic acid,
4- (2,4-dichlorophenylacetylamino) -N-acetyl-piperidine-4-carboxylic acid,
4- (2,4-dichlorophenylacetylamino) -N-carboxyethyl-piperidine-4-carboxylic acid,
N- (2,6-dichlorophenylacetyl) -1-aminothiolanecarboxylic acid,
N- (2,6-dichlorophenylacetyl) -1-amino-tetrahydrothiopyran-carboxylic acid, -
N- (2,6-dichlorophenylacetyl) -1-aminotetrahydropyranecarboxylic acid,
4- (2,6-dichlorophenylacetylamino) -N-methyl-piperidine-4-carboxylic acid,
4- (2,6-dichlorophenylacetylamino) -N-acetyl-piperidine-4-carboxylic acid,
4- (2,6-dichlorophenylacetylamino) -N-carboxyethyl-piperidine-4-carboxylic acid,
N- (2-chloro-6-fluoro-phenyl-acetyl) -1-aminothiolanecarboxylic acid,
N- (2-chloro-6-fluoro-phenyl-acetyl) -1-amino-tetrahydrothiopyranecarboxylic acid,
N- (2-chloro-6-fluoro-phenyl-acetyl) -1-amino-tetrahydropyran-carboxylic acid e,
4- (2-chloro-6-fluoro-phenyl-acetylamino) -N-methyl-piperidine-4-carboxylic acid,
4- (2-chloro-6-fluoro-phenyl-acetylamino) -N-acetyl-piperidine-4-carboxylic acid,
4- (2-chloro-6-fluoro-phenyl-acetylamino) -N-carboxyethyl-piperidine-4-ca-rbonic acid,
N- (2,4,6-trimethylphenyl-acetyl) -1-aminothiolanecarboxylic acid,
N- (2,4,6-trimethylphenyl-acetyl) -1-amino-tetrahydrothiopyranecarboxylic acid,
N- (2,4,6-trimethylphenyl-acetyl) -1-amino-tetrahydropyranecarboxylic acid, -
4- (2,4,6-trimethylphenyl-acetylamino) -N-methyl-piperidine-4-carboxylic acid,
4- (2,4,6-trimethylphenyl-acetylamino) -N-acetyl-piperidine-4-carboxylic acid,
4- (2,4,6-trimethylphenyl-acetylamino) -N-carboxyethyl-piperidin-4-car-bonic acid,
N- (2,4-dimethylphenyl-acetyl) -1-aminothiolanecarboxylic acid,
N- (2,4-dimethylphenyl-acetyl) -1-amino-tetrahydrothiopyran-carboxylic acid-e,
N- (2,4-dimethylphenyl-acetyl) -1-amino-tetrahydropyran-carboxylic acid,
4- (2,4-dimethylphenyl-acetylamino) -N-methyl-piperidine-4-carboxylic acid,
4- (2,4-dimethylphenyl-acetylamino) -N-acetyl-p iperidine-4-carboxylic acid,
4- (2,4-Dimethylphenyl-acetylamino) -N-carboxyethyl-piperidine-4-carboxylic acid.

In addition to the intermediates mentioned in the preparation examples, the following compounds of the formula (XVII) may be mentioned as examples, but not by way of limitation:
N- (2,4-dichlorophenylacetyl) -1-aminothiolanecarbonitrile,
N- (2,4-dichlorophenylacetyl) -1-amino-tetrahydrothiopyran-carboxylic acid itrile,
N- (2,4-dichlorophenylacetyl) -1-amino-tetrahydropyranecarboxylic acid nitri-l,
4- (2,4-dichlorophenylacetylamino) -N-methyl-piperidine-4-carboxylic acid nitrile,
4- (2,4-dichlorophenylacetylamino) -N-acetyl-piperidine-4-carboxylic acid nitrile,
4- (2,4-dichlorophenylacetylamino) -N-carboxyethyl-piperidine-4-carboxylic acid urenitrile,
N- (2,6-dichlorophenylacetyl) -1-aminothiolanecarbonitrile,
N- (2,6-dichlorophenylacetyl) -1-amino-tetrahydrothiopyran-carboxylic acid itrile,
N- (2,6-dichlorophenylacetyl) -1-amino-tetrahydropyranecarboxylic acid nitri-l,
4- (2,6-dichlorophenylacetylamino) -N-methyl-piperidine-4-carboxylic acid nitrile,
4- (2,6-dichlorophenylacetylamino) -N-acetyl-piperidine-4-carboxylic acid nitrile,
4- (2,6-dichlorophenylacetylamino) -N-carboxyethyl-piperidine-4-carboxylic acid urenitrile,
N- (2-chloro-6-fluorophenylacetyl) -1-aminothiolanecarbonitrile,
N- (2-chloro-6-fluorophenylacetyl) -1-amino-tetrahydrothiopyranocarbonitrile,
N- (2-chloro-6-fluoro-phenyl-acetyl) -1-amino-tetrahydropyran-carboxylic acid enitrile,
4- (2-chloro-6-fluoro-phenyl-acetylamino) -N-methyl-piperidine-4-carboxylic acid-nitrile,
4- (2-chloro-6-fluoro-phenyl-acetylamino) -N-acetyl-piperidine-4-carboxylic acid itrile,
4- (2-chloro-6-fluoro-phenyl-acetylamino) -N-carboxyethyl-piperidine-4-ca-r-acrylonitrile,
N- (2,4,6-trimethylphenyl-acetyl) -1-aminothiolanecarbonitrile,
N- (2,4,6-trimethylphenylacetyl) -1-aminotetrahydrothiopyranecarbonsaurenitrile,
N- (2,4,6-trimethylphenyl-acetyl) -1-amino-tetrahydropyranecarboxylic acid itril,
4- (2,4,6-trimethylphenyl-acetylamino) -N-methyl-piperidine-4-carboxylic acid renitrile,
4- (2,4,6-trimethylphenyl-acetylamino) -N-acetyl-piperidine-4-carboxylic acid renitrile,
4- (2,4,6-trimethylphenyl-acetylamino) -N-carboxyethyl-piperidine-4-car-bonsonitrile,
N- (2,4-dimethylphenyl-acetyl) -1-aminothiolanecarbonitrile,
N- (2,4-dimethylphenyl-acetyl) -1-amino-tetrahydrothiopyran-carboxylic acid enitrile,
N- (2,4-dimethylphenyl-acetyl) -1-amino-tetrahydropyran-carboxylic acid nitrile,
4- (2,4-dimethylphenyl-acetylamino) -N-methyl-piperidine-4-carboxylic acid itrile,
4- (2,4-dimethylphenyl-acetylamino) -N-acetyl-piperidine-4-carboxylic acid itrile,
4- (2,4-dimethylphenyl-acetylamino) -N-carboxyethyl-piperidine-4-carbon-acrylonitrile,
Compounds of the formula (IIa) are available, for example, from the phenylacetic acid halides of the formula (XV) and amino acids of the formula (XIVa) according to Schotten-Baumann (Organikum, 9th edition, 446 (1970) VEB German Publishing House of Sciences, Berlin).

The processes (B), (C), (D), (E), (F), (G) and (H) acid halides of the formula (III) required as starting materials, Carboxylic acid anhydrides of the formula (IV), chloroformic acid esters or chloric ants acid thioesters of the formula (V), chloromothio formic acid esters or chlorodi thio formic acid esters of the formula (VI), alkyl halides of the formula (VII), Sulfonic acid chlorides of the formula (VIII), phosphorus compounds of the formula (IX) and Metal hydroxides or amines of the formula (X) and (XI) and isocyanates of the formula (XII) or carbamic acid chloride of the formula (XIII) are generally known Compounds of organic or inorganic chemistry.  

Process (A) is characterized in that compounds of the formula (II) in which A, B, X, Y, Z, n and R⁸ have the meaning given above, in Presence of bases to intramolecular condensation.

All inert substances can be used as diluents in process (A) according to the invention organic solvents are used. Are preferably usable Hydrocarbons, such as toluene and xylene, furthermore ethers, such as dibutyl ether, Tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, as well polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N- Methyl pyrrolidone, and alcohols such as methanol, ethanol, propanol, isopropanol, Butanol, iso-butanol and tert-butanol.

As bases (deprotonating agents) can be in the implementation of the Invention according to method (A) 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 in Presence of phase transfer catalysts such. B. Triethylbenzylammonium chloride, tetrabutylammonium bromide, ®Adogen 464 or TDA 1) (Adogen 464 = methyltrialkyl (C₈-C₁₀) ammonium chloride, TDA 1 = tris (methoxyethoxyethyl) amine) can be used can.

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 temperatures can be carried out when carrying out the process according to the invention Process (A) can be varied within a wide range. Generally ar  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 guided.

When carrying out process (A) according to the invention, the Re Action components of the formulas (II) and the deprotonating bases in general in about double equimolar amounts. However, it is also possible to use one or the other use other components in a larger excess (up to 3 moles).

The process (Bα) is characterized in that compounds of the formula (Ia) with carboxylic acid halides of the formula (III).

In the process according to the invention, (Bα) can be used as diluent Use of the acid halides all inert to these compounds 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, as well as ketones such as acetone and methyl isopropyl ketone Ethers such as diethyl ether, tetrahydrofuran and dioxane, and also carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as 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.

If the corresponding carboxylic acid halides are used, they come as the acid binder in the implementation of the process (Bα) all usual acid acceptors into consideration. Tertiary amines are preferably usable, such as triethylamine, pyridine, diazabiyclooctane (DABCO), diazabicycloundecene (DBU), Diazabicyclonones (DBN), 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 Alkali hydroxides such as sodium hydroxide and potassium hydroxide.  

The reaction temperatures can also in the process (Bα) according to the invention even when using carboxylic acid halides within a larger one Range can be varied. Generally one works at temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.

When performing the method (Bα) according to the invention, the off Starting materials of the formula (Ia) and the carboxylic acid halide of the formula (III) in generally used in approximately equivalent amounts. However, it is also possible, the carboxylic acid halide in a larger excess (up to 5 mol) to use. The processing takes place according to usual methods.

The process (Bβ) is characterized in that compounds of the formula (Ia) with carboxylic anhydrides of the formula (IV).

Is used in the process (Bβ) according to the invention as a reaction Component of formula (IV) carboxylic anhydrides, can be used as a diluent medium preferably those diluents are also used, which also the use of acid halides are preferred. in the a carboxylic anhydride used in excess can also be used at the same time act as a diluent.

The reaction temperatures can also in the process (Bβ) according to the invention when using carboxylic anhydrides within a wide range can be varied. In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.

When carrying out the process according to the invention, the starting materials of formula (Ia) and the carboxylic anhydride of formula (IV) in general in approximately equivalent amounts are used. However, it is also possible that Use carboxylic anhydride in a large excess (up to 5 mol). The Refurbishment is carried out using customary methods.

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.

Process (C) is characterized in that compounds of the formula (Ia) with chloroformate or chloroformate thiol ester of the formula (V) implements.

Use the corresponding chloroformate or chlor ants acid thiol esters come as acid binders in the implementation after Process (C) according to the invention takes into account all customary acid acceptors. Tertiary 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.

As diluents in process (C) according to the invention at Ver use of the chloroformate or chloroformate thiolester all against inert solvents are used over these compounds. Preferably ver hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin are applicable, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride hydrogen, chlorobenzene and o-dichlorobenzene, also ketones such as acetone and Methyl isopropyl ketone, further ethers, such as diethyl ether, tetrahydrofuran and di oxane, moreover carboxylic acid esters, such as ethyl acetate, and also strongly polar ones Solvents such as dimethyl sulfoxide and sulfolane.

When using the chloroformate or chloroformate as Carboxylic acid derivatives of the formula (V) can have the reaction temperatures at the Carrying out process (C) according to the invention within a larger one Range can be varied. If you work in the presence of a diluent and an acid binder, the reaction temperatures are generally between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° 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 Starting materials of the formula (Ia) and the corresponding chloroformate or Chloroformic acid thiol esters of formula (V) in general approximate equivalent amounts used. However, it is also possible to use one or the other Use component in a larger excess (up to 2 moles). The Aufar Processing then takes place according to customary methods. In general, one proceeds in such a way that precipitated salts are removed and the remaining reaction mixture by stripping hen the diluent is concentrated.

In the production process (D), the for mel (Ia) approx. 1 mol chloromothio formic acid ester or chlorodithio formic acid esters of formula (VI) at 0 to 120 ° C, preferably at 20 to 60 ° C.

All inert polar come as optionally added diluents organic solvents in question, such as ethers, amides, alcohols, sulfones, sulfoxides.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dime are preferred thyl sulfide used.

Is made in a preferred embodiment by adding strong Deprotonating agents such. B. sodium hydride or potassium tert-butylate the enolate Salt of the compound Ia can be the further addition of acid binders to 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, triethylamine listed.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing takes place according to usual methods.

In the production process (D _ß ), the equimolar amount or an excess of carbon disulfide is added per mole of starting compound of the formula (Ia).

It is preferably carried out at temperatures from 0 to 50 ° C. and in particular at 20 to 30 ° C.

It is often expedient to add the compound of the formula (Ia) first a deprotonating agent (such as potassium tertiary butylate or sodium hydride) produce appropriate salt. The connection (Ia) is used as long Carbon disulfide until the formation of the intermediate compound is complete, e.g. B. after stirring for several hours at room temperature.

The further reaction with the alkyl halide of the formula (VII) takes place preferably at 0 to 70 ° C and in particular 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.

Production process (E) uses per mole of starting compound of the formula (Ia) about 1 mol of sulfonic acid chloride (VIII) at 0 to 150 ° C, preferably at 20 to 70 ° C around.

All inert polar come as optionally added diluents organic solvents in question such as ethers, amides, nitriles, alcohols, sulfones, Sulfoxides or halogenated hydrocarbons such as methylene chloride.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, di methyl sulfide, methyloenchloride used.

Is made in a preferred embodiment by adding strong Deprotonating agents (such as sodium hydride or potassium tertiary butoxide) Enolate salt of compound Ia can be added to the further addition of acid binders to be dispensed with.  

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

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing takes place according to usual methods.

In the manufacturing process (E), a phase transfer condition may be used (W. J.Süillane et. al .; J. Chem. Soc., Perkin Trans I, (3) 677-9 (1982)). In this case, per mol of starting compound of the formula (Ia) 0.3 to 1.5 mol of sulfonic acid chloride VIII, preferably 0.5 mol at 00 to 150 ° C, preferably at 20 to 70 ° C.

All quaternary ammonium salts can be used as phase transfer catalysts are, preferably tetraoctylammonium bromide and benzyltriethylammonium chloride. In this case, all non-polar inert solvents can be used as organic solvents Solvents are used, preferably benzene and toluene.

The manufacturing process (F) uses structural connections to obtain compounds (Ie) to 1 mol of the compound (Ia), 1 to 2, preferably 1 to 1.3 mol of the Phosphorus compound of formula (IX) at temperatures between -40 ° C and 150 ° C, preferably between -10 and 110 ° C.

Any inert, polar diluents that may be added organic solvents in question such as ethers, amides, nitriles, alcohols, sulfides, Sulfones, sulfoxides etc.

Acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethyl are preferred formamide, dimethyl sulfide used.

Conventional inorganic or organic bases in question such as hydroxides, carbonates. Exemplary are Natri umhydroxid, sodium carbonate, potassium carbonate, pyridine listed.  

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing takes place according to the usual methods of organic chemistry. Cleaning the accruing end products are preferably done by crystallization, chromatographic purification supply or by so-called "distillation", d. H. Removal of volatile be components in a vacuum.

Process (G) is characterized in that compounds of the formula (Ia) with metal compounds (X) or amines (XI).

Preferred diluents in the process according to the invention Ethers such as tetrahydrofuran, dioxane, diethyl ether or alcohols such as methanol, Ethanol, isopropanol, but also water can be used. The invention Process (G) is generally carried out under normal pressure. The reaction temperatures are generally between -20 ° C and 100 ° C, preferably between 0 ° C and 50 ° C.

Production process (Hα) uses per mole of starting compound of the formula (Iα) about 1 mol of isocyanate of the formula (XII) at 0 to 100 ° C, preferably at 20 to 50 ° C around.

All inert organic come as optionally added diluents Solvents in question, such as ethers, amides, nitriles, sulfones, sulfoxides.

If necessary, catalysts can be added to accelerate the reaction become. Organotin compounds such as e.g. B. Dibutyltin dilaurate can be used. It is preferably at normal pressure worked.

In the production process (H _β ), about 1 mol of carbamic acid chloride of the formula (XIII) is reacted at 0 to 150 ° C., preferably at 20 to 70 ° C., per mole of starting compound of the formula (Ia).

All inert polar come as optionally added diluents organic solvents in question such as ethers, amides, alcohols, sulfones or Sulfoxides.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or 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 compound (Ia), can on the further addition of acid binders are 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 called carbonate, triethylamine or pyridine.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing takes place according to usual methods.

The active compounds are suitable for controlling animal pests, preferably Arthropods and nematodes, especially insects and arachnids, which in the Agriculture, in forests, in the protection of stocks and materials as well as on the Hygiene sector occur. They are against normally sensitive and resistant types as well effective against all or individual stages of development. To the above Pests 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, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., 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., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

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

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

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

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

They can be used to combat particularly well plant-damaging insects, such as against the larvae of the Horseradish leaf beetle (Phaedon cochleariae) or against the larvae of green rice cicada (Nephotettix cincticeps) to control plant-damaging mites,  such as against the common spider mite or the bean spider mite (Tetranychus urticae).

The active compounds according to the invention can also be used as defoliants, desiccants, Herbicide and especially used as a herb for destroying weeds become. Weeds in the broadest sense are understood to mean all plants that are on Growing up in places where they are undesirable. Whether the substances according to the invention as total or selective herbicides act depends essentially on the applied Amount off.

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

Dicot weeds of the genera:

Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthi um, convolvulus, ipomoea, polygonum, sesbania, ambrosia, cirsium, carduus, Sonchus, Solanum, Rorippa, Rotala, 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.

Monocot weeds of the genera:

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

Monocot cultures of the genera:

Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

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

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 wood, fruit, wine, citrus, Nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and Hop plants, on ornamental and sports turf and pastures and for selective Weed control can be used in annual crops.

The active compounds according to the invention are very suitable for selective control monocotyledon weeds in dicotyledon crops before and after emergence. she can be used for example in cotton or sugar beet with very good success Control of harmful grass can be used.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, sol Liche powder, granules, suspension emulsion concentrates, impregnated with active ingredient Natural and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid Carriers, if necessary using surface-active agents, that is Emulsifiers and / or dispersants and / or foaming agents.

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: Alomatics, such as xylene, toluene, or Alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic Hydrocarbons 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. aminonium 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 Ta bakstems; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

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

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine substances 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 compounds according to the invention can be used as such or in their formulations also used in a mixture with known herbicides for weed control find, where ready formulations or tank mixes are possible.

Known herbicides such as z. B. 1-Amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) -dione (AMETHYDIONE) or N- (2-  Benzthiazolyl) -N, N'-dimethyl-urea (METABENZTHIAZURON) to weed fighting in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one (META MITRON) for weed control in sugar beet and 4-amino-6- (1,1-dimethyl ethyl) -3-methylthio-1,2,4-triazin-5 (4H) -one (METRIBUZIN) for weed control in soybeans, in question. Furthermore, 2,4-dichlorophenoxyacetic acid (2,4-D); 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4- DP); 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (BENTAZON); Methyl-5- (2,4-dichlorophenoxy) -2-nitrobenzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL); 2-chloro-N - [(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] - carbonyl-benzenesulfonamide (CHLORSULFURON); 2- [4- (2,4-dichlorophenoxy) -phen oxy] propionic acid, its methyl or its ethyl ester (DICLOFOPMETHYL); 4- Amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5 (4H) -one (ETHIOZIN); 2-4 - [(6-chloro-2- benzoxazolyl) -oxy] -phenoxy-propanoic acid, its methyl or its ethyl ester (FENOXAPROP); [(4-Amino-3,5-dichloro-6-fluoro-2-pyridinyl) -oxy] acetic acid or their 1-methylheptyl ester (FLUROXYPYR); Methyl 2- [4,5-dihydro-4-methyl-4- (1- methylethyl) -5-oxo-1H-imidazol-2-yl] -4 (5) methylbenzoate (IMAZAMETHABENZ); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL); N, N-dimethyl-N ′ - (4-isopropylphenyl) - urea (ISOPROTURON); (2-methyl-4-chlorophenoxy) acetic acid (MCPA); (4- Chloro-2-methylphenoxy) propionic acid (MCPP); N-methyl-2- (1,3-benzothiazol-2-yl- oxy) acetanilide (MEFENACET); 2 - [[((4-methoxy-6-methyl-1,3,5-triazin-2-yl) -ami no) -carbonyl] -amino] -sulfonyl-benzoic acid or its (METSULFURON); N- (1- Ethyl propyl) -3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALINE); 0- (6-chloro-3-phe nylpyridazin-4-yl) -S-octyl-thiocarbonate (PYRIDATE), 4-ethylamino-2-t-butylamino- 6-methylthio-s-triazine (TERBUTRYNE), 3 - [[[((4-methoxy-6-methyl-1,3,5-triazine-2- yl) -amino] -carbonyl] -amino] -sulfonyl] -thiophene-2-carboxylic acid (THIAMETURON) in question. Surprisingly, some mixtures also show synergistic effects Effect.

Also a mixture with other known active ingredients, such as fungicides, insects ziden, acaricides, nematicides, bird repellants, plant nutrients and soil structure improvers are possible.  

Insecticides include, for example, phosphoric acid esters, carbamates, Carboxylic acid esters, chlorinated hydrocarbons, phenylureas, by Mikroorga nisms manufactured u. a.

The following connections are mentioned:
Acrinathrin, Alphamethrin, Betacyfluthrin, Bifenthrin, Brofenprox, Cis-Resmethrin, Clocythrin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Deltamethrin, Esfenvalerin, Pyrenolhrin, Pyrenolhrin, Pyrenolhrin, Fluvalhrin, Pyrenolate Tralomethrin, Zeta-methrin, Alanycarb, Bendiocarb, Benfuracarb, Bufencarb, Butocarboxim, Carbaryl, Cartap, Ethiofencarb, Fenobucarb, Fenoxycarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propicuran, Trimoxarban, Trimoxarbiod, Tarbox XMC, Xylylcarb, Acephate, Azinphos A, Azinphos M, Bromophos A, Cadusafos, Carbophenothion, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cyanophos. Demeton M, Demeton-S-methyl, Demeton S, Diazinon, Dichlorvos, Dicliphos, Dichlorfenthion, Dicrotophos, Dimethoate, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Ethion, Etrimphos, Fenitrothion, Fenthion, Fonophos, Isothophophos, Hepthophosus, Hepten Isoxathion, Phorate, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Methacrifos, Methamidophos, Naled, Omethoate, Oxydemeton M, Oxydeprofos, Parathion A, Parathion M, Phentoate, Phorate, Phosalone, Phosmet, Phosphamdon, Moxim, Pirimiphos. Pirimiphos , Prothiophos, Prothoate, Pyraclophos, Pyridaphenthion, Quinalphos, Salithion, Sebufos, Sulfotep, Sulprofos, Tetrachlorvinphos, Temephos, Thiomethon, Thionazin, Trichlorfon, Triazophos, Vamidothion, Buprofezin, Chlorfluazubononifonuron, Fluofluronuron, Fluorofluoriduron, Fluorofluoriduron, Fluorofluoriduron, Fluorofluoriduron, Fluorofluoriduron, Fluorofluoriduron, Fluorofluoriduron, Fluorofluoriduron, Fluofluoriduron Teflubenzuron, triflumuron, imidacloprid, nitenpyram, N - [(6-chloro-3-pyridinyl) methyl] -N'-cyano-N-methyl ethanimidamide (NI-25), abamectin, amitrazine , Avermectin, azadirachtin, bensultap, bacillus thuringiensis, cyromazine, diafenthiuron, emamectin, ethofenprox, fen pyrad, fipronil, flufenprox, lufenuron, metaldehyde, milbemectin, pymetrozine, tebufenpyrad, triazuron, carbocarbon, carbocarbon, carbocarbon, carbohydrate, aldarbarbox, carbohydrate, chlorobarbone, carbohydrate, alfalfa , Disulfoton, Ethophrophos, Etrimphos, Fenamiphos, Fipronil, Fonofos, Fosthiazate, Furathiocarb, HCH, Isazophos, Isofenphos, Methiocarb, Monocrotophos, Nitenpyram, Oxamyl, Phorate, Phoxim, Prothiofos, Pyrachlofefufufuf, Tofachlofosufufuf , Thiafenox, azocyclotin, Butylpyridaben, clofentezine, cyhexatin, diafenthiuron, Diethion, emamectin, fenazaquin, fenbutatin oxide, fenothiocarb, fenpropathrin, fenpyrad, fenpyroximate, fluazinam, fluazuron, flucycloxuron, flufenoxuron, fluvalinate, fubfenprox, hexythiazox, Ivemectin, methidathion, monocrotophos, Moxidectin, Naled, Phosalone, Profenofos, Pyraclofos, Pyridaben, Pyrimidifen, Tebufenpyrad, T huringiensin, triarathenes and 4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (AC 303630).

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

The active compounds according to the invention can be used both before and after emergence of the plants are applied.

They can also be worked into the soil before sowing.

The amount of active ingredient used can vary over a wide range. she depends essentially on the type of effect desired. In general the application rates are between 0.01 and 10 kg of active ingredient per hectare Soil area, preferably between 0.05 and 5 kg per ha.

The manufacture and use of the active compounds according to the invention are based on following examples.

Manufacturing examples At 13483 00070 552 001000280000000200012000285911337200040 0002004415334 00004 13364spiel Ia-1

49.9 g of potassium t-butoxide are placed in 130 ml of dry tetrahydrofuran and under reflux with a solution of 65 g of N- (2,4,6-trimethylphenyl) acetyl methyl tetrahydrothiophene-3-amino-carboxylate in 420 ml of dry toluene added and boiled under reflux for 90 min. After cooling, the reaction solution mixed with 650 ml of water, the aqueous phase separated. The organic phase is washed again with 300 ml of water. The aqueous phases are combined acidified with 70 ml of concentrated hydrochloric acid and the precipitate is suctioned off and dried. 56 g (96% of theory), mp <230 ° C., are obtained.

The following compounds are obtained analogously:  

Table 1a

Table 1b

Table 1c

Table 1d

Table 1e

Table 1f

Example Ib-1

5.8 g of the compound of Example Ia-1 are dissolved in 70 ml of dry methylene chloride mixed with 2.8 ml of triethylamine and at 0 to 10 ° C 1.5 ml of acetyl chloride in 5 ml dry methylene chloride added. The reaction solution is twice with Washed 200 ml of 0.5 N sodium hydroxide solution, dried over magnesium sulfate and that Distilled off solvent. 1.7 g (26% of theory) of mp 211 ° C. remain.

The following compounds are obtained analogously:

Table 2a

Table 2b

Table 2c

Table 2d

Table 2e

Table 2f

Example Ic-1

5.8 g of the compound of Example Ia-1 are dissolved in 70 ml of dry methylene chloride mixed with 2.8 ml triethylamine and at 0 to 10 ° C 2.7 g chloroformic acid sec. Butyl ester in 5 ml of dry methylene chloride added. The reaction solution is washed twice with 200 ml of 0.5 N sodium hydroxide solution, dried over magnesium sulfate and the solvent is distilled off. 1.7 g (22% of theory) of mp 157 ° C. remain.

The following compounds are obtained analogously:

Table 3a

Table 3b

Table 3c

3d table

Table 3e

Table 3f

Example Id-1

5.8 g of the compound of Example Ia-11 are dried in 70 ml Methylene chloride mixed with 2.8 ml of triethylamine and at 0 to 10 ° C 1.7 g of methane sulfonic acid chloride in 5 ml of dry methylene chloride added. The reaction solution is washed twice with 200 ml of 0.5 N sodium hydroxide solution, over magnesium dried sulfate and the solvent was distilled off. 3.2 g (56% of theory) remain Mp 220 ° C.

Example Ie-1

3 g of the compound of Example Ia-11 are in 20 ml of dry tetrahydrofuran submitted, mixed with 1.5 ml of triethylamine and then 2.1 g of ethanthio phosphonic acid chloride sec-butyl thioester added. The mixture is stirred at 50 ° C. for 1 day, the solvent is evaporated off and the residue is chromatographed on silica gel Hexane / acetone 9: 1 as eluent. The solution is obtained after evaporation using 1.1 g (= 23% of theory) of the compound shown above, mp. 216 ° C.

The example (Ie-2) of mp. 208 C was obtained analogously:

Example If-1

5.8 g of the compound of Example Ia-11 are dried in 70 ml Methylene chloride with 6.24 ml tetrabutylammonium hydroxide (in the form of 40% aqueous solution) and at 0 to 10 ° C for 15 min. touched. The reaction solution is concentrated and the residue by adding diisopropyl ether to the crystals sation brought. After the precipitate has been suctioned off, 5.4 g (99% of theory) of mp remain. 110 ° C.

Example Ig-1

5.8 g of the compound of Example Ia-11 are dried in 70 ml Methylene chloride mixed with 2.8 ml of triethylamine and 1.76 ml at 0 to 10 ° C Morpholine carbamic acid chloride in 5 ml dry methylene chloride added. The Reaction solution is washed twice with 200 ml of 0.5 N sodium hydroxide solution Dried magnesium sulfate and the solvent was distilled off. There remain 1.2 g (19% of theory) mp 198 ° C.

Examples for the preparation of the intermediates of formula XVII Example XVII-1

56.2 g of 51.2 g of 3-amino-3-cyano-thiolan in 600 ml of dry tetrahydrofuran ml of triethylamine and a solution of 78.6 g of mesitylene at 0 ° C. Acetic acid chloride added dropwise in 80 ml of dry tetrahydrofuran. The reaction mixture is poured onto 1.2 l of ice water, 200 ml of 1N hydrochloric acid are added, the the resulting precipitate is suction filtered and dried. 89.5 g (78% of theory) Mp. 174-175 ° C of the following compound obtained.

The following compounds XVII are obtained analogously.

Examples for the preparation of the intermediates of formula II Example II-1

A suspension of 89.5 g of the compound of Example XVII-1 in 500 ml Methylene chloride is concentrated in 152.4 g. Added sulfuric acid, stirred for 2 h and 218 ml of methanol were added dropwise at 40 ° C. The mixture is stirred at 40-70 ° C for 6 h. The Reaction solution is poured onto 1.5 l of ice, extracted with 500 ml of methylene chloride, the methylene chloride phase is dried and the solvent is distilled off. You get 65 g (65% of theory) mp 111-113 ° C. of the compound of the formula

The following compounds of the formula II are obtained analogously:

In the application examples, the following were from the prior art known comparison compounds used:

Example A Myzus test

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

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

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

After the desired time, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphid is killed has been.

In this test z. B. the compounds according to the preparation examples Ia-17 and Ib-128 at an exemplary active ingredient concentration of 0.01% Killing at least 90% after 6 days, while from the state of the Technology known compound (A) caused no killing and that from the prior art Compound (B) known in the art at an active substance concentration of 0.1% a kill of only 20% caused.  

Example B Plutella test

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

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

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

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

In this test, z. B. the compound according to preparation example Ib-132 an exemplary active ingredient concentration of 0.1% after a kill of 100% 3 days.  

Example C Nephotettix test

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

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

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

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

In this test z. B. the compounds according to the preparation examples Ic-194 and Ic-198 at an exemplary active ingredient concentration of 0.01% 100% kill.  

Example D Tetranychus test (OP-resistant)

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

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

Bean plants (Phaseolus vulgaris), strongly affected by all stages of development common spider mite (Tetranychus urticae) are infected with a Active ingredient preparation of the desired concentration injected.

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

In this test z. B. the compounds according to the preparation examples Ia-17, Ib-132 and Ic-198 at an exemplary active ingredient concentration of 0.02% a 100% kill after 14 days.  

Example E Panonychus test

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

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

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

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

In this test z. B. the compounds according to the preparation examples Ia-17, Ib-132 and Ic-198 at an exemplary active ingredient concentration of 0.02% a 100% kill after 14 days.

Claims (14)

1. Substituted spirocyclic 1-H-3-aryl-pyrrolidine-2,4-dione derivatives of the formula (I) in which
A and B together with the carbon atom to which they are attached represent an unsubstituted or substituted 5-6-membered cycle interrupted by heteroatoms,
X represents alkyl, halogen or alkoxy,
Y represents hydrogen alkyl, halogen, alkoxy or haloalkyl,
Z represents alkyl, halogen or alkoxy,
n stands for a number 0, 1, 2 or 3,
G for hydrogen (a) or for the groups stands,
E represents a metal ion equivalent or an ammonium ion,
L and M each represent oxygen or sulfur,
R1 represents alkyl, alkenyl, alkoxy alkyl, alkylthioalkyl, polyalkoxyalkyl or cycloalkyl which may be interrupted by hetero atoms, optionally substituted phenyl, optionally substituted phenylalkyl, optionally substituted phenylalkyl, substituted hetaryl, substituted phenoxyalkyl or substituted hetaryloxyalkyl,
R² represents alkyl, cycloalkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or phenyl or benzyl which is optionally substituted by halogen,
R³, R⁴ and R⁵ independently of one another each represent optionally substituted by halogen alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio and optionally substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another represent hydrogen, optionally substituted by halogen-substituted alkyl, alkenyl, alkoxy, alkoxyalkyl, optionally substituted phenyl, optionally substituted benzyl, or together with the adjacent N atom for a cycle optionally interrupted by oxygen or sulfur stand. 2. Substituted spirocyclic 1-H-3-aryl-pyrrolidine-2,4-dione derivatives according to claim 1 of the following formulas (Ia) to (Ig): wherein
A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and n have the meanings given in Claim 1. 3. Substituted spirocyclic 1H-3-aryl-pyrrolidine-2,4-dione derivatives of the formula (I) according to Claim 1, in which
A, B and the carbon atom to which they are attached represent a 5-6-membered spirocycle which is the group and / or contains oxygen and / or sulfur, which may be unsubstituted or mono- or polysubstituted by alkyl, cycloalkyl, haloalkyl, alkoxy, thioalkyl, halogen or phenyl,
X represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy,
Y represents hydrogen-C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy or C₁-C₃- haloalkyl,
Z represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy,
G for hydrogen (a) or for the groups stands in which
E represents a metal ion equivalent or an ammonium ion and
L and M each represent oxygen or sulfur,
R¹ for each optionally substituted by halogen C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl, C₁-C₈-polyalkoxy-C₁ -C₈-alkyl or cycloalkyl with 3 to 8 ring atoms, which can be interrupted by oxygen and / or sulfur atoms and substituted by C₁-C₆-alkyl,
for phenyl optionally substituted by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy,
for phenyl-C₁-C₆-alkyl optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy
for hetaryl optionally substituted by halogen and / or C₁-C₆alkyl,
for optionally substituted by halogen and / or C₁-C₆-alkyl phenoxy-C₁-C₆-alkyl or
represents hetaryloxy-C₁-C₆-alkyl optionally substituted by halogen, amino and / or C₁-C₆-alkyl,
R² for C₁-C₂₀-alkyl optionally substituted by halogen, C₃-C₁₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl, C₁-C₈-polyalkoxy-C₂-C₈- alkyl
for C₃-C₆-cycloalkyl optionally substituted by halogen or C₁-C₆-alkyl or
represents phenyl or benzyl optionally substituted by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkyl,
R³, R⁴ and R⁵ independently of one another each optionally substituted by halogen C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino, di- (C₁-C₈) -alkylamino, C₁-C₈-alkylthio, C₃-C₅ -Alkenylthio, C₃-C₇- cycloalkylthio, for each optionally by halogen, nitro, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-halo genalkylthio, C₁-C₄-alkyl, C₁-C₄ haloalkyl substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another for hydrogen, in each case optionally substituted by halogen C₁-C₁₀-alkyl, C₃-C₁ Cycl-cycloalkyl, C₁-C₁₀-alkoxy, C₃-C₈-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl, for phenyl optionally substituted by halogen, C₁-C₈-haloalkyl, C₁-C₈-alkyl or C₁-C₈-alkoxy, optionally substituted by halogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl or C₁-C₈-alkoxy or together with the N atom to which they are attached represent a 3- to 7-membered ring which may be interrupted by oxygen or sulfur,
R⁹ represents hydrogen R¹, COR¹ or CO₂R², where R¹ or R² can assume the meanings given in claim 3 for R¹ or R² and
n stands for a number from 0 to 3. 4. Substituted spirocyclic 1H-3-aryl-pyrrolidine-2,4-dione derivatives of the formula (I) according to Claim 1, in which
A, B and the carbon atom to which they are attached represent a 5-6 membered spirocycle, which is the group and / or contains oxygen and / or sulfur which is unsubstituted or singly or multiply by C₁-C₆-alkyl, C₁-C₈-cycloalkyl, C₁-C₃-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-thioalkyl, fluorine, chlorine or can be substituted with phenyl,
X represents C₁-C₄-alkyl, halogen or C₁-C₄-alkoxy,
Y represents hydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy or C₁-C₂- haloalkyl,
Z represents C₁-C₄-alkyl, halogen or C₁-C₄-alkoxy,
G for hydrogen (a) or for the groups stands in which
E represents a metal ion equivalent or an ammonium ion and
L and M each represent oxygen or sulfur,
R¹ for each optionally substituted by halogen C₁-C₁₆-alkyl, C₂-C₈-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl, C₁-C₆-polyalkoxy-C₁ -C₆-alkyl or cycloalkyl with 3 to 7 ring atoms, which can be interrupted by 1-2 oxygen and / or sulfur atoms and substituted by C₁-C₄-alkyl,
for phenyl optionally substituted by halogen, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy,
for phenyl-C₁-C₄-alkyl optionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy,
for furanyl, thienyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl optionally substituted by fluorine, chlorine, bromine and / or C₁-C₄alkyl,
for optionally substituted by fluorine, chlorine, bromine and / or C₁-C₄-alkyl phenoxy-C₁-C₅-alkyl or
represents in each case optionally substituted by fluorine, chlorine, bromine, amino and / or C₁-C₄-alkyl pyridyloxy-C₁-C₆-alkyl, pyrimidinyloxy-C₁-C₆-alkyl or thiazolyloxy-C₁-C₆-alkyl,
R² is in each case optionally substituted by halogen C₁-C₁₆-alkyl, C₃-Cyl-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl, C₁-C₆-polyalkoxy-C₂-C₆- alkyl,
for optionally substituted by fluorine, chlorine or C₁-C₄-alkyl C₃-C₆-cydoalkyl or
represents phenyl or benzyl optionally substituted by halogen, nitro, C₁-C₄-alkyl, C₁-C₃- alkoxy or C₁-C₃-haloalkyl,
R³, R⁴ and R⁵ independently of one another are optionally substituted by halogen C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylamino, di- (C₁- C₆) -alkylamino, C₁-C₆-alkylthio, C₃-C₄- Alkenylthio, C₃-C₆-Cyc loalkylthio, for each optionally by fluorine, chlorine, bromine, nitro, cyano, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, C₁-C₃-alkylthio, C₁-C₃- haloalkylthio, C₁-C₃ -Alkyl, C₁-C₃-haloalkyl substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another for hydrogen each optionally substituted by halogen C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy, C₃-C₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, for optionally phenyl substituted by halogen, C₁-C₅-haloalkyl, C₁-C₅-alkyl or C₁-C₅-alkoxy, optionally substituted by halogen, C₁-C₅-alkyl, C₁-C₅-haloalkyl or C₁-C₅-alkoxy or together with the N atom to which they are attached represent a 4- to 7-membered ring which may be interrupted by oxygen or sulfur,
R⁹ represents hydrogen COR¹ or CO₂R¹ ', where R¹' represents C₁-C₆ alkyl, phenyl or benzyl and
n stands for a number from 0 to 2. 5. Substituted spirocyclic 1H-3-aryl-pyrrolidine-2,4-dione derivatives of the formula (I) according to Claim 1, in which
A, B and the carbon atom to which they are attached represent a 5- to 6-membered spirocycle, which is the group and / or contains oxygen and / or sulfur which is unsubstituted or singly or multiply by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. -butyl, tert. Butyl, cyclohexyl, trifluoromethyl, methoxy, methylthio, fluorine, chlorine or phenyl may be substituted,
X represents methyl, ethyl, propyl, 2-propyl, fluorine, chlorine, bromine, methoxy or ethoxy,
Y represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl,
Z represents methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy or ethoxy,
G for hydrogen (a) or for the groups stands in which
E represents a metal ion equivalent or an ammonium ion and
L and M each represent oxygen or sulfur,
R¹ for C₁-C₁₄ alkyl, C₂-C₆ alkenyl, C₁-C₄ alkoxy-C₁-C₆-alkyl, C₁-C₄-alkylthio-C₁-C₆-alkyl, C₁-C₄-polyalkoxy, each optionally substituted by fluorine or chlorine -C₁-C₄-alkyl or cycloalkyl with 3 to 6 ring atoms, which can be interrupted by 1 or 2 oxygen and / or sulfur atoms and substituted by methyl or ethyl,
for phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or nitro,
for phenyl-C₁-C₃-alkyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,
for furanyl, thienyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl,
for optionally substituted by fluorine, chlorine, methyl, ethyl phenoxy-C₁-C₄-alkyl or for each optionally substituted by fluorine, chlorine, amino, methyl, ethyl pyridyloxy-C₁-C₄-alkyl, pyrimidinyloxy-C₁-C₄-alkyl or thiazolyloxy -C₁-C₄-alkyl,
R² for C₁-C₁₄-alkyl, C₃-C₆-alkenyl, C₁-C₄-alkoxy-C₂-C₆-alkyl, C₁-C₄-polyalkoxy-C₂-C₆-alkyl, optionally substituted by fluorine or chlorine, for optionally substituted by fluorine, Chlorine, methyl or ethyl substituted C₃-C₆ cycloalkyl
or represents phenyl or benzyl optionally substituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl,
R³, R⁴ and R⁵ independently of one another for C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino, di- (C₁-C₄) -alkylamino, C₁-C₄-alkylthio, each optionally substituted by fluorine or chlorine, for each given by fluorine, chlorine, bromine, nitro, cyano, C₁-C₂-alkoxy, C₁-C₂-fluoroalkoxy, C₁-C₂-alkylthio, C₁-C₂-fluoroalkylthio, C₁-C₃-alkyl substituted phenyl, phenoxy or Phenylthio,
R⁶ and R⁷ independently of one another are preferably hydrogen, in each case optionally substituted by fluorine, chlorine, bromine, substituted C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₁-C₄-alkyl, for phenyl optionally substituted by fluorine, chlorine, bromine, C₁-C₄-haloalkyl, C₁-C₄-alkyl or C₁-C₄-alkoxy, for optionally by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄alkoxy-substituted benzyl or together with the N atom to which they are attached represent a 5- to 7-membered ring which may be interrupted by oxygen or sulfur,
R⁹ represents hydrogen-COR¹ 'or CO₂R¹', where R¹¹ represents C₁-C₄-alkyl, phenyl or benzyl and
n stands for 0 or 1. 6. A process for the preparation of the spirocyclic substituted 1H-3-aryl-pyrroli din-2,4-dione derivatives of the formula (I) according to claim 1, characterized in that

• (A) 1-H-3-aryl-pyrrolidine-2,4-diones or their enols of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given in claim 1, is obtained if
  N-acylamino acid esters of the formula (II) in which
  A, B, X, Y, Z and n have the meaning given above, and
  R⁸ represents alkyl,
  intramolecularly condensed in the presence of a diluent and in the presence of a base; or
• (B) that compounds of the formula (Ib) in which
  A, B, X, Y, Z, R¹ and n have the meaning given above, is obtained if
  Compounds of the formula (Ia), in which
  A, B, X, Y, Z and n have the meaning given above,
• α) with acid halides of the formula (III) in which
  R¹ has the meaning 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
• β) with carboxylic anhydrides of the formula (IV) R¹-CO-O-CO-R¹ (IV) 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
• (C) that compounds of the formula (Ic-1) in which
  A, B, X, Y, Z, R² and n have the meaning given above, and
  M stands for oxygen or sulfur, if you get
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with chloroformate or chloroformate thiol ester of the formula (V) R²-M-CO-Cl (V) in which
  R² and M have the meaning given above,
  if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid binder; or
• (D) that compounds of the formula (Ic-2) in which
  A, B, R², X, Y, Z and n have the meaning given above
  and
  M stands for oxygen or sulfur, if you get
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
• α) with chloromothio formic acid esters or chlorodithio formic acid esters of the formula (VI) in which
  M and R² have the meaning given above,
  optionally in the presence of a diluent and if appropriate
  in the presence of an acid binder, or
• β) with carbon disulfide and then with alkyl halides of the general formula (VII) R²-Hal (VII) 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
• (E) that compounds of the formula (Id) in which
  A, B, X, Y, Z, R³ and n have the meaning given above, is obtained if one
  Compounds of formula (Ia) A, B, X, Y, Z and n have the meaning given above,
  with sulfonic acid chlorides of the formula (VIII) R³-SO₂-Cl (VIII) 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; or
• (F) that 3-aryl-pyrrolidine-2,4-diones of the formula (Ie) in which
  A, B, L, X, Y, Z, R⁴, R⁵ and n have the meaning given above,
  if 1-H-3-aryl-pyrrolidine-2,4-diones of the formula (Ia) or their enols in which
  A, B, X, Y, Z and n have the meaning given above, with phosphorus compounds of the formula (IX) in which
  L, R⁴ and R⁵ have the meaning 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
• (G) that compounds of the formula (If) in which
  A, B, X, Y, Z and n have the meaning given above, and
  E stands for a metal ion equivalent or for an ammonium ion, is obtained if
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with metal compounds or amines of the formulas (X) and (XI) in which
  Me for mono- or divalent metal ions,
  t for the number 1 or 2
  R¹⁰, R¹¹ and R¹² independently represent hydrogen and alkyl and
  R¹³ represents hydrogen, hydroxy or C₁-C₄ alkoxy,
  if appropriate in the presence of a diluent,
• H) that compounds of the formula (g) in which
  A, B, L, X, Y, Z, R⁶, R⁷ and n have the meaning given above,
  if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
• α) with compounds of the formula (XII) R⁶-N = C = L (XII) in which
  L and R⁶ have the meaning given above
  optionally 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 (XIII) in which
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

7. Compounds of the formula (XVII) in which
A, B, X, Y, Z and n have the meaning given in claim 1. 8. A process for the preparation of compounds of the formula (XVII) according to claim 7, characterized in that aminonitriles of the formula (XVI) in which
A and B have the meaning given in claim 1,
with phenylacetic acid halides of the formula (XV) in which
X, Y, Z and n have the meaning given in claim 1 and
Hal stands for chlorine or bromine. 9. Compounds of formula (II) in which
A, B, X, Y, Z, n have the meaning given in claim 1
and R⁸ represents alkyl. 10. A process for the preparation of compounds of the formula (II), characterized in that amino acid derivatives of the formula (XIV), in which
R⁸ represents hydrogen (XIVa) or alkyl (XIVb) and
A have the meaning given in claim 1
with phenylacetic acid halides of the formula (XV) in which
X, Y, Z and n have the meaning given in claim 1 and
Hal represents chlorine or bromine,
acylated and optionally the acyl amino acids of the formula (IIa) formed for R⁸ ′ = hydrogen in which
A, B, X, Y, Z and n have the meaning given in claim 1,
esterified or subjecting the compounds of formula (XVII) according to claim 7 to sulfuric acid alcoholysis. 11. pesticides and herbicides, characterized by a Content of at least one substituted spirocyclic 1-H-3-aryl-pyrroli din-2,4-dione derivative of the formula (I) according to Claim 1. 12. Use of substituted spirocyclic 1-H-3-aryl-pyrrolidine-2,4-dione Derivatives of formula (I) according to claim 1 for combating pests and unwanted vegetation.   13. A method for controlling pests, characterized in that Substituted spirocyclic 1-H-3-aryl-pyrrolidine-2,4-dione derivatives of the formula (I) according to claim 1 for pests, undesirable plant growth and / or let their living space take effect. 14. Process for the preparation of pesticides and herbicides, characterized in that substituted spirocyclic 1-H-3-aryl pyrrolidine-2,4-dione derivatives of the formula (I) according to Claim 1 with extenders and / or surfactants mixed.