The invention relates to novel phenyl-substituted cyclic ketoenols, to a plurality of processes and intermediates for their preparation and to their use as pesticides.
It has akready been discosed that certain phenyl-substituted cyc ketoenols are active as insectidces, acaricides and/or herbicides.
Also known are 1H-arylpyrrolidine-dione derivatives (BP-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, WO 95/01 358, WO 95126 954, WO 95/20 572, EP-A-0 668 267, WO 96/15 395, WO 96/35 664, WO 97/01 535 and WO 97/02 243).
It is known that certain substituted xcex943-dihydrofuran-2-one derivatives have herbicidal properties (cf. DE-A-4 014 420). The synthesis of the tetronic acid derivatives used as staring materials (such as, for example, 3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-xcex943-dihydrofuran-2-one) is likewise described in DE-A-4 014 420. Compounds of similar struftre without details of an insecticidal and/or acaricidal activity are known from the publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985, (S) 1567-76. Furthermore, 3-aryl-xcex943-dihydrofuranone derivatives having herbicidal, acaricidal and insecticidal properties are disclosed in EP-A-528 156, EP-A 0 647 637, WO 95/26345, WO 96/20 196, WO 96/25 395, WO 96/35 664, WO 97/01 535 and WO 97/02 243.
Certain phenytl-pyrone derivatives unsubstituted in the phenyl ring have already been dislosed (cf. AM. Chirazi, T. Kappe and E. Ziegler, Arch. Phatin. 309, 558 (1976) and K. -H. Boltze and K. Heidenbluth, Chem. Ber. 91, 2849), a possible utility for these compounds as pesticides not being indicated. Phenyl-pyrone dertves substituted in the phenyl ring and having herbicidal, acaricidal and insecticidal propeties are descnrbed in EP-A-588 137, WO 96/25 395, WO 96/35 664 WO 97/01 535 and WO 97/02 243.
However, the acaricidal and insecticidal activity and/or spectrum of action, and/or the toleration of the known compounds by plants, in parficular by crops, is not always satisfactory.
The invention, accordingly, provides compounds of the formula (I) 
in which
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, benzyloxy, halogenoalkyl, halogenoalkoxy, cyano or nitro,
Z represents hydrogen, amino, halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, hydroxyl, cyano, nitro or respectively optionally substituted phenoxy, phenylthio, 5- or 6-membered hetaryloxy, 5- or 6-membered hetarylthio, phenylalkyloxy or phenylalkylthio and
Het represents one of the groups 
xe2x80x83in which
A represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl and alkylthioalkyl, represents respectively saturated or unsaturated and optionally substituted cycloalkyl or heterocyclyl or represents respectively optionally halogen-, alkyl-, halogenoalkyl-, alkoxy-, hatogenoalkoxy-, cyano- or nitro-substituted aryl, arylalkyl or hetaryl,
B represents alkyl or alkoxyalkyl or
A and B together with the carbon atom that they are attached to represent a saturated or unsaturated, optionally substituted carbocycle or heterocycle,
D represents hydrogen or represents an optionally substituted radical from the group 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 that they are attached to represent a respectively optionally substituted carbocycle or heterocycle,
G represents hydrogen (a) or represents one of the groups 
xe2x80x83in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R1 represents respectively optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl or represents respectively optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl or heterocyclyl or represents respectively optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetarytoxyalkyl,
R2 represents respectively optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl or represents respectively optionally substituted cycloalkyl, phenyl or benzyl,
R3, R4 and R5 independently of one another each represent respectively optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio or represent respectively optionally substituted phenyl, benzyl, phenoxy or phenylthio,
R6 and R7 independently of one another each represent hydrogen, represent respectively optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent respectively optionally substituted phenyl or benzyl, or form together with the nitrogen atom that they are attached to an optionally oxygen- or sulphur-containing, optionally substituted cycle.
The compounds of the formula (I) can also be present, depending on the nature of the substituents, as geometric and/or optical isomers and isomer mixtures of differing composition which, if appropriate, can be separated in a customary manner. Both the pure isomers and the isomer mixtures, their preparation and use, and compositions comprising them are part of the subject matter of the present invention. In the following, for simplicity, however, compounds of the formula (I) are always referred to, although both pure compounds and, if appropriate, mixtures having different proportions of isomer compounds are intended.
Including the meanings (1) to (4) of the group Het, the following principal structures (I-1) to (I-4) result: 
in which
A, B, D, G, X and Z are each as defined above.
Including the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-1-a) to (I-1-g) result if Het represents the group (1) 
in which
A, B, E, L, M, X, Z, R1, R2, R3, R4, R5, R6 and R7 are each as defined above.
Including the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-2-a) to (I-2-g) result if Het represents the group (2) 
in which
A, B, E, L, M, X, Z, R1, R2, R3, R4, R5, R6 and R7 are each as defined above.
Including the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-3-a) to (I-3-g) result if Het represents the group (3) 
in which
A, B, E, L, M, X, Z, R1, R2 R3, R4, R5, R6 and R7 are each as defined 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 formulae (I-4)a and (I-4)b
which is intended to be expressed by the dashed line in the formula (I-4).
The compounds of the formulae (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 formulae (I4)a and (I-4)b can, if desired, be separated by physical methods in a manner known per se, for example by chromatographic methods.
For better clarity, in the following in each case only one of the possible isomers is shown. This does not exclude the possibility that the compounds can optionally be present in the form of the isomer mixtures or in the other respective isomer form.
Including the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-4-a) to (I-4-g) result if Het represents the group (4) 
in which
A, D, E, L, M, X, Z, R1, R2, R3, R4, R5, R6 and R7 are each as defined above.
Furthermore, it has been found that the novel compounds of the formula (I) are 10 obtained by one of the processes described below:
(A) Compounds of the formula (I-1-a) 
in which
A, B, X and Z are each as defined above, are obtained by the intramolecular condensation of compounds of the formula (II) 
xe2x80x83in which
A, B, X and Z are each as defined above, and
R8 represents alkyl (preferably C1-C6-alkyl), in the presence of a diluent and in the presence of a base.
(B) Furthermore, it was found that compounds of the formula (I-2-a) 
in which
A, B, X and Z are each as defined above,
are obtained by the intramolecular condensation of compounds of the formula (III) 
xe2x80x83in which
A, B, X, Z and R8 are each as defined above,
in the presence of a diluent and in the presence of a base.
(C) Furthermore, it was found that compounds of the formula (I-3-a) 
in which
A, B, X and Z are each as defined above,
are obtained by the intramolecular cyclization of compounds of the formula (IV) 
xe2x80x83in which
A, B, X, Z and R8 are each as defined above and
W represents hydrogen, halogen, alkyl (preferably C1-C6-alkyl) or alkoxy (preferably C1-C8-alkoxy), if appropriate in the presence of a diluent and in the presence of an acid.
(D) Furthermore, it was found that compounds of the formula (I-4-a) 
in which
A, D, X and Z are each as defined above,
are obtained by reacting compounds of the formula (V) 
xe2x80x83in which
A and D are each as defined above,
or their silyl enol ethers of the formula (Va) 
xe2x80x83in which
A and D are each as defined above and
R8xe2x80x2 represents alkyl (preferably methyl),
with compounds of the formula (VI) 
xe2x80x83in which
X and Z are each as defined 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.
Furthermore, it was found
(E) that the compounds of the formulae (I-1-b) to (I-4-b) shown above in which A, B, D, R1, X and Z are each as defined above are obtained by reacting compounds of the formulae (I-1-a) to (I-4-a) shown above in which A, B, D, X and Z are each as defined above
xcex1) with acid halides of the formula (VII) 
xe2x80x83in which
R1 is as defined above and
Hal represents halogen (in particular chlorine or bromine), or
xcex2) with carboxylic anhydrides of the formula (VIII)
R1xe2x80x94COxe2x80x94Oxe2x80x94COxe2x80x94R1xe2x80x83xe2x80x83(VIII)
xe2x80x83in which
R1 is as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent;
(F) that the compounds of the formulae (I-1-c) to (I-4-c) shown above in which A, B, D, R2, M, X and Z are each as defined above and L represents oxygen are obtained by reacting compounds of the formulae (I-1-a) to
(I-4-a) shown above in which A, B, D, X and Z are each as defined above, in each case
with chloroformic esters or chloroformic thioesters of the formula (IX)
R2xe2x80x94Mxe2x80x94COxe2x80x94Clxe2x80x83xe2x80x83(IX)
xe2x80x83in which
R2 and M are each as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent;
(G) that compounds of the formulae (I-1-c) to (I-4-c) shown above in which A, B, D, R2, M, X and Z are each as defined above and L represents sulphur are obtained by reacting compounds of the formulae (I-1-a) to (I-4-a) shown above in which A, B, D, X and Z are each as defined above, in each case
with chloromonothioformic esters or chlorodithioformic esters of the formula (X) 
xe2x80x83in which
M and R2 are each as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid-bindina agent,
(H) that compounds of the formulae (I-1-d) to (I-4-d) shown above in which A, B, D, R3, X and Z are each as defined above are obtained by reacting compounds of the formulae (I-1-a) to (I-4-a) shown above in which A, B, D, X and Z are each as defined above, in each case
with sulphonyl chlorides of the formula (XII)
R3xe2x80x94SO2xe2x80x94Clxe2x80x83xe2x80x83(XII)
xe2x80x83in which
R3 is as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent,
(I) that compounds of the formulae (I-1-e) to (I-4-e) shown above in which A, B, D, L, R4, R5, X and Z are each as defined above are obtained by reacting compounds of the formulae (I-1-a) to (I-4-a) shown above in which A, B, D, X and Z are each as defined above, in each case
with phosphorus compounds of the formula (XIII) 
xe2x80x83in which
L, R4 and R5 are each as defined above and
Hal represents halogen (in particular chlorine or bromine),
if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent,
(J) that compounds of the formulae (I-1-f) to (I-4-f) shown above in which A, B, D, E, X and Z are each as defined above are obtained by reacting compounds of the formulae (I-1-a) to (I-4-a) in which A, B, D, X and Z are each as defined above, in each case
with metal compounds or amines of the formulae (XIV) or (XV) 
xe2x80x83in which
Me represents a mono- or divalent metal (preferably an alkali metal or alkaline earth metal, such as lithium, sodium, potassium, magnesium or calcium),
t represents the number 1 or 2 and
R10, R11, R12 independently of one another each represent hydrogen or alkyl (preferably C1-C8-alkyl),
if appropriate in the presence of a diluent;
(K) that compounds of the formulae (I-1-g) to (I-4-g) shown above in which A, B, D, L, R6, R7, X and Z are each as defined above are obtained by reacting compounds of the formulae (I-1-a) to (I-4-a) shown above in which A, B, D, X and Z are each as defined above, in each case
xcex1) with isocyanates or isothiocyanates of the formula (XVI)
R6xe2x80x94Nxe2x95x90Cxe2x95x90Lxe2x80x83xe2x80x83(XVI)
xe2x80x83in which
R6 and L are each as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or
xcex2) with carbamoyl chlorides or thiocarbamoyl chlorides of the formula (XVII) 
xe2x80x83in which
L, R6 and R7 are each as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent.
Furthermore, it has been found that the novel compounds of the formula (I) have a very good activity as pesticides, preferably as insecticides and acaricides, and that they additionally are very well tolerated by plants, in particular by crops.
Formula (I) provides a general definition of the compounds according to the invention. Preferred substituents or ranges of the radicals shown in the formulae mentioned hereinabove and hereinbelow are illustrated below:
X preferably represents halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, benzyloxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, cyano or nitro.
Z preferably represents hydrogen, amino, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, hydroxyl, cyano, nitro or respectively optionally halogen-, C1-C4-alkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkyl-, C1-C4-halogenoalkoxy-, nitro- or cyano-substituted phenoxy, phenylthio, thiazolyloxy, pyridinyloxy, pyrimidinyloxy, pyrazolyloxy, phenyl-C1-C4-alkyloxy or phenyl-C1-C7-alkylthio.
Het preferably represents one of the groups 
A preferably represents respectively optionally 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, preferably represents optionally halogen-, C1-C6-alkyl- or C1-C6-alkoxy-substituted C3-C8-cycloalkyl in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur, or preferably represents respectively optionally halogen-, C1-C6-alkyl-, C1-C6-halogenoalkyl-, C1-C6-alkoxy-, C1-C6-halogenoalkoxy-, cyano- or nitro-substituted phenyl, naphthyl, phenyl-C1-C6-alkyl, naphthyl-C1-C6-alkyl or hetaryl having 5 or 6 ring atoms and one to three hetero atoms from the group consisting of oxygen, sulphur and nitrogen (in particular from the group consisting of furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, indolyl, thiazolyl and thienyl).
B preferably represents C1-C12-alkyl or C1-C8-alkoxy-C1-C6-alkyl or
A, B and the carbon atom that they are attached to preferably represent C3-C10-cycloalkyl or C1-C10-cycloalkenyl where in each case one methylene group is optionally replaced by oxygen or sulphur and which are optionally substituted by C1-C8-alkyl, C3-C10-cycloalkyl, C1-C8-halogenoalkyl, C1-C8-alkoxy, C1-C8-alkylthio, halogen or phenyl or
A, B and the carbon atom that they are attached to preferably represent C5-C6-cycloalkyl which is substituted by an alkylenediyl group optionally containing one or two not directly adjacent oxygen and/or sulphur atoms, or by an alkylenedioxy group or an alkylenedithioyl group forming a further five- to eight-membered ring with the carbon atom that it is attached to, or
A, B and the carbon atom that they are attached to preferably represent C3-C8-cycloalkyl or C5-C8-cycloalkenyl in which two carbon atoms are linked to each other by respectively optionally C1-C6-alkyl-, C1-C6-alkoxy- or halogen-substituted C3-C6-alkanediyl, C1-C6-alkenediyl or C4-C6-alkanedienediyl, one methylene group in each case being optionally replaced by oxygen or sulphur.
D preferably represents hydrogen, preferably represents respectively optionally halogen-substituted 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, preferably represents optionally halogen-, C1-C4-alkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkyl-substituted C3-C8-cycloalkyl in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur, or preferably represents respectively optionally halogen-, C1-C6 alkyl-, C1-C6-halogenoalkyl-, C1-C6-alkoxy-, C1-C6-halogenoalkoxy-, cyano- or nitro-substituted phenyl, hetaryl having 5 or 6 ring atoms and one or two hetero atoms from the group consisting of oxygen, sulphur and nitrogen (in particular from the group consisting of furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl and triazolyl), phenyl-C1-C6-alkyl or hetaryl-C1-C6-alkyl having 5 or 6 ring atoms and one or two hetero atoms from the group consisting of oxygen, sulphur and nitrogen (in particular from the group consisting of furanyl-, imidazolyl-, pyridyl-, thiazolyl-, pyrazolyl-, pyrimidyl-, pyrrolyl-, thienyl- and triazolyl-C1-C6-alkyl) or
A and D together preferably represent a C3-C6-alkanediyl, C3-C6-alkenediyl or C4-C6-alkadienediyl group in which respectively optionally one methylene group is replaced by oxygen or sulphur and which are respectively optionally substituted by halogen or respectively optionally halogen-substituted C1-C10-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C7-cycloalkyl, phenyl or benzyloxy or by a further C3-C6-alkanediyl, C3-C6-alkenediyl or C4-C6-alkadienediyl group forming a fused ring, in which optionally respectively one methylene group is replaced by oxygen or sulphur and which are optionally substituted by C1-C6-alkyl, or
A and D together represent a C3-C6-alkanediyl or C3-C6-alkenediyl group containing in each case optionally one of the following groups 
G preferably represents hydrogen (a) or represents one of the groups 
xe2x80x83in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur.
R1 preferably represents respectively optionally halogen-substituted 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 preferably represents optionally halogen-, C1-C6-alkyl- or C1-C6-alkoxy-substituted C3-C8-cycloalkyl in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur,
preferably represents optionally halogen-, cyano-, nitro-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-halogenoalkyl-, C1-C6-halogenoalkoxy-, C1-C6-alkylthio- or C1-C6-alkylsulphonyl-substituted phenyl,
preferably represents optionally halogen-, nitro-, cyano-, C1-C6-alkyl, C1-C6-alkoxy-, C1-C6-halogenoalkyl- or C1-C6-halogenoalkoxy-substituted phenyl-C1-C6-alkyl,
preferably represents optionally halogen- or C1-C6-alkyl-substituted 5- or 6-membered hetaryl having one or two hetero atoms from the group consisting of oxygen, sulphur and nitrogen (in particular from the group consisting of pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl and thienyl), preferably represents optionally halogen- or C1-C6-alkyl-substituted phenoxy-C1-C6-alkyl or
preferably represents optionally halogen-, amino- or C1-C6-alkyl-substituted 5- or 6-membered hetaryloxy-C1-C6-alkyl having one or two hetero atoms from the group consisting of oxygen, sulphur and nitrogen (in particular from the group consisting of pyridyloxy-C1-C6-alkyl, pyrimidyloxy-C1-C6-alkyl and thiazolyloxy-Ci-C6-alkyl).
R2 preferably represents respectively optionally halogen-substituted C1-C20-alkyl, C2-C20-alkenyl, C1-C8-alkoxy-C2-C8-alkyl or poly-C1-C8-alkoxy-C2-C8-alkyl,
preferably represents optionally halogen-, C1-C6-alkyl- or C1-C6-alkoxy-substituted C3-C8-cycloalkyl or
preferably represents respectively optionally halogen-, cyano-, nitro-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-halogenoalkyl- or C1-C6-halogenoalkoxy-substituted phenyl or benzyl.
R3 preferably represents optionally halogen-substituted C1-C8-alkyl or respectively optionally halogen-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C4-halogenoalkyl-, C1-C4-halogenoalkoxy-, cyano- or nitro-substituted phenyl or benzyl.
R4 and R5 independently of one another each preferably represent respectively optionally halogen-substituted C1-C8-alkyl, C1-C8-alkoxy, C1-C8-alkylamino, di-(C1-C8-alkyl)-amino, C1-C8-alkylthio or C3-C8-alkenylthio or preferably represent respectively optionally halogen-, nitro-, cyano-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C4-alkyl- or C1-C4-halogenoalkyl-substituted phenyl, phenoxy or phenylthio.
R6 and R7 independently of one another each preferably represent hydrogen, preferably represent respectively optionally halogen-substituted C1-C8-alkyl, C3-C8-cycloalkyl, C1-C8-alkoxy, C3-C8-alkenyl or C1-C8-alkoxy-C2-C8-alkyl, preferably represent respectively optionally halogen-, C1-C8-alkyl-, C1-C8-halogenoalkyl- or C1-C8-alkoxy-substituted phenyl or benzyl or together preferably represent an optionally C1-C6-alkyl-substituted C3-C6-alkylene radical in which optionally one methylene group is replaced by oxygen or sulphur.
R13 preferably represents hydrogen or respectively optionally halogen-substituted C1-C8-alkyl or C1-C8-alkoxy, preferably represents optionally halogen-, C1-C4-alkyl- or C1-C4-alkoxy-substituted C3-C8-cycloalkyl in which optionally one methylene group is replaced by oxygen or sulphur, or preferably represents respectively optionally halogen-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C4-halogenoalkyl-, C1-C4-halogenoalkoxy-, nitro- or cyano-substituted phenyl, phenyl-C1-C4-alkyl or phenyl-C1-C4-alkoxy.
R14 preferably represents hydrogen or C1-C8-alkyl or
R13 and R14 together preferably represent C4-C6-alkanediyl.
R15 and R16 are identical or different and each preferably represent C1-C6-alkyl or
R15 and R16 together preferably represent a C2-C4-alkanediyl radical which is optionally substituted by C1-C6-alkyl or by optionally halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, nitro- or cyano-substituted phenyl.
R17 and R18 independently of one another each preferably represent hydrogen, preferably represent optionally halogen-substituted C1-C8-alkyl or preferably represent optionally halogen-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C4-halogenoalkyl-, C1-C4-halogenoalkoxy-, nitro- or cyano-substituted phenyl or
R17 and R18 together with the carbon atom that they are attached to preferably represent optionally C1-C4-alkyl-substituted C5-C7-cycloalkyl in which optionally one methylene group is replaced by oxygen or sulphur.
R19 and R20 independently of one another each preferably represent C1-C10-alkyl, C1-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, benzyloxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, cyano or nitro.
Z particularly preferably represents hydrogen, amino, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, hydroxyl, cyano, nitro or respectively optionally fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-alkoxy-, C1-C2-halogenoalkyl-, C1-C2-halogenoalkoxy-, nitro- or cyano-substituted phenoxy or benzyloxy.
Het particularly preferably represents one of the groups 
A particularly preferably represents respectively optionally 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 particularly preferably represents optionally fluorine-, chlorine-, C1-C4-alkyl- or C1-C4-alkoxy-substituted C3-C7-cycloalkyl in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur, or particularly preferably represents respectively optionally fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, cyano, or nitro-substituted phenyl, furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, indolyl, thiazolyl, thienyl or phenyl-C1-C4-alkyl.
B particularly preferably represents C1-C10-alkyl or C1-C6-alkoxy-C1-C4-alkyl or
A, B and the carbon atom that they are attached to particularly preferably represent C3-C8-cycloalkyl or C5-C8-cycloalkenyl where one methylene group in each case is optionally replaced by oxygen or sulphur and which are optionally substituted by C1-C6-alkyl, C3-C8-cycloalkyl, C1-C3-haloogenoalkyl, C1-C6-alkoxy, C1-C6-alkylthio, fluorine, chlorine or phenyl or
A, B and the carbon atom that they are attached to particularly preferably represent C1-C6-cycloalkyl which is substituted by an alkylenediyl group optionally containing one or two not directly adjacent oxygen or sulphur atoms or by an alkylenedioxy group or by an alkylenedithiol group which forms together with the carbon atom that it is attached to a further five- to seven-membered ring or
A, B and the carbon atom that they are attached to particularly preferably represent C3-C6-cycloalkyl or C5-C6-cycloalkenyl in which two carbon atoms are linked to each other by respectively optionally C1-C4-alkyl-, C1-C4-alkoxy-, fluorine-, chlorine- or bromine-substituted C3-C5-alkanediyl or C3-C5-alkenediyl, one methylene group in each case being optionally replaced by oxygen or sulphur, or are linked to each other by butadienediyl.
D particularly preferably represents hydrogen, particularly preferably represents respectively optionally fluorine- or chlorine-substituted C1-C6-alkyl or C1-C6-alkoxy, particularly preferably represents optionally fluorine-, chlorine-, C1-C4-alkyl-, C1-C4-alkoxy- or C1-C2-halogenoalkyl-substituted C3-C7-cycloalkyl in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur, or particularly preferably represents respectively optionally fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-halogenoalkyi, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, cyano- or nitro-substituted phenyl, furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl, triazolyl or phenyl-C1-C4-alkyl or
A and D together particularly preferably represent a C3-C5-alkanediyl or C1-C5-alkenediyl group in which in each case one methylene group is optionally replaced by oxygen or sulphur and which are optionally substituted by fluorine, chlorine or by respectively optionally fluorine- or chlorine-substituted C1-C6-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-cycloalkyl, phenyl or benzyloxy or
in which in each case optionally one of the following groups is contained: 
G particularly preferably represents hydrogen (a) or represents one of the groups 
xe2x80x83in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur.
R1 particularly preferably represents respectively optionally fluorine- or chlorine-substituted C1-C 16-alkyl, C2-C16-alkenyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkylthio-C1-C6-alkyl or poly-C1-C6-alkoxy-C1-C6-alkyl or particularly preferably represents optionally fluorine-, chlorine-, C1-C5-alkyl- or C1-C5-alkoxy-substituted C3-C7-cycloalkyl in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur,
particularly preferably represents optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, C1-C4-alkoxy-, C1-C3-halogenoalkyl-, C1-C3-halogenoalkoxy-, C1-C4-alkylthio- or C1-C4-alkylsulphonyl-substituted phenyl,
particularly preferably represents optionally fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-alkoxy-, C1-C3-halogenoalkyl- or C1-C3-halogeno-alkoxy-substituted phenyl-C1-C4-alkyl,
particularly preferably represents respectively optionally fluorine-, chlorine-, bromine- or C1-C4-alkyl-substituted pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl,
particularly preferably represents optionally fluorine-, chlorine-, bromine- or C1-C4-alkyl-substituted phenoxy-C1-C5-alkyl or
particularly preferably represents respectively optionally 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 respectively optionally fluorine- or chlorine-substituted C1-C16-alkyl, C2-C16-alkenyl, C1-C6-alkoxy-C2-C6-alkyl or poly-C1-C6-alkoxy-C2-C6-alkyl,
particularly preferably represents optionally fluorine-, chlorine-, C1-C4-alkyl- or C1-C4-alkoxy-substituted C3-C7-cycloalkyl or
particularly preferably represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, C1-C3-alkoxy-, C1-C3-halogenoalkyl- or C1-C3-halogenoalkoxy-substituted phenyl or benzyl.
R3 particularly preferably represents optionally fluorine- or chlorine-substituted C1-C6-alkyl or respectively optionally fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-alkoxy-, C1-C2-halogenoalkoxy-, C1-C2-halogenoalkyl-, cyano-, or nitro-substituted phenyl or benzyl.
R4 and R5 independently of one another each particularly preferably represent respectively optionally fluorine- or chlorine-substituted C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylamino, di-(C1-C6-alkyl)-amino, C1-C6-alkylthio or C3-C4-alkenylthio or particularly preferably represent respectively optionally fluorine-, chlorine-, bromine-, nitro-, cyano-, C1-C3-alkoxy-, C1-C3-haloge-noalkoxy-, C1-C3-alkylthio-, C1-C3-halogenoalkylthio-, C1-C3-alkyl- or C1-C3-halogenoalkyl-substituted phenyl, phenoxy or phenylthio.
R6 and R7 independently of one another each particularly preferably represent hydrogen, particularly preferably represent respectively optionally fluorine- or chlorine-substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-alkenyl or C1-C6-alkoxy-C2-C6-alkyl, particularly preferably represent respectively optionally fluorine-, chlorine-, bromine-, C1-C5-halogenoalkyl-, C1-C5-alkyl- or C1-C5-alkoxy-substituted phenyl or benzyl, or together particularly preferably represent an optionally C1-C4-alkyl-substituted C3-C6-alkylene radical in which optionally one methylene group is replaced by oxygen or sulphur.
R13 particularly preferably represents hydrogen or respectively optionally fluorine- or chlorine-substituted C1-C6-alkyl or C1-C6-alkoxy, particularly preferably represents optionally fluorine-, C1-C2-alkyl- or C1-C2-alkoxy-substituted C3-C7-cycloalkyl in which optionally one methylene group is replaced by oxygen or sulphur, or particularly preferably represents respectively optionally fluorine-, chlorine-, bromine-, C1-C5-alkyl-, C1-C5-alkoxy-, C1-C2-halogenoalkyl-, C1-C2-halogenoalkoxy-, 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 particularly preferably represent C4-C6-alkanediyl.
R15 and R16 are identical or different and each particularly preferably represent C1-C4-alkyl or
R15 and R16 together particularly preferably represent a C2-C3-alkanediyl radical which is optionally substituted by C1-C4-alkyl or by optionally fluorine-, chlorine-, bromine-, C1-C2-alkyl-, C1-C2-halogenoalkyl-, C1-C2-alkoxy-, C1-C2-halogenoalkoxy-, nitro- or cyano-substituted phenyl.
X very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro,
Z very particularly preferably represents hydrogen, amino, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro.
Het very particularly preferably represents one of the groups 
A very particularly preferably represents respectively optionally fluorine- or chlorine-substituted 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 very particularly preferably represents optionally fluorine-, chlorine-, methyl- or methoxy-substituted C3-C6-cycloalkyl in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur, or very particularly preferably represents respectively optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n-propyl-, iso-propyl-, methoxy-, ethoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- or nitro-substituted phenyl, pyridyl or benzyl.
B very particularly preferably represents C1-C8-alkyl or C1-C4-alkoxy-C1-C2-alkyl or
A, B and the carbon atom that they are attached to very particularly preferably represent C3-C8-cycloalkyl or C5-C8-cycloalkenyl in which in each case optionally one methylene group is replaced by oxygen or sulphur and which are optionally substituted 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 or
A, B and the carbon atom that they are attached to very particularly preferably represent C3-C6-cycloalkyl or C5-C6-cycloalkenyl in which two carbon atoms are linked together by C3-C4-alkanediyl or C3-C4-alkenediyl in which in each case optionally one methylene group is replaced by oxygen or sulphur, or are linked together by butadienediyl.
D very particularly preferably represents hydrogen, very particularly preferably represents respectively optionally fluorine-substituted C1-C4-alkyl or C1-C4-alkoxy or C3-C6-cycloalkyl in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur, or very particularly preferably represents respectively optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n-propyl-, iso-propyl-, methoxy-, ethoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- or nitro- substituted phenyl, furanyl, pyridyl, thienyl or benzyl, or
A and D together very particularly preferably represent a C3-C5-alkanediyl or C3-C5-alkenediyl group in which in each case optionally one methylene group is replaced by oxygen or sulphur and which are optionally substituted by fluorine, chlorine or by respectively optionally fluorine- or chlorine-substituted C1-C6-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-cycloalkyl, phenyl or benzyloxy.
G very particularly preferably represents hydrogen (a) or represents one of the groups 
xe2x80x83in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur.
R1 very particularly preferably represents respectively optionally fluorine- or chlorine-substituted C1-C14-alkyl, C2-C14-alkenyl, C1-C4-alkoxy-C1-C6-alkyl, C1-C4-alkylthio-C1-C6-alkyl, poly-C1-C4-alkoxy-C1-C4-alkyl or very particularly preferably represents optionally 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 optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur,
very particularly preferably represents optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-, ethoxy-, trifluoromethyl-, trifluoromethoxy-, methylthio-, ethylthio-, methylsulphonyl- or ethylsulphonyl-substituted phenyl,
very particularly preferably represents optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-, ethoxy-, trifluoromethyl- or trifluoromethoxy-substituted benzyl,
very particularly preferably represents respectively optionally fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted furanyl, thienyl or pyridyl,
very particularly preferably represents optionally fluorine-, chlorine-, methyl- or ethyl-substituted phenoxy-C1-C4-alkyl or
very particularly preferably represents respectively optionally fluorine-, chlorine-, amino-, methyl- or ethyl-substituted pyridyloxy-C1-C4-alkyl, pyrimidyloxy-C1-C4-alkyl or thiazolyloxy-C1-C4-alkyl.
R2 very particularly preferably represents respectively optionally fluorine- or chlorine-substituted C1-C14-alkyl, C2-C14-alkenyl, C1-C4-alkoxy-C2-C6-alkyl or poly-C1-C4-alkoxy-C2-C6-alkyl,
very particularly preferably represents optionally fluorine-, chlorine-, methyl-, ethyl-, n-propyl-, iso-propyl- or methoxy-substituted C3-C6-cycloalkyl,
or very particularly preferably represents respectively optionally fluorine-, chlorine-, cyano-, nitro-, methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-, ethoxy-, trifluoromethyl- or trifluoromethoxy-substituted phenyl or benzyl.
R3 very particularly preferably represents optionally fluorine- or chlorine-substituted methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl or respectively optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, iso-propyl-, tert-butyl-, methoxy-, ethoxy-, iso-propoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- or nitro-substituted phenyl or benzyl.
R4 and R5 independently of one another each very particularly preferably represent respectively optionally fluorine- or chlorine-substituted C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino or C1-C4-alkylthio or very particularly preferably represent respectively optionally fluorine-, chlorine-, bromine-, nitro-, cyano-, methyl-, methoxy-, trifluoromethyl- or trifluoromethoxy-subsfituted phenyl, phenoxy or phenylthio.
R6 and R7 independently of one another each very particularly preferably represent hydrogen, very particularly preferably represent respectively optionally fluorine- or chlorine-substituted C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C3-C4-alkenyl or C1-C4-alkoxy-C2-C4-alkyl, very particularly preferably represent respectively optionally fluorine-, chlorine-, bromine-, methyl-, methoxy- or trifluoromethyl-substituted phenyl or benzyl, or together very particularly preferably represent an optionally methyl- or ethyl-substituted C5-C6-alkylene radical in which optionally one methylene group is replaced by oxygen or sulphur.
Particular preference is given to compounds of the formula (I) in which Z does not represent hydrogen.
Preference is also given to those compounds where D does not represent methyl.
The abovementioned definitions or illustrations of radicals mentioned generally or in preferred ranges can be combined with each other as desired, i.e. also between the respective ranges and preferred ranges. They apply correspondingly to the final products and to the precursors and intermediates.
For the purpose of the invention, preference is given to compounds of the formula (I) in which there exists a combination of the meanings mentioned above as preferred (preferably).
For the purpose of the invention, particular preference is given to compounds of the formula (I) in which there exists a combination of the meanings mentioned above as particularly preferred.
For the purpose of the invention, very particular preference is given to compounds of the formula (I) in which there exists a combination of the meanings mentioned above as very particularly preferred.
Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can, as far as possible, in each case be straight-chain or branched, also in combination with hetero atoms, for example in alkoxy.
Optionally substituted radicals can be mono- or polysubstituted, it being possible in the case of polysubstitution for the substituents to be identical or different.
In addition to the compounds mentioned in the Preparation Examples, the following compounds of the formula (I-1-a) may be specifically mentioned:
In addition to the compounds mentioned in the preparation examples, the following compounds of the formula (1-2-a) may be specifically mentioned:
In addition to the compounds mentioned in the preparation examples, the following compounds of the formula (I-3-a) may be specifically mentioned:
In addition to the compounds mentioned in the Preparation Examples, the following compounds of the formula (I-4-a) may be specifically mentioned:
If according to process (A) ethyl N-[(3-chloro-6-methyl)-phenylacetyl]-1-amino-4-ethyl-cyclohexane-carboxylate is used as starting material, the course of the process according to the invention can be represented by the following reaction scheme: 
If according to process (B) ethyl O-[(2,5-dichloro)-phenylacetyl]-2-hydroxy-isobutyrate is used, the course of the process according to the invention can be represented by the following reaction scheme: 
If according to process (C) ethyl 2-[(2-chloro-5-methyl)-phenyl]-4-(4-methoxy)-benzylmercapto-4-methyl-3-oxo-valerate is used, the course of the process according to the invention can be represented by the following reaction scheme: 
If, for example, according to process (D) (chlorocarbonyl)-2-[(3-chloro-6-methyl)-phenyl]-ketene and 4-fluoro-propiophenone are used as starting materials, the course of the process according to the invention can be represented by the following reaction scheme: 
If according to process (Excex1) 3-[(2,5-dichloro)-phenyl]-5,5-dimethylpyrrolidine-2,4-dione and pivaloyl chloride are used as starting materials, the course of the process according to the invention can be represented by the following reaction scheme: 
If according to process (E) (variant xcex2) 3-[(2,5-dichloro)-phenyl]-4-hydroxy-5-methyl-5-phenyl-xcex943-dihydrofuran-2-one and acetic anhydride are used as starting materials, the course of the process according to the invention can be represented by the following reaction scheme: 
If according to process (F) 8-[(2-chloro-5-methyl)-phenyl]-5,5-pentamethylene-pyrrolidine-2,4-dione and ethoxyethyl chloroformate are used as starting materials, the course of the process according to the invention can be represented by the following reaction scheme: 
If according to process (G) 3-[(2-bromo-5-methyl)-phenyl]-4-hydroxy-5-methyl-6-(3-pyridyl)-pyrone and methyl chloromonothioformate are used as starting materials, the course of the reaction can be represented in the following manner: 
If according to process (H) 2-[(2,5-dimethyl)-phenyl]-5,5-[(3-methyl)-pentamethylene]pyrrolidine-2,4-dione and methanesulphonyl chloride are used as starting materials, the course of the reaction can be represented by the following reaction scheme: 
If according to process (I) 2-[(2-chlroro-5methyl)-phenyl]-4-hydroxy-5-methyl-6-(2-pyridyl)-pyrone and 2,2,2-trifluoroethyl chloromethanethio-phosphonate are used as starting materials, the course of the reaction can be represented by the following reaction scheme: 
If according to process (J) 3-[(2,5-dichloro)-phenyl]-5-cyclopropyl-5-methyl-pyrrolidine-2,4-dione and NaOH are used as components, the course of the process according to the invention can be represented by the following reaction scheme: 
If according to process (K) (variant xcex1) 3-[(2-chloro-5-methyl)-phenyl]-4-hydroxy-5,5-tetramethylene-xcex943-dihydro-furan-2-one and ethyl isocyanate are used as starting materials, the course of the reaction can be represented by the following reaction scheme: 
If according to process (K) (variant xcex2) 3-[(2-chloro-5-methyl)-phenyl]-5,5-dimethyl-pyrrolidine-2,4-dione and dimethylcarbamoyl chloride are used as starting materials, the course of the reaction can be represented by the following scheme: 
The compounds of the formula (II) 
in which
5 A, B, X, Z and R8 are each as defined above,
required as starting materials in process (A) according to the invention are novel.
The acylamino acid esters of the formula (II) are obtained, for example, when amino acid derivatives of the formula (XVIII) 
in which
A, B and R8 are as defined above,
are acylated using substituted phenylacetyl halides of the formula (XIX) 
xe2x80x83in which
X and Z are each as defined above and
Hal represents chlorine or bromine,
(Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem. 6, 341-5, 1968)
or when acylamino acids of the formula (XX) 
xe2x80x83in which
A, B, X and Z are each as defined above,
are esterified (Chem. Ind. (London) 1568 (1968)).
The compounds of the formula (XX) 
in which
A, B, X and Z are each as defined above,
are novel.
The compounds of the formula (XX) are obtained when amino acids of the formula (XXI) 
in which
A and B are each as defined above,
are acylated using substituted phenylacetyl halides of the formula (XIX) 
xe2x80x83in which
X and Z are each as defined above and
Hal represents chlorine or bromine,
according to Schotten-Baumann (Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. 505).
Some of the compounds of the formula (XIX) are novel. They can be prepared by known methods.
The compounds of the formula (XIX) are obtained, for example, by reacting substituted phenylacetic acids of the formula (XXII) 
in which
X and Z are each as defined above,
with halogenating agents (for example thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride), if appropriate in the presence of a diluent (for example optionally chlorinated aliphatic or aromatic hydrocarbons such as toluene or methylene chloride) at temperatures from xe2x88x9220xc2x0 C. to 150xc2x0 C., preferably from xe2x88x9210xc2x0 C. to 100xc2x0 C.
The compounds of the formula (XXII) are novel with the exception of 2,5-dichlorophenylacetic acid (CAS 5398798), 5-chloro-2-methoxyphenylacetic acid (CAS 7569-6-22), 2-chloro-5-methylphenylacetic acid (CAS 81682-39-5), 2,5-difluorophenylacetic acid (CAS 85068-27-5), 2-bromo-5-methylphenylacetic acid (BRN 3 249 577) and 2-chloro-5-trifluoromethylphenylacetic acid (CAS 22893-39-6), they can be prepared by methods known from the literature (Organikum, 15th edition, p. 533, VEB Deutscher Verlag der Wissenschaften, Berlin 1977). The compounds of the formula (XMI) are obtained, for example, by hydrolysing substituted phenylacetic acid esters of the formula (XXIII) 
in which
X, Z and R8 are each as defined above,
at temperatures between 0xc2x0 C. and 150xc2x0 C., preferably between 20xc2x0 C. and 100xc2x0 C., in the presence of an acid (for example an inorganic acid such as hydrochloric acid) or of a base (for example of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide) and, if appropriate, of a diluent (for example of an aqueous alcohol such as methanol or ethanol).
The compounds of the formula (XXIII) are novel with the exception of methyl 2,5-dichlorophenylacetate (CAS 96129-66-7) and methyl 5-chloro-2-methoxy-phenylacetate (CAS 26939-01-5), they can be prepared by methods known in principle.
The compounds of the formula (XXIII) are obtained, for example, by reacting substituted 1,1,1-trichloro-2-phenylethanes of the formula (XXIV) 
in which
X and Z are each as defined above,
first with alkoxides (for example alkali metal alkoxides such as sodium methoxide or sodium ethoxide) in the presence of a diluent (for example the alcohol derived from the alkoxide) at temperatures between 0xc2x0 C. and 150xc2x0 C., preferably between 20xc2x0 C. and 120xc2x0 C., and then reacting with an acid (preferably an inorganic acid, such as sulphuric acid) at temperatures between xe2x88x9220xc2x0 C. and 150xc2x0 C., preferably 0xc2x0 C. and 100xc2x0 C. (cf. DE 3 314 249).
The compounds of the formula (XXIV) are novel, they can be prepared by methods known in principle.
The compounds of the formula (XXIV) are obtained, for example, when anilines of the formula (XXV) 
in which
X and Z are as defined above,
are reacted with vinylidene chloride (CH2=CCl2) in the presence of an alkyl nitrite of the formula (XXVI)
R21xe2x80x94ONOxe2x80x83xe2x80x83(XXVI)
xe2x80x83in which
R21 represents alkyl, preferably C1-C6-alkyl,
in the presence of copper(II) chloride and, if appropriate, in the presence of a diluent (for example of an aliphatic nitrile such as acetonitrile) at a temperature of xe2x88x9220xc2x0 C. to 80xc2x0 C., preferably 0xc2x0 C. to 60xc2x0 C.
The compounds of the formulae (XXV) and (XXVI) are known compounds of organic chemistry. Copper(II) chloride and vinylidene chloride have long been known and are commercially available.
Some of the compounds of the formulae (XVIII) and (XXI) are known and/or they can be prepared by known processes (see, for example, Compagnon, Miocque Ann. Chim. (Paris) [14]5, p. 11-22, 23-27 (1970)).
The substituted cyclic aminocarboxylic acids of the formula (XXIa), in which A and B form a ring, are in general obtainable by the Bucherer-Bergs synthesis or by the Strecker synthesis and are in each case obtained here in different isomeric forms. Thus, according to the conditions of the Bucherer-Bergs synthesis mainly the isomers (in the following designated as xcex2 for the sake of simplicity) in which the radicals R and the carboxyl group are equatorial are obtained, while according to the conditions of the Strecker synthesis mainly the isomers (in the following designated as xcex1 for the sake of simplicity) are obtained 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 materials of the formula (II) 
in which
A, B, X, Z and R8 are each as defined above,
used in the above process (A) can be prepared by reacting aminonitriles of the formula (XXVII) 
xe2x80x83in which
A and B are each as defined above,
with substituted phenylacetyl halides of the formula (XIX) 
xe2x80x83in which
X, Z and Hal are each as defined above,
to give compounds of the formula (XXVIII) 
xe2x80x83in which
A, B, X and Z are each as defined above,
and then subjecting these to an acidic alcoholysis.
The compounds of the formula (XXVIII) are also novel.
The compounds of the formula (III) 
in which
A, B, X, Z and R8 are each as defined above,
required as starting materials in process (B) according to the invention are novel.
They can be prepared in a simple manner by methods known in principle.
The compounds of the formula (III) are obtained, for example, when 2-hydroxycarboxylic acid esters of the formula (XXIX) 
in which
A, B and R8 are each as defined above,
are acylated using substituted phenylacetyl halides of the formula (XIX) 
xe2x80x83in which
X, Z and Hal are each as defined above
(Chem. Reviews 52, 237-416 (1953)).
The compounds of the formula (IV) 
in which
A, B, W, X, Z and R8 are each as defined above,
required as starting materials in the above process (C) are novel.
They can be prepared by methods known in principle.
The compounds of the formula (IV) are obtained, for example, when substituted phenylacetic acid esters of the formula (XXIII) 
in which
X, R8 and Z are each as defined above,
are acylated using 2-benzylthio-carbonyl halides of the formula (XXX) 
in which
A, B and W are each as defined above and
Hal represents halogen (in particular chlorine or bromine),
in the presence of strong bases (see, for example, M. S. Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228).
The benzylthio-carbonyl halides of the formula (XXX) are known in some cases and/or can be prepared by known methods (J. Antibiotics (1983), 26, 1589).
The halogenocarbonylketenes of the formula (VI) in which Z does not represent hydrogen, which are required as starting materials in process (D), are novel. They can be prepared in a simple manner by methods known in principle (cf., for example, Org. Prep. Proced. Int., 7, (4), 155-158, 1975 and DE 1 945 703).
The compounds of the formula (VI) 
in which
X and Z are each as defined above and
Hal represents chlorine or bromine,
are obtained when substituted phenylmalonic acids of the formula (XXXI) 
xe2x80x83in which
X and Z are each as defined above,
are reacted with acid halides, for example thionyl chloride, phosphorus(V) chloride, phosphorus(III) chloride, oxalyl chloride, phosgene or thionyl bromide, if appropriate in the presence of catalysts, for example diethylformamide, methylstearylformamide or triphenylphosphine and, if appropriate, in the presence of bases, for example pyridine or triethylamine, at a temperature between xe2x88x9220xc2x0 C. and 200xc2x0 C., preferably between 0xc2x0 C. and 150xc2x0 C.
The substituted phenylmalonic acids of the formula (XXXI) in which Z does not represent hydrogen are novel. However, they may be prepared in a simple manner by known processes (cf., for example, Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. 517 ff), for example by hydrolysis of substituted phenylmalonic esters of the formula (XXXI) 
in which
X, Z and R8 are each as defined above.
The carbonyl compounds of the formula (V) or their silyl enole ethers of the formula (Va) 
in which
A, D and R8 xe2x80x2are each as defined above,
required as starting materials for process (D) according to the invention are compounds which are commercially available, generally known or accessible by known processes.
The malonic acid esters of the formula (XXXII) 
in which
R8, X and Z are each as defined above, and Z is not hydrogen, are novel.
They can be prepared by generally known methods of organic chemistry (cf., for example, Tetrahedron Lett. 27, 2763 (1986) and Organikum VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p.587 ff).
The acid halides of the formula (VII), carboxylic anhydrides of the formula (VIII), chloroformic acid esters or chloroformic acid thioesters of the formula (IX), chloromonothioformic acid esters or chlorodithioformic acid esters of the formula (X), sulphonyl chlorides of the formula (XII), phosphorus compounds of the formula (XIII) and metal hydroxides, metal alkoxides or amines of the formula (XIV) and (XV) and isocyanates of the formula (XVI) and carbamoyl chlorides of the formula (XVII) additionally required as starting materials for carrying out processes (F), (G), (H), (I), (J) and (K) according to the invention are generally known compounds of organic or inorganic chemistry.
The compounds of the formulae (V), (VII) to (XVII), (XVIII), (XXI), (XXII), (XXIX), (XXX) and (XXXI) are moreover disclosed in the patent applications cited at the outset and/or can be prepared by the methods given there.
Process (A) is characterized in that compounds of the formula (II) in which A, B, X, Z and R8 are each as defined above are subjected to an intramolecular condensation in the presence of a diluent and in the presence of a base.
Suitable diluents for the process (A) according to the invention are all organic solvents which are inert to the reaction participants. Those preferably utilizable are hydrocarbons, such as toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, additionally polar solvents, such as dimethyl sulphoxide, sulpholane, dimethyl-formamide and n-methyl-pyrrolidone, and also alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and tert-butanol.
Suitable bases (deprotonating agents) for carrying out process (A) according to the invention are all customary proton acceptors. Those preferably utilizable are 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, each of which can also be employed in the presence of a phase-transfer catalyst, for example triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogene 464 (=methyltrialkyl(C8-C10)ammonium chloride) or TDA 1 (=tris-(methoxyethoxyethyl)-amine. Alkali metals such as sodium or potassium can also be used. Furthermore, alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide can be employed.
When carrying out process (A) according to the invention, the reaction temperature can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between 0xc2x0 C. and 250xc2x0 C., preferably between 50xc2x0 C. and 150xc2x0 C.
Process (A) according to the invention is generally carried out under atmospheric pressure.
When carrying out process (A) according to the invention, the reaction component of the formula (II) and the deprotonating base are generally employed in equimolar to approximately double equimolar amounts. However, it is also possible to use one component or the other in a relatively large excess (up to 3 mol).
Process (B) is characterized in that compounds of the formula (III) in which A, B, X, Z and R8 are each as defined above are condensed intramolecularly in the presence of a diluent and in the presence of a base.
Suitable diluents for the process (B) according to the invention are all organic solvents which are inert to the reaction participants. Those preferably utilizable are hydrocarbons, such as toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, and additionally polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone. Alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and tert-butanol can also be used.
Suitable bases (deprotonating agents) for carrying out the process (B) according to the invention are all customary proton acceptors. Those preferably utilizable are 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, each of which can also be employed in the presence of phase-transfer catalysts, for example triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogene 464 (=methyltrialkyl(C8-C10-ammonium chloride) or TDA 1 (=tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium or potassium can also be used. Suitable are also alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.
When carrying out process (B) according to the invention, the reaction temperature can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between 0xc2x0 C. and 250xc2x0 C., preferably between 50xc2x0 C. and 150xc2x0 C.
Process (B) according to the invention is generally carried out under atmospheric pressure.
When carrying out the process (B) according to the invention, the reaction components of the formula (III) and the deprotonating bases are generally employed in approximately equimolar amounts. However, it is also possible to use one component or the other in a relatively large excess (up to 3 mol).
Process (C) is characterized in that compounds of the formula (IV) in which A, B, W, X, Z and R8 are each as defined above are cyclized intramolecularly in the presence of an acid and, if appropriate, in the presence of a diluent.
Suitable diluents for the process (C) according to the invention are all organic solvents which are inert to the reaction participants. Those preferably utilizable are hydrocarbons, such as toluene and xylene, furthermore halogenated hydrocarbons, such as dichloromethane, chloroform, ethylene chloride, chlorobenzene, dichlorobenzene, and additionally polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone. Alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and tert-butanol can also be used.
The acid employed can, if appropriate, also be used as a diluent.
Acids which can be employed in process (C) according to the invention are all customary inorganic and organic acids, for example hydrohalic acids, sulphuric acid, alkyl-, aryl- and haloalkyl sulphonic acids; halogenated alkylcarboxylic acids, for example trifluoroacetic acid, are used in particular.
When carrying out process (C) according to the invention, the reaction temperature can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between 0xc2x0 C. and 250xc2x0 C., preferably between 50xc2x0 C. and 150xc2x0 C.
Process (C) according to the invention is generally carried out under atmospheric pressure.
When carrying out process (C) according to the invention, the reaction components of the formulae (IV) and the acid are employed, for example, in equimolar amounts. However, it is, if appropriate, also possible to employ the acid in catalytic amounts.
Process (D) according to the invention is characterized in that carbonyl compounds of the formula (V) or their silyl enol ethers of the formula (Va) are reacted with ketene acid halides of the formula (VI), if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor.
Suitable diluents for the process (D) according to the invention are all organic solvents which are inert to the reaction participants. Those preferably utilizable are hydrocarbons, such as o-dichlorobenzene, tetraline, toluene and xylene, furthermore ethers, such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, and additionally polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide or N-methyl-pyrrolidone.
Acid acceptors which can be used when carrying out process (D) according to the invention are all customary acid acceptors.
Those preferably utilizable are tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig base or N,N-dimethyl-aniline.
When carrying out process (D) according to the invention, the reaction temperature can be varied within a relatively wide range. The reaction is expediently carried out at temperatures between 0xc2x0 C. and 250xc2x0 C., preferably between 50xc2x0 C. and 220xc2x0 C.
Process (D) according to the invention is preferably carried out under atmospheric pressure.
When carrying out process (D) according to the invention, the reaction components of the formulae (V) and (VI) and, if appropriate, the acid acceptor are in general employed in approximately equimolar amounts. However, it is also possbile to use one component or the other in a relatively large excess (up to 5 mol).
Process (Excex1) is characterized in that compounds of the formulae (I-1-a) to (I-4-a) are in each case reacted with carboxylic acid halides of the formula (VII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent.
Suitable diluents for the process (Eac) according to the invention are all solvents inert to the acid halides. Those preferably utilizable are hydrocarbons, such as benzine, benzene, toluene, xylene and tetraline, furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, and also ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxan, moreover carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethylformamide, dimethylsulphoxide and sulpholane. If the stability to hydrolysis of the acid halide permits, the reaction can also be carried out in the presence of water.
Suitable acid-binding agents in the reaction of process (Es) according to the invention are all customary acid acceptors. Those preferably utilizable are tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Huinig base and N,N-dimethyl-aniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, and also alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate and also alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
The reaction temperature in the process (Excex1) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between xe2x88x9220xc2x0 C. and +150xc2x0 C., preferably between 0xc2x0 C. and 110xc2x0 C.
When carrying out process (Excex1) according to the invention, the starting materials of the formulae (I-1-a) to (I-4-a) and the carboxylic acid halide of the formula (VII) are in general each used in approximately equivalent amounts. However, it is also possible to employ the carboxylic acid halide in a relatively large excess (up to 5 mol). Work-up is carried out according to customary methods.
Process (Excex2) is characterized in that compounds of the formulae (I-1-a) to (I-4-a) are each reacted with carboxylic anhydrides of the formula (VIII), if appropriate in the presence of a diluent and if appopriate in the presence of an acid-binding agent.
Preferred diluents for the process (Excex2) according to the invention are those diluents which are also preferred when using acid halides. Otherwise, a carboxylic anhydride employed in excess may also simultaneously function as diluent.
Possible acid-binding agents added in process (Excex2) are preferably those acid-binding agents that are also preferred when using acid-halides.
The reaction temperature in the process (Excex2) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between xe2x88x9220xc2x0 C. and +150xc2x0 C., preferably between 0xc2x0 C. and 100xc2x0 C.
When carrying out process (Excex2) according to the invention, the starting materials of the formulae (I-1-a) to (I-4-a) and the carboxylic anhydride of the formula (VIII) are in general each used in approximately equivalent amounts. However, it is also possible to employ the carboxylic anhydride in a relatively large excess (up to 5 mol). Work-up is carried out according to customary methods.
In general, a procedure is used in which diluent and excess carboxylic anhydride and the resulting carboxylic acid are removed by distillation or by washing with an organic solvent or with water.
Process (F) is characterized in that compounds of the formulae (I-1-a) to (I-4-a) are in each case reacted with chloroformic acid esters or chloroformic acid thioesters of the formula (IX), if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent.
Suitable acid-binding agents for process (F) according to the invention are all customary acid acceptors. Those preferably utilizable are tertiary amines, such as triethylamine, pyridine, DABCO, DBU, DBA, Hunig base and N,N-dimethyl-aniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, additionally alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate and also alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
Suitable diluents for the process (F) according to the invention are all solvents which are inert to the chloroformic acid esters or chloroformic acid thioesters. Those preferably utilizable are hydrocarbons, such as benzine, benzene, toluene, xylene and tetraline, furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, additionally ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxan, moreover carboxylic acid esters, such as ethyl acetate, furthermore nitriles, such as acetonitrile, and also strongly polar solvents, such as dimethylformamide, dimethyl sulphoxide and sulpholane.
When carrying out process (F) according to the invention, the reaction temperature can be varied within a relatively wide range. The reaction temperature is generally between xe2x88x9220xc2x0 C. and +100xc2x0 C., preferably between 0xc2x0 C. and 50xc2x0 C.
Process (F) according to the invention is in general carried out under atmospheric pressure.
When carrying out process (F) according to the invention, the starting materials of the formulae (I-1-a) to (I-4-a) and the appropriate chloroformic acid ester or chloroformic acid thioester of the formula (IX) are in general each used in approximately equivalent amounts. However, it is also possible to employ one component or the other in a relatively large excess (up to 2 mol). Work-up is carried out according to customary methods. In general, a procedure is used in which precipitated salts are removed and the reaction mixture which remains is concentrated by stripping off the diluent.
Process (G) according to the invention is characterized in that compounds of the formula (I-1-a) to (I-4-a) are in each case reacted with compounds of the formula (X) in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent.
In preparation process (G), about 1 mol of chloromonothioformic acid ester or chlorodithioformic acid ester of the formula (X) is reacted per mol of a starting material of the formulae (I-1-a) to (I-4-a), at 0 to 120xc2x0 C., preferably at 20 to 60xc2x0 C.
Diluents which may be added, if appropriate, are all inert polar organic solvents, such as ethers, amides, sulphones, sulphoxides, and also halogenoalkanes.
Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride are preferably employed.
If, in a preferred embodiment, the enolate salt of the compounds (I-1-a) to (I-4-a) is prepared by addition of strong deprotonating agents, for example sodium hydride or potassium tert-butoxide, the further addition of acid-binding agents can be dispensed with.
If acid-binding agents are used, customary inorganic or organic bases are suitable; sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned by way of example.
The reaction can be carried out at atmospheric pressure or at elevated pressure; it is preferably carried out at atmospheric pressure. Work-up takes place according to customary methods.
Process (H) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-4-a) are in each case reacted with sulphonyl chlorides of the formula (XII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent.
In preparation process (H), about 1 mol of sulphonyl chloride of the formula (XII) is reacted per mol of starting material of the formulae (I-1-a) to (I-4-a) at xe2x88x9220 to 150xc2x0 C., preferably at 0 to 70xc2x0 C.
Process (H) is preferably carried out in the presence of a diluent.
Suitable diluents are all inert polar organic solvents, such as ethers, amides, ketones, carboxylic acid esters, nitriles, sulphones, sulphoxides or halogenated hydrocarbons such as methylene chloride.
Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide and methylene chloride are preferably employed.
If, in a preferred embodiment, the enolate salt of the compounds (I-1-a) to (I-4-a) is prepared by addition of strong deprotonating agents (for example sodium hydride or potassium tert-butoxide), the further addition of acid-binding agents can be dispensed with.
If acid-binding agents are employed, customary inorganic or organic bases are suitable; sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned by way of example.
The reaction can be carried out at atmospheric pressure or at elevated pressure; it is preferably carried out at atmospheric pressure. Work-up takes place according to customary methods.
The process (I) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-4-a) are in each case reacted with phosphorus compounds of the formula (XIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent.
In preparation process (I), 1 to 2, preferably 1 to 1.3, mol of the phosphorus compound of the formula (XIII) is reacted per 1 mol of the compounds (I-1-a) to (I-4-a) at temperatures between xe2x88x9240xc2x0 C. and 150xc2x0 C., preferably between xe2x88x9210xc2x0 C. and 110xc2x0 C., to give compounds of the formulae (I-1-e) to (I-4-e).
The process (I) is preferably carried out in the presence of a diluent.
Suitable diluents are all inert polar organic solvents, such as ethers, carboxylic acid esters, halogenated hydrocarbons, ketones, amides, nitriles, sulphones, sulphoxides, etc.
Acetonitrile, dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride are preferably employed.
Acid-binding agents which may be added, if appropriate, are customary inorganic or organic bases, such as hydroxides, carbonates or amines. By way of example, sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned.
The reaction may be carried out at atmospheric pressure or at elevated pressure; it is preferably carried out at atmospheric pressure. Work-up takes place according to conventional methods of organic chemistry. The end products are preferably purified by crystallization, chromatographic purification or by so-called xe2x80x9cincipient distillationxe2x80x9d, i.e. removal of the volatile constituents in vacuo.
Process (J) is characterized in that compounds of the formulae (I-1-a) to (I-4-a) are in each case reacted with metal hydroxides or metal alkoxides of the formula (XIV) or amines of the formula (XV), if appropriate in the presence of a diluent.
Preferred diluents for process (J) according to the invention are ethers such as tetrahydrofuran, dioxan and diethyl ether or else alcohols such as methanol, ethanol and isopropanol, but also water. Process (J) according to the invention is generally carried out under atmospheric pressure. The reaction temperature is in general between xe2x88x9220xc2x0 C. and 100xc2x0 C., preferably between 0xc2x0 C. and 50xc2x0 C.
Process (K) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-4-a) are in each case reacted with (Kxcex1) compounds of the formula (XVI), if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or (Kxcex2) with compounds of the formula (XVII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent.
In preparation process (Kxcex1), about 1 mol of isocyanate of the formula (XVI) is reacted per mole of starting material of the formulae (I-1-a) to (I-4-a) at 0 to 100xc2x0 C., preferably at 20 to 50xc2x0 C.
Process (Kxcex1) is preferably carried out in the presence of a diluent.
Suitable diluents are all inert organic solvents, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, amides, nitriles, sulphones or sulphoxides.
Catalysts may, if desired, be added to accelerate the reaction. The catalysts employed can very advantageously be organotin compounds, for example dibutyltin dilaurate.
The reaction is preferably carried out at atmospheric pressure.
In preparation process (Kxcex2), about 1 mol of carbamoyl chloride of the formula (XVII) is reacted at 0 to 150xc2x0 C., preferably at 20 to 70xc2x0 C., per mole of starting material of the formulae (I-1-a) to (I-4-a).
Possible diluents optionally added are all inert polar organic solvents, such as ethers, carboxylic acid esters, nitriles, ketones, amides, sulphones, sulphoxides or halogenated hydrocarbons.
Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride are preferably employed.
If, in a preferred embodiment, the enolate salt of the compound (I-1-a) to (I-4-a) is prepared by addition of strong deprotonating agents (e.g. sodium hydride or potassium tertiary butoxide), the further addition of acid-binding agents can be dispensed with.
If acid-binding agents are employed, customary inorganic or organic bases are suitable; those which may be mentioned by way of example are sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.
The reaction can be carried out at atmospheric pressure or at elevated pressure, preferably at atmospheric pressure. Work-up takes place according to customary methods.
The active compounds are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnida, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber. 
From the order of the Diplopoda, for example, Blaniulus guttulatus. 
From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
From the order of the Symphyla, for example, Scutigerella immaculata. 
From the order of the Thysanura, for example, Lepisma saccharina. 
From the order of the Collembola, for example, Onychiurus armatus. 
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria. 
From the order of the Dermaptera, for example, Forficula auricularia. 
From the order of the Isoptera, for example, Reticulitermes spp.
From the order of the Anoplura, for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.
From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci. 
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
From the order of the Homoptera, for example, 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. and Psylla spp.
From the order of the Lepidoptera, for example, 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 and Tortrix viridana. 
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, 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., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica. 
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
From the order of the Diptera, for example, 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 and Tipula paludosa. 
From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans. 
From the order of the Acarina, for example, 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. and Tetranychus spp.
The active compounds according to the invention are distinguished by a high insecticidal and acaricidal activity.
They can be used to particularly good effect for controlling insects which are injurious to plants, such as, for example, against the larvae of the mustard beetle (Phaedon cochleariae), against the larvae of the green rice leaf hopper (Nephotettix cincticeps) or against the caterpillars of the cabbage moth (Plutella maculipennis) (cf. the Use Examples).
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes of methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
As solid carriers there are suitable:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumen hydrolysis products, as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compound according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms.