U.S. patent application number 10/903550 was filed with the patent office on 2005-07-28 for alkyl dihalogenated phenyl-substituted ketoenols useful as pesticides and herbicides.
This patent application is currently assigned to Bayer AG. Invention is credited to Andersch, Wolfram, Bretschneider, Thomas, Dahmen, Peter, Dollinger, Markus, Erdelen, Christoph, Fischer, Reiner, Graff, Alan, Hagemann, Hermann, Lieb, Folker, Mencke, Norbert, Ruther, Michael, Santel, Hans-Joachim, Turberg, Andreas, Wachendorff-Neumann, Ulrike, Widdig, Arno.
Application Number | 20050164885 10/903550 |
Document ID | / |
Family ID | 26014850 |
Filed Date | 2005-07-28 |
United States Patent
Application |
20050164885 |
Kind Code |
A1 |
Lieb, Folker ; et
al. |
July 28, 2005 |
Alkyl dihalogenated phenyl-substituted ketoenols useful as
pesticides and herbicides
Abstract
The present invention relates to new compounds of the formula
(I) 1 in which X represents halogen, Y represents halogen or alkyl
and Z represents halogen or alkyl, with the proviso that always one
of the radicals Y and Z represents halogen while the other
represents alkyl, and Het represents one of the groups 2 3 in which
A, B, D and G have the meanings given in the description, to a
plurality of processes for their preparation and to their use as
pesticides and herbicides.
Inventors: |
Lieb, Folker; (Leverkusen,
DE) ; Hagemann, Hermann; (Leverkusen, DE) ;
Widdig, Arno; (Odenthal, DE) ; Ruther, Michael;
(Monheim, DE) ; Fischer, Reiner; (Monheim, DE)
; Bretschneider, Thomas; (Lohmar, DE) ; Erdelen,
Christoph; (Leichlingen, DE) ; Wachendorff-Neumann,
Ulrike; (Neuwied, DE) ; Dahmen, Peter; (Neuss,
DE) ; Dollinger, Markus; (Leverkusen, DE) ;
Santel, Hans-Joachim; (Leverkusen, DE) ; Graff,
Alan; (Koln, DE) ; Andersch, Wolfram;
(Bergisch Gladbach, DE) ; Mencke, Norbert;
(Leverkusen, DE) ; Turberg, Andreas; (Erkrath,
DE) |
Correspondence
Address: |
NORRIS, MCLAUGHLIN & MARCUS, PA
875 THIRD STREET
18TH FLOOR
NEW YORK
NY
10022
US
|
Assignee: |
Bayer AG
Leverkusen
DE
|
Family ID: |
26014850 |
Appl. No.: |
10/903550 |
Filed: |
July 30, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10903550 |
Jul 30, 2004 |
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10017695 |
Dec 14, 2001 |
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6858741 |
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10017695 |
Dec 14, 2001 |
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09404424 |
Sep 23, 1999 |
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6380246 |
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09404424 |
Sep 23, 1999 |
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08945664 |
Oct 31, 1997 |
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6316486 |
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08945664 |
Oct 31, 1997 |
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PCT/EP96/17871 |
Apr 29, 1996 |
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Current U.S.
Class: |
504/221 ;
504/280; 504/283; 504/289; 504/299; 544/54; 548/366.1; 548/544;
549/313; 549/62 |
Current CPC
Class: |
C07D 307/94 20130101;
C07C 69/757 20130101; A01N 43/40 20130101; C07D 209/54 20130101;
A01N 43/36 20130101; A01N 43/38 20130101; C07D 309/08 20130101;
A01N 43/90 20130101; C07C 323/56 20130101; C07D 309/36 20130101;
A01N 47/06 20130101; A01N 53/00 20130101; A01N 47/02 20130101; A01N
43/10 20130101; C07D 491/10 20130101; C07D 207/38 20130101; A01N
43/16 20130101; C07D 333/32 20130101; C07D 333/50 20130101; C07D
311/46 20130101; C07D 493/10 20130101; C07D 333/38 20130101; A01N
43/12 20130101 |
Class at
Publication: |
504/221 ;
504/280; 504/283; 504/289; 504/299; 544/054; 548/366.1; 548/544;
549/062; 549/313 |
International
Class: |
A01N 043/72; A01N
043/56; A01N 043/36; A01N 043/10; A01N 043/08 |
Foreign Application Data
Date |
Code |
Application Number |
May 9, 1995 |
DE |
195 16 258.7 |
Dec 6, 1995 |
DE |
195 45 467.7 |
Claims
1-7. (canceled)
8. A compound of the formula (XXII) 224in which X represents
halogen, Y represents halogen or alkyl, Z represents halogen or
alkyl, with the proviso that always one of the radicals Y and Z
represents halogen and the other represents alkyl, and Hal
represents chlorine or bromine.
9. A compound of the formula (XXV) 225in which X represents
halogen, Y represents halogen or alkyl, Z represents halogen or
alkyl, with the proviso that always one of the radicals Y and Z
represents halogen and the other represents alkyl, and with the
exception of 2,4-dichloro-6-methylphenylacetic acid.
10. A compound of the formula (XXVI) 226in which X represents
halogen, Y represents halogen or alkyl, Z represents halogen or
alkyl, with the proviso that always one of the radicals Y and Z
represents halogen and the other represents alkyl, and R.sup.8
represents alkyl.
11. A compound of the formula (XXVII) 227in which X represents
halogen, Y represents halogen or alkyl, Z represents halogen or
alkyl, with the proviso that always one of the radicals Y and Z
represents halogen and the other represents alkyl.
12-14. (canceled)
15. A compound of the formula (V) 228in which X represents halogen,
Y represents halogen or alkyl, Z represents halogen or alkyl, with
the proviso that always one of the radicals Y and Z represents
halogen and the other represents alkyl, and Hal represents chlorine
or bromine.
16. A compound of the formula (XXXV) 229in which X represents
halogen, Y represents halogen or alkyl, Z represents halogen or
alkyl, with the proviso that always one of the radicals Y and Z
represents halogen and the other represents alkyl.
17-21. (canceled)
22. The compound of claim 8, wherein X represents halogen, Y
represents halogen or C.sub.1-C.sub.6-alkyl, Z represents halogen
or C.sub.1-C.sub.6-alkyl.
23. The compound of claim 22, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl, Z represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl.
24. The compound of claim 23, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine,
methyl, ethyl, n-propyl or iso-propyl, Z represents fluorine,
chlorine, bromine, methyl, ethyl, n-propyl or iso-propyl.
25. The compound of claim 9, wherein X represents halogen, Y
represents halogen or C.sub.1-C.sub.6-alkyl, Z represents halogen
or C.sub.1-C.sub.6-alkyl.
26. The compound of claim 25, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl, Z represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl.
27. The compound of claim 26, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine,
methyl, ethyl, n-propyl or iso-propyl, Z represents fluorine,
chlorine, bromine, methyl, ethyl, n-propyl or iso-propyl.
28. The compound of claim 10, wherein X represents halogen, Y
represents halogen or C.sub.1-C.sub.6-alkyl, Z represents halogen
or C.sub.1-C.sub.6-alkyl.
29. The compound of claim 28, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl, Z represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl.
30. The compound of claim 29, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine,
methyl, ethyl, n-propyl or iso-propyl, Z represents fluorine,
chlorine, bromine, methyl, ethyl, n-propyl or iso-propyl.
31. The compound of claim 11, wherein X represents halogen, Y
represents halogen or C.sub.1-C.sub.6-alkyl, Z represents halogen
or C.sub.1-C.sub.6-alkyl.
32. The compound of claim 31, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl, Z represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl.
33. The compound of claim 32, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine,
methyl, ethyl, n-propyl or iso-propyl, Z represents fluorine,
chlorine, bromine, methyl, ethyl, n-propyl or iso-propyl.
34. The compound of claim 15, wherein X represents halogen, Y
represents halogen or C.sub.1-C.sub.6-alkyl, Z represents halogen
or C.sub.1-C.sub.6-alkyl.
35. The compound of claim 34, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl, Z represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl.
36. The compound of claim 35, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine,
methyl, ethyl, n-propyl or iso-propyl, Z represents fluorine,
chlorine, bromine, methyl, ethyl, n-propyl or iso-propyl.
37. The compound of claim 16, wherein X represents halogen, Y
represents halogen or C.sub.1-C.sub.6-alkyl, Z represents halogen
or C.sub.1-C.sub.6-alkyl.
38. The compound of claim 37, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl, Z represents fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl.
39. The compound of claim 38, wherein X represents fluorine,
chlorine or bromine, Y represents fluorine, chlorine, bromine,
methyl, ethyl, n-propyl or iso-propyl, Z represents fluorine,
chlorine, bromine, methyl, ethyl, n-propyl or iso-propyl.
Description
[0001] The invention relates to new phenyl-substituted cyclic
ketoenols, to a plurality of processes and intermediates for their
preparation, and to their use as pesticides and herbicides.
[0002] 3-Acyl-pyrrolidine-2,4-diones have already been described as
having pharmaceutical properties (S. Suzuki et al. Chem. Pharm.
Bull. 15 1120 (1967)). Furthermore, N-phenylpyrrolidine-2,4-diones
were synthesized by R. Schmierer and H. Mildenberger (Liebigs Ann.
Chem. 1985, 1095). A biological activity of these compounds has not
been described.
[0003] EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a
similar structure (3-aryl-pyrrolidine-2,4-diones), which, however,
have not been disclosed as having a herbicidal, insecticidal or
acaricidal action. Unsubstituted, bicyclic
3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-355 599 and EP-A-415
211) and substituted monocyclic 3-aryl-pyrrolidine-2,4-dione
derivatives (EP-A-377 893 and EP-A-442 077) having a herbicidal,
insecticidal or acaricidal action are known.
[0004] Also known are polycyclic 3-arylpyrrolidine-2,4-dione
derivatives (EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives
(EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613
885, WO 94/01 997, WO 93/26954 and WO 95/01 358).
[0005] It is known that certain substituted
.DELTA..sup.3-dihydrofuran-2-o- ne derivatives have herbicidal
properties (cf. DE-A-4 014 420). The synthesis of the tetronic acid
derivatives used as starting compounds (such as, for example,
3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-.-
DELTA..sup.3-dihydrofuran-2-one) is also described in DE-A-4 014
420. Compounds of a similar structure are known from the
publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985,
(8) 1567-76, but no mention is made of insecticidal and/or
acaricidal activity. 3-Aryl-.DELTA..sup.3-dihydrofuranone
derivatives having herbicidal, acaricidal and insecticidal
properties are furthermore known from EP-A-528 156, but the action
described in this publication is not always sufficient.
Thiotetronic acids are known from WO 95/26345.
[0006] Furthermore, certain 3H-pyrazole-3-one derivatives, such as,
for example,
1,2-diethyl-1,2-dihydro-5-hydroxy-4-phenyl-3H-pyrazol-3-one or
{[5-oxo-1,2-diphenyl-4-(p-sulphophenyl)-3-pyrazolin-3-yl]-oxy}-disodium
salt or
p-(3-hydroxy-5-oxo-1,2-diphenyl-3-pyrazolin-4-yl)-benzenesulphoni-
c acid are known from the literature (cf. J. Heterocycl. Chem.,
25(5), 1301-1305, 1988 or J. Heterocycl. Chem. 25(5), 1307-1310,
1988 or Zh. Obshch. Khim., 34(7), 2397-2402, 1964). However, a
biological action of these compounds is not described.
[0007] It is furthermore known that the trisodium salt of
4,4',4"-(5-hydroxy-3-oxo-1H-pyrazol-1,2,4(3H)-triyl)-tris-benzenesulphoni-
c acid has pharmacological properties (cf. Farmakol. Toksikol.
(Moscow), 38(2), 180-186, 1976). However, its use in plant
protection is not known.
[0008] Moreover, 4-arylpyrazolidine-3,5-dione derivatives having
herbicidal, acaricidal and insecticidal properties are described in
EP-A-508 126 and in WO 92/16 510.
[0009] Certain phenyl-pyrone derivatives which are unsubstituted in
the phenyl ring have already been described (cf. A. M. Chirazi, T.
Kappe and E. Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze
and K. Heidenbluth, Chem. Ber. 91, 2849), a potential use of these
compounds as pesticides not being indicated. Phenyl-pyrone
derivatives which are substituted in the phenyl ring and have
herbicidal, acaricidal and insecticidal properties are described in
EP-A-588 137.
[0010] Certain 5-phenyl-1,3-thiazine derivatives which are
unsubstituted in the phenyl ring have already been described (cf.
E. Ziegler and E. Steiner, Monatsh. 95, 147 (1964), R. Ketcham, T.
Kappe and E. Ziegler, J. Heterocycl. Chem. 10, 223 (1973)), a
potential use of these compounds as pesticides not being indicated.
5-Phenyl-1,3-thiazine derivatives which are substituted in the
phenyl ring and have a herbicidal, acaricidal and insecticidal
action are described in WO 94/14 785.
[0011] However, the activity and spectrum of action of these
compounds are not always entirely satisfactory, in particular at
low application rates and concentrations. Furthermore, the
tolerance, by plants, of the known compounds is not always
sufficient.
[0012] There have now been found new compounds of the formula (I)
4
[0013] in which
[0014] X represents halogen,
[0015] Y represents halogen or alkyl and
[0016] Z represents halogen or alkyl,
[0017] with the proviso that always one of the radicals Y and Z
represents halogen and the other represents alkyl,
[0018] Het represents one of the groups 5
[0019] in which
[0020] A represents hydrogen, or represents alkyl, alkenyl,
alkoxyalkyl, polyalkoxyalkyl or alkylthioalkyl, each of which is
optionally substituted by halogen, or represents in each case
saturated or unsaturated and optionally substituted cycloalkyl or
heterocyclyl, or represents aryl, arylalkyl or hetaryl, each of
which is optionally substituted by halogen, alkyl, halogenoalkyl,
alkoxy, halogenoalkoxy, cyano or nitro,
[0021] B represents hydrogen, alkyl or alkoxyalkyl, or
[0022] A and B together with the carbon atom to which they are
bonded represent a saturated or unsaturated, optionally substituted
carbocycle or heterocycle,
[0023] D represents hydrogen or an optionally substituted radical
from the series consisting of alkyl, alkenyl, alkinyl, alkoxyalkyl,
polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated
cycloalkyl, saturated or unsaturated heterocyclyl, arylalkyl, aryl,
hetarylalkyl or hetaryl, or
[0024] A and D together with the atoms to which they are bonded
represent a saturated or unsaturated and optionally substituted
carbocycle or heterocycle,
[0025] G, in the event that Het represents one of the radicals (1),
(2), (3), (5) or (6), represents hydrogen (a) or, in the event that
Het represents one of the radicals (1), (2), (3), (4), (5) or (6),
represents one of the groups 6
[0026] in which
[0027] E represents a metal ion equivalent or an ammonium ion,
[0028] L represents oxygen or sulphur,
[0029] M represents oxygen or sulphur,
[0030] R.sup.1 represents alkyl, alkenyl, alkoxyalkyl,
alkylthioalkyl or polyalkoxyalkyl, each of which is optionally
substituted by halogen, or represents cycloalkyl or heterocyclyl,
each of which is optionally substituted by halogen, alkyl or
alkoxy, or represents in each case optionally substituted phenyl,
phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
[0031] R.sup.2 represents alkyl, alkenyl, alkoxyalkyl or
polyalkoxyalkyl, each of which is optionally substituted by
halogen, or represents in each case optionally substituted
cycloalkyl, phenyl or benzyl,
[0032] R.sup.3, R.sup.4 and R.sup.5 independently of one another
represent alkyl, alkoxy, alkylamino, dialkylamino, alkylthio,
alkenylthio or cycloalkylthio, each of which is optionally
substituted by halogen, or in each case represent optionally
substituted phenyl, benzyl, phenoxy or phenylthio,
[0033] R.sup.6 and R.sup.7 independently of one another represent
hydrogen, or represent alkyl, cycloalkyl, alkenyl, alkoxy or
alkoxyalkyl, each of which is optionally substituted by halogen, or
represent in each case optionally substituted phenyl or benzyl, or
together with the N atom to which they are bonded represent an
optionally substituted cycle which optionally contains oxygen or
sulphur.
[0034] Depending on the nature of the substituents, the compounds
of the formula (I) can exist as geometric and/or optical isomers or
variously composed isomer mixtures which, if desired, can be
separated in the customary manner. The pure isomers and the isomer
mixtures, their preparation and their use, and the compositions
comprising them are all objects of the present invention. For the
sake of simplicity, however, the following text will always mention
compounds of the formula (I), even though this is to be understood
as meaning the pure compounds and, if appropriate, also mixtures
containing various proportions of isomeric compounds.
[0035] Taking into consideration the meanings (1) to (6) of the
group Het, the following main structures (I-1) to (I-6) result:
7
[0036] in which
[0037] A, B, D, G, X, Y and Z have the abovementioned meanings.
[0038] Taking into consideration the various meanings (a), (b),
(c), (d), (e), (f) and (g) of group G, the following main
structures (I-1-a) to (I-1-g) result if Het represents the group
(1): 8910
[0039] in which
[0040] A, B, D, E, L, M, X, Y, Z, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 have the above-mentioned
meanings.
[0041] Taking into consideration the various meanings (a), (b),
(c), (d), (e), (f) and (g) of group G, the following main
structures (I-2-a) to (I-2-g) result if Het represents the group
(2): 1112
[0042] in which
[0043] A, B, E, L, M, X, Y, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 have the above-mentioned meanings.
[0044] Taking into consideration the various meanings (a), (b),
(c), (d), (e), (f) and (g) of group G, the following main
structures (I-3-a) to (I-3-g) result if Het represents the group
(3): 1314
[0045] in which
[0046] A, B, E, L, M, X, Y, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 have the above-mentioned meanings.
[0047] Depending on the position of the substituent G, the
compounds of the formula (I-4) can exist in the two isomeric forms
of the formulae (I-4).sub.a and (I-4).sub.b 15
[0048] which is indicated by the broken line in formula (I-4).
[0049] The compounds of the formulae (I-4).sub.a and (I-4).sub.b
can exist as mixtures and also in the form of their pure isomers.
If appropriate, mixtures of the compounds of the formulae
(I-4).sub.a and (I-4).sub.b can be separated by physical methods in
a manner known per se, for example by chromatographic methods.
[0050] For reasons of clarity, only one of the isomers which are
possible in each case will be given in the following text. This
does not exclude that, if appropriate, the compounds may exist in
the form of the isomer mixtures or in the respective other isomeric
form.
[0051] Taking into consideration the various meanings (b), (c),
(d), (e), (f) and (g) of group G, the following main structures
(I-4-b) to (I-4-g) result if Het represents the group (4): 1617
[0052] in which
[0053] A, D, E, L, M, X, Y, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 have the above-mentioned meanings.
[0054] Depending on the position of the substituent G, the
compounds of the formula (I-5) can exist in the two isomeric forms
of the formulae (I-5).sub.a and (I-5).sub.b 18
[0055] which is indicated by the broken line in formula (I-5).
[0056] The compounds of the formulae (I-5).sub.a and (I-5).sub.b
can exist as mixtures and also in the form of their pure isomers.
If appropriate, mixtures of the compounds of the formulae
(I-5).sub.a and (I-5).sub.b can be separated by physical methods in
a manner known per se, for example by chromatographic methods.
[0057] For reasons of clarity, only one of the isomers which are
possible in each case will be given in the following text. This
does not exclude that, if appropriate, the compounds may exist in
the form of the isomer mixtures or in the respective other isomeric
form.
[0058] Taking into consideration the various meanings (a), (b),
(c), (d), (e), (f) and (g) of group G, the following main
structures (I-5-a) to (I-5-g) result if Het represents the group
(5): 192021
[0059] in which
[0060] A, D, E, L, M, X, Y, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 have the above-mentioned meanings.
[0061] Taking into consideration the various meanings (a), (b),
(c), (d), (e), (f) and (g) of group G, the following main
structures (I-6-a) to (I-6-g) result if Het represents the group
(6): 2223
[0062] in which
[0063] A, E, L, M, X, Y, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 have the abovementioned meanings.
[0064] Furthermore, it has been found that the new compounds of the
formula (I) are obtained by one of the processes described
below:
[0065] (A) Compounds of the formula (I-1-a) 24
[0066] in which
[0067] A, B, D, X, Y and Z have the abovementioned meanings, are
obtained when compounds of the formula (II) 25
[0068] in which
[0069] A, B, D, X, Y and Z have the abovementioned meanings and
[0070] R.sup.8 represents alkyl (preferably
C.sub.1-C.sub.6-alkyl),
[0071] are subjected to intramolecular condensation in the presence
of a diluent and in the presence of a base.
[0072] (B) Furthermore, it has been found that compounds of the
formula (I-2-a) 26
[0073] in which
[0074] A, B, X, Y and Z have the abovementioned meanings, are
obtained when compounds of the formula (III) 27
[0075] in which
[0076] A, B, X, Y, Z and R.sup.8 have the abovementioned
meanings,
[0077] are subjected to intramolecular condensation in the presence
of a diluent and in the presence of a base.
[0078] (C) Furthermore, it has been found that compounds of the
formula (I-3-a) 28
[0079] in which
[0080] A, B, X, Y and Z have the abovementioned meanings, are
obtained when compounds of the formula (IV) 29
[0081] in which
[0082] A, B, X, Y, Z and R.sup.8 have the abovementioned meanings
and
[0083] W represents hydrogen, halogen, alkyl (preferably
C.sub.1-C.sub.6-alkyl) or alkoxy (preferably
C.sub.1-C.sub.8-alkoxy),
[0084] are subjected to intramolecular cyclization, if appropriate
in the presence of a diluent and in the presence of an acid.
[0085] (E) Furthermore, it has been found that the compounds of the
formula (I-5-a) 30
[0086] in which
[0087] A, D, X, Y and Z have the abovementioned meanings are
obtained when compounds of the formula (VIII) 31
[0088] in which
[0089] A and D have the abovementioned meanings
[0090] or their silyl enol ethers of the formula (VIIIa) 32
[0091] in which
[0092] A and D have the abovementioned meanings and
[0093] R.sup.8 represents alkyl (preferably methyl)
[0094] are reacted with compounds of the formula (V) 33
[0095] in which
[0096] X, Y and Z have the abovementioned meanings and
[0097] Hal represents halogen (preferably chlorine or bromine),
[0098] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid acceptor.
[0099] (F) Furthermore, it has been found that the compounds of the
formula (I-6-a) 34
[0100] in which
[0101] A, X, Y and Z have the abovementioned meanings,
[0102] are obtained when compounds of the formula (IX) 35
[0103] in which
[0104] A has the abovementioned meaning,
[0105] are reacted with compounds of the formula (V) 36
[0106] in which
[0107] Hal, X, Y and Z have the abovementioned meanings,
[0108] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid acceptor.
[0109] Moreover, it has been found
[0110] (G) that the compounds of the formulae (I-1-b) to (I-3-b),
(I-5-b) and (I-6-b) shown above in which A, B, D, R.sup.1, X, Y and
Z have the abovementioned meanings are obtained when compounds of
the formulae (I-1-a) to (I-3-a), (I-5-a) and (I-6-a) shown above in
which A, B, D, X, Y and Z have the above-mentioned meanings, and
that compounds of the formulae (I-4-b) shown above in which A, D,
R.sup.1, X, Y and Z have the abovementioned meanings are obtained
when compounds of the formula (I-4-a) 37
[0111] in which
[0112] A, D, X, Y and Z have the abovementioned meanings are in
each case reacted
[0113] .alpha.) with acid halides of the formula (X) 38
[0114] in which
[0115] R.sup.1 has the abovementioned meaning and
[0116] Hal represents halogen (in particular chlorine or bromine)
or
[0117] .beta.) with carboxylic anhydrides of the formula (XI)
R.sup.1--CO--O--CO--R.sup.1 (XI)
[0118] in which
[0119] R.sup.1 has the abovementioned meaning,
[0120] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid-binding agent;
[0121] (H) that the compounds of the formulae (I-1-c) to (I-6-c)
shown above in which A, B, D, R.sup.2, M, X, Y and Z have the
abovementioned meanings and L represents oxygen are obtained when
compounds of the formulae (I-1-a) to (I-6-a) shown above in which
A, B, D, X, Y and Z have the abovementioned meanings are reacted in
each case with chloroformic esters or chloroformic thioesters of
the formula (XII)
R.sup.2-M-CO--Cl (XII)
[0122] in which
[0123] R.sup.2 and M have the abovementioned meanings,
[0124] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid-binding agent;
[0125] (I) that compounds of the formulae (I-1-c) to (I-6-c) shown
above in which A, B, D, R.sup.2, M, X, Y and Z have the
abovementioned meanings and L represents sulphur are obtained when
compounds of the formulae (I-1-a) to (I-6-a) shown above in which
A, B, D, X, Y and Z have the abovementioned meanings are reacted in
each case
[0126] .alpha.) with chloromonothioformic esters or
chlorodithioformic esters of the formula (XIII) 39
[0127] in which
[0128] M and R.sup.2 have the abovementioned meanings,
[0129] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid-binding agent, or
[0130] .beta.) with carbon disulphide and subsequently with
compounds of the formula (XIV)
R.sup.2-Hal (XIV)
[0131] in which
[0132] R.sup.2 has the abovementioned meaning and
[0133] Hal represents chlorine, bromine or iodine,
[0134] if appropriate in the presence of a diluent and if
appropriate in the presence of a base,
[0135] (J) that compounds of the formulae (I-1-d) to (I-6-d) shown
above in which A, B, D, R.sup.3, X, Y and Z have the abovementioned
meanings are obtained when compounds of the formulae (I-1-a) to
(I-6-a) shown above in which A, B, D, X, Y and Z have the
abovementioned meanings are reacted in each case with sulphonyl
chlorides of the formula (XV)
R.sup.3--SO.sub.2--Cl (XV)
[0136] in which
[0137] R.sup.3 has the abovementioned meaning,
[0138] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid-binding agent,
[0139] (K) that compounds of the formulae (I-1-e) to (I-6-e) shown
above in which A, B, D, L, R.sup.4, R.sup.5, X, Y and Z have the
abovementioned meanings are obtained when compounds of the formulae
(I-1-a) to (I-6-a) shown above in which A, B, D, X, Y and Z have
the abovementioned meanings are reacted in each case with
phosphorus compounds of the formula (XVI) 40
[0140] in which
[0141] L, R.sup.4 and R.sup.5 have the abovementioned meanings
and
[0142] Hal represents halogen (in particular chlorine or
bromine),
[0143] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid-binding agent,
[0144] (L) that compounds of the formulae (I-1-f) to (I-6-f) shown
above in which A, B, D, E, X, Y and Z have the abovementioned
meanings are obtained when compounds of the formulae (I-1-a) to
(I-6-a) in which A, B, D, X, Y and Z have the abovementioned
meanings are reacted in each case with metal compounds or amines of
the formulae (XVII) or (XVIII) 41
[0145] in which
[0146] Me represents a mono- or divalent metal (preferably an
alkali metal or alkaline earth metal, such as lithium, sodium,
potassium, magnesium or calcium),
[0147] t represents the number 1 or 2 and
[0148] R.sup.10, R.sup.11 and R.sup.12 independently of one another
represent hydrogen or alkyl (preferably C.sub.1-C.sub.8-alkyl),
[0149] if appropriate in the presence of a diluent,
[0150] (M) that compounds of the formulae (I-1-g) to (I-6-g) shown
above in which A, B, D, L, R.sup.6, R.sup.7, X, Y and Z have the
abovementioned meanings are obtained when compounds of the formulae
(I-1-a) to (I-6-a) shown above in which A, B, D, X, Y and Z have
the abovementioned meanings are reacted in each case
[0151] .alpha.) with isocyanates or isothiocyanates of the formula
(XIX)
R.sup.6--N.dbd.C.dbd.L (XIX)
[0152] in which
[0153] R.sup.6 and L have the abovementioned meanings,
[0154] if appropriate in the presence of a diluent and if
appropriate in the presence of a catalyst, or
[0155] .beta.) with carbamoyl chlorides or thiocarbamoyl chlorides
of the formula (XX) 42
[0156] in which
[0157] L, R.sup.6 and R.sup.7 have the abovementioned meanings,
[0158] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid-binding agent.
[0159] A preferably represents hydrogen, or represents
C.sub.1-C.sub.12-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.1-C.sub.10-alkoxy-- C.sub.1-C.sub.8-alkyl,
poly-C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl or
C.sub.1-C.sub.10-alkylthio-C.sub.1-C.sub.6-alkyl, each of which is
optionally substituted by halogen, or represents
C.sub.3-C.sub.8-cycloalk- yl which is optionally substituted by
halogen, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy and in
which one or two methylene groups which are not directly adjacent
are optionally replaced by oxygen and/or sulphur, or represents
phenyl, naphthyl, phenyl-C.sub.1-C.sub.6-alkyl,
naphthyl-C.sub.1-C.sub.6-alkyl or hetaryl having 5 or 6 ring atoms
and one to three hetero atoms from the series consisting of oxygen,
sulphur and nitrogen, in each case optionally substituted by
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenoalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-halogenoalkoxy, cyano or
nitro.
[0160] B preferably represents hydrogen, C.sub.1-C.sub.12-alkyl or
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.6-alkyl, or
[0161] A, B and the carbon atom to which they are bonded preferably
represent C.sub.3-C.sub.10-cycloalkyl or
C.sub.5-C.sub.10-cycloalkenyl in each of which a methylene group is
optionally replaced by oxygen or sulphur and which are optionally
substituted by C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.10-cycloalkyl,
C.sub.1-C.sub.8-halogenoalkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.1-C.sub.8-alkylthio, halogen or phenyl, or
[0162] A, B and the carbon atom to which they are bonded preferably
represent C.sub.5-C.sub.6-cycloalkyl which is substituted by an
alkylenediyl group which optionally contains one or two oxygen
and/or sulphur atoms or by an alkylenedioxy or by an
alkylenedithioyl group, this group, together with the carbon atom
to which it is bonded forming a further five to eight-membered
ring, or
[0163] A, B and the carbon atom to which they are bonded preferably
represent C.sub.3-C.sub.8-cycloalkyl or
C.sub.5-C.sub.8-cycloalkenyl in which two substituents together
with the carbon atoms to which they are bonded represent
C.sub.3-C.sub.6-alkanediyl, C.sub.3-C.sub.6-alkenediyl or
C.sub.4-C.sub.6-alkanedienediyl, each of which is optionally
substituted by C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy or
halogen and in which in each case one methylene group is optionally
replaced by oxygen or sulphur.
[0164] D preferably represents hydrogen, or represents
C.sub.1-C.sub.12-alkyl, C.sub.3-C.sub.8-alkenyl,
C.sub.3-C.sub.8-alkinyl,
C.sub.1-C.sub.10-alkoxy-C.sub.2-C.sub.8-alkyl,
poly-C.sub.1-C.sub.8-alkox- y-C.sub.2-C.sub.8-alkyl or
C.sub.1-C.sub.10-alkylthio-C.sub.2-C.sub.8-alky- l, each of which
is optionally substituted by halogen, or represents
C.sub.3-C.sub.8-cycloalkyl which is optionally substituted by
halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-halogeno- alkyl and in which one or two methylene
groups which are not directly adjacent are optionally replaced by
oxygen and/or sulphur, or represents phenyl, hetaryl having 5 to 6
ring atoms and one or two hetero atoms from the series consisting
of oxygen, sulphur and nitrogen, phenyl-C.sub.1-C.sub.6-alkyl or
hetaryl-C.sub.1-C.sub.6-alkyl having 5 to 6 ring atoms and one or
two hetero atoms from the series consisting of oxygen, sulphur and
nitrogen, in each case optionally substituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenoalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-halogenoalkoxy, cyano or
nitro, or
[0165] A and D together preferably represent a
C.sub.3-C.sub.6-alkanediyl, C.sub.3-C.sub.6-alkenediyl or
C.sub.4-C.sub.6-alkanedienediyl group in each of which one
methylene group is optionally replaced by oxygen or sulphur and
which is in each case optionally substituted by halogen, hydroxyl,
mercapto, or by C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.3-C.sub.7-cycloalkyl, phenyl or
benzyloxy, each of which is optionally substituted by halogen, or
by a further C.sub.3-C.sub.6-alkanediyl, C.sub.3-C.sub.6-alkenediyl
or C.sub.4-C.sub.6-alkanedienediyl group which forms a fused ring
and in each of which one methylene group is optionally replaced by
oxygen or sulphur and which is optionally substituted by
C.sub.1-C.sub.6-alkyl or in which two adjacent substituents
together with the carbon atoms to which they are bonded optionally
form a further saturated or unsaturated carbocycle having 5 or 6
ring atoms, or
[0166] A and D together represent a C.sub.3-C.sub.6-alkanediyl or
C.sub.3-C.sub.6-alkenediyl group in each of which one of the
following groups 43
[0167] is optionally present.
[0168] G preferably, in the event that Het represents one of the
radicals (1), (2), (3), (5) or (6), represents hydrogen (a) or, in
the event that Het represents one of the radicals (1), (2), (3),
(4), (5) or (6), represents one of the groups 44
[0169] in which
[0170] E represents a metal ion equivalent or an ammonium ion,
[0171] L represents oxygen or sulphur and
[0172] M represents oxygen or sulphur.
[0173] R.sup.1 preferably represents C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-alkylthio-C.sub.1-C.sub.8-alkyl or
poly-C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl, each of which is
optionally substituted by halogen, or represents
C.sub.3-C.sub.8-cycloalk- yl which is optionally substituted by
halogen, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy and in
which one or two methylene groups which are not directly adjacent
are optionally replaced by oxygen and/or sulphur,
[0174] or represents phenyl which is optionally substituted by
halogen, cyano, nitro, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-halogenoalkyl,
C.sub.1-C.sub.6-halogenoalkoxy, C.sub.1-C.sub.6-alkylthio or
C.sub.1-C.sub.6-alkylsulphonyl,
[0175] or represents phenyl-C.sub.1-C.sub.6-alkyl which is
optionally substituted by halogen, nitro, cyano,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-halogenoalkyl or
C.sub.1-C.sub.6-halogenoalkoxy,
[0176] or represents 5- or 6-membered hetaryl having one or two
hetero atoms from the series consisting of oxygen, sulphur and
nitrogen which is optionally substituted by halogen or
C.sub.1-C.sub.6-alkyl,
[0177] or represents phenoxy-C.sub.1-C.sub.6-alkyl which is
optionally substituted by halogen or C.sub.1-C.sub.6-alkyl,
[0178] or represents 5- or 6-membered
hetaryloxy-C.sub.1-C.sub.6-alkyl having one or two hetero atoms
from the series consisting of oxygen, sulphur and nitrogen which is
optionally substituted by halogen, amino or
C.sub.1-C.sub.6-alkyl.
[0179] R.sup.2 preferably represents C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl or
poly-C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, each of which is
optionally substituted by halogen,
[0180] or represents C.sub.3-C.sub.8-cycloalkyl which is optionally
substituted by halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy, or
[0181] represents phenyl or benzyl, each of which is optionally
substituted by halogen, cyano, nitro, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-halogenoalkyl or
C.sub.1-C.sub.6-halogenoalkoxy.
[0182] R.sup.3 preferably represents C.sub.1-C.sub.8-alkyl which is
optionally-substituted by halogen, or represents phenyl or benzyl,
each of which is optionally substituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
cyano or nitro.
[0183] R.sup.4 and R.sup.5 independently of one another preferably
represent C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.1-C.sub.8-alkylamino, di-(C.sub.1-C.sub.8-alkyl)amino,
C.sub.1-C.sub.8-alkylthio or C.sub.2-C.sub.8-alkenylthio, each of
which is optionally substituted by halogen, or represent phenyl,
phenoxy or phenylthio, each of which is optionally substituted by
halogen, nitro, cyano, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-halogenoalkoxy, C.sub.1-C.sub.4-alkylthio,
C.sub.1-C.sub.4-halogenoalkylthio, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-halogenoalkyl.
[0184] R.sup.6 and R.sup.7 independently of one another preferably
represent hydrogen, or represent C.sub.1-C.sub.8-alkyl,
C.sub.3-C.sub.8-cycloalkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.3-C.sub.8-alkenyl or
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, each of which is
optionally substituted by halogen, or represent phenyl or benzyl,
each of which is optionally substituted by halogen,
C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-halogenoalkyl or
C.sub.1-C.sub.8-alkoxy, or together represent a
C.sub.3-C.sub.6-alkylene radical which is optionally substituted by
C.sub.1-C.sub.6-alkyl and in which one methylene group is
optionally replaced by oxygen or sulphur.
[0185] R.sup.13 preferably represents hydrogen, or represents
C.sub.1-C.sub.8-alkyl or C.sub.1-C.sub.8-alkoxy, each of which is
optionally substituted by halogen, or represents
C.sub.3-C.sub.8-cycloalk- yl which is optionally substituted by
halogen, C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy and in
which one methylene group is optionally replaced by oxygen or
sulphur, or represents phenyl, phenyl-C.sub.1-C.sub.4-alkyl or
phenyl-C.sub.1-C.sub.4-alkoxy, each of which is optionally
substituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, nitro or cyano.
[0186] R.sup.14 preferably represents hydrogen or
C.sub.1-C.sub.8-alkyl or
[0187] R.sup.13 and R.sup.14 together preferably represent
C.sub.4-C.sub.6-alkanediyl.
[0188] R.sup.15 and R.sup.16 are identical or different and
preferable represent C.sub.1-C.sub.6-alkyl or
[0189] R.sup.15 and R.sup.16 together preferably represent a
C.sub.2-C.sub.4-alkanediyl radical which is optionally substituted
by C.sub.1-C.sub.6-alkyl or by phenyl which is optionally
substituted by halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-halogenoalkoxy, nitro or cyano.
[0190] R.sup.17 and R.sup.18 independently of one another
preferably represent hydrogen, or represent C.sub.1-C.sub.8-alkyl
which is optionally substituted by halogen, or represent phenyl
which is optionally substituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, nitro or cyano, or
[0191] R.sup.17 and R.sup.18 together with the carbon atom to which
they are bonded represent C.sub.5-C.sub.7-cycloalkyl which is
optionally substituted by C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy and in which one methylene group is
optionally replaced by oxygen or sulphur.
[0192] R.sup.19 and R.sup.20 independently of one another
preferably represent C.sub.1-C.sub.10-alkyl,
C.sub.2-C.sub.10-alkenyl, C.sub.1-C.sub.10-alkoxy,
C.sub.1-C.sub.10-alkylamino, C.sub.3-C.sub.10-alkenylamino,
di-(C.sub.1-C.sub.10-alkyl)amino or
di-(C.sub.3-C.sub.10-alkenyl)amino.
[0193] X particularly preferably represents fluorine, chlorine or
bromine.
[0194] Y particularly preferably represents fluorine, chlorine,
bromine or C.sub.1-C.sub.4-alkyl.
[0195] Z particularly preferably represents fluorine, chlorine,
bromine or C.sub.1-C.sub.4-alkyl.
[0196] One of the radicals Y and Z always represents halogen while
the other represents alkyl.
[0197] Het particularly preferably represents one of the groups
45
[0198] A particularly preferably represents hydrogen, or represents
C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.8-alkoxy-C- .sub.1-C.sub.6-alkyl,
poly-C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.8-alkylthio-C.sub.1-C.sub.6-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represents
C.sub.3-C.sub.7-cycloalkyl which is optionally substituted by
fluorine, chlorine, C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy
and in which one or two methylene groups which are not directly
adjacent are optionally replaced by oxygen and/or sulphur, or
represents phenyl, furanyl, pyridyl, imidazolyl, triazolyl,
pyrazolyl, indolyl, thiazolyl, thienyl or
phenyl-C.sub.1-C.sub.4-alkyl, each of which is optionally
substituted by fluorine, chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-halogenoalkoxy, cyano or nitro.
[0199] B particularly preferably represents hydrogen,
C.sub.1-C.sub.10-alkyl or
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, or
[0200] A, B and the carbon atom to which they are bonded
particularly preferably represent C.sub.3-C.sub.8-cycloalkyl or
C.sub.5-C.sub.8-cycloalkenyl in each of which one methylene group
is optionally replaced by oxygen or sulphur and which are
optionally substituted by C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.8-cycloalkyl, C.sub.1-C.sub.3-halogenoalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio, fluorine,
chlorine or phenyl, or
[0201] A, B and the carbon atom to which they are bonded
particularly preferably represent C.sub.5-C.sub.6-cycloalkyl which
is substituted by an alkylenediyl group which optionally contains
one or two oxygen or sulphur atoms or by an alkylenedioxy or by an
alkylenedithioyl group, this group, together with the carbon atom
to which it is bonded forming a further five to seven-membered
ring, or
[0202] A, B and the carbon atom to which they are bonded
particularly preferably represent C.sub.3-C.sub.6-cycloalkyl or
C.sub.5-C.sub.6-cycloalkenyl in which two substituents together
with the carbon atoms to which they are bonded represent
C.sub.3-C.sub.5-alkanediy- l, C.sub.3-C.sub.5-alkenediyl or
butadienediyl, each of which is optionally substituted by
C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy, fluorine, chlorine
or bromine and in which in each case one methylene group is
optionally replaced by oxygen or sulphur.
[0203] D particularly preferably represents hydrogen, or represents
C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkinyl,
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.6-alkyl,
poly-C.sub.1-C.sub.6-alkoxy- -C.sub.2-C.sub.6-alkyl or
C.sub.1-C.sub.8-alkylthio-C.sub.2-C.sub.6-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represents
C.sub.3-C.sub.7-cycloalkyl which is optionally substituted by
fluorine, chlorine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy
or C.sub.1-C.sub.2-halogenoalkyl and in which one or two methylene
groups which are not directly adjacent are optionally replaced by
oxygen and/or sulphur, or represents phenyl, furanyl, imidazolyl,
pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl,
triazolyl or phenyl-C.sub.1-C.sub.4-alkyl, each of which is
optionally substituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-halogenoalkoxy, cyano or
nitro, or
[0204] A and D together particularly preferably represent a
C.sub.3-C.sub.5-alkanediyl or C.sub.3-C.sub.5-alkenediyl group in
each of which one methylene group is optionally replaced by oxygen
or sulphur and which are optionally substituted by fluorine,
chlorine, hydroxyl, mercapto, or by C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio,
C.sub.3-C.sub.6-cycloalkyl, phenyl or benzyloxy, each of which is
optionally substituted by fluorine or chlorine, or
[0205] in which in each case one of the following groups 46
[0206] is optionally present;
[0207] or A and D (in the case of the compounds of the formula
(I-1)) together with the atoms to which they are bonded represent
one of the groups AD-1 to AD-27 47484950
[0208] G particularly preferably, in the event that Het represents
one of the radicals (1), (2), (3), (5) or (6), represents hydrogen
(a) or, in the event that Het represents one of the radicals (1),
(2), (3), (4), (5) or (6), represents one of the groups 51
[0209] in which
[0210] E represents a metal ion equivalent or an ammonium ion,
[0211] L represents oxygen or sulphur and
[0212] M represents oxygen or sulphur.
[0213] R.sup.1 particularly preferably represents
C.sub.1-C.sub.16-alkyl, C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represents
C.sub.3-C.sub.7-cycloalkyl which is optionally substituted by
fluorine, chlorine, C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-alkoxy
and in which one or two methylene groups which are not directly
adjacent are optionally replaced by oxygen and/or sulphur,
[0214] or represents phenyl which is optionally substituted by
fluorine, chlorine, bromine, cyano, nitro, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.3-halogenoalkyl,
C.sub.1-C.sub.3-halogenoalkoxy, C.sub.1-C.sub.4-alkylthio or
C.sub.1-C.sub.4-alkylsulphonyl,
[0215] or represents phenyl-C.sub.1-C.sub.4-alkyl which is
optionally substituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.3-halogenoalkyl or
C.sub.1-C.sub.3-halogenoalkoxy,
[0216] or represents pyrazolyl, thiazolyl, pyridyl, pyrimidyl,
furanyl or thienyl, each of which is optionally substituted by
fluorine, chlorine, bromine or C.sub.1-C.sub.4-alkyl,
[0217] or represents phenoxy-C.sub.1-C.sub.5-alkyl which is
optionally substituted by fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl, or
[0218] represents pyridyloxy-C.sub.1-C.sub.5-alkyl,
pyrimidyloxy-C.sub.1-C.sub.5-alkyl or
thiazolyloxy-C.sub.1-C.sub.5-alkyl, each of which is optionally
substituted by fluorine, chlorine, bromine, amino or
C.sub.1-C.sub.4-alkyl.
[0219] R.sup.2 particularly preferably represents
C.sub.1-C.sub.16-alkyl, C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, each of which is
optionally substituted by fluorine or chlorine,
[0220] or represents C.sub.3-C.sub.7-cycloalkyl which is optionally
substituted by fluorine, chlorine, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy, or
[0221] represents phenyl or benzyl, each of which is optionally
substituted by fluorine, chlorine, bromine, cyano, nitro,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.3-alkoxy,
C.sub.1-C.sub.3-halogenoal- kyl or
C.sub.1-C.sub.3-halogenoalkoxy.
[0222] R.sup.3 particularly preferably represents
C.sub.1-C.sub.6-alkyl which is optionally substituted by fluorine
or chlorine, or represents phenyl or benzyl, each of which is
optionally substituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy,
C.sub.1-C.sub.3-halogenoalkyl, C.sub.1-C.sub.3-halogenoalkoxy,
cyano or nitro.
[0223] R.sup.4 and R.sup.5 independently of one another
particularly preferably represent C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylamino,
di-(C.sub.1-C.sub.6-alkyl)amino, C.sub.1-C.sub.6-alkylthio or
C.sub.3-C.sub.4-alkenylthio, each of which is optionally
substituted by fluorine or chlorine, or represent phenyl, phenoxy
or phenylthio, each of which is optionally substituted by fluorine,
chlorine, bromine, nitro, cyano, C.sub.1-C.sub.3-alkoxy,
C.sub.1-C.sub.3-halogenoalkoxy, C.sub.1-C.sub.3-alkylthio,
C.sub.1-C.sub.3-halogenoalkylthio, C.sub.1-C.sub.3-alkyl or
C.sub.1-C.sub.3-halogenoalkyl.
[0224] R.sup.6 and R.sup.7 independently of one another
particularly preferably represent hydrogen, or represent
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-alkenyl or
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represent phenyl
or benzyl, each of which is optionally substituted by fluorine,
chlorine, bromine, C.sub.1-C.sub.5-halogenoalkyl,
C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-alkoxy, or together
represent a C.sub.3-C.sub.6-alkylene radical which is optionally
substituted by C.sub.1-C.sub.4-alkyl and in which one methylene
group is optionally replaced by oxygen or sulphur.
[0225] R.sup.13 particularly preferably represents hydrogen, or
represents C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy, each of
which is optionally substituted by fluorine or chlorine, or
represents C.sub.3-C.sub.7-cycloalkyl which is optionally
substituted by fluorine, C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy and in which one methylene group is
optionally replaced by oxygen or sulphur, or represents phenyl,
phenyl-C.sub.1-C.sub.3-alkyl or phenyl-C.sub.1-C.sub.2-alkoxy, each
of which is optionally substituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy,
C.sub.1-C.sub.2-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
nitro or cyano.
[0226] R.sup.14 particularly preferably represents hydrogen or
C.sub.1-C.sub.6-alkyl or
[0227] R.sup.13 and R.sup.14 together particularly preferably
represent C.sub.4-C.sub.6-alkanediyl.
[0228] R.sup.15 and R.sup.16 are identical or different and
particularly preferably represent C.sub.1-C.sub.4-alkyl or
[0229] R.sup.15 and R.sup.16 together particularly preferably
represent a C.sub.2-C.sub.3-alkanediyl radical which is optionally
substituted by C.sub.1-C.sub.4-alkyl or by phenyl which is
optionally substituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-halogenoalkyl,
C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-halogenoalkoxy, nitro or
cyano.
[0230] R.sup.17 and R.sup.18 independently of one another
particularly preferably represent hydrogen, or represent
C.sub.1-C.sub.8-alkyl which is optionally substituted by fluorine
or chlorine, or represent phenyl which is optionally substituted by
fluorine, chlorine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoal- kyl, C.sub.1-C.sub.2-halogenoalkoxy,
nitro or cyano, or
[0231] R.sup.17 and R.sup.18 particularly preferably together with
the carbon atom to which they are bonded represent
C.sub.5-C.sub.6-cycloalkyl which is optionally substituted by
C.sub.1-C.sub.3-alkyl or C.sub.1-C.sub.3-alkoxy and in which one
methylene group is optionally replaced by oxygen or sulphur.
[0232] R.sup.19 and R.sup.20 independently of one another
particularly preferably represent C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylamino, C.sub.3-C.sub.6-alkenylamino,
di-(C.sub.1-C.sub.6-alkyl)amino or
di-(C.sub.3-C.sub.6-alkenyl)amino.
[0233] X very particularly preferably represents fluorine, chlorine
or bromine.
[0234] Y very particularly preferably represents fluorine,
chlorine, bromine, methyl, ethyl, n-propyl or iso-propyl.
[0235] Z very particularly preferably represents fluorine,
chlorine, bromine, methyl, ethyl, n-propyl or iso-propyl.
[0236] One of the radicals Y and Z always represents halogen while
the other represents alkyl.
[0237] Het very particularly preferably represents one of the
groups 52
[0238] A very particularly preferably represents hydrogen, or
represents C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.- sub.1-C.sub.4-alkyl,
poly-C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.4-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represents
C.sub.3-C.sub.6-cycloalkyl which is optionally substituted by
fluorine, chlorine, methyl or methoxy and in which one or two
methylene groups which are not directly adjacent are optionally
replaced by oxygen and/or sulphur, or represents phenyl, pyridyl or
benzyl, each of which is optionally substituted by fluorine,
chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl, methoxy,
ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro.
[0239] B very particularly preferably represents hydrogen,
C.sub.1-C.sub.8-alkyl or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, or
[0240] A, B and the carbon atom to which they are bonded very
particularly preferably represent C.sub.3-C.sub.8-cycloalkyl or
C.sub.5-C.sub.8-cycloalkenyl in each of which one methylene group
is optionally 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
[0241] A, B and the carbon atom to which they are bonded very
particularly preferably represent C.sub.5-C.sub.6-cycloalkyl which
is substituted by an alkylenediyl group which optionally contains
an oxygen or sulphur atom or by an alkylenedioxy group, this
alkylenediyl or alkylenedioxy group together with the carbon atom
to which it is bonded forming a further five to six-membered ring,
or
[0242] A, B and the carbon atom to which they are bonded very
particularly preferably represent C.sub.3-C.sub.6-cycloalkyl or
C.sub.5-C.sub.6-cycloalkenyl in which two substituents together
with the carbon atoms to which they are bonded represent
C.sub.3-C.sub.4-alkanediy- l, C.sub.3-C.sub.4-alkenediyl or
butadienediyl, in each of which one methylene group is optionally
replaced by oxygen or sulphur.
[0243] D very particularly preferably represents hydrogen, or
represents C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.4-alkenyl,
C.sub.3-C.sub.4-alkinyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.4-alkyl,
poly-C.sub.1-C.sub.4-alkoxy- -C.sub.2-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.2-C.sub.4-alkyl or
C.sub.3-C.sub.6-cycloalkyl, in which one or two methylene groups
which are not directly adjacent are replaced by oxygen and/or
sulphur, in each case optionally substituted by fluorine or
chlorine, or represents phenyl, furanyl, pyridyl, thienyl or
benzyl, each of which is optionally substituted by fluorine,
chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl, methoxy,
ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, or
[0244] A and D together very particularly preferably represent a
C.sub.3-C.sub.5-alkanediyl or C.sub.3-C.sub.5-alkenediyl group in
each of which one methylene group is optionally replaced by oxygen
or sulphur and which are optionally substituted by fluorine,
chlorine, hydroxyl, mercapto, or by C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio,
C.sub.3-C.sub.6-cycloalkyl, phenyl or benzyloxy, each of which is
optionally substituted by fluorine or chlorine, or
[0245] in which in each case one of the following groups 53
[0246] is optionally present,
[0247] or A and D, in the case of the compounds of the formula
(I-1), together with the atoms to which they are bonded represent
one of the following groups: 545556
[0248] G very particularly preferably, in the event that Het
represents one of the radicals (1), (2), (3), (5) or (6),
represents hydrogen (a) or, in the event that Het represents one of
the radicals (1), (2), (3), (4), (5) or (6), represents one of the
groups 57
[0249] in which
[0250] E represents a metal ion equivalent or an ammonium ion,
[0251] L represents oxygen or sulphur and
[0252] M represents oxygen or sulphur.
[0253] R.sup.1 very particularly preferably represents
C.sub.1-C.sub.14-alkyl, C.sub.2-C.sub.14-alkenyl,
C.sub.1-C.sub.4-alkoxy-- C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.6-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represents
C.sub.3-C.sub.6-cycloalkyl which is optionally substituted by
fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl,
i-butyl, tert-butyl, methoxy, ethoxy, n-propoxy or iso-propoxy and
in which one or two methylene groups which are not directly
adjacent are optionally replaced by oxygen and/or sulphur,
[0254] or represents phenyl which is optionally substituted by
fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl,
i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,
methylthio, ethylthio, methylsulphonyl or ethylsulphonyl,
[0255] or represents benzyl which is optionally substituted by
fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl,
methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
[0256] or represents furanyl, thienyl or pyridyl, each of which is
optionally substituted by fluorine, chlorine, bromine, methyl or
ethyl,
[0257] or represents phenoxy-C.sub.1-C.sub.4-alkyl which is
optionally substituted by fluorine, chlorine, methyl or ethyl,
or
[0258] represents pyridyloxy-C.sub.1-C.sub.4-alkyl,
pyrimidyloxy-C.sub.1-C.sub.4-alkyl or
thiazolyloxy-C.sub.1-C.sub.4-alkyl, each of which is optionally
substituted by fluorine, chlorine, amino, methyl or ethyl.
[0259] R.sup.2 very particularly preferably represents
C.sub.1-C.sub.14-alkyl, C.sub.2-C.sub.14-alkenyl,
C.sub.1-C.sub.4-alkoxy-- C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.6-alkyl- , each of which
is optionally substituted by fluorine or chlorine,
[0260] or represents C.sub.3-C.sub.6-cycloalkyl which is optionally
substituted by fluorine, chlorine, methyl, ethyl, n-propyl,
iso-propyl or methoxy,
[0261] or represents phenyl or benzyl, each of which is optionally
substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl,
n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or
trifluoromethoxy,
[0262] R.sup.3 very particularly preferably represents methyl,
ethyl, propyl or isopropyl, each of which is optionally substituted
by fluorine or chlorine, or represents phenyl or benzyl, each of
which is optionally substituted by fluorine, chlorine, bromine,
methyl, ethyl, propyl, iso-propyl, tert-butyl, methoxy, ethoxy,
isopropoxy, tert-butoxy, trifluoromethyl, trifluoromethoxy, cyano
or nitro.
[0263] R.sup.4 and R.sup.5 independently of one another very
particularly preferably represent C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylamino,
di-(C.sub.1-C.sub.4-alkyl)amino or C.sub.1-C.sub.4-alkylthio, each
of which is optionally substituted by fluorine or chlorine, or
represent phenyl, phenoxy or phenylthio, each of which is
optionally substituted by fluorine, chlorine, bromine, nitro,
cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy.
[0264] R.sup.6 and R.sup.7 independently of one another very
particularly preferably represent hydrogen, or represent
C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.4-alkenyl or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represent phenyl
or benzyl, each of which is optionally substituted by fluorine,
chlorine, bromine, methyl, methoxy or trifluoromethyl, or together
represent a C.sub.5-C.sub.6-alkylene radical which is optionally
substituted by methyl or ethyl and in which one methylene group is
optionally replaced by oxygen or sulphur.
[0265] R.sup.13 very particularly preferably represents hydrogen,
or represents C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy, each
of which is optionally substituted by fluorine or chlorine, or
represents C.sub.3-C.sub.6-cycloalkyl, or represents phenyl,
phenyl-C.sub.1-C.sub.2-- alkyl or benzyloxy, each of which is
optionally substituted by fluorine, chlorine, bromine, methyl,
ethyl, iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy,
tert-butoxy, trifluoromethyl, trifluoromethoxy, nitro or cyano.
[0266] R.sup.14 very particularly preferably represents hydrogen or
C.sub.1-C.sub.4-alkyl, or
[0267] R.sup.13 and R.sup.14 together very particularly preferably
represent C.sub.4-C.sub.6-alkanediyl.
[0268] R.sup.15 and R.sup.16 are identical or different and very
particularly preferably represent methyl or ethyl, or
[0269] R.sup.15 and R.sup.16 together very particularly preferably
represent a C.sub.2-C.sub.3-alkanediyl radical which is optionally
substituted by methyl, ethyl, n-propyl, iso-propyl, n-butyl,
iso-butyl, sec-butyl or tert-butyl, or by phenyl which is
optionally substituted by fluorine, chlorine, methoxy,
trifluoromethyl, trifluoromethoxy, nitro or cyano.
[0270] The abovementioned definitions of radicals or illustrations,
in general or where preferred ranges have been given, can be
combined with each other as desired, that is to say combinations
between the respective ranges and preferred ranges are also
possible. They apply to the end products and, analogously, to the
precursors and intermediates.
[0271] Preferred according to the invention are the compounds of
the formula (I) in which a combination of the meanings mentioned
above as being preferred (preferable) is present.
[0272] Particularly preferred according to the invention are the
compounds of the formula (I) in which a combination of the meanings
mentioned above as being particularly preferred is present.
[0273] Very particularly preferred according to the invention are
the compounds of the formula (I) in which a combination of the
meanings mentioned above as being very particularly preferred is
present.
[0274] Saturated or unsaturated hydrocarbon radicals, such as alkyl
or alkenyl, also in connection with hetero atoms, such as, for
example, in alkoxy, can be in each case straight-chain or branched
as far as this is possible.
[0275] Optionally substituted radicals can be monosubstituted or
polysubstituted, it being possible for the substituents in multiple
substitutions to be identical or different.
[0276] Individual compounds of the formula (I-1-a) which may be
mentioned in addition to the compounds mentioned in the preparation
examples are those which follow:
1TABLE 1 58 A B D CH.sub.3 H H C.sub.2H.sub.5 H H C.sub.3H.sub.7 H
H i-C.sub.3H.sub.7 H H C.sub.4H.sub.9 H H i-C.sub.4H.sub.9 H H
s-C.sub.4H.sub.9 H H t-C.sub.4H.sub.9 H H CH.sub.3 CH.sub.3 H
C.sub.2H.sub.5 CH.sub.3 H C.sub.3H.sub.7 CH.sub.3 H
i-C.sub.3H.sub.7 CH.sub.3 H C.sub.4H.sub.9 CH.sub.3 H
i-C.sub.4H.sub.9 CH.sub.3 H s-C.sub.4H.sub.9 CH.sub.3 H
-C.sub.4H.sub.9 CH.sub.3 H C.sub.2H.sub.5 C.sub.2H.sub.5 H
C.sub.3H.sub.7 C.sub.3H.sub.7 H 59 CH.sub.3 H 60 CH.sub.3 H 61
CH.sub.3 H --(CH.sub.2).sub.2-- H --(CH.sub.2).sub.4-- H
--(CH.sub.2).sub.5-- H --(CH.sub.2).sub.6-- H --(CH.sub.2).sub.7--
H --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2-- H
--CH.sub.2--CHCH.sub.3--(CH.sub.2).sub.3-- H
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHC.sub.2H.sub.5--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHC.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHOC.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--C(CH.sub.3).sub.2--(CH.sub.2).sub.2-- H
--CH.sub.2--(CHCH.sub.3).sub.2--(CH.sub.2).sub.2-- H 62 H 63 H 64 H
65 H 66 H --(CH.sub.2).sub.3-- H --(CH.sub.2).sub.4-- H
--CH.sub.2--CHCH.sub.3--CH.sub.2-- H
--CH.sub.2--CH.sub.2--CHCH.sub.3-- H --CH.sub.2--CHCH.sub.3--CH-
CH.sub.3-- H --CH.sub.2--S--CH.sub.2-- H
--CH.sub.2--S--(CH.sub.2).sub.2-- H --(CH.sub.2).sub.2--S--CH.sub-
.2-- H 67 H H CH.sub.3 H H C.sub.2H.sub.5 H H C.sub.3H.sub.7 H H
i-C.sub.3H.sub.7 H H 68 H H 69 H H 70 H CH.sub.3 CH.sub.3 H
CH.sub.3 C.sub.2H.sub.5 H CH.sub.3 C.sub.3H.sub.7 H CH.sub.3
i-C.sub.3H.sub.7 H CH.sub.3 71 H CH.sub.3 72 H CH.sub.3 73 H
C.sub.2H.sub.5 CH.sub.3 H C.sub.2H.sub.5 C.sub.2H.sub.5 H
[0277]
2TABLE 2 74 A B D CH.sub.3 H H C.sub.2H.sub.5 H H C.sub.3H.sub.7 H
H i-C.sub.3H.sub.7 H H C.sub.4H.sub.9 H H i-C.sub.4H.sub.9 H H
s-C.sub.4H.sub.9 H H t-C.sub.4H.sub.9 H H CH.sub.3 CH.sub.3 H
C.sub.2H.sub.5 CH.sub.3 H C.sub.3H.sub.7 CH.sub.3 H
i-C.sub.3H.sub.7 CH.sub.3 H C.sub.4H.sub.9 CH.sub.3 H
i-C.sub.4H.sub.9 CH.sub.3 H s-C.sub.4H.sub.9 CH.sub.3 H
t-C.sub.4H.sub.9 CH.sub.3 H C.sub.2H.sub.5 C.sub.2H.sub.5 H
C.sub.3H.sub.7 C.sub.3H.sub.7 H 75 CH.sub.3 H 76 CH.sub.3 H 77
CH.sub.3 H --(CH.sub.2).sub.2-- H --(CH.sub.2).sub.4-- H
--(CH.sub.2).sub.5-- H --(CH.sub.2).sub.6-- H --(CH.sub.2).sub.7--
H --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2-- H
--CH.sub.2--CHCH.sub.3--(CH.sub.2).sub.3-- H
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHC.sub.2H.sub.5--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHC.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHOC.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--C(CH.sub.3).sub.2--(CH.sub.2).sub.2-- H
--CH.sub.2--(CHCH.sub.3).sub.2--(CH.sub.2).sub.2-- H 78 H 79 H 80 H
81 H 82 H --(CH.sub.2).sub.3-- H --(CH.sub.2).sub.4-- H
--CH.sub.2--CHCH.sub.3--CH.sub.2-- H
--CH.sub.2--CH.sub.2--CHCH.sub.3-- H --CH.sub.2--CHCH.sub.3--CH-
CH.sub.3-- H --CH.sub.2--S--CH.sub.2-- H
--CH.sub.2--S--(CH.sub.2).sub.2-- H --(CH.sub.2).sub.2--S--CH.sub-
.2-- H 83 H H CH.sub.3 H H C.sub.2H.sub.5 H H C.sub.3H.sub.7 H H
i-C.sub.3H.sub.7 H H 84 H H 85 H H 86 H CH.sub.3 CH.sub.3 H
CH.sub.3 C.sub.2H.sub.5 H CH.sub.3 C.sub.3H.sub.7 H CH.sub.3
i-C.sub.3H.sub.7 H CH.sub.3 87 H CH.sub.3 88 H CH.sub.3 89 H
C.sub.2H.sub.5 CH.sub.3 H C.sub.2H.sub.5 C.sub.2H.sub.5 H
[0278] Individual compounds of the formula (I-2-a) which may be
mentioned in addition to the compounds mentioned in the preparation
examples are those which follow:
3TABLE 3 90 A B CH.sub.3 H C.sub.2H.sub.5 H C.sub.3H.sub.7 H
i-C.sub.3H.sub.7 H C.sub.4H.sub.9 H i-C.sub.4H.sub.9 H
s-C.sub.4H.sub.9 H t-C.sub.4H.sub.9 H CH.sub.3 CH.sub.3
C.sub.2H.sub.5 CH.sub.3 C.sub.3H.sub.7 CH.sub.3 i-C.sub.3H.sub.7
CH.sub.3 C.sub.4H.sub.9 CH.sub.3 i-C.sub.4H.sub.9 CH.sub.3
s-C.sub.4H.sub.9 CH.sub.3 --C.sub.4H.sub.9 CH.sub.3 C.sub.2H.sub.5
C.sub.2H.sub.5 C.sub.3H.sub.7 C.sub.3H.sub.7 91 CH.sub.3 92
CH.sub.3 93 CH.sub.3 --(CH.sub.2).sub.2-- --(CH.sub.2).sub.4--
--(CH.sub.2).sub.5-- --(CH.sub.2).sub.6-- --(CH.sub.2).sub.7--
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2--
--CH.sub.2--CHCH.sub.3--(CH.sub.2).sub.3-- --(CH.sub.2).sub.2--CHC-
H.sub.3--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHC.sub.2H.sub.5--(- CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHC.sub.3H.sub.7--(CH.sub.2).- sub.2--
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOC.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--C(CH.sub.3).sub.2--(CH.sub.2).sub.2--
--CH.sub.2--(CHCH.sub.3).sub.2--(CH.sub.2).sub.2-- 94 95 96 97
98
[0279]
4TABLE 4 99 A B CH.sub.3 H C.sub.2H.sub.5 H C.sub.3H.sub.7 H
i-C.sub.3H.sub.7 H C.sub.4H.sub.9 H i-C.sub.4H.sub.9 H
s-C.sub.4H.sub.9 H t-C.sub.4H.sub.9 H CH.sub.3 CH.sub.3
C.sub.2H.sub.5 CH.sub.3 C.sub.3H.sub.7 CH.sub.3 i-C.sub.3H.sub.7
CH.sub.3 C.sub.4H.sub.9 CH.sub.3 i-C.sub.4H.sub.9 CH.sub.3
s-C.sub.4H.sub.9 CH.sub.3 --C.sub.4H.sub.9 CH.sub.3 C.sub.2H.sub.5
C.sub.2H.sub.5 C.sub.3H.sub.7 C.sub.3H.sub.7 100 CH.sub.3 101
CH.sub.3 102 CH.sub.3 --(CH.sub.2).sub.2-- --(CH.sub.2).sub.4--
--(CH.sub.2).sub.5-- --(CH.sub.2).sub.6-- --(CH.sub.2).sub.7--
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2--
--CH.sub.2--CHCH.sub.3--(CH.sub.2).sub.3-- --(CH.sub.2).sub.2--CHC-
H.sub.3--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHC.sub.2H.sub.5--(- CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHC.sub.3H.sub.7--(CH.sub.2).- sub.2--
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOC.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--C(CH.sub.3).sub.2--(CH.sub.2).sub.2--
--CH.sub.2--(CHCH.sub.3).sub.2--(CH.sub.2).sub.2-- 103 104 105 106
107
[0280] Individual compounds of the formula (I-3-a) which may be
mentioned in addition to the compounds mentioned in the preparation
exaples are those which follow:
5TABLE 5 108 A B CH.sub.3 H C.sub.2H.sub.5 H C.sub.3H.sub.7 H
i-C.sub.3H.sub.7 H C.sub.4H.sub.9 H i-C.sub.4H.sub.9 H
s-C.sub.4H.sub.9 H t-C.sub.4H.sub.9 H CH.sub.3 CH.sub.3
C.sub.2H.sub.5 CH.sub.3 C.sub.3H.sub.7 CH.sub.3 i-C.sub.3H.sub.7
CH.sub.3 C.sub.4H.sub.9 CH.sub.3 i-C.sub.4H.sub.9 CH.sub.3
s-C.sub.4H.sub.9 CH.sub.3 t-C.sub.4H.sub.9 CH.sub.3 C.sub.2H.sub.5
C.sub.2H.sub.5 C.sub.3H.sub.7 C.sub.3H.sub.7 109 CH.sub.3 110
CH.sub.3 111 CH.sub.3 --(CH.sub.2).sub.2-- --(CH.sub.2).sub.4--
--(CH.sub.2).sub.5-- --(CH.sub.2).sub.6-- --(CH.sub.2).sub.7--
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2--
--CH.sub.2--CHCH.sub.3--(CH.sub.2).sub.3-- --(CH.sub.2).sub.2--CHC-
H.sub.3--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHC.sub.2H.sub.5--(- CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHC.sub.3H.sub.7--(CH.sub.2).- sub.2--
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOC.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHi--C.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--C(CH.sub.3).sub.2--(CH.sub.2).sub.2--
--CH.sub.2--(CHCH.sub.3).sub.2--(CH.sub.2).sub.2-- 112 113 114 115
116
[0281] Individual compounds of the formula (I-5-a) which may be
mentioned in addition to the compounds mentioned in the preparation
examples are those which follow:
6TABLE 6 117 A D H CH.sub.3 H C(CH.sub.3).sub.3 H
C(CH.sub.3).sub.2CH.sub.2Cl CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.2CHCH.sub.3CH.sub.2CH.sub.3 H CH.dbd.C(CH.sub.3).sub.2
CH.sub.3 118 CH.sub.3 119 CH.sub.3 120 CH.sub.3 121 CH.sub.3 122
123 CH.sub.3 H 124 CH.sub.3 125 CH.sub.3 126 CH.sub.3 127 CH.sub.3
128 H 129 CH.sub.3 C.sub.5H.sub.9 CH.sub.3 C.sub.3H.sub.5 H
C.sub.3H.sub.4Cl (CH.sub.2).sub.3 (CH.sub.2).sub.4
C(CH.sub.3).sub.2OC(CH.sub.3).sub.2 H CH.sub.3 H C(CH.sub.3).sub.3
H C(CH.sub.3).sub.2CH.sub.2Cl CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.2CHCH.sub.3CH.sub.2CH.sub.3 H CH.dbd.C(CH.sub.3).sub.2
CH.sub.3 130 CH.sub.3 131 CH.sub.3 132 CH.sub.3 133 134 CH.sub.3 H
135 CH.sub.3 136 CH.sub.3 137 CH.sub.3 138 CH.sub.3 139 CH.sub.3
C.sub.5H.sub.9 CH.sub.3 C.sub.3H.sub.5 H C.sub.3H.sub.4Cl
(CH.sub.2).sub.3 (CH.sub.2).sub.4
C(CH.sub.3).sub.2OC(CH.sub.3).sub.2 CH.sub.3 CH(CH.sub.3).sub.2 140
141 142 143 CH.sub.3 CH(CH.sub.3).sub.2 144 145 146 147
[0282] If, in accordance with process (B), ethyl
O-[(2,6-dichloro-4-methyl- )-phenylacetyl]-hydroxyacetate is used,
the course of the process according to the invention can be
represented by the following equation: 148
[0283] If, in accordance with process (C), ethyl
2-[(2-chloro-6-fluoro-4-m-
ethyl)-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 equation: 149
[0284] If, for example, in accordance with process (E),
chlorocarbonyl 2-[(2,4-dichloro-6-methyl)-phenyl]ketene and acetone
are used as starting compounds, the course of the
methyl)-phenyl]ketene and thiobenzamide are used as starting
compounds, the course of the process according to the invention can
be represented by the following equation: 150
[0285] If, in accordance with process (G.alpha.),
3-[(2,6-dichloro-4-methy-
l)-phenyl]-5,5-dimethyl-pyrrolidine-2,4-dione and pivaloyl chloride
are used as starting substances, the course of the process
according to the invention can be represented by the following
equation: 151
[0286] If, in accordance with process (G) (variant .beta.),
3-[(2,4-dichloro-6-methyl)-phenyl]-4-hydroxy-5-phenyl-.DELTA..sup.3-dihyd-
rofuran-2-one and acetic anhydride are used as starting compounds,
the course of the process according to the invention can be
represented by.
[0287] If, in accordance with process (H),
8-[(2,4-dichloro-6-methyl)-phen-
yl]-1,6-diazabicyclo-(4,3,0.sup.1,6)-nonane-7,9-dione and
ethoxyethyl chloroformate are used as starting compounds, the
course of the process according to the invention can be represented
by the following equation: 152
[0288] If, in accordance with process (I), variant .alpha.,
3-[(2,6-dichloro-4-methyl)-phenyl]-4-hydroxy-6-(3-pyridyl)-pyrone
and methyl chloromonothioformate are used as starting materials,
the course of the reaction can be represented as follows: 153
[0289] If, in accordance with process (K), variant .beta.,
5-[(2-chloro-6-fluoro-4-methyl)-phenyl]-6-hydroxy-2-(4-chlorophenyl)-thia-
zin-4-one, carbon disulphide and methyl iodide are used
pyrrolidine-2,4-dione and methanesulphonyl chloride are used as
starting materials, the course of the reaction can be represented
by the following equation: 154
[0290] If, in accordance with process (K),
2-[(2,6-dichloro-4-methyl)-phen-
yl]-4-hydroxy-5-methyl-6-(2-pyridyl)-pyrone and
2,2,2-trifluoroethyl methanethiochlorophosphonate are used as
starting materials, the course of the reaction can be represented
by the following equation: 155
[0291] If, in accordance with process (L),
3-[(2,4-dichloro-6-methyl)-phen-
yl]-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 equation:
[0292] If, in accordance with process (M), variant .alpha.,
3-[(2,6-dichloro-4-methyl)-phenyl]-4-hydroxy-5,5-tetramethylene-.DELTA..s-
up.3-dihydro-furan-2-one and ethyl isocyanate are used as starting
materials, the course of the reaction can be represented by the
following equation: 156
[0293] If, in accordance with process (M), variant .beta.,
3-[(2,6-dichloro-4-methyl)-phenyl]-5-methyl-pyrrolidine-2,4-dione
and dimethylcarbamoyl chloride are used as starting materials, the
course of the reaction can be represented by the following
equation:
[0294] The compounds of the formula (II) 157
[0295] in which
[0296] A, B, D, X, Y, Z and R.sup.8 have the abovementioned
meanings,
[0297] and which are required as starting substances in process (A)
according to the invention are new.
[0298] The acylamino acid esters of the formula (II) are obtained,
for example, when amino acid derivatives of the formula (XXI)
158
[0299] in which
[0300] in which
[0301] X, Y and Z have the abovementioned meanings and
[0302] Hal represents chlorine or bromine
[0303] (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J.
Chem. 6, 341-5, 1968)
[0304] or when acylamino acids of the formula (XXIII) 159
[0305] in which
[0306] A, B, D, X, Y and Z have the abovementioned meanings,
[0307] are esterified (Chem. Ind. (London) 1568 (1968)).
[0308] The compounds of the formula (XXIII) are new.
[0309] The compounds of the formula (XXIII) are obtained when amino
acids of the formula (XXIV) 160
[0310] in which
[0311] A, B and D have the abovementioned meanings,
[0312] are acylated with substituted phenylacetyl halides of the
formula (XXII) 161
[0313] in which
[0314] X, Y and Z have the abovementioned meanings and
[0315] Hal represents chlorine and bromine, 162
[0316] in which
[0317] X, Y and Z have the abovementioned meanings,
[0318] with halogenating agents (for example thionyl chloride,
thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride,
phosphorus tribromide or phosphorus pentachloride) at temperatures
from -20.degree. C. to 150.degree. C., preferably from -10.degree.
C. to 100.degree. C., if appropriate in the presence of a diluent
(for example optionally chlorinated aliphatic or aromatic
hydrocarbons, such as toluene or methylene chloride).
[0319] The compounds of the formula (XXV) are new with the
exception of 2,4-dichloro-6-methyl-phenylacetic acid (see Crosby et
al., J. Agric. Food Chem. 33, 569-73 (1985).
[0320] The compounds of the formula (XXV) are obtained, for
example, by hydrolysing substituted phenylacetic esters of the
formula (XXVI) 163
[0321] aqueous alcohol, such as methanol or ethanol).
[0322] The compounds of the formula (XXVI) are new.
[0323] The compounds of the formula (XXVI) are obtained, for
example, by reacting substituted 1,1,1-trichloro-2-phenylethanes of
the formula (XXVII) 164
[0324] in which
[0325] X, Y and Z have the abovementioned meanings,
[0326] first with alcoholates (for example alkali metal
alcoholates, such as sodium methylate or sodium ethylate) at
temperatures between 0.degree. C. and 150.degree. C., preferably
between 20.degree. C. and 120.degree. C., in the presence of a
diluent (for example the alcohol derived from the alcoholate), and
subsequently with an acid (preferably an inorganic acid such as,
for example, sulphuric acid) at temperatures between -20.degree. C.
and 150.degree. C., preferably 0.degree. C. and 100.degree. C.
[0327] The compounds of the formula (XXVII) are new.
[0328] in which
[0329] X, Y and Z have the abovementioned meanings,
[0330] are reacted with vinylidene chloride
(CH.sub.2.dbd.CCl.sub.2) at a temperature from -20.degree. C. to
80.degree. C., preferably 0.degree. C. to 60.degree. C.,
[0331] in the presence of an alkyl nitrite of the formula
(XXIX)
R.sup.21--ONO (XXIX)
[0332] in which
[0333] R.sup.21 represents alkyl, preferably
C.sub.1-C.sub.6-alkyl,
[0334] in the presence of copper(II) chloride and, if appropriate,
in the presence of a diluent (for example an aliphatic nitrile,
such as acetonitrile).
[0335] The compounds of the formulae (XXVIII) and (XXIX) are known
compounds of organic chemistry. Copper(II) chloride and vinylidene
chloride have been known for a long time and are commercially
available.
[0336] Some of the compounds of the formulae (XXI) and (XXIV) are
known and/or can be synthesized from known processes (see, for
example, Compagnon, Miocque Ann. Chim. (Paris) [14] 5, p. 11-22,
23-27 (1970)).
[0337] position. 165
[0338] (L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C.
Jitrangeri, Can. J. Chem. 53, 3339 (1975).
[0339] Furthermore, the starting substances of the formula (II)
166
[0340] in which
[0341] A, B, D, X, Y, Z and R.sup.8 have the abovementioned
meanings,
[0342] and which are used in the above process (A) can be prepared
when aminonitriles of the
[0343] A, B and D have the abovementioned meanings,
[0344] are reacted with substituted phenylacetyl halides of the
formula (XXII) 167
[0345] in which
[0346] X, Y, Z and Hal have the abovementioned meanings,
[0347] to give compounds of the formula (XXXI) 168
[0348] in which
[0349] A, B, D, X, Y and Z have the abovementioned meanings,
169
[0350] in which
[0351] A, B, X, Y, Z and R.sup.8 have the abovementioned
meanings,
[0352] and which are required as starting substances in process (B)
according to the invention are new.
[0353] They can be prepared in a simple manner by methods known in
principle.
[0354] The compounds of the formula (III) are obtained, for
example, when 2-hydroxycarboxylic esters of the formula (XXXII)
170
[0355] in which
[0356] A, B and R.sup.8 have the abovementioned meanings,
[0357] are acylated with substituted phenylacetyl halides of the
formula (XXII)
[0358] (Chem. Reviews 52, 237416 (1953)).
[0359] Furthermore, compounds of the formula (III) are obtained
when substituted phenylacetic acids of the formula (XXV) 171
[0360] in which
[0361] X, Y and Z have the abovementioned meanings,
[0362] are reacted with .alpha.-halogenocarboxylic esters of the
formula (XXXIII) 172
[0363] in which
[0364] A, B and R.sup.8 have the abovementioned meanings and
173
[0365] in which
[0366] A, B, W, X, Y, Z and R.sup.8 have the abovementioned
meanings
[0367] and which are required as starting substances in the above
process (C) are new.
[0368] They can be prepared by methods known in principle.
[0369] The compounds of the formula (IV) are obtained, for example,
when substituted phenylacetic esters of the formula (XXVI) 174
[0370] in which
[0371] in which
[0372] A, B and W have the abovementioned meanings and
[0373] Hal represents halogen (in particular chlorine or
bromine),
[0374] 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).
[0375] Some of the benzylthio-carbonyl halides of the formula
(XXXIV) are known and/or can be prepared by known processes (J.
Antibiotics (1983), 26, 1589).
[0376] The halogenocarbonyl ketenes of the formula (V) which are
required as starting substances in process (E) are new. 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 (V) 175
[0377] in which 176
[0378] in which
[0379] X, Y and Z have the abovementioned meanings
[0380] are reacted with acid halides, such as, for example, thionyl
chloride, phosphorus(V) chloride, phosphorus(III) chloride, oxalyl
chloride, phosgene or thionyl bromide, at a temperature between
-20.degree. C. and 200.degree. C., preferably between 0.degree. C.
and 150.degree. C., if appropriate in the presence of catalysts,
such as, for example, diethylformamide, methyl-stearylformamide or
triphenylphosphine, and, if appropriate, in the presence of bases,
such as, for example, pyridine or triethylamine.
[0381] The substituted phenylmalonic acids of the formula (XXXV)
are new. However, they can be prepared in a simple manner by known
processes (cf., for example, Organikum [Laboratory Practical in
Organic Chemistry], VEB Deutscher Verlag der Wissenschaften, Berlin
1977, p. 517 et seq.).
[0382] The carbonyl compounds of the formula (VIII) or their silyl
enol ethers of the formula (VIIIa) and which are required as
starting substances for the process (E) according to the invention
are commercially available, generally known or accessible by known
processes.
[0383] The preparation of the ketene acid chlorides of the formula
(V) which are required as starting substances for carrying out
process (F) according to the invention were already described in
process (E) according to the invention. The thioamides of the
formula (IX) 177
[0384] in which
[0385] A has the abovementioned meaning
[0386] and which are required for carrying out process (F)
according to the invention are compounds generally known in organic
chemistry.
[0387] The compounds of the formula (I-4-a) which are required as
starting substances in process (G) are known and/or can be prepared
in a simple manner by known methods (cf. also WO 92/16510).
[0388] The compounds of the formula (I-4-a) are obtained, for
example, when compounds of the formula (V) 178
[0389] in which
[0390] X, Y and Z have the abovementioned meanings and
[0391] Hal represents halogen (in particular chlorine or bromine)
or
[0392] compounds of the formula (VI) 179
[0393] in which
[0394] R.sup.8, X, Y and Z have the abovementioned meanings
[0395] are reacted with hydrazines of the formula (VII)
A-NH--NH-D (VII)
[0396] in which
[0397] A and D have the abovementioned meanings,
[0398] at temperatures between -20.degree. C. and 250.degree. C.,
preferably between 0.degree. C. and 150.degree. C.,
[0399] if appropriate in the presence of a diluent,
[0400] the following being suitable: hydrocarbons, such as toluene
and xylene, furthermore ethers, such as dibutyl ether,
tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol
dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone,
and, only in the event that compounds of the formula (VI) are
employed, alcohols, such as methanol, ethanol, propanol,
iso-propanol, butanol, iso-butanol and tert-butanol, and, if
appropriate, in the presence of a base, suitable bases being, in
the event that compounds of the formula (V) are employed, inorganic
bases, in particular alkali metal carbonates or alkaline earth
metal carbonates, such as sodium carbonate, potassium carbonate or
calcium carbonate, and organic bases, such as, for example,
pyridine or triethylamine, and, in the event that compounds of the
formula (V) are employed, alkali metal oxides, alkali metal
hydroxides and alkali metal carbonates, alkaline earth metal
oxides, alkaline earth metal hydroxides and alkaline earth metal
carbonates, such as sodium hydroxide, potassium hydroxide,
magnesium oxide, calcium oxide, sodium carbonate, potassium
carbonate and calcium carbonate, all of which can also be employed
in the presence of phase transfer catalysts, such as, for example,
triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen
464 (=methyltrialkyl(C.sub.8-C.sub.10)ammonium chloride) or TDA 1
(=tris-(methoxyethoxyethyl)-amine), alkali metals, such as sodium
or potassium, alkali metal amides, alkali metal hydrides, alkaline
earth metal amides and alkaline earth metal hydrides, such as
sodium amide, sodium hydride and calcium hydride, and, moreover,
also alkali metal alcoholates, such as sodium methylate, sodium
ethylate and potassium tert-butylate.
[0401] The malonic esters of the formula (VI) 180
[0402] in which
[0403] R.sup.8, X, Y and Z have the abovementioned meanings,
[0404] are new. They can be synthesized by generally known methods
of organic chemistry (cf., for example, Tetrahedron Lett. 27, 2763
(1986) and Organikum [Laboratory Practical in Organic Chemistry]
VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. 587 et
seq.).
[0405] The hydrazines of the formula (VII)
A-NH--NH-D (VII),
[0406] in which
[0407] A and D have the abovementioned meanings,
[0408] are known in some cases and/or can be prepared by methods
known from the literature (cf., for example, Liebigs Ann. Chem.
585, 6 (1954); Reaktionen der organischen Synthese [Reactions in
Organic Synthesis], C. Ferri, pages 212, 513; Georg Thieme Verlag
Stuttgart, 1978; Liebigs Ann. Chem. 443, 242 (1925); Chem. Ber. 98,
2551 (1965), EP 508 126).
[0409] The acid halides of the formula (X), carboxylic anhydrides
of the formula (XI), chloroformic esters or chloroformic thioesters
of the formula (XII), chloromonothioformic esters or
chlorodithioformic esters of the formula (XIII), alkyl halides of
the formula (XIV), sulphonyl chlorides of the formula (XV),
phosphorus compounds of the formula (XVI), metal hydroxides, metal
alkoxides or amines of the formulae (XVII) and (XVIII), isocyanates
of the formula (XIX) and carbamoyl chlorides of the formula (XX),
all of which are furthermore required as starting substances for
carrying out processes (G), (H), (I), (J), (K), (L) and (M)
according to the invention are generally known compounds of organic
or inorganic chemistry.
[0410] Moreover, the compounds of the formulae (VII), (VIII), (IX)
to (XXI), (XXIV) and (XXXII) to (XXXIV) are disclosed in the patent
applications cited at the outset and/or can be prepared by the
methods described in these publications.
[0411] Process (A) is characterized in that compounds of the
formula (II) in which A, B, D, X, Y, Z and R.sup.8 have the
abovementioned meanings are subjected to intramolecular
condensation in the presence of a diluent and in the presence of a
base.
[0412] Diluents which can be employed in process (A) according to
the invention are all organic solvents which are inert to the
reactants. The following can preferably be used: hydrocarbons, such
as toluene and xylene, furthermore ethers, such as dibutyl ether,
tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol
dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone,
and also alcohols, such as methanol, ethanol, propanol,
iso-propanol, butanol, iso-butanol and tert-butanol.
[0413] Bases (deprotonating agents) which can be employed for
carrying out process (A) according to the invention are all
customary proton acceptors. The following can preferably be used:
alkali metal oxides, alkali metal hydroxides, alkali metal
carbonates, alkaline earth metal oxides, alkaline earth metal
hydroxides and alkaline earth metal carbonates, such as sodium
hydroxide, potassium hydroxide, magnesium oxide, calcium oxide,
sodium carbonate, potassium carbonate and calcium carbonate, all of
which can be employed in the presence of phase transfer catalysts,
such as, for example, triethylbenzylammonium chloride,
tetrabutylammonium bromide, Adogen 464
(=-methyltrialkyl(C.sub.8-C.sub.10- )ammonium chloride) or TDA 1
(=tris-(methoxyethoxyethyl)-amine. Alkali metals, such as sodium or
potassium, can furthermore be used. It is also possible to employ
alkali metal amides, alkali metal hydrides, alkaline earth metal
amides and alkaline earth metal hydrides, such as sodium amide,
sodium hydride and calcium hydride, and furthermore also alkali
metal alcoholates, such as sodium methylate, sodium ethylate and
potassium tert-butylate.
[0414] When carrying out process (A) according to the invention,
the reaction temperature can be varied within a substantial range.
In general, the process is carried out at temperatures between
0.degree. C. and 250.degree. C., preferably between 50.degree. C.
and 150.degree. C.
[0415] Process (A) according to the invention is generally carried
out under atmospheric pressure.
[0416] When carrying out process (A) according to the invention,
the reactant of the formula (II) and the deprotonating base are
generally employed in an equimolar to approximately twice the
equimolar amounts. However, it is also possible to use one or the
other reactant in a larger excess (up to 3 mol).
[0417] Process (B) is characterized in that compounds of the
formula (III) in which A, B, X, Y, Z and R.sup.8 have the
abovementioned meanings are subjected to intramolecular
condensation in the presence of a diluent and in the presence of a
base.
[0418] Diluents which can be employed in process (B) according to
the invention are all organic solvents which are inert to the
reactants. The following can preferably be used: hydrocarbons, such
as toluene and xylene, furthermore ethers, such as dibutyl ether,
tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol
dimethyl ether, moreover 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 furthermore be
employed.
[0419] Bases (deprotonating agents) which can be employed for
carrying out process (B) according to the invention are all
customary proton acceptors. The following can preferably be used:
alkali metal oxides, alkali metal hydroxides, alkali metal
carbonates, alkaline earth metal oxides, alkaline earth metal
hydroxides and alkaline earth metal carbonates, such as sodium
hydroxide, potassium hydroxide, magnesium oxide, calcium oxide,
sodium carbonate, potassium carbonate and calcium carbonate, all of
which can be employed in the presence of phase transfer catalysts,
such as, for example, triethylbenzylammonium chloride,
tetrabutylammonium bromide, Adogen 464
(=methyltrialkyl(C.sub.8-C.sub.10)- ammonium chloride) or TDA 1
(=tris-(methoxyethoxyethyl)-amine. Alkali metals, such as sodium or
potassium, can furthermore be used. It is also possible to employ
alkali metal amides, alkali metal hydrides, alkaline earth metal
amides and alkaline earth metal hydrides, such as sodium amide,
sodium hydride and calcium hydride, and furthermore also alkali
metal alcoholates, such as sodium methylate, sodium ethylate and
potassium tert-butylate.
[0420] When carrying out process (B) according to the invention,
the reaction temperature can be varied within a substantial range.
In general, the process is carried out at temperatures between
0.degree. C. and 250.degree. C., preferably between 50.degree. C.
and 150.degree. C.
[0421] Process (B) according to the invention is generally carried
out under atmospheric pressure.
[0422] When carrying out process (B) according to the invention,
the reactants of the formula (III) and the deprotonating base are
generally employed in approximately equimolar amounts. However, it
is also possible to use one or the other reactant in a larger
excess (up to 3 mol).
[0423] Process (C) is characterized in that compounds of the
formula (IV) in which A, B, W, X, Y, Z and R.sup.8 have the
abovementioned meanings are subjected to intramolecular cyclization
in the presence of an acid, and, if appropriate, in the presence of
a diluent.
[0424] Diluents which can be employed in process (C) according to
the invention are all organic solvents which are inert to the
reactants. The following can preferably be used: hydrocarbons, such
as toluene and xylene, furthermore halogenated hydrocarbons, such
as dichloromethane, chloroform, ethylene chloride, chlorobenzene,
dichlorobenzene, moreover 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 furthermore be
employed.
[0425] If appropriate, the acid employed can also act as the
diluent.
[0426] Acids which can be employed in process (C) according to the
invention are all customary inorganic and organic acids, such as,
for example, hydrohalic acids, sulphuric acid, alkyl-, aryl- and
haloalkylsulphonic acids; acids which are used in particular are
halogenated alkylcarboxylic acids, such as, for example,
trifluoroacetic acid.
[0427] When carrying out process (C) according to the invention,
the reaction temperature can be varied within a substantial range.
In general, the process is carried out at temperatures between
0.degree. C. and 250.degree. C., preferably between 50.degree. C.
and 150.degree. C.
[0428] Process (C) according to the invention is generally carried
out under atmospheric pressure.
[0429] When carrying out process (C) according to the invention,
the reactants of the formula (IV) and the acid are employed, for
example, in equimolar amounts. If appropriate, however, it is also
possible to employ the acid in catalytic amounts.
[0430] Process (E) according to the invention is characterized in
that carbonyl compounds of the formula (VIII) or their silyl enol
ethers of the formula (VIIIa) are reacted with ketene acid halides
of the formula (V), if appropriate in the presence of a diluent and
if appropriate in the presence of an acid acceptor.
[0431] Diluents which can be employed in process (E) according to
the invention are all organic solvents which are inert to the
reactants. The following can preferably be used: hydrocarbons, such
as o-dichlorobenzene, tetralin, toluene and xylene, furthermore
ethers, such as dibutyl ether, glycol dimethyl ether and diglycol
dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide N-methyl-pyrrolidone.
[0432] Acid acceptors which can be used when carrying out process
(E) according to the invention are all customary acid
acceptors.
[0433] The following can preferably be used: tertiary amines, such
as triethylamine, pyridine, diazabicyclooctane (DABCO),
diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base or
N,N-dimethyl-aniline.
[0434] When carrying out process (E) according to the invention,
the reaction temperature can be varied within a substantial range.
Expediently, the process is carried out at temperatures between
0.degree. C. and 250.degree. C., preferably between 50.degree. C.
and 220.degree. C.
[0435] Process (E) according to the invention is preferably carried
out under atmospheric pressure.
[0436] When carrying out process (E) according to the invention,
the reactants of the formulae (VIII) or (VIIIa) and (V) and, if
appropriate, the acid acceptor are generally employed in
approximately equimolar amounts. However, it is also possible to
use one or the other reactant in a larger excess (up to 5 mol).
[0437] Process (F) according to the invention is characterized in
that thioamides of the formula (IX) are reacted with ketene acid
halides of the formula (V), if appropriate in the presence of a
diluent and if appropriate in the presence of an acid acceptor.
[0438] Diluents which can be employed in process variant (F)
according to the invention are all inert organic solvents. The
following can preferably be used: hydrocarbons, such as
o-dichlorobenzene, tetralin, toluene and xylene, furthermore
ethers, such as dibutyl ether, glycol dimethyl ether and diglycol
dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide or
N-methyl-pyrrolidone.
[0439] Acid acceptors which can be used when carrying out process
(F) according to the invention are all customary acid
acceptors.
[0440] The following can preferably be used: tertiary amines, such
as triethylamine, pyridine, diazabicyclooctane (DABCO),
diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base or
N,N-dimethyl-aniline.
[0441] When carrying out process (F) according to the invention,
the reaction temperature can be varied within a substantial range.
Expediently, the process is carried out at temperatures between
0.degree. C. and 250.degree. C., preferably between 20.degree. C.
and 220.degree. C.
[0442] Process (F) according to the invention is preferably carried
out under atmospheric pressure.
[0443] When carrying out process (F) according to the invention,
the reactants of the formulae (IX) and (V) and, if appropriate, the
acid acceptors are generally employed in approximately equimolar
amounts. However, it is also possible to use one or the other
reactant in a larger excess (up to 5 mol).
[0444] Process (G.alpha.) is characterized in that compounds of the
formulae (I-1-a) to (I-6-a) are reacted in each case with
carboxylic acid halides of the formula (X), if appropriate in the
presence of a diluent and if appropriate in the presence of an
acid-binding agent.
[0445] Diluents which can be employed in process (Ga) according to
the invention are all solvents which are inert to the acid halides.
The following can preferably be used: hydrocarbons, such as
benzine, benzene, toluene, xylene and tetralin, furthermore
halogenated hydrocarbons, such as methylene chloride, chloroform,
carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover
ketones, such as acetone and methyl isopropyl ketone, furthermore
ethers, such as diethyl ether, tetrahydrofuran and dioxane,
additionally carboxylic esters, such as ethyl acetate, and also
strongly polar solvents, such as dimethyl sulphoxide and
sulpholane. If the acid halide is sufficiently stable to
hydrolysis, the reaction can also be carried out in the presence of
water.
[0446] Acid-binding agents which are suitable for the reaction in
accordance with process (G.alpha.) according to the invention are
all customary acid acceptors. The following can preferably be used:
tertiary amines, such as triethylamine, pyridine,
diazabicyclooctane (DABCO), diazabicycloundecane (DBU),
diazabicyclononene (DBN), Hunig base and N,N-dimethyl-aniline,
furthermore alkaline earth metal oxides, such as magnesium oxide
and calcium oxide, moreover alkali metal carbonates and alkaline
earth metal carbonates, such as sodium carbonate, potassium
carbonate and calcium carbonate, and alkali metal hydroxides, such
as sodium hydroxide and potassium hydroxide.
[0447] When carrying out process (G.alpha.) according to the
invention, the reaction temperature can be varied within a
substantial range. In general, the process is carried out at
temperatures between -20.degree. C. and +150.degree. C., preferably
between 0.degree. C. and 100.degree. C.
[0448] When carrying out process (G.alpha.) according to the
invention, the starting substances of the formulae (I-1-a) to
(I-6-a) and the carboxylic acid halide of the formula (X) are
generally employed in each case in approximately equivalent
amounts. However, it is also possible to employ the carboxylic acid
halide in a larger excess (up to 5 mol). Working-up is carried out
by customary methods.
[0449] Process (G.beta.) is characterized in that compounds of the
formulae (I-1-a) to (I-6-a) are reacted in each case with
carboxylic anhydrides of the formula (XI), if appropriate in the
presence of a diluent and if appropriate in the presence of an
acid-binding agent.
[0450] Diluents which can be used in process (G.beta.) according to
the invention are preferably those which are also preferably
suitable when using acid halides. Moreover, a carboxylic anhydride
employed in an excess may also simultaneously act as the
diluent.
[0451] Acid-binding agents which are optionally added in process
(G.beta.) are preferably those acid-binding agents which are also
preferably suitable when using acid halides.
[0452] When carrying out process (G.beta.) according to the
invention, the reaction temperature can be varied within a
substantial range. In general, the process is carried out at
temperatures between -20.degree. C. and +150.degree. C., preferably
between 0.degree. C. and 100.degree. C.
[0453] When carrying out process (G.beta.) according to the
invention, the starting substances of the formulae (I-1-a) to
(I-6-a) and the carboxylic anhydride of the formula (XI) are
generally employed in each case in approximately equivalent
amounts. However, it is also possible to employ the carboxylic
anhydride in a larger excess (up to 5 mol). Working-up is carried
out by customary methods.
[0454] In general, a procedure is followed in which diluents and an
excess of carboxylic anhydride and the carboxylic acid which forms
are removed by distillation or by washing with an organic solvent
or with water.
[0455] Process (H) is characterized in that compounds of the
formulae (I-1-a) to (I-6-a) are reacted in each case with
chloroformic esters or chloroformic thioesters of the formula
(XII), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid-binding agent.
[0456] Acid-binding agents which are suitable in process (H)
according to the invention are all customary acid acceptors. The
following can preferably be used: 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, moreover alkali metal
carbonates 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.
[0457] Diluents which can be employed in process (H) according to
the invention are all solvents which are inert to the chloroformic
esters or chloroformic thioesters. The following can preferably be
used: hydrocarbons, such as benzine, benzene, toluene, xylene and
tetralin, furthermore halogenated hydrocarbons, such as methylene
chloride, chloroform, carbon tetrachloride, chlorobenzene and
o-dichlorobenzene, moreover ketones, such as acetone and methyl
isopropyl ketone, furthermore ethers, such as diethyl ether,
tetrahydrofuran and dioxane, additionally carboxylic esters, such
as ethyl acetate, and also strongly polar solvents, such as
dimethyl sulphoxide and sulpholane.
[0458] When carrying out process (H) according to the invention,
the reaction temperature can be varied within a substantial range.
The reaction temperature is generally between -20.degree. C. and
+100.degree. C., preferably between 0.degree. C. and 50.degree.
C.
[0459] Process (H) according to the invention is generally carried
out under atmospheric pressure.
[0460] When carrying out process (H) according to the invention,
the starting substances of the formulae (I-1-a) to (I-6-a) and the
relevant chloroformic ester or chloroformic thioester of the
formula (XII) are generally employed in each case in approximately
equimolar amounts. However, it is also possible to employ one or
the other reactant in a larger excess (up to 2 mol). Working up is
carried out by customary methods. In general, a procedure is
followed in which precipitated salts are removed and the reaction
mixture which remains is concentrated by stripping off the
diluent.
[0461] Process (I) according to the invention is characterized in
that compounds of the formulae (I-1-a) to (I-6-a) are reacted in
each case with (I.alpha.) compounds of the formula (XIII) in the
presence of a diluent and, if appropriate, in the presence of an
acid-binding agent, or (I.beta.) carbon disulphide and subsequently
with alkyl halides of the formula (XIV), if appropriate in the
presence of a diluent and if appropriate in the presence of a
base.
[0462] In preparation process (I.alpha.), approximately 1 mol of
chloromonothioformic ester or chlorodithioformic ester of the
formula (XIII) is reacted per mol of starting compound of the
formulae (I-1-a) to (I-6-a) at 0 to 120.degree. C., preferably at
20 to 60.degree. C.
[0463] Suitable diluents which are optionally added are all inert
polar organic solvents, such as ethers, amides, sulphones,
sulphoxides, but also halogenoalkanes.
[0464] Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or
methylene chloride are preferably employed.
[0465] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-6-a) is synthesized by adding strong
deprotonating agents, such as, for example, sodium hydride or
potassium tertiary butylate, a further addition of acid-binding
agents can be dispensed with.
[0466] If acid-binding agents are employed, then suitable
substances are customary inorganic or organic bases, examples which
may be mentioned being sodium hydroxide, sodium carbonate,
potassium carbonate, pyridine and triethylamine.
[0467] The reaction can be carried out under atmospheric pressure
or elevated pressure, preferably under atmospheric pressure.
Working-up is carried out by customary methods.
[0468] In preparation process (I.beta.), the equimolar amount or an
excess of carbon disulphide is added in each case per mol of
starting compounds of the formulae (I-1-a) to (I-6-a). This process
is preferably carried out at temperatures from 0 to 50.degree. C.,
in particular 20 to 30.degree. C.
[0469] Frequently, it is expedient first to prepare the
corresponding salt from the compounds of the formulae (I-1-a) to
(I-6-a) by adding a base (such as, for example, potassium tertiary
butylate or sodium hydride). The compounds (I-1-a) to (I-6-a) are
reacted with carbon disulphide in each case for such a period of
time that the formation of the intermediate is complete, for
example after stirring at room temperature for several hours.
[0470] Bases which can be employed in process (I.beta.) are all
customary proton acceptors. The following are preferably suitable:
alkali metal hydrides, alkali metal alcoholates, alkali metal
carbonates, alkali metal hydrogen carbonates, alkaline earth metal
carbonates, alkaline earth metal hydrogen carbonates or nitrogen
bases. Examples which may be mentioned are, for example, sodium
hydride, sodium methanolate, sodium hydroxide, calcium hydroxide,
potassium carbonate, sodium hydrogen carbonate, triethylamine,
dibenzylamine, diisopropylamine, pyridine, quinoline,
diazabicyclooctane (DABCO), diazabicyclononene (DBN) and
diazabicycloundecene (DBU).
[0471] Diluents which can be used in this process are all customary
solvents.
[0472] The following can preferably be used: aromatic hydrocarbons,
such as benzene or toluene, alcohols, such as methanol, ethanol,
isopropanol or ethylene glycol, nitrites, such as acetonitrile,
ethers, such as tetrahydrofuran or dioxane, amides, such as
dimethylformamide, or other polar solvents, such as dimethyl
sulphoxide or sulpholane.
[0473] The further reaction with the alkyl halide of the formula
(XIV) is preferably carried out at 0 to 70.degree. C., in
particular at 20 to 50.degree. C. At least the equimolar amount of
alkyl halide is employed.
[0474] The process is carried out under atmospheric pressure or
under elevated pressure, preferably under atmospheric pressure.
[0475] Again, working-up is carried out by customary methods.
[0476] Process (J) according to the invention is characterized in
that compounds of the formulae (I-1-a) to (I-6-a) are reacted in
each case with sulphonyl chlorides of the formula (XV), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid-binding agent.
[0477] In preparation process (J), approximately 1 mol of sulphonyl
chloride of the formula (XV) is reacted per mole of starting
compound of the formulae (I-1-a) to (I-6-a) at -20 to 150.degree.
C., preferably at 20 to 70.degree. C.
[0478] Process (J) is preferably carried out in the presence of a
diluent.
[0479] Diluents which can be used are all inert polar organic
solvents, such as ethers, amides, nitrites, sulphones, sulphoxides,
or halogenated hydrocarbons, such as methylene chloride.
[0480] Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or
methylene chloride are preferably employed.
[0481] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-6-a) is synthesized by adding strong
deprotonating agents (such as, for example, sodium hydride or
potassium tertiary butylate) a further addition of acid-binding
agents can be dispensed with.
[0482] If acid-binding agents are employed, then suitable
substances are customary inorganic or organic bases, examples which
may be mentioned being sodium hydroxide, sodium carbonate,
potassium carbonate, pyridine and triethylamine.
[0483] The reaction can be carried out under atmospheric pressure
or elevated pressure, preferably under atmospheric pressure.
Working-up is carried out by customary methods.
[0484] Process (K) according to the invention is characterized in
that compounds of the formulae (I-1-a) to (I-6-a) are reacted in
each case with phosphorus compounds of the formula (XVI), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid-binding agent.
[0485] In preparation process (K), 1 to 2, preferably 1 to 1.3, mol
of the phosphorus compound of the formula (XVI) are reacted per mol
of the compounds (I-1-a) to (I-6-a) at temperatures between
40.degree. C. and 150.degree. C., preferably between -10 and
110.degree. C., to obtain compounds of the formulae (I-1-e) to
(I-6-e).
[0486] Process (K) is preferably carried out in the presence of a
diluent.
[0487] Suitable diluents are all inert polar organic solvents, such
as ethers, amides, nitrites, alcohols, sulphides, sulphones,
sulphoxides and the like.
[0488] Acetonitrile, dimethyl sulphoxide, tetrahydrofuran,
dimethylformamide or methylene chloride are preferably
employed.
[0489] Suitable acid-binding agents which are optionally added are
customary inorganic or organic bases, such as hydroxides,
carbonates or amines. Examples which may be mentioned are sodium
hydroxide, sodium carbonate, potassium carbonate, pyridine and
triethylamine.
[0490] The reaction can be carried out under atmospheric pressure
or under elevated pressure, preferably under atmospheric pressure.
Working-up is carried out by customary methods of organic
chemistry. The end products are preferably purified by
crystallization, chromatography or by so-called "incipient
distillation", i.e. removal of the volatile components in
vacuo.
[0491] Process (L) is characterized in that compounds of the
formulae (I-1-a) to (I-6-a) are reacted in each case with metal
hydroxides or metal alkoxides of the formula (XVII) or amines of
the formula (XVIII), if appropriate in the presence of a
diluent.
[0492] Diluents which can be employed in process (L) according to
the invention are, preferably, ethers, such as tetrahydrofuran,
dioxane or diethyl ether, or else alcohols, such as methanol,
ethanol or isopropanol, but also water. Process (L) according to
the invention is generally carried out under atmospheric pressure.
The reaction temperature is generally between -20.degree. C. and
100.degree. C., preferably between 0.degree. C. and 50.degree.
C.
[0493] Process (M) according to the invention is characterized in
that compounds of the formulae (I-1-a) to (I-6-a) are reacted in
each case with (M.alpha.) compounds of the formula (XIX), if
appropriate in the presence of a diluent and if appropriate in the
presence of a catalyst, or (M.beta.) with compounds of the formula
(XX), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid-binding agent.
[0494] In preparation process (M.alpha.), approximately 1 mol of
isocyanate of the formula (XIX) is reacted per mole of starting
compound of the formulae (I-1-a) to (I-6-a) at 0 to 100.degree. C.,
preferably at 20 to 50.degree. C.
[0495] Process (M.alpha.) is preferably carried out in the presence
of a diluent.
[0496] Suitable diluents are all inert organic solvents, such as
ethers, amides, nitrites, sulphones or sulphoxides.
[0497] If appropriate, catalysts may be added to accelerate the
reaction. Catalysts which can be employed very advantageously are
organotin compounds, such as, for example, dibutyltin
dilaurate.
[0498] The process is preferably carried out under atmospheric
pressure.
[0499] In preparation process (M.beta.), approximately 1 mol of
carbamoyl chloride of the formula (XX) is reacted per mole of
starting compound of the formulae (I-1-a) to (I-6-a) at 0 to
150.degree. C., preferably at 20 to 70.degree. C.
[0500] Diluents which are optionally added are all inert polar
organic solvents, such as ethers, amides, sulphones, sulphoxides or
halogenated hydrocarbons.
[0501] Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or
methylene chloride are preferably employed.
[0502] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-6-a) is synthesized by adding strong
deprotonating agents, such as, for example, sodium hydride or
potassium tertiary butylate, a further addition of acid-binding
agents can be dispensed with.
[0503] If acid-binding agents are employed, then suitable
substances are customary inorganic or organic bases, examples which
may be mentioned being sodium hydroxide, sodium carbonate,
potassium carbonate, triethylamine or pyridine.
[0504] The reaction can be carried out under atmospheric pressure
or elevated pressure, preferably under atmospheric pressure.
Working-up is carried out by customary methods.
[0505] The active compounds are suitable for combating animal
pests, preferably arthropods and nematodes, particularly insects
and arachnids, encountered in agriculture, in forests, in the
protection of stored products and materials, and in the hygiene
sector. They are active against normally sensitive and resistant
species and against all or some stages of development. The
abovementioned pests include:
[0506] From the order of the Isopoda, for example, Oniscus asellus,
Armadillidium vulgare and Porcellio scaber.
[0507] From the order of the Diplopoda, for example, Blaniulus
guttulatus.
[0508] From the order of the Chilopoda, for example, Geophilus
carpophagus and Scutigera spec.
[0509] From the order of the Symphyla, for example, Scutigerella
immaculata.
[0510] From the order of the Thysanura, for example, Lepisma
saccharina.
[0511] From the order of the Collembola, for example, Onychiurus
armatus.
[0512] From the order of the Orthoptera, for example, Blatta
orientalis, Periplaneta americana, Leucophaea maderae, Blattella
germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria
migratorioides, Melanoplus differentialis and Schistocerca
gregaria.
[0513] From the order of the Dermaptera, for example, Forficula
auricularia.
[0514] From the order of the Isoptera, for example, Reticulitermes
spp.
[0515] From the order of the Anoplura, for example, Phylloxera
vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus
spp. and Linognathus spp.
[0516] From the order of the Mallophaga, for example, Trichodectes
spp. and Damalinea spp.
[0517] From the order of the Thysanoptera, for example,
Hercinothrips femoralis and Thrips tabaci.
[0518] From the order of the Heteroptera, for example, Eurygaster
spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius,
Rhodnius prolixus and Triatoma spp.
[0519] 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.
[0520] 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.
[0521] 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.
[0522] From the order of the Hymenoptera, for example, Diprion
spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa
spp.
[0523] 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.
[0524] From the order of the Siphonaptera, for example, Xenopsylla
cheopis and Ceratophyllus spp.
[0525] From the order of the Arachnida, for example, Scorpio maurus
and Latrodectus mactans.
[0526] 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.
[0527] The active compounds according to the invention are
distinguished by a high insecticidal and acaricidal activity.
[0528] They can be employed particularly successfully for combating
insects which damage plants, such as, for example, against the
larvae of the mustard beetle (Phaedon cochleariae) or against the
larvae of the green rice leafhopper (Nephotettix cincticeps) or
against the caterpillars of the diamond-back moth (Plutella
maculipennis).
[0529] The active compounds according to the invention can
furthermore be used as defoliants, desiccants, agents for
destroying broad-leaved plants and, especially, as weed-killers. By
weeds, in the broadest sense, there are to be understood all plants
which grow in locations where they are not wanted. Whether the
substances according to the invention act as total or selective
herbicides depends essentially on the amount used.
[0530] The dosage rates of the active compounds according to the
invention which are required for combating weeds are between 0.001
and 10 kg/ha, preferably between 0.005 and 5 kg/ha.
[0531] The active compounds according to the invention can be used,
for example, in connection with the following plants:
[0532] Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium,
Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica,
Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea,
Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum,
Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex,
Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus
and Taraxacum.
[0533] Dicotyledon cultures of the genera: Gossypium, Glycine,
Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia,
Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and
Cucurbita.
[0534] Monocotyledon 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 and Apera.
[0535] Monocotyledon cultures of the genera: Oryza, Zea, Triticum,
Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas,
Asparagus and Allium.
[0536] However, the use of the active compounds according to the
invention is in no way restricted to these genera, but also extends
in the same manner to other plants.
[0537] The compounds are suitable, depending on the concentration,
for the total combating of weeds, for example on industrial terrain
and rail tracks, and on paths and squares with or without tree
plantings. Equally, the compounds can be employed for combating
weeds in perennial cultures, for example afforestations, decorative
tree plantings, orchards, vineyards, citrus groves, nut orchards,
banana plantations, coffee plantations, tea plantations, rubber
plantations, oil palm plantations, cocoa plantations, soft fruit
plantings and hopfields, in lawns, turf and pasture-land, and for
the selective combating of weeds in annual cultures.
[0538] The active compounds according to the invention are highly
suitable for selectively combating monocotyledon weeds in
dicotyledon cultures by the pre- and post-emergence method. For
example they can be employed very successfully for combating grass
weeds in cotton or sugar beet.
[0539] The active compounds can be converted into the customary
formulations, such as solutions, emulsions, wettable powders,
suspensions, powders, dusts, pastes, soluble powders, granules,
suspension-emulsion concentrates, natural and synthetic materials
impregnated with active compound, and very fine capsules in
polymeric substances.
[0540] 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.
[0541] 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 or methylene chloride, aliphatic hydrocarbons, such
as cyclohexane or paraffins, for example mineral oil 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.
[0542] As solid carriers there are suitable:
[0543] 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, alkyl
sulphates, arylsulphonates as well as albumen hydrolysis products;
as dispersing agents there are suitable: for example lignin
sulphite waste liquors and methylcellulose.
[0544] 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. Other
additives can be mineral and vegetable oils.
[0545] 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.
[0546] The formulations in general comprise between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90%.
[0547] The active compound according to the invention can be
present in their commercially available formulations and in the use
forms, prepared from these formulations, as a mixture with other
active compounds, such as insecticides, attractants, sterilants,
acaricides, nematicides, fungicides, growth-regulating substances
or herbicides. The insecticides include, for example, phosphates,
carbamates, carboxylates, chlorinated hydrocarbons, phenylureas,
substances produced by microorganisms, and the like.
[0548] Examples of particularly advantageous components for the
mixtures are the following:
[0549] Fungicides:
[0550] 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;
2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazo-
le-5-carboxanilide;
2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;
(E)-2-methoxyimino-N-methyl-2-(2-phenoxy-phenyl)acetamide;
8-hydroxyquinoline sulphate; methyl
(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidi-
n-4-yloxy]-phenyl}-3-methoxyacrylate; methyl
(E)-methoximino[alpha-(o-toly- loxy)-o-tolyl]acetate;
2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine,
azaconazole,
[0551] benalaxyl, benodanil, benomyl, binapacryl, biphenyl,
bitertanol, blasticidin-S, bromuconazole, bupirimate,
buthiobate,
[0552] calcium polysulphide, captafol, captan, carbendazim,
carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil,
chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
[0553] dichlorophen, diclobutrazol, diclofluanid, diclomezin,
dicloran, diethofencarb, difenoconazole, dimethirimol,
dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion,
ditalimfos, dithianon, dodine, drazoxolon,
[0554] edifenphos, epoxyconazole, ethirimol, etridiazole,
[0555] fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,
fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide,
ferbam, ferimzone, fluazinam, fludioxonil, fluoromide,
fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol,
folpet, fosetylaluminium, fthalide, fuberidazole, furalaxyl,
furmecyclox,
[0556] guazatine,
[0557] hexachlorobenzene, hexaconazole, hymexazol,
[0558] imazalil, imibenconazole, iminoctadine, iprobenfos (IBP),
iprodione, isoprothiolane, kasugamycin, copper preparations such
as: copper hydroxide, copper naphthenate, copper oxychloride,
copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,
mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,
metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax,
myclobutanil,
[0559] nickel dimethyldithiocarbamate, nitrothal-isopropyl,
nuarimol,
[0560] ofurace, oxadixyl, oxamocarb, oxycarboxin,
[0561] pefurazoate, penconazole, pencycuron, phosdiphen, phthalide,
pimaricin, piperalin, polycarbamate, polyoxin, probenazole,
prochloraz, procymidone, propamocarb, propiconazole, propineb,
pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
[0562] quintozene (PCNB),
[0563] sulphur and sulphur preparations,
[0564] tebuconazole, tecloftalam, tecnazene, tetraconazole,
thiabendazole, thicyofen, thiophanate-methyl, thiram,
tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,
triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,
triforine, triticonazole,
[0565] validamycin A, vinclozolin,
[0566] zineb, ziram
[0567] Bactericides:
[0568] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furanecarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
[0569] Insecticides/Acaricides/Nematicides:
[0570] abamectin, AC 303 630, acephate, acrinathrin, alanycarb,
aldicarb, alphamethrin, amitraz, avermectin, AZ 60541,
azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus
thuringiensis, bendiocarb, benfuiracarb, bensultap, betacyfluthrin,
bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin,
butocarboxin, butylpyridaben, cadusafos, carbaryl, carbofuran,
carbophenothion, carbosulfan, cartap, CGA 157419, CGA 184699,
chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron,
chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin,
clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin,
cyhalothrin, cyhexatin, cypemmethrin, cyromazine, deltamethrin,
demeton-M, demeton-S, demeton-5-methyl, diafenthiuron, diazinon,
dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,
diflubenzuron, dimethoate, dimethylvinphos, dioxathion,
disulfoton,
[0571] edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,
ethofenprox, ethoprophos, etrimphos,
[0572] fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,
fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,
fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,
flucycloxuron, flucythrinate, flufenoxuron, flufenprox,
fluvalinate, fonophos, formothion, fosthiazate, fubfenprox,
furathiocarb,
[0573] HCH, heptenophos, hexaflumuron, hexythiazox,
[0574] imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,
isoxathion, ivermectin, lambda-cyhalothrin, lufenuron,
[0575] malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde,
methacrifos, methamidophos, methidathion, methiocarb, methomyl,
metolcarb, milbemectin, monocrotophos, moxidectin,
[0576] naled, NC 184, NI 25, nitenpyram,
[0577] omethoate, oxamyl, oxydemethon M, oxydeprofos,
[0578] parathion A, parathion M, permethrin, phenthoate, phorate,
phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,
pirimiphos A, profenofos, promecarb, propaphos, propoxur,
prothiofos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion,
pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,
quinalphos,
[0579] RH 5992,
[0580] salithion, sebufos, silafluofen, sulfotep, sulprofos,
[0581] tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,
tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos,
thiafenox, thiodicarb, thiofanox, thiomethon, thionazin,
thuringiensin, tralomethrin, triarathen, triazophos, triazuron,
trichlorfon, triflumuron, trimethacarb,
[0582] vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.
[0583] Herbicides:
[0584] for example anilides such as, for example, diflufenican and
propanil; arylcarboxylic acids such as, for example,
dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids
such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP
and triclopyr; aryloxy-phenoxy-alkanoic esters such as, for
example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl,
haloxyfop-methyl and quizalofop-ethyl; azinones such as, for
example, chloridazon and norflurazon; carbamates such as, for
example, chlorpropham, desmedipham, phenmedipham and propham;
chloroacetanilides such as, for example, alachlor, acetochlor,
butachlor, metazachlor, metolachlor, pretilachlor and propachlor;
dinitroanilines such as, for example, oryzalin, pendimethalin and
trifluralin; diphenyl ethers such as, for example, acifluorfen,
bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and
oxyfluorfen; ureas such as, for example, chlorotoluron, diuron,
fluometuron, isoproturon, linuron and methabenzthiazuron;
hydroxylamines such as, for example, alloxydim, clethodim,
cycloxydim, sethoxydim and tralkoxydim; imidazolinones such as, for
example, imazethapyr, imazamethabenz, imazapyr and imazaquin;
nitriles such as, for example, bromoxynil, dichlobenil and ioxynil;
oxyacetamides such as, for example, mefenacet; sulphonylureas such
as, for example, amidosulfuron, bensulfuron-methyl,
chlorimuron-ethyl, chlorsulfuron, cinosulfiron, metsulfuron-methyl,
nicosulfuron, primisulfuron, pyrazosulfuron-ethyl,
thifensulfuron-methyl, triasulfuron and tribenuron-methyl;
thiocarbamates such as, for example, butylate, cycloate, diallate,
EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate;
triazines such as, for example, atrazine, cyanazine, simazine,
simetryn, terbutryn and terbutylazine; triazinones such as, for
example, hexazinone, metamitron and metribuzin; others such as, for
example, aminotriazole, benfuresate, bentazone, cinmethylin,
clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate,
fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate,
quinchlorac, quinmerac, sulphosate and tridiphane.
[0585] The active compound according to the invention can
furthermore be present in its commercially available formulations
and in the use forms, prepared from these formulations, as a
mixture with synergistic agents. Synergistic agents are compounds
which increase the action of the active compounds, without it being
necessary for the synergistic agent added to be active itself.
[0586] The active compound content of the use forms prepared from
the commercially available formulations can vary within wide
limits. The active compound concentration of the use forms can be
from 0.0000001 up to 95% by weight of active compound, preferably
between 0.0001 and 1% by weight.
[0587] The compounds are employed in a customary manner appropriate
for the use forms.
[0588] When used against hygiene pests and stored-product pests,
the active compound is distinguished by an outstanding residual
action on wood and clay and by a good stability to alkali on limed
substrates.
[0589] The active compounds according to the invention are not only
active against plant pests, hygiene pests and stored-product pests
but also, in the field of veterinary medicine, against animal
parasites (ectoparasites) such as scaly ticks, Argasidae, scab
mites, Trombidae, flies (stinging and sucking), parasitic fly
larvae, lice, hair lice, bird lice and fleas. These parasites
include:
[0590] From the order of the Anoplurida, for example, Haematopinus
spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes
spp.
[0591] From the order of the Mallophagida and the sub-orders
Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon
spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron
spp., Damalina spp., Trichodectes spp., Felicola spp.
[0592] From the order Diptera and the sub-orders Nematocerina and
Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,
Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,
Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp.,
Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp.,
Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp.,
Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia
spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus
spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp.,
Lipoptena spp., Melophagus spp.
[0593] From the order of the Siphonapterida, for example, Pulex
spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
[0594] From the order of the Heteropterida, for example, Cimex
spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
[0595] From the order of the Blattarida, for example, Blatta
orientalis, Periplaneta americana, Blattela germanica, Supella
spp.
[0596] From the sub-class of the Acaria (Acarida) and the orders of
the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus
spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,
Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus
spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp.,
Stemostoma spp., Varroa spp.
[0597] From the order of the Actinedida (Prostigmata) and Acaridida
(Astigmata), for example, Acarapis spp., Cheyletiella spp.,
Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,
Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,
Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes
spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres
spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
[0598] For example, they show an outstanding activity against
Boophilus microplus and Lucilia cuprina.
[0599] The active compounds of the formula (I) according to the
invention are also suitable for combating arthropods which infest
agricultural productive livestock such as, for example, cattle,
sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits,
chickens, turkeys, ducks, geese and bees, other domestic animals,
such as, for example, dogs, cats, cage birds and aquarium fish, and
also so-called experimental animals, such as, for example,
hamsters, guinea pigs, rats and mice. By combating these
arthropods, cases of death and reductions in productivity (for
meat, milk, wool, hides, eggs, honey etc) should be diminished, so
that more economic and simpler animal husbandry is possible by use
of the active compounds according to the invention.
[0600] The active compounds according to the invention are used in
the veterinary sector in a known manner by enteral administration
in the form of, for example, tablets, capsules, potions, drenches,
granules, pastes, boli, the feed-through process and suppositories,
by parenteral administration, such as, for example, by injections
(intra-muscular, subcutaneous, intravenous, intraperitoneal, etc.),
implants, by nasal administration, by dermal use in the form, for
example, of dipping or bathing, spraying, pouring on and spotting
on, washing and powdering, and also with the aid of moulded
articles containing the active compound, such as collars, ear
marks, tail marks, limb bands, halters, marking devices, etc.
[0601] When used for livestock, poultry, domestic animals and the
like, the active compounds of the formula (I) can be used as
formulations (for example powders, emulsions, flowables) which
comprise the active compounds in an amount of 1 to 80% by weight,
either directly or after dilution by a factor of 100 to 10 000, or
they may be used as a chemical bath.
[0602] Furthermore, it has been found that the compounds of the
formula I according to the invention have a potent insecticidal
action against insects which destroy industrial materials.
[0603] The following insects may be mentioned by way of example and
of being preferred, but not by way of limitation:
[0604] Beetles, such as
[0605] Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,
Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex,
Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus
africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,
Trogoxylon aequale, Minthes rugicollis, Xyleborus spec.,
Tryptodendron spec., Apate monachus, Bostrychus capucins,
Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.
[0606] Dermaptera, such as
[0607] Sirex juvencus, Urocerus gigas, Urocerus gigas taignus,
Urocerus augur.
[0608] Termites, such as
[0609] Kalotermes flavicollis, Cryptotermes brevis, Heterotermes
indicola, Reticulitermes flavipes, Reticulitermes santonensis,
Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis
nevadensis, Coptotermes formosanus.
[0610] bristletails, such as
[0611] Lepisma saccharina.
[0612] Industrial materials are to be listed as meaning, in the
present context, non-live materials such as, preferably, synthetic
materials, glues, sizes, paper and board, leather, wood and derived
timber products, and paints.
[0613] The material to be protected against attack by insects is
very particularly preferably wood and derived timber products.
[0614] Wood and derived timber products which can be protected by
the agent according to the invention or by compositions comprising
it are to be understood as meaning, for example, construction
timber, wooden beams, railway sleepers, bridge components, jetties,
wooden vehicles, boxes, pallets, containers, telephone poles, wood
laggings, windows and doors made of wood, plywood, particle board,
joiner's work, or wood products which, quite generally, are used in
construction or in joinery.
[0615] The active compounds can be used as such, in the form of
concentrates or generally customary formulations, such as powders,
granules, solutions, suspensions, emulsions or pastes.
[0616] The abovementioned formulations can be prepared in a manner
known per se, for example by mixing the active compounds with at
least one solvent or diluent, emulsifier, dispersant and/or binder
or fixative, water repellant, if appropriate desiccants and UV
stabilizers, and, if appropriate, colorants and pigments, and other
processing auxiliaries.
[0617] The insecticidal compositions or concentrates used for the
protection of wood and timber products comprise the active compound
according to the invention in a concentration of 0.0001 to 95% by
weight, in particular 0.001 to 60% by weight.
[0618] The amount of the compositions or concentrates employed
depends on the species and the occurrence of the insects and on the
medium. The optimum amount used can be determined in each case upon
use by test series. However, in general it suffices to employ
0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the
active compound based on the material to be protected.
[0619] The solvent and/or diluent used is an organochemical solvent
or solvent mixture and/or an oily or oil-like organochemical
solvent or solvent mixture of low volatility and/or a polar
organochemical solvent or solvent mixture and/or water and, if
appropriate, an emulsifier and/or wetting agent.
[0620] The organochemical solvents employed are preferably oily or
oil-like solvents with an evaporation number of above 35 and a
flash point of above 30.degree. C., preferably above 45.degree. C.
Substances which are used as such oily and oil-type solvents of low
volatility which are insoluble in water are suitable mineral oils
or their aromatic fractions or mineral-oil-comprising solvent
mixtures, preferably white spirit, petroleum and/or
alkylbenzene.
[0621] It is advantageous to use mineral oils with a boiling range
of -170 to 220.degree. C., white spirit with a boiling range of 170
to 220.degree. C., spindle oil with a boiling point of 250 to
350.degree. C., petroleum or aromatics of a boiling range of 160 to
280.degree. C., spirit of turpentine and the like.
[0622] In a preferred embodiment, the substances used are liquid
aliphatic hydrocarbons with a boiling range of 180 to 210.degree.
C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons
with a boiling range of 180 to 220.degree. C. and/or spindle oil
and/or monochloronaphthalene, preferably
.alpha.-monochloronaphthalene.
[0623] The organic oily or oil-type solvents of low volatility with
an evaporation number above 35 and a flashpoint of above 30.degree.
C., preferably 45.degree. C., can be replaced in part by
organochemical solvents of high or medium volatility, with the
proviso that the solvent mixture also has an evaporation number of
above 35 and a flashpoint of above 30.degree. C., preferably above
45.degree. C., and that the insecticide/fungicide mixture is
soluble or emulsifiable in this solvent mixture.
[0624] In a preferred embodiment, part of the organo-chemical
solvent or solvent mixture is replaced by an aliphatic polar
organochemical solvent or solvent mixture. Substances which are
preferably used are aliphatic organochemical solvents containing
hydroxyl and/or ester and/or ether groups, such as, for example,
glycol ethers, esters and the like.
[0625] Organochemical binders which are used within the scope of
the present invention are the binding drying oils and/or synthetic
resins which are known per se, can be diluted with water and/or are
soluble, dispersible or emulsifiable in the organochemical solvents
employed, in particular binders composed of or comprising an
acrylate resin, a vinyl resin, for example polyvinyl acetate,
polyester resin, polycondensation or polyaddition resin,
polyurethane resin, alkyd resin or modified alkyd resin, phenol
resin, hydrocarbon resin, such as indene-coumarone resin, silicone
resin, drying vegetable and/or drying oils and/or physically drying
binders based on a natural and/or synthetic resin.
[0626] The synthetic resin used as binder can be employed in the
form of an emulsion, dispersion or solution. Substances which can
also be used as binders are bitumen or bituminous substances in
amounts of up to 10% by weight. In addition, colorants, pigments,
water repellants, odoriferous substances and inhibitors or
anticorrosives which are known per se can be employed, inter
alia.
[0627] The composition or concentrate preferably comprises, in
accordance with the invention, at least one alkyd resin or modified
alkyd resin and/or a drying vegetable oil as the organochemical
binder. Substances which are preferably used according to the
invention are alkyd resins with an oil content of over 45% by
weight, preferably 50 to 68% by weight.
[0628] All or some of the abovementioned binder can be replaced by
a fixative (mixture) or a plasticizer (mixture). These additives
are intended to prevent volatilization of the active compounds or
crystallization or precipitation. They preferably replace 0.01 to
30% of the binder (based on 100% of binder employed).
[0629] The plasticizers are from the chemical classes of the
phthalic esters, such as dibutyl phthalate, dioctyl phthalate or
benzylbutyl phthalate, phosphoric esters, such as tributyl
phosphate, adipic esters, such as di-(2-ethylhexyl) adipate,
stearates, such as butyl stearate or amyl stearate, oleates, such
as butyl oleate, glycerol ethers or higher-molecular-weight glycol
ethers, glycerol esters and p-toluenesulphonic esters.
[0630] Fixatives are based chemically on polyvinyl alkyl ethers,
such as, for example, polyvinyl methyl ether, or ketones, such as
benzophenone or ethylenebenzophenone.
[0631] Another suitable solvent or diluent is, in particular,
water, if appropriate in a mixture with one or more of the
abovementioned organochemical solvents or diluents, emulsifiers and
dispersants.
[0632] A particularly effective protection of wood is achieved by
means of industrial-scale impregnating processes, for example
vacuum, double-vaccum or pressure processes.
[0633] If appropriate, the ready-to-use compositions can comprise
other insecticides and, if appropriate, one or more other
fungicides.
[0634] Additional components which may be admixed are preferably
the insecticides and fungicides mentioned in WO 94/29 268. The
compounds mentioned in the above document are expressly part of the
present application.
[0635] Components which may very particularly preferably be admixed
are insecticides, such as chlorpyriphos, phoxim, silafluofin,
alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin,
imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron,
and fungicides, such as epoxyconazole, hexaconazole, azaconazole,
propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,
dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl butylcarbamate,
N-octyl-isothiazolin-3-one and
4,5-dichloro-N-octylisothiazolin-3-one.
[0636] Preparation and use of the active compounds according to the
invention can be seen from the examples which follow.
PREPARATION EXAMPLES
Example (I-1-a-1)
[0637] 181
[0638] 25.1 g (0.072 mol) of the compound of Example (II-1) in 160
ml of anhydrous toluene are added dropwise at reflux temperature to
17.36 g (0.159 mol) of potassium tert-butylate in 55 ml of
anhydrous tetrahydrofuran (THF), and the mixture is stirred under
reflux for 1.5 hours. For working up, 230 ml of water are added,
the aqueous phase is separated off, the toluene phase is extracted
using 120 ml of water, and the aqueous phases are combined, washed
with toluene and acidified with approximately 25 ml of concentrated
HCl at 10 to 20.degree. C. The product is filtered off with
suction, washed, dried and washed by stirring in methyl tert-butyl
(MTB) ethyl/n-hexane.
[0639] Yield: 16.7 g (73% of theory), m.p.: 159.degree. C.
[0640] The following compounds of the formula (I-1-a) are obtained
analogously or in accordance with the general preparation
instructions:
7TABLE 10 (I-1-a) 182 Example No. X Y Z B A D M.p..degree. C.
Isomer I-1-a-2 Cl Cl CH.sub.3
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H 192 .beta. I-1-a-3 Cl
Cl CH.sub.3 --(CH.sub.2).sub.5-- H 176 -- I-1-a-4 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H 189 .beta.
I-1-a-5 Cl Cl CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).su- b.2--
H >220 -- I-1-a-6 Cl Cl CH.sub.3 --(CH.sub.2).sub.2--CHOCH-
.sub.3--(CH.sub.2).sub.2-- H 216 .beta. I-1-a-7 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H >220 .beta.
I-1-a-8 Cl CH.sub.3 Cl --(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H
209 .beta. I-1-a-9 Cl CH.sub.3 Cl --(CH.sub.2).sub.5-- H >220 --
I-1-a-10 Cl CH.sub.3 Cl --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2- --
H >220 -- I-1-a-11 Cl CH.sub.3 Cl i-C.sub.3H.sub.7 CH.sub.3 H
>220 -- I-1-a-12 Cl CH.sub.3 Cl --(CH.sub.2).sub.2--CHOCH.sub.3-
--(CH.sub.2).sub.2-- H >220 .beta. I-1-a-13 Cl Cl CH.sub.3 H
--(CH.sub.2).sub.4-- >220 -- I-1-a-14 Cl Cl CH.sub.3 H H
i-C.sub.3H.sub.7 >220 -- I-1-a-15 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H >220
.alpha. I-1-a-16 Br Cl CH.sub.3
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H 148 .beta. I-1-a-17 Br
Cl CH.sub.3 --(CH.sub.2).sub.2--CHOCH.sub.3- --(CH.sub.2).sub.2-- H
>220 .beta. I-1-a-18 Br Cl CH.sub.3 CH.sub.3 CH.sub.3 H >220
-- I-1-a-19 Br Cl CH.sub.3 CH.sub.3 i-C.sub.3H.sub.7 H >200 --
I-1-a-20 Br CH.sub.3 Cl
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H 219 .beta.
I-1-a-21 Br CH.sub.3 Cl CH.sub.3 CH.sub.3 H 206 -- I-1-a-22 Cl Br
CH.sub.3 --(CH.sub.2).sub.2--CH(CH.sub.3)--(CH.sub.2).sub.2-- H
>220 .beta. I-1-a-23 Cl Br CH.sub.3 --(CH.sub.2).sub.2--O--(CH.-
sub.2).sub.2-- H >220 -- I-1-a-24 Cl Br CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H >220
.beta. I-1-a-25 Cl CH.sub.3 Cl CH.sub.3 CH.sub.3 H >220 --
I-1-a-26 Cl CH.sub.3 Cl H --CH.sub.2--CHCH.sub.3--CHCH.sub.3--
201
Example (I-1-b-1)
[0641] 183
[0642] 4.7 g of (0.015 mol) of the compound of Example (I-1-a-1)
and 4.2 ml (30 mmol) of triethylamine in 70 ml of absolute
methylene chloride are treated with 2.14 ml (0.03 mol) of acetyl
chloride in 5 ml of absolute methylene chloride at 0 to 10.degree.
C. The mixture is stirred at room temperature until a thin-layer
chromatography check confirms that the reaction has ended. For
working up, the mixture is washed twice using 50 ml of 0.5 N sodium
hydroxide solution, dried over magnesium sulphate and evaporated.
The crude product is recrystallized from MTB ether/n-hexane.
[0643] Yield: 2.30 g (43% of theory), m.p.: 211.degree. C.
[0644] The following compounds of the formula (I-b-1) are obtained
analogously or in accordance with the general preparation
instructions:
8TABLE 11 (I-1-b) 184 Example No. X Y Z B A D R.sup.1 M.p..degree.
C. Isomer I-1-b-2 Cl Cl CH.sub.3
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H CH.sub.3-- >220
.beta. I-1-b-3 Cl Cl CH.sub.3
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H i-C.sub.3H.sub.7-- 191
.beta. I-1-b-4 Cl Cl CH.sub.3 --(CH.sub.2).sub.3--CHCH.sub.3--CH.s-
ub.2-- H H.sub.5C.sub.2--O--CH.sub.2-- 168 .beta. I-1-b-5 Cl Cl
CH.sub.3 --(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H
C.sub.6H.sub.5-- >220 .beta. I-1-b-6 Cl Cl CH.sub.3
--(CH.sub.2).sub.3--CHCH.sub- .3--CH.sub.2-- H
t-C.sub.4H.sub.9--CH.sub.2-- 218 .beta. I-1-b-7 Cl Cl CH.sub.3
--(CH.sub.2).sub.5-- H CH.sub.3-- >220 -- I-1-b-8 Cl Cl CH.sub.3
--(CH.sub.2).sub.5-- H i-C.sub.3H.sub.7-- 188 -- I-1-b-9 Cl Cl
CH.sub.3 --(CH.sub.2).sub.5-- H t-C.sub.4H.sub.9--CH.sub.2--
>220 -- I-1-b-10 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3--
>220 .beta. I-1-b-11 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH- .sub.2).sub.2-- H
i-C.sub.3H.sub.7-- 189 .beta. I-1-b-12 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
4-Cl--C.sub.6H.sub.4-- >220 .beta. I-1-b-13 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
H.sub.3CO--CH.sub.2-- >220 .beta. CHCH.sub.3-- I-1-b-14 Cl Cl
CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H CH.sub.3-- 216
-- I-1-b-15 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H i-C.sub.3H.sub.7-- 187
-- I-1-b-16 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H s-C.sub.4H.sub.9-- 198
-- I-1-b-17 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H C.sub.2H.sub.5--
>220 -- I-1-b-18 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).s- ub.2-- H
i-C.sub.3H.sub.7-- >220 .beta. I-1-b-19 Cl CH.sub.3 Cl
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H CH.sub.3-- >220
.beta. I-1-b-20 Cl CH.sub.3 Cl
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H i-C.sub.3H.sub.7-- 190
.beta. I-1-b-21 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H CH.sub.3-- >220 --
I-1-b-22 Cl CH.sub.3 Cl --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
i-C.sub.3H.sub.7-- 215 -- I-1-b-23 Cl CH.sub.3 Cl
i-C.sub.3H.sub.7-- CH.sub.3 H CH.sub.3-- 209 -- I-1-b-24 Cl
CH.sub.3 Cl i-C.sub.3H.sub.7-- CH.sub.3 H i-C.sub.3H.sub.7-- 105 --
I-1-b-25 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).su- b.2-- H
i-C.sub.3H.sub.7-- 183 .beta. I-1-b-26 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
H.sub.5C.sub.2--O--CH.sub.2-- >220 .beta. I-1-b-27 Cl CH.sub.3
Cl --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
t-C.sub.4H.sub.9--CH.sub.2-- 219 .beta. I-1-b-28 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
i-C.sub.3H.sub.7-- >220 .beta. I-1-b-29 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.s- ub.3--(CH.sub.2).sub.2-- H
H.sub.5C.sub.2--O--CH.sub.2-- >220 .beta. I-1-b-30 Cl Cl
CH.sub.3 --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).s- ub.2-- H
t-C.sub.4H.sub.9--CH.sub.2-- 197 .beta. I-1-b-31 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
i-C.sub.3H.sub.7-- 193 .alpha..sup.a) I-1-b-32 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
H.sub.5C.sub.2--O--CH.sub.2-- 171 .alpha..sup.a) I-1-b-33 Cl Cl
CH.sub.3 --(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
C.sub.2H.sub.5O--CH.sub.2-- 156 .beta. I-1-b-34 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H 185 219 .beta.
I-1-b-35 Cl Cl CH.sub.3 --(CH.sub.2).sub.2--CHCH.s-
ub.3--(CH.sub.2).sub.2-- H 186 185 .beta. I-1-b-36 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
i-C.sub.4H.sub.9-- 160 .beta. I-1-b-37 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H 187 141 .beta.
I-1-b-38 Cl Cl CH.sub.3 --(CH.sub.2).sub.2--CHCH.sub.3--(CH.s-
ub.2).sub.2-- H cyclohexyl >220 .beta. I-1-b-39 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
C(CH.sub.3).sub.2.dbd.CH-- 219 .beta. I-1-b-40 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
3-(6-Cl-pyridyl) 167 .beta. I-1-b-41 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3-- -(CH.sub.2).sub.2-- H 2-thienyl-
213 .beta. I-1-b-42 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H 2-furanyl-
>220 .beta. I-1-b-43 Cl Cl CH.sub.3 H --(CH.sub.2).sub.4--
t-C.sub.4H.sub.9-- 147 -- I-1-b-44 Br Cl CH.sub.3 CH.sub.3 CH.sub.3
H i-C.sub.4H.sub.9-- 164 -- I-1-b-45 Cl Br CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3--
>220 .beta. I-1-b-46 Cl Br CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH- .sub.2).sub.2-- H
i-C.sub.3H.sub.7-- 210 .beta. I-1-b-47 Cl Br CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
C.sub.2H.sub.5--O--CH.sub.2-- 158 .beta. I-1-b-48 Cl Br CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
4-Cl--C.sub.6H.sub.4-- 213 .beta. I-1-b-49 Cl Br CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H i-C.sub.3H.sub.7-- 216
-- I-1-b-50 Cl Br CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H i-C.sub.4H.sub.9--
>220 -- I-1-b-51 Cl Br CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
C.sub.2H.sub.5--O--CH.sub.2-- 217 -- I-1-b-52 Cl Br CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2)- .sub.2-- H
C(CH.sub.3).sub.2.dbd.CH-- 205 -- I-1-b-53 Cl Br CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
i-C.sub.3H.sub.7-- 192 .beta. I-1-b-54 Cl Br CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
C.sub.2H.sub.5--O--CH.sub.2-- 173 .beta. I-1-b-55 Cl CH.sub.3 Cl
CH.sub.3 CH.sub.3 H i-C.sub.3H.sub.7-- 161 -- I-1-b-56 Cl CH.sub.3
Cl H H i-C.sub.3H.sub.7-- t-C.sub.4H.sub.9-- 104 I-1-b-57 Cl
CH.sub.3 Cl H --CH.sub.2--CHCH.sub.3--CHCH.sub.3-- t-C.sub.4H.sub.9
oil .sup.a)The .alpha. isomers were obtained by chromatographic
separation of a mixture of .alpha. and .beta. isomers on silica gel
using methylene chloride/ethyl acetate 2:1 as the eluent.
Example (I-1-c-1)
[0645] 188
[0646] 1.8 ml (18 mmol) of ethyl chloroformate in 5 ml of absolute
methylene chloride are added dropwise at 0 to 10.degree. C. to 4.7
g (0.015 mol) of the compound of Example (I-1-a-1) and 2.1 ml of
triethylamine in 70 ml of absolute THF, and the mixture is stirred
at room temperature until a thin-layer chromatography check
confirms the reaction has ended. For working-up, the mixture is
washed twice using 50 ml of 0.5 N sodium hydroxide solution, dried
over magnesium sulphate and evaporated.
[0647] Yield: 4.0 g (69% of theory), m.p.: >220.degree. C.
[0648] The following compounds of the formula (I-1-c) are obtained
analogously or in accordance with the general preparation
instructions:
9TABLE 12 (I-1-c) 189 Example No. X Y Z B A D L M R.sup.2
M.p..degree. C. Isomer I-1-c-2 Cl Cl CH.sub.3
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H O O C.sub.2H.sub.5--
196 .beta. I-1-c-3 Cl Cl CH.sub.3 --(CH.sub.2).sub.5-- H O O
C.sub.2H.sub.5-- 182 -- I-1-c-4 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H O O
C.sub.2H.sub.5-- 196 .beta. I-1-c-5 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H O O C.sub.2H.sub.5--
>220 -- I-1-c-6 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.- 2).sub.2-- H O O
C.sub.2H.sub.5-- 201 .beta. I-1-c-7 Cl CH.sub.3 Cl
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H O O C.sub.2H.sub.5--
206 .beta. I-1-c-8 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--O--(CH.sub.2).su- b.2-- H O O C.sub.2H.sub.5--
197 -- I-1-c-9 Cl CH.sub.3 Cl CH.sub.3 i-C.sub.3H.sub.7 H O O
C.sub.2H.sub.5-- 174 -- I-1-c-10 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H O O
C.sub.2H.sub.5-- >220 .beta. I-1-c-11 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H O O
C.sub.2H.sub.5-- 176 .beta. I-1-c-12 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H O O
C.sub.2H.sub.5-- 198 .alpha..sup.a) I-1-c-13 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H O O
i-C.sub.4H.sub.9-- 201 .beta. I-1-c-14 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H O O
C.sub.6H.sub.5-- >220 .beta. I-1-c-15 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.su- b.3--(CH.sub.2).sub.2-- H O O
C.sub.6H.sub.5--CH.sub.2-- >220 .beta. I-1-c-16 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).su- b.2-- H O O
s-C.sub.4H.sub.9-- 206 .beta. I-1-c-17 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H O S
t-C.sub.4H.sub.9--CH.sub.2-- 232 .beta. I-1-c-18 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H O S
s-C.sub.4H.sub.9-- 205 .beta. I-1-c-19 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H O S
i-C.sub.3H.sub.7-- 218-220 .beta. I-1-c-20 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H O S
C.sub.6H.sub.5--CH.sub.2-- 179-181 .beta. I-1-c-21 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H O S
t-C.sub.4H.sub.9-- 245-247 .beta. I-1-c-22 Cl Cl CH.sub.3 H
--(CH.sub.2).sub.4-- O S t-C.sub.4H.sub.9-- oil I-1-c-23 Cl Cl
CH.sub.3 H --(CH.sub.2).sub.4-- O S t-C.sub.4H.sub.9--CH.sub.2--
oil I-1-c-24 Cl Cl CH.sub.3 H --(CH.sub.2).sub.4-- O S
s-C.sub.4H.sub.9-- oil I-1-c-25 Cl Cl CH.sub.3 H H i-C.sub.3H.sub.7
O S t-C.sub.4H.sub.9--CH.sub.2-- oil I-1-c-26 Cl Cl CH.sub.3 H H
i-C.sub.3H.sub.7 O S s-C.sub.4H.sub.9-- 84-86 I-1-c-27 Cl Br
CH.sub.3 --(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H O O
C.sub.2H.sub.5-- >220 .beta. I-1-c-28 Cl Br CH.sub.4
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H O O C.sub.2H.sub.5--
>220 -- I-1-c-29 Cl Br CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2- -- H O O
i-C.sub.4H.sub.9-- >220 -- I-1-c-30 Cl CH.sub.3 Cl CH.sub.3
CH.sub.3 H O O i-C.sub.4H.sub.9-- 132 -- I-1-c-31 Cl CH.sub.3 Cl H
H i-C.sub.3H.sub.7 O S t-C.sub.4H.sub.9-- 141 -- I-1-c-32 Cl
CH.sub.3 Cl H --CH.sub.2--CHCH.sub.3--CHCH.sub.3-- O S
t-C.sub.4H.sub.9-- 160 -- .sup.a)The compound was obtained by
chromatographic separation of a mixture of .alpha. and .beta.
isomers on silica gel using methylene chloride/ethyl acetate 2:1 as
the eluent.
Example (I-1-d-1)
[0649] 190
[0650] 0.93 ml (0.012 mmol) of methanesulphonyl chloride in 5 ml of
absolute methylene chloride is added dropwise at 0.degree. C. to
10.degree. C. to 4.08 g of the compound of Example I-1-a-4 and 1.7
ml (0.012 mol) of triethylamine in 70 ml of absolute methylene
chloride, and the mixture is stirred at room temperature until the
reaction has ended (TLC check). The mixture is washed 2.times.
using 50 ml of 0.5 N NaOH, dried and concentrated, and the residue
is recrystallized from methyl tert-butyl ether (MTB
ether)/n-hexane.
[0651] Yield: 2.80 g (52% of theory), m.p.: 211.degree. C.
Example (I-1-f-1)
[0652] 191
[0653] 0.85 ml (0.01 mol) of anhydrous isopropylamine is added to
2.04 g of the compound of Example I-1-a-4 in 40 ml of MTB ether and
the mixture is stirred for 10 minutes at room temperature. It is
subsequently evaporated to dryness in vacuo.
[0654] Yield: 2.20 g (91% of theory), m.p.: >220.degree. C.
Example (II-1)
[0655] 192
[0656] 30.8 g of the compound of Example (XXI-1) are carefully
added dropwise at 30 to 40.degree. C. to 48.4 g (0.493 mol) of
concentrated sulphuric acid and the mixture is stirred for 2 hours
at this temperature. 67 ml of absolute methanol are then added
dropwise in such a way that an internal temperature of
approximately 40.degree. C. is established, and the mixture is
stirred for a further 6 hours at 40 to 70.degree. C.
[0657] For working-up, the mixture is poured onto 0.48 kg of ice
and extracted using methylene chloride, and the methylene chloride
phase is washed using aqueous sodium hydrogen carbonate solution,
dried and evaporated. The crude product is recrystallized from MTB
ether/n-hexane.
[0658] Yield: 25.1 g (73% of theory), m.p.: 114.degree. C.
Example (II-2)
[0659] 193
[0660] 26.3 g (0.12 mol) of 2,4-dichloro-6-methyl-phenylacetic acid
according to Example (XXV-2) and 17.7 ml (0.24 mol) of thionyl
chloride are stirred at 80.degree. C. until the evolution of gas
has ended. Excess thionyl chloride is removed in vacuo at
50.degree. C. 50 ml of absolute toluene are then added and the
mixture is evaporated once more. The residue is taken up in 100 ml
of absolute THF (solution 1).
[0661] Solution 1 is added dropwise at 0 to 10.degree. C. to 25.03
g of methyl 4-methylcyclohexylamine-1-carboxylate and 37 ml (0.264
mol) of triethylamine in 250 ml of absolute THF, and the mixture is
subsequently stirred for 1 hour at room temperature. It is then
filtered with suction, washed with absolute THF and evaporated. The
residue is taken up in methylene chloride, and the mixture is
washed with 0.5 N HCl, dried and evaporated. The crude product is
recrystallized from MTB ether/n-hexane.
[0662] Yield: 34.6 g (77% of theory), m.p.: 145.degree. C.
[0663] The following compounds of the formula (II) are prepared
analogously to Examples (II-1) and (II-2) or in accordance with the
general preparation instructions.
10TABLE 13 (II) 194 Example No. X Y Z B A D R.sup.8 Isomer
M.p..degree. C. II-3 Cl Cl CH.sub.3
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H CH.sub.3 .beta. 141
II-4 Cl Cl CH.sub.3 --(CH.sub.2).sub.5-- H CH.sub.3 -- 139 II-5 Cl
Cl CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H CH.sub.3 --
129 II-6 Cl Cl CH.sub.3 --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.su-
b.2).sub.2-- H CH.sub.3 .beta. 141 II-7 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3
.beta. 93 II-8 Cl CH.sub.3 Cl
--(CH.sub.2).sub.3--CHCH.sub.3--(CH.sub.2)-- H CH.sub.3 .beta. 112
II-9 Cl CH.sub.3 Cl --(CH.sub.2).sub.5-- H CH.sub.3 -- 121 II-10 Cl
CH.sub.3 Cl --(CH.sub.2).sub.2--O--(CH.su- b.2).sub.2-- H CH.sub.3
-- 146 II-11 Cl CH.sub.3 Cl i-C.sub.3H.sub.7 CH.sub.3 H CH.sub.3 --
128 II-12 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3
.beta. 158 II-13 Cl Cl CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 -- 175
II-14 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3
.alpha. 141 II-15 Br CH.sub.3 Cl CH.sub.3 CH.sub.3 H CH.sub.3 --
137 II-16 Br CH.sub.3 Br --(CH.sub.2).sub.2--CHCH.sub.-
3--(CH.sub.2).sub.2-- H CH.sub.3 .beta. 203 II-17 Br CH.sub.3 Br
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3
.beta. 149 II-18 Br CH.sub.3 Br
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H CH.sub.3 -- 172 II-19
Br Br CH.sub.3 --(CH.sub.2).sub.2--CHCH.sub.- 3--(CH.sub.2).sub.2--
H CH.sub.3 .beta. 159 II-20 Br Br CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3
.beta. 138 II-21 Br Br CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 -- 158
II-22 Br Br CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
CH.sub.3 -- 152 II-23 Br Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.su- b.2).sub.2-- H CH.sub.3
.beta. 163 II-24 Br Cl CH.sub.3
--(CH.sub.2).sub.3--CHCH.sub.3--CH.sub.2-- H CH.sub.3 .beta. 139
II-25 Br Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3
.beta. 133 II-26 Br Cl CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 -- 164
II-27 Br Cl CH.sub.3 --(CH.sub.2).sub.2--O--(CH.su- b.2).sub.2-- H
CH.sub.3 -- 184 II-28 Br Cl CH.sub.3 i-C.sub.3H.sub.7 CH.sub.3 H
CH.sub.3 -- 102 II-29 Br CH.sub.3 Cl
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3
.beta. 141 II-30 Br CH.sub.3 Cl CH.sub.3 CH.sub.3 H CH.sub.3 -- 127
II-31 Br CH.sub.3 Cl --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
CH.sub.3 -- 174 II-32 Cl Br CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.su- b.2).sub.2-- H CH.sub.3 --
169 II-33 Cl Br CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
H CH.sub.3 -- 158 II-34 Cl Br CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3
.beta. 158 II-35 Cl Cl CH.sub.3 H --(CH.sub.2).sub.4--
C.sub.2H.sub.5 -- oil II-36 Cl Cl CH.sub.3 H H i-C.sub.3H.sub.7
C.sub.2H.sub.5 -- oil II-37 Cl CH.sub.3 Cl H
--CH.sub.2--S--(CH.sub.2).sub.2-- C.sub.2H.sub.5 -- oil II-38 Cl
CH.sub.3 Cl H --CH.sub.2--CHCH.sub.3--CHCH.sub.3-- C.sub.2H.sub.5
-- oil
Example (XXXI-1)
[0664] 195
[0665] Solution 1 is prepared as described in Example (II-2)
starting from 26.3 g of 2,4-dichloro-6-methyl-phenylacetic
acid.
[0666] Solution 1 is added dropwise at 0 to 10.degree. C. to 13.46
g of 2-amino-2,3-dimethylbutyronitrile and 18.5 ml (0.132 mol) of
triethylamine in 150 ml of absolute THF, and the mixture is stirred
for a further hour at room temperature. It is then filtered off
with suction, washed with absolute THF and evaporated. The residue
is taken up in methylene chloride, washed using 0.5 N HCl, dried
and evaporated. The crude product is recrystallized from MTB
ether/n-hexane.
[0667] Yield: 30.8 g (81% of theory), m.p.: 112.degree. C.
[0668] The following compounds of the formula (XXXI) were prepared
analogously to Example (XXXI-1) or in accordance with the general
preparation instructions.
11TABLE 14 (XXXI) 196 Example No. X Y Z A B D M.p..degree. C.
XXXI-2 Cl Cl CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
117 XXXI-3 Cl CH.sub.3 Cl --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
H 119 XXXI-4 Cl CH.sub.3 Cl CH.sub.3 i-C.sub.3H.sub.7 H 71 XXXI-5
Br CH.sub.3 Br --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H >220
XXXI-6 Br Br CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
196 XXXI-7 Br Cl CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
H 172 XXXI-8 Br Cl CH.sub.3 CH.sub.3 i-C.sub.3H.sub.7 H 128 XXXI-9
Br CH.sub.3 Cl --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H 139
XXXI-10 Cl Br CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
171
Example (I-2-a-1)
[0669] 197
[0670] 8.42 g (75 mmol) of potassium tert-butylate are introduced
into 50 ml of DMF, a solution of 18.6 g (50 mmol) of
1-ethyloxycarbonyl-cyclohexy- l 2,4-dichloro-6-methyl-phenylacetate
according to Example (III-1) in 50 ml of DMF is added dropwise at 0
to 10.degree. C., and the mixture is stirred overnight at room
temperature.
[0671] For working-up, the reaction mixture is added dropwise to
500 ml of ice-cold 1 N HCl, and the product which has precipitated
is filtered off with suction, washed with water and dried in a
vacuum drying oven. For further purification, the crude product is
then boiled with n-hexane/acetone.
[0672] Yield: 6.71 g (41% of theory) of
3-(2,4-dichloro-6-methyl-phenyl)-5- -spirocyclohexyltetronic acid,
m.p.: >240.degree. C.
[0673] The following compounds of the formula (I-2-a) are obtained
analogously or in accordance with the general preparation
instructions:
12TABLE 15 (I-2-a) 198 Example No. X Y Z A B M.p..degree. C.
I-2-a-2 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- >240 I-2-a-3
Cl Cl CH.sub.3 --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-
-- oil.sup.1) I-2-a-4 Cl Cl CH.sub.3 --(CH.sub.2).sub.4-- >230
I-2-a-5 Cl CH.sub.3 Cl --(CH.sub.2).sub.5-- >260 I-2-a-6 Cl
CH.sub.3 Cl --(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2--
>230 I-2-a-7 Cl CH.sub.3 Cl --(CH.sub.2).sub.4-- >260 I-2-a-8
Br CH.sub.3 Cl --(CH.sub.2).sub.5-- 284-285 I-2-a-9 Br Cl CH.sub.3
--(CH.sub.2).sub.5-- 282 I-2-a-10 Br Cl CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- 218-219 I-2-a-11 Cl Cl
CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- 230 I-2-a-12 Cl
CH.sub.3 Cl --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- 280 I-2-a-13
Br Br CH.sub.3 --(CH.sub.2).sub.5-- 245 I-2-a-14 Br CH.sub.3 Br
--(CH.sub.2).sub.5-- 248 .sup.1) .sup.1H-NMR, d.sub.6-DMSO: .delta.
= 1.4-2.1 (m, 8H); 2.15/2.20 (2s, 3H); 3.2/3.55 (2m, 1H); 3.24/3.27
(2s, 3H); 7.25-7.50 (m, 2H).
Example (I-2-b-1)
[0674] 199
[0675] 3.27 g (10 mmol) of the compound in accordance with Example
I-2-a-1 are introduced into 40 ml of dichloromethane, 1.52 g (15
mmol) of triethylamine are added, a solution of 1.57 g (13 mmol) of
pivaloyl chloride in 40 ml of dichloromethane is added dropwise
with ice-cooling, and stirring is continued for 1 to 2 h at room
temperature. For working-up, the mixture is washed in succession
with 10% strength citric acid, 1N NaOH and NaCl solution, and the
organic phase is dried over MgSO.sub.4 and evaporated. For further
purification, the crude product is then stirred with a little
petroleum ether.
[0676] Yield: 3.6 g (88% of theory) of
4-pivaloyl-oxy-3-(2,4-dichloro-6-me-
thyl-phenyl)-5-spiro-cyclohexyl-tetronic acid, m.p.: 137.degree.
C.
[0677] The following compounds of the formula (I-2-b) are obtained
analogously or in accordance with the general preparation
instructions:
13TABLE 16 (I-2-b) 200 Example No. X Y Z A B R.sup.1 M.p..degree.
C. I-2-b-2 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2--
t-C.sub.4H.sub.9-- 154 I-2-b-3 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
t-C.sub.4H.sub.9-- 147 I-2-b-4 Cl Cl CH.sub.3 --(CH.sub.2).sub.4--
t-C.sub.4H.sub.9-- 112 I-2-b-5 Cl CH.sub.3 Cl --(CH.sub.2).sub.5--
t-C.sub.4H.sub.9-- 123-128 I-2-b-6 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--CHCH.sub.3--(CH- .sub.2).sub.2--
t-C.sub.4H.sub.9-- 125-127 I-2-b-7 Cl CH.sub.3 Cl
--(CH.sub.2).sub.4-- t-C.sub.4H.sub.9-- 116-118 I-2-b-8 Br Cl
CH.sub.3 --(CH.sub.2).sub.5-- t-C.sub.4H.sub.9-- 133 I-2-b-9 Br Cl
CH.sub.3 --(CH.sub.2).sub.5-- t-C.sub.4H.sub.9--CH.sub.2-- 140
I-2-b-10 Cl Cl CH.sub.3 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
t-C.sub.4H.sub.9--CH.sub.2-- 149 I-2-b-11 Cl Cl CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- t-C.sub.4H.sub.9-- 124
I-2-b-12 Cl CH.sub.3 Cl --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
t-C.sub.4H.sub.9--CH.sub.2-- 114 I-2-b-13 Cl CH.sub.3 Cl
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- t-C.sub.4H.sub.9--
133-135 I-2-b-14 Br Br CH.sub.3 --(CH.sub.2).sub.5--
t-C.sub.4H.sub.9-- oil I-2-b-15 Br Br CH.sub.3 --(CH.sub.2).sub.5--
t-C.sub.4H.sub.9--CH.sub.- 2-- 113-115 I-2-b-16 Br CH.sub.3 Br
--(CH.sub.2).sub.5-- t-C.sub.4H.sub.9-- 175 I-2-b-17 Br CH.sub.3 Br
--(CH.sub.2).sub.5-- t-C.sub.4H.sub.9--CH.sub.2-- 160-162
Example (III-1)
[0678] 201
[0679] 10.95 g (50 mmol) of 2,4-dichloro-6-methyl-phenylacetic acid
are introduced into 50 ml of toluene, 11.9 g (100 mmol) of thionyl
chloride are added, and the mixture is stirred at 80.degree. C.
until the evolution of hydrogen has ceased and is then evaporated.
The crude acid chloride is boiled overnight in 50 ml of toluene
together with 8.6 g (50 mmol) of ethyl
1-hydroxy-cyclohexanecarboxylate, and the mixture is subsequently
evaporated.
[0680] Yield: 18.6 g (quantitative) of 1-ethoxycarbonyl-cyclohexyl
2,4-dichloro-6-methyl-phenylacetate as a colourless oil.
[0681] .sup.1H NMR (CDCl.sub.3): .delta.=1.2 (t, 3H); 1.3-2.0 (m,
9H); 2.3 (s, 3H); 3.8 (s, 2H); 4.15 (q, 2H); 7.3 (m, 2H).
[0682] The following compounds of the formula (III) are obtained
analogously or in accordance with the general preparation
instructions:
14TABLE 17 (III) 202 Example No. A B X Y Z R.sup.8 M.p..degree. C.
III-2 --(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- Cl Cl
CH.sub.3 C.sub.2H.sub.5 oil III-3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.- 2).sub.2-- Cl Cl
CH.sub.3 C.sub.2H.sub.5 oil III-4 --(CH.sub.2).sub.4-- Cl Cl
CH.sub.3 C.sub.2H.sub.5 oil III-5 --(CH.sub.2).sub.5-- Cl CH.sub.3
Cl C.sub.2H.sub.5 oil III-6
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- Cl CH.sub.3 Cl
C.sub.2H.sub.5 oil III-7 --(CH.sub.2).sub.4-- Cl CH.sub.3 Cl
C.sub.2H.sub.5 oil III-8 --(CH.sub.2).sub.5-- Br CH.sub.3 Cl
C.sub.2H.sub.5 oil III-9 --(CH.sub.2).sub.5-- Br Cl CH.sub.3
C.sub.2H.sub.5 oil III-10 --(CH.sub.2).sub.5-- Br CH.sub.3 Br
C.sub.2H.sub.5 oil III-11 --(CH.sub.2).sub.5-- Br Br CH.sub.3
C.sub.2H.sub.5 oil III-12 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
- Br Cl CH.sub.3 C.sub.2H.sub.5 oil III-13
--(CH.sub.2).sub.2--O--(- CH.sub.2).sub.2-- Cl Cl CH.sub.3
C.sub.2H.sub.5 oil III-14 --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
Cl CH.sub.3 Cl C.sub.2H.sub.5 oil
Example (I-3-a-1)
[0683] 203
[0684] 10.8 g (23 mmol) of the compound in accordance with Example
(IV-1) are refluxed for 5 hours in 25 ml of trifluoroacetic acid
and 50 ml of toluene. The mixture is concentrated to dryness, the
residue is treated with 120 ml of water and 40 ml of MTB ether, and
NaOH is added until a pH of 14 is reached. The mixture is extracted
twice using MTB ether. The aqueous phase is then acidified and
extracted 3 times using MTB ether. The organic phase is dried and
concentrated, and the residue is stirred with cyclohexane and
filtered with suction.
[0685] Yield: 0.60 g (8% of theory), m.p.: 222.degree. C.
[0686] The following compounds of the formula (I-3-a) were obtained
analogously or in accordance with the general preparation
instructions:
15TABLE 18 (I-3-a) 204 Example No. X Y Z A B M.p..degree. C.
I-3-a-2 Cl CH.sub.3 Cl --(CH.sub.2).sub.5-- >250 I-3-a-3 Cl Cl
CH.sub.3 --(CH.sub.2).sub.5-- >230
Example (I-3-b-1)
[0687] 205
[0688] 1 g (2.9 mmol) of the compound in accordance with Example
(I-3-a-2) are introduced into. 12 ml of absolute methylene
chloride, and 0.6 ml (1.5 eq.) of triethylamine are added. A
solution of 0.47 ml (0.45 g, 3.77 mmol) of pivaloyl chloride in 3
ml of absolute methylene chloride is added dropwise with
ice-cooling. The batch is stirred at room temperature for 1 to 2
hours. Due to the incomplete reaction, 0.3 ml of triethylamine and
0.24 ml of acid chloride are additionally metered in. The mixture
is subsequently washed twice using 10% strength citric acid, and
the combined aqueous phases are extracted using methylene chloride.
The combined organic phases are washed twice using 1 N NaOH and the
aqueous phases are extracted using methylene chloride. The combined
organic phases are dried and concentrated. The residue is stirred
into petroleum ether, filtered off with suction and dried.
[0689] Yield: 0.70 g (56% of theory), m.p.: 100-108.degree. C.
Example (I-3-c-1)
[0690] 206
[0691] 1 g (2.9 mmol) of the compound in accordance with Example
(I-3-a-2) are introduced into 12 ml of absolute methylene chloride,
and 0.6 ml (1.5 eq.) of triethylamine are added. A solution of 0.49
ml (0.51 g, 3.77 mmol) of isobutyl chloroformate in 3 ml of
absolute methylene chloride is added dropwise with ice-cooling. The
batch is stirred for 1 to 2 hours at room temperature. Working-up
as in Example (I-3-b-1).
[0692] Yield: 0.60 g (47% of theory), m.p.: 174-176.degree. C.
Example (IV-1)
[0693] 207
[0694] A: 208
[0695] 100 ml (160 mmol) of n-butyllithium (1.6 N in n-hexane) are
added dropwise at -78.degree. C. to 17.65 g (173.2 mmol) of
diisopropylamine in 130 ml of absolute THF, and the mixture is
stirred for 20 minutes. 15.5 g (133.2 mmol) of methyl
2-methylbutyrate in 30 ml of absolute THF are then added, and the
mixture is stirred for 60 minutes. 40.63 g (133.2 mmol) of
bis-(4-methoxybenzyl) disulphide, dissolved in 120 ml of THF, are
subsequently added dropwise, and the mixture is allowed to come to
room temperature and stirred for 1 hour. 300 ml of MTB ether are
added, and the mixture is washed using 150 ml of water, dried and
concentrated.
[0696] Yield: 35.1 g
[0697] B: 209
[0698] 1.5 g (5.6 mmol) of the above compound prepared in
accordance with A and 2.0 g of KOH are stirred for 48 hours at
40.degree. C. in 20 ml of methanol. After the mixture has been
worked up as usual and the crude product purified by column
chromatography (eluent: cyclohexane/ethyl acetate 1/1), 0.6 g (42%
of theory) of the acid is obtained.
[0699] C:
[0700] 25 g (98 mmol) of the above carboxylic acid prepared in
accordance with B in 107 ml of toluene are treated with one drop of
dimethylformamide (DMF) and 17.5 g (147 mmol) of thionyl chloride,
and the mixture is stirred at 100.degree. C. until evolution of gas
has ceased. The mixture is subsequently evaporated to dryness and
the acid chloride dissolved in 40 ml of absolute THF (acid chloride
solution).
[0701] 71.6 ml (118 mmol) of butyllithium (1.6 M in n-hexane) are
added dropwise at 0.degree. C. to 13.0 g (129 mmol) of
diisopropylamine in 100 ml of THF. After 15 minutes, 25.05 g (108
mmol) of methyl 2,4-dichloro-6-methylphenylacetate in 40 ml of THF
are added dropwise at 0.degree. C. and the mixture is stirred for
30 minutes. The acid chloride solution prepared above is
subsequently added dropwise at 0.degree. C., and the mixture is
stirred for one hour at room temperature. 350 ml of MTB ether are
added, the mixture is washed twice using 10% strength ammonium
chloride solution, and the organic phase is dried and concentrated.
After purification of the crude product by column chromatography
(eluent cyclohexane/ethyl acetate 20/1 to 10/1), 11.3 g (25% of
theory) of the compound of the formula (IV-1) are obtained.
[0702] The compounds of the formula (IV) listed in the table below
are obtained analogously or in accordance with the general
preparation instructions:
16TABLE 19 (IV) 210 Example No. X Y Z A B R.sup.8 M.p. .degree. C.
IV-2 Cl Cl CH.sub.3 --(CH.sub.2).sub.5-- CH.sub.3 oil IV-3 Cl
CH.sub.3 Cl --(CH.sub.2).sub.5-- CH.sub.3 130-135
Example (I-5-a-1)
[0703] 211
[0704] 2.6 g (10 mmol) of 2,4-dichloro-6-methyl-phenyl
chlorocarbonyl ketene is introduced into 20 ml of absolute toluene,
1.3 g (10 mmol) of ethyl 2-pyridyl ketene is added at 20.degree.
C., and the mixture is refluxed for 8 hours. The precipitate is
separated off under cold conditions and chromatographed on 200 g of
silica gel (35 to 70 .mu.m. (eluent: toluene/ethanol 10:1).
[0705] 1.0 g (28%) of solid of m.p. 96-100.degree. C. are
obtained.
[0706] R.sub.f=0.14 (toluene/ethanol=10/1).
[0707] The compounds of the formula (I-5-a) listed in the table
below are obtained analogously or in accordance with the general
preparation instructions:
17TABLE 20 (I-5-a) 212 Example No. X Y Z A D M.p. .degree. C.
I-5-a-2 Cl Cl CH.sub.3 CH.sub.3 4-F--C.sub.6H.sub.4-- 194-197
I-5-a-3 Cl Cl CH.sub.3 CH.sub.3 t-C.sub.4H.sub.9-- 243-245 I-5-a-4
Cl CH.sub.3 Cl CH.sub.3 4-F--C.sub.6H.sub.4-- 235-238 I-5-a-5 Cl
CH.sub.3 Cl --(CH.sub.2).sub.4-- 253-256 I-5-a-6 Cl CH.sub.3 Cl
CH.sub.3 t-C.sub.4H.sub.9-- 245-246 I-5-a-7 Cl CH.sub.3 Cl CH.sub.3
cyclopentyl 260-261 I-5-a-8 Cl Cl CH.sub.3 --(CH.sub.2).sub.4--
295-296
Example (V-1)
[0708] 213
[0709] 85 ml of thionyl chloride are added at room temperature to
26 g (0.1 mol) of the compound in accordance with Example (XXXV-1)
in 115 ml of toluene. The mixture is subsequently refluxed
overnight. It is allowed to cool and evaporated to dryness.
[0710] Yield: 26.2 g (99% of theory).
[0711] .sup.1H NMR (200 MHz, CDCl.sub.3): .delta.=2.35, 2.37 (2s,
3H, Ar--CH.sub.3), 7.05-7.45 (m, 2H Ar--H).
Example (V-2)
[0712] Starting from the compound in accordance with Example
(XXXV-2), 2-(2,6-dichloro-4-methylphenyl) chlorocarbonyl ketene is
obtained analogously as an oil.
Example (XXXV-1)
[0713] 214
[0714] A solution of 6.4 g (0.114 mol) of KOH in 8.6 ml of water is
added dropwise to 10 g (0.034 mol) of the compound in accordance
with Example (VI-1) in 20 ml of methanol at room temperature. The
mixture is subsequently refluxed for 10 hours.
[0715] After the mixture has been worked up as usual, 4.7 g (53% of
theory) of a solid of m.p.: 176-179.degree. C. are obtained.
Example (XXXV-2)
[0716] Starting from the compound in accordance with Example
(VI-2), 2-(2,6-dichloro-4-methylphenyl)malonic acid of m.p.
199-207.degree. C. are obtained analogously.
Example (VI-1)
[0717] 215
[0718] 21.7 g (0.7 mol) of 80% pure sodium hydride are added at
room temperature to 820 ml of dimethyl carbonate. 125 g (0.54 mol)
of methyl 2,4-dichloro-6-methylphenylacetate are subsequently added
dropwise at 80 to 90.degree. C., and the mixture is stirred
overnight at this temperature. A little methanol is added, and the
mixture is poured into ice-water and acidified using 20% strength
HCl. The phases are dried and repeatedly extracted with methylene
chloride, and the combined organic phases are dried and
evaporated.
[0719] Yield: 132.1 g (84% of theory), m.p.: 96-99.degree. C.
Example (VI-2)
[0720] Dimethyl 2-(2,6-dichloro-4-methylphenyl)-malonate is
obtained analogously as an oil.
[0721] .sup.1H NMR (200 MHz, CDCl.sub.3): .delta.=2.31 (s, 3H,
4-CH.sub.3--Ar), 2.77 (s, 6H, OCH.sub.3), 5.43 (s, 1H, CH), 7.18
(s, 1H, Ar--H).
Example (XXII-1)
[0722] 216
[0723] 63 g (0.531 mol) of thionyl chloride are added dropwise at
room temperature to 38.9 g (0.177 mol) of
2,6-dichloro-4-methylphenylacetic acid, and the mixture is
subsequently heated at 70.degree. C. until the evolution of gas has
ceased. Excess thionyl chloride is distilled off in vacuo, and the
residue is distilled under a high vacuum.
[0724] 37.8 g (92% of theory) of the phenylacetyl chloride (XXII-1)
of b.p..sub.0.06-0.03 mbar 109-115.degree. C. are obtained.
[0725] The compounds of the formula (XXII) listed in the table
below were prepared analogously or in accordance with the general
preparation instructions:
18TABLE 21 (XXII) 217 Example No. X Y Z b.p. .degree. C. mbar
XXII-2 Cl Cl CH.sub.3 108-116 0.07 XXII-3 Br CH.sub.3 Cl 124 0.35
XXII-4 Br Br CH.sub.3 136 0.39
[0726] All the other acid chlorides which were employed for the
synthesis of the compounds (II), (III) and (XXXI) were employed in
the form of crude products and not characterized in greater
detail.
Example (XXV-1)
[0727] 218
[0728] 228.6 g (0.98 mol) of the compound of Example (XXVI-1) (94%
pure) are added dropwise at room temperature to a mixture of 88.51
g (1.58 mol) of KOH in 115 ml of water and 230 ml of methanol, and
the mixture is refluxed for 5 hours. After cooling, it is diluted
with 300 ml of water and extracted using ethyl acetate. The aqueous
phase is acidified using semiconcentrated hydrochloric acid, and
the precipitate is filtered off with suction and dried.
[0729] Yield: 183 g (90% f theory), m.p.: 201-203.degree. C.
[0730] The compounds of formula (XXV) listed in the table below
were obtained analogously or in accordance with the general
preparation instructions:
19TABLE 22 (XXV) 219 Example No. X Y Z M.p. .degree. C. XXV-2 Cl Cl
CH.sub.3 191-193 XXV-3 Br Cl CH.sub.3 187-189 XXV-4 Br Br CH.sub.3
196-198 XXV-5 Br CH.sub.3 Br 206-208 XXV-6 Br CH.sub.3 Cl 208-210
XXV-7 Cl Br CH.sub.3 188-190
Example (XXVI-1)
[0731] 220
[0732] 740 ml of a 30% strength solution of sodium methylate in
methanol are added dropwise at room temperature to a solution of
283.5 g (0.97 mol) of the compound in accordance with Example
(XXVII-1) in 410 ml of methanol, the mixture is refluxed for 5
hours and cooled to room temperature, and 110 ml of concentrated
sulphuric acid are added dropwise. The mixture is refluxed for one
hour, the methanol is distilled off, and the solid residue is taken
up in water. The organic phase is separated off, and the aqueous
phase is extracted twice using 1.5 l of methylene chloride. The
combined organic phases are dried over MgSO.sub.4 and
concentrated.
[0733] Yield: 228.6 g of an oil (quantitative yield) of
b.p..sub.0.1 mbar 104-108.degree. C.
[0734] The compounds of the formula (XXVI) listed in the table
below were obtained analogously or in accordance with the general
preparation instructions:
20TABLE 23 (XXVI) 221 Example No. X Y Z M.p. .degree. C. mbar
XXVI-2 Cl Cl CH.sub.3 98-110 0.5 XXVI-3.sup.1) Cl Br CH.sub.3 oil
XXVI-4 Br CH.sub.3 Cl 109-112 0.1 XXVI-5 Br Cl CH.sub.3 113-133
0.35 XXVI-6 Br Br CH.sub.3 126-130 0.35 XXIV-7.sup.1) Br CH.sub.3
Br oil .sup.1)To prepare the acids (XXV), the compounds were
employed as crude oils.
Example (XXVII-1)
[0735] 222
[0736] 886.5 g (9.135 mol) of 1,1-dichloroethene are added dropwise
to a well-cooled mixture of 92.37 g (0.914 mol) of tert-butyl
nitrite and 102.5 g (0.715 mol) of anhydrous copper(II) chloride in
360 ml of anhydrous acetonitrile, the mixture being kept at room
temperature. A mixture of 106.5 g (0.6 mol) of
2,6-dichloro-4-methylaniline and 600 ml of anhydrous acetonitrile
is then added dropwise at a temperature of below 30.degree. C. The
mixture is stirred at room temperature until the evolution of gas
has ceased, the mixture is then poured carefully into 2.4 l of 20%
strength HCl and extracted repeatedly with a total of 2.5 l of
methyl tert-butyl ether (MTBE). The combined organic phases are
washed with 20% strength HCl, dried and concentrated. The oil which
remains is rectified.
[0737] Yield: 72 g (42% of theory), b.p..sub.0.8 mbar
130-135.degree. C.
[0738] The compounds of the formula (XXVII) listed in the table
below were obtained analogously or in accordance with the general
preparation instructions:
21TABLE 24 (XXVII) 223 M.p .degree. C. Example No. X Y Z b.p.
.degree.0 C. mbar XXVII-2 Cl Cl CH.sub.3 50-52 XXVII-3 Cl Br
CH.sub.3 79-81 XXVII-4.sup.1) Br Cl CH.sub.3 oil XXVII-5.sup.1) Br
Br CH.sub.3 oil XXVll-6.sup.1) Br CH.sub.3 Br oil XXVII-7.sup.1) Br
CH.sub.3 Cl oil .sup.1)In the reactions to the esters of the
formula (XXVI), the compounds were employed as crude products.
USE EXAMPLES
Example 1
[0739] Phaedon Larvae Test
[0740] Solvent: 7 parts by weight of dimethylformamide
[0741] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0742] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0743] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of the active compound of the desired
concentration and are infested with mustard beetle larvae (Phaedon
cochleariae) while the leaves are still moist.
[0744] After the specified period of time, the destruction in % is
determined. 100% means that all the beetle larvae have been killed;
0% means that none of the beetle larvae have been killed.
[0745] In this test, a destruction of 100% was caused, after 7
days, for example by the compounds of Preparation Examples
(I-3-a-1), (I-3-a-2), (I-3-a-3), (I-5-a-3), (I-5-a-4), (I-2-b-5),
(I-2-a-6), (I-1-a-2), (I-1-b-7), (I-1-a-8), (I-1-a-9), (I-1-a-10)
and (I-1-a-11) at an exemplary active compound concentration of
0.1% and a destruction of at least 80% by the compounds of
Preparation Examples (I-3-b-1) and (I-3-c-1).
Example 2
[0746] Plutella Test
[0747] Solvent: 7 parts by weight of dimethylformamide
[0748] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0749] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0750] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are infested with caterpillars of the
diamond-back moth (Plutella maculipennis) while the leaves are
still most.
[0751] After the specified period of time, the destruction in % is
determined. 100% means that all the caterpillars have been killed;
0% means that none of the caterpillars have been killed.
[0752] In this test, a destruction of 100% was caused, after 7
days, for example by the compounds of Preparation Examples
(I-3-a-3), (I-3-b-1), (I-3-a-1), (I-5-a-3), (I-5-a-4), (I-1-a-3),
(I-1-a-4), (I-1-b-2), (I-1-c-2), (I-1-a-1) and (I-1-a-7) at an
exemplary active compound concentration of 0.1%.
Example 3
[0753] Nephotettix Test
[0754] Solvent: 7 parts by weight of dimethylformamide
[0755] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0756] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0757] Rice seedlings (Oryza sativa) are treated by being dipped
into the preparation of active compound of the desired
concentration and are infested with the green rice leafhopper
(Nephotettix cincticeps) while the seedlings are still moist.
[0758] After the specified period of time, the destruction in % is
determined. 100% means that all the leafhoppers have been killed;
0% means that none of the leafhoppers have been killed.
[0759] In this test, a destruction of 100% was caused, after 6
days, for example by the compounds of Preparation Examples
(I-3-a-2), (I-5-a-3), (I-5-a-4), (I-5-a-8), (I-3-b-1), (I-5-a-4),
(I-1-a-2), (I-1-a-3), (I-1-a-4), (I-1-c-3), (I-1-a-1), (I-1-b-10),
(I-1-c-4), (I-1-b-13), (I-1-a-7), (I-1-a-8), (I-1-a-9) and
(I-1-a-11) at an exemplary active compound concentration of
0.1%.
Example 4
[0760] Spodoptera Test
[0761] Solvent: 7 parts by weight of dimethylformamide
[0762] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0763] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0764] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are infested with caterpillars of the fall
armyworm (Spodoptera frugiperda) while the leaves are still
moist.
[0765] After the specified period of time, the destruction in % is
determined. 100% means that all the caterpillars have been killed;
0% means that none of the caterpillars have been killed.
[0766] In this test, a destruction of 100% was caused, after 7
days, for example by the compound of Preparation Example (I-1-b-5)
at an exemplary active compound concentration of 0.1%.
Example 5
[0767] Myzus Test
[0768] Solvent: 7 parts by weight of dimethylformamide
[0769] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0770] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[0771] Cabbage leaves (Brassica oleracea) which are severely
infested with the green peach aphid (Myzus persicae) are treated by
being dipped into the preparation of active compound of the desired
concentration.
[0772] After the specified period of time, the destruction in % is
determined. 100% means that all the aphids have been killed; 0%
means that none of the aphids have been killed.
[0773] In this test, a destruction of 100% was caused, after 6
days, for example by the compounds of Preparation Examples
(I-2-a-5), (I-2-b-5), (I-2-a-6), (I-1-b-7) and (I-1-a-1) at an
exemplary active compound concentration of 0.1%.
Example 6
[0774] Panonychus Test
[0775] Solvent: 3 parts by weight of dimethylformamide
[0776] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0777] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentrations.
[0778] Plum trees (Prunus domestica) approx. 30 cm high which are
severely infested with all stages of the fruit tree spider mite
(Panonychus ulmi) are sprayed with a preparation of active compound
of the desired concentration.
[0779] After the specified period of time, the activity in % is
determined. 100% means that all the spider mites have been killed;
0% means that none of the spider mites have been killed.
[0780] In this test, a destruction of at least 95% was caused,
after 7 days, for example by the compounds of Preparation Examples
(I-2-a-1), (I-2-b-1), (I-2-a-2), (I-2-b-2), (I-2-b-4) and (I-2-b-5)
at an exemplary active compound concentration of 0.004%.
Example 7
[0781] Tetranychus Test (OP-Resistant/Spray Treatment)
[0782] Solvent: 3 parts by weight of dimethylformamide
[0783] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0784] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentrations.
[0785] Bean plants (Phaseolus vulgaris) which are severely infested
with all development stages of the greenhouse red spider mite or
two-spotted spider-mite (Tetranychus urticae) are sprayed with a
preparation of active compound of the desired concentration.
[0786] After the specified period of time, the destruction in % is
determined. 100% means that all the spider mites have been killed;
0% means that none of the spider mites have been killed.
[0787] In this test, an activity of 100% was caused, after 7 days,
for example by the compounds of Preparation Examples (I-2-b-1),
(I-2-b-4) and (I-2-b-5) at an exemplary active compound
concentration of 0.004%.
Example 8
[0788] Tetranychus Test (OP-Resistant/Immersion Treatment)
[0789] Solvent: 3 parts by weight of dimethylformamide
[0790] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0791] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentrations.
[0792] Bean plants (Phaseolus vulgaris) which are severely infested
with all development stages of the greenhouse red spider mite or
two-spotted spider-mite (Tetranychus urticae) are immersed in a
preparation of active compound of the desired concentration.
[0793] After the specified period of time, the destruction in % is
determined. 100% means that all the spider mites have been killed;
0% means that none of the spider mites have been killed.
[0794] In this test, an activity of 100% was caused, after 13 days,
for example by the compounds of Preparation Examples (I-2-b-2),
(I-2-b-6), (I-1-b-7), (I-1-b-10), (I-1-c-4), (I-1-a-7), (I-1-a-11),
(I-3-a-2), (I-3-b-1), (I-3-c-1), (I-5-a-4), (I-5-a-3) and (I-5-a-8)
at an exemplary active compound concentration of 0.1%.
Example 9
[0795] Pre-Emergence Test
[0796] Solvent: 5 parts by weight of acetone
[0797] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0798] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent, the stated amount of emulsifier is added and the
concentrate is diluted with water to the desired concentration.
[0799] Seeds of the test plants are sown in normal soil and, after
24 hours, watered with the preparation of the active compound. It
is expedient to keep constant the amount of water per unit area.
The concentration of the active compound in the preparation is of
no importance, only the amount of active compound applied per unit
area being decisive. After three weeks, the degree of damage to the
plants is rated in % damage in comparison to the development of the
untreated control. The figures denote:
[0800] 0%=no action (like untreated control)
[0801] 100%=total destruction
Example 9a
[0802] Post-Emergence Test
[0803] Solvent: 5 parts by weight of acetone
[0804] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0805] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent, the stated amount of emulsifier is added and the
concentrate is diluted with water to the desired concentration.
[0806] Test plants which have a height of 5-15 cm are sprayed with
the preparation of the active compound in such a way as to apply
the particular amounts of active compound desired per unit area.
The concentration of the spray liquor is so chosen that the
particular amounts of active compound desired are applied in 2,000
l of water/ha. After three weeks, the degree of damage to the
plants is rated in % damage in comparison to the development of the
untreated control.
[0807] The figures denote:
[0808] 0%=no action (like untreated control)
[0809] 100%=total destruction
22 Beta Alopecurus Avena Setaria Sinapis Example No. g/ha vulgaris
myosuroides fatua viridis arvensis I-1-a-2 250 0 100 90 100 --
I-1-a-3 250 0 100 -- 100 80 I-1-a-4 250 0 100 100 100 95 I-1-b-2
250 0 100 80 100 70 I-1-b-4 250 0 95 80 100 80 I-1-b-7 250 30 95 80
100 100 I-1-b-8 250 0 95 50 100 100 I-1-c-3 250 30 80 80 100 100
I-1-b-10 250 20 100 100 100 100 I-1-b-11 250 30 95 40 100 90
I-1-b-12 250 20 100 80 100 95 I-1-c-4 250 50 100 100 100 100
I-1-b-13 250 30 100 80 100 90 I-1-a-7 250 -- 100 90 100 100 I-l-a-8
250 -- 100 40 100 100 I-1-c-6 250 -- 100 100 100 95 I-1-b-20 250 30
95 -- 90 80 I-1-c-7 250 0 100 80 100 80 Beta Alopecurus Amaran-
Sinapis Example No. g/ha vulgaris myosuroides thus arvensis I-3-a-2
250 0 -- 60 -- I-3-c-1 250 0 -- 70 -- I-5-a-7 250 0 80 -- 95
I-5-a-1 250 0 80 -- -- I-5-a-1* 250 0 80 -- -- *Post-emergence
Test
Example 10
[0810] Test with Resistant Boophilus microplus/SP Resistant
Parkhurst Strain
[0811] Test animals: Female adults which have sucked themselves
full
[0812] Solvent: Dimethyl sulphoxide
[0813] 20 mg of active compound are dissolved in 1 ml of dimethyl
sulphoxide, and lesser concentrations are prepared by dilution with
the same solvent.
[0814] The test is carried out in 5 applications. 1 .mu.l of the
solutions is injected into the abdomen, and the animals are
transferred into dishes and kept in a controlled-environment
cabinet. The activity is determined via the inhibition of
oviposition. 100% means that no tick has produced eggs.
[0815] In this test, an activity of 100% was shown, for example, by
the compounds of Preparation Examples (I-2-b-5), (I-2-a-6),
(I-1-b-3) and (I-1-a-5) at an exemplary active compound
concentration of 20 .mu.g/animal.
Example 11
[0816] Test with Fly Larvae/Development-Inhibitory Action
[0817] Test animals: All larval stages of Lucilia cuprina
(OP-resistant) [Pupae and adults (without contact with active
compound)]
[0818] Solvent: 35 parts by weight of ethylene glycol monomethyl
ether
[0819] Emulsifier: 35 parts by weight of nonylphenol polyglycol
ether
[0820] To produce a suitable formulation, 3 parts by weight of
active compound are mixed with 7 parts of the abovementioned
solvent/emulsifier mixture, and the resulting emulsion concentrate
is diluted with water to the concentration desired in each
case.
[0821] For each concentration, 30 to 50 larvae are transferred to
horsemeat (1 cm.sup.3) located in glass tubes and 500 .mu.l of the
test dilution are pipetted onto the meat. The glass tubes are
placed into plastic beakers whose bottom is covered with sea sand
and kept in a control-environment cabinet (26.degree.
C..+-.1.5.degree. C., 70% relative humidity .+-.10%). The activity
is checked after 24 hours and 48 hours (larvicidal action). After
the larvae have left the glass tubes (approximately 72 hours), the
tubes are removed, and perforated plastic lids are placed on the
beakers. After 11/2 times the development period (hatching of the
control flies), the hatched flies and the pupae/puparia are
counted.
[0822] The criterion for the action is death in the treated larvae
after 48 hours (larvicidal effect) or inhibition of adults hatching
from the pupae or inhibition of pupation. The criterion for the
in-vitro action of a substance is the inhibition of fly development
or a standstill of development prior to the adult stage. 100%
larvicidal activity means that all larvae have died after 48 hours.
100% development-inhibitory activity means that no adult flies have
hatched.
[0823] In this test, an activity of 100% was shown, for example, by
the compounds of Preparation Examples (I-2-b-5), (I-2-a-6),
(I-1-b-3) and (I-1-a-5) at an exemplary active compound
concentration of 1000 ppm.
* * * * *