U.S. patent application number 12/788741 was filed with the patent office on 2010-10-21 for n-heterocyclylphenyl-substituted cyclic ketoenols.
Invention is credited to Thomas Auler, Guido Bojack, Thomas Bretschneider, Mark Wilhelm Drewes, Dieter Feucht, Reiner Fischer, Martin Hills, Heinz Kehne, Jorg Konze, Karl-Heinz Kuck, Klaus Kunz, Stefan Lehr, Olga Malsam, Wahed Ahmed Moradi, Astrid Ullmann, Ulrike Wachendorff-Neumann.
Application Number | 20100267964 12/788741 |
Document ID | / |
Family ID | 33482807 |
Filed Date | 2010-10-21 |
United States Patent
Application |
20100267964 |
Kind Code |
A1 |
Fischer; Reiner ; et
al. |
October 21, 2010 |
N-HETEROCYCLYLPHENYL-SUBSTITUTED CYCLIC KETOENOLS
Abstract
The invention relates to novel intermediates for the preparation
of N-heterocyclylphenyl-substituted cyclic ketoenols of the formula
(I) ##STR00001## in which CKE, W, X, Y and Z are as defined in the
disclosure.
Inventors: |
Fischer; Reiner; (Monheim,
DE) ; Ullmann; Astrid; (Koln, DE) ;
Bretschneider; Thomas; (Lohmar, DE) ; Lehr;
Stefan; (Liederbach, DE) ; Kunz; Klaus;
(Dusseldorf, DE) ; Konze; Jorg; (Koln, DE)
; Malsam; Olga; (Rosrath, DE) ; Drewes; Mark
Wilhelm; (Langelfeld, DE) ; Feucht; Dieter;
(Eschborn, DE) ; Kuck; Karl-Heinz; (Langenfeld,
DE) ; Wachendorff-Neumann; Ulrike; (Neuwied, DE)
; Moradi; Wahed Ahmed; (Koln, DE) ; Bojack;
Guido; (Wiesbaden, DE) ; Auler; Thomas;
(Leichlingen, DE) ; Hills; Martin; (Idstein,
DE) ; Kehne; Heinz; (Hofheim, DE) |
Correspondence
Address: |
BAYER CROPSCIENCE LP
Patent Department, 2 T .W. ALEXANDER DRIVE
RESEARCH TRIANGLE PARK
NC
27709
US
|
Family ID: |
33482807 |
Appl. No.: |
12/788741 |
Filed: |
May 27, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10559703 |
Dec 7, 2005 |
7776791 |
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PCT/EP2004/006127 |
Jun 7, 2004 |
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12788741 |
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Current U.S.
Class: |
548/377.1 |
Current CPC
Class: |
C07D 491/04 20130101;
C07D 231/18 20130101; C07D 231/36 20130101; C07D 405/10 20130101;
A01N 43/90 20130101; C07D 403/10 20130101; C07D 495/10 20130101;
C07D 491/10 20130101; C07D 487/04 20130101; C07D 493/10 20130101;
A01N 43/56 20130101; A01N 43/653 20130101; C07D 513/04 20130101;
C07D 231/16 20130101 |
Class at
Publication: |
548/377.1 |
International
Class: |
C07D 231/12 20060101
C07D231/12 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 12, 2003 |
DE |
103 26 386.1 |
Claims
1-35. (canceled)
36. A compound of formula (XXVIII) ##STR00385## in which X
represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy,
alkylthio, alkyl-sulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro, cyano; or represents optionally substituted
phenyl, phenoxy, phenylthio, phenylalkoxy, or phenylalkylthio, W
and Y independently of one another represent hydrogen, halogen,
alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro, or cyano, and Z represents an optionally
saturated or unsaturated, optionally substituted heterocycle that
is attached to the phenyl ring via a nitrogen atom and that is
optionally interrupted by one or two carbonyl groups.
37. A compound of formula (XXXII) ##STR00386## in which X
represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy,
alkylthio, alkyl-sulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro, cyano; or represents optionally substituted
phenyl, phenoxy, phenylthio, phenylalkoxy, or phenylalkylthio, W
and Y independently of one another represent hydrogen, halogen,
alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro, or cyano, Z represents an optionally
saturated or unsaturated, optionally substituted heterocycle that
is attached to the phenyl ring via a nitrogen atom and that is
optionally interrupted by one or two carbonyl groups, and R.sup.8
represents alkyl.
Description
[0001] The present invention relates to novel
N-heterocyclylphenyl-substituted cyclic ketoenols, to a plurality
of processes for their preparation and to their use as pesticides
and/or herbicides and/or microbicides.
[0002] Moreover, the invention relates to novel selective
herbicidal active compound combinations comprising firstly the
N-heterocyclylphenyl-substituted cyclic ketoenols and secondly at
least one compound which improves crop plant tolerance, which
combinations can be used with particularly good results for the
selective control of weeds and crops of various useful plants.
[0003] Pharmaceutical properties of 3-acylpyrrolidine-2,4-diones
have already been described (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.
[0004] EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a
similar structure (3-arylpyrrolidine-2,4-diones), of which,
however, no herbicidal, insecticidal or acaricidal action has been
disclosed. Unsubstituted, bicyclic 3-arylpyrrolidine-2,4-dione
derivatives (EP-A-355 599, EP-A-415 211 and JP-A-12-053670) and
substituted monocyclic 3-arylpyrrolidine-2,4-dione derivatives
(EP-A-377 893 and EP-A-442 077) having herbicidal, insecticidal or
acaricidal action have been disclosed.
[0005] There have also been disclosed polycyclic
3-arylpyrrolidine-2,4-dione derivatives (EP-A-442 073) and
1H-arylpyrrolidinedione derivatives (EP-A-456 063, EP-A-521 334,
EP-A-596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO 95/26
954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO
97/01 535, WO 97/02 243, WO 97/36 868, WO 97/43275, WO 98/05638, WO
98/06721, WO 98/25928, WO 99/16748, WO 99/24437, WO 99/43649, WO
99/48869, WO 99/55673, WO 01/17972, WO 01/23354, WO 01/74770, WO
03/062244, DE-A-10 231 333 and DE-A-10 239 479).
[0006] It is known that certain substituted
.DELTA..sup.3-dihydrofuran-2-one derivatives have herbicidal
properties (cf. DE-A-4 014 420). The synthesis of the tetronic acid
derivatives used as starting materials (such as, for example,
3-(2-methylphenyl)-4-hydroxy-5-(4-fluorophenyl)-.DELTA..sup.3-dihydrofura-
n-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
insecticidal and/or acaricidal activity is mentioned.
3-Aryl-.DELTA..sup.3-dihydrofuranone derivatives having herbicidal,
acaricidal and insecticidal properties are also known from EP-A-528
156, EP-A-0 647 637, WO 95/26 345, WO 96/20 196, WO 96/25 395, WO
96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 98/05638,
WO 98/25928, WO 99/16748, WO 99/43649, WO 99/48869, WO 99/55673, WO
01/17972, WO 01/23354, WO 01/74770, WO 03/062244 and DE-A-10 239
479. 3-Aryl-.DELTA..sup.3-dihydrothiophenone derivatives are
likewise known (WO 95/26 345, 96/25 395, WO 97/01 535, WO 97/02
243, WO 97/36 868, WO 98/05638, WO 98/25928, WO 99/16748, WO
99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/23354, WO
01/74770 and WO 03/062244).
[0007] Certain phenylpyrone derivatives which are unsubstituted in
the phenyl ring are already known (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), but a possible use of these
compounds as pesticides has not been mentioned. Phenylpyrone
derivatives which are substituted in the phenyl ring and have
herbicidal, acaricidal and insecticidal properties are described in
EP-A-588 137, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02
243, WO 97/16 436, WO 97/19 941, WO 97/36 868, WO 98/05638, WO
99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770 and WO
03/062244.
[0008] Certain 5-phenyl-1,3-thiazine derivatives which are
unsubstituted in the phenyl ring are already known (cf. E. Ziegler
and E. Steiner, Monatsh. 95, 147 (1964), R. Ketcham, T. Kappe and
E. Ziegler, J. Heterocycl. Chem. 10, 223 (1973)), but a possible
use of these compounds as pesticides has not been mentioned.
5-Phenyl-1,3-thiazine derivatives which are substituted in the
phenyl ring and have herbicidal, acaricidal and insecticidal action
are described in WO 94/14 785, WO 96/02 539, WO 96/35 664, WO 97/01
535, WO 97/02 243, WO 97/02 243, WO 97/36 868, WO 99/05638, WO
99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770 and WO
03/062244.
[0009] It is known that certain substituted
2-arylcyclopentanediones have herbicidal and acaricidal properties
(cf., for example, U.S. Pat. No. 4,283,348; 4,338,122; 4,436,666;
4,526,723; 4,551,547; 4,632,698; WO 96/01 798; WO 96/03 366, WO
97/14 667 and also WO 98/39281, WO 99/43649, WO 99/48869, WO
99/55673, WO 01/17972, WO 01/74770 and WO 03/062244). Moreover,
compounds having similar substitutions are known;
3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-en-1-one from the
publication Micklefield et al., Tetrahedron, (1992), 7519-26, and
the natural product involutin
(-)-cis-5-(3,4-dihydroxyphenyl)-3,4-dihydroxy-2-(4-hydroxypheny-
l)cyclopent-2-enone from the publication Edwards et al., J. Chem.
Soc. S, (1967), 405-9. An insecticidal or acaricidal action is not
described. Moreover, 2-(2,4,6-trimethylphenyl)-1,3-indanedione is
known from the publication J. Economic Entomology, 66, (1973), 584
and the Offenlegungsschrift (German Published Specification) DE-A 2
361 084, with herbicidal and acaricidal actions being
mentioned.
[0010] It is known that certain substituted 2-arylcyclohexanediones
have herbicidal and acaricidal properties (U.S. Pat. No. 4,175,135,
4,209,432, 4,256,657, 4 256 658, 4 256 659, 4 257 858, 4 283 348, 4
303 669, 4 351 666, 4 409 153, 4 436 666, 4 526 723, 4 613 617, 4
659 372, DE-A 2 813 341, and also Wheeler, T. N., J. Org. Chem. 44,
4906 (1979)), WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972,
WO 01/74770 and WO 03/062244).
[0011] It is known that certain substituted
4-arylpyrazolidine-3,5-diones have acaricidal, insecticidal and
herbicidal properties (cf., for example, WO 92/16 510, EP-A-508
126, WO 96/11 574, WO 96/21 652, WO 99/43649, WO 99/47525, WO
99/48869, WO 99/55673, WO 01/17 351, WO 01/17 352, WO 01/17 353, WO
01/17 972, WO 01/17 973, WO 03/028446 and WO 03/062244).
[0012] However, the activity and/or activity spectrum of these
compounds is, in particular at low application rates and
concentrations, not always entirely satisfactory. Furthermore,
these compounds are not always sufficiently well tolerated by
plants.
[0013] We have now found novel compounds of the formula (I)
##STR00002##
in which [0014] X represents halogen, alkyl, alkenyl, alkynyl,
alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl,
haloalkyl, haloalkoxy, haloalkenyloxy, nitro, cyano or in each case
optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or
phenylalkylthio, [0015] W and Y independently of one another
represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxy,
alkenyloxy, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano,
[0016] Z represents an in each case optionally saturated or
unsaturated, optionally substituted heterocycle which is attached
to the phenyl ring via a nitrogen atom and which may be interrupted
by one or two carbonyl groups, [0017] CKE represents one of the
groups
[0017] ##STR00003## [0018] in which [0019] A represents hydrogen,
represents in each case optionally halogen-substituted alkyl,
alkenyl, alkoxyalkyl, alkylthioalkyl, saturated or unsaturated,
optionally substituted cycloalkyl in which optionally at least one
ring atom is replaced by a heteroatom, or in each case optionally
halogen-, alkyl-, haloalkyl-, alkoxy-, halo-alkoxy-, cyano- or
nitro-substituted aryl, arylalkyl or hetaryl, [0020] B represents
hydrogen, alkyl or alkoxyalkyl, or [0021] A and B together with the
carbon atom to which they are attached represent a saturated or
unsaturated, unsubstituted or substituted cycle which optionally
contains at least one heteroatom, [0022] D represents hydrogen or
represents an optionally substituted radical from the group
consisting of alkyl, alkenyl, alkynyl, alkoxyalkyl, saturated or
unsaturated cycloalkyl, in which optionally one or more ring
members are replaced by heteroatoms, arylalkyl, aryl, hetarylalkyl
or hetaryl or [0023] A and D together with the atoms to which they
are attached represent a saturated or unsaturated cycle which
optionally contains at least one (in the case of CKE=8 further)
heteroatom and which is unsubstituted or substituted in the A,D
moiety, or [0024] A and Q.sup.1 together represent optionally
halogen- or hydroxy-substituted alkenediyl or alkanediyl or
alkenediyl substituted by in each case optionally substituted
alkyl, alkoxy, alkylthio, cycloalkyl, benzyloxy or aryl or [0025]
Q.sup.1 represents hydrogen or alkyl, [0026] Q.sup.2, Q.sup.4,
Q.sup.5 and Q.sup.6 independently of one another represent hydrogen
or alkyl, [0027] Q.sup.3 represents hydrogen, in each case
optionally substituted alkyl, alkoxyalkyl, alkylthioalkyl,
optionally substituted cycloalkyl (in which optionally one
methylene group is replaced by oxygen or sulphur) or optionally
substituted phenyl, or [0028] Q.sup.3 and Q.sup.4 together with the
carbon atom to which they are attached represent a saturated or
unsaturated, unsubstituted or substituted cycle which optionally
contains a heteroatom, [0029] G represents hydrogen (a) or
represents one of the groups
[0029] ##STR00004## [0030] in which [0031] E represents a metal ion
equivalent or an ammonium ion, [0032] L represents oxygen or
sulphur, [0033] M represents oxygen or sulphur, [0034] R.sup.1
represents in each case optionally halogen-substituted alkyl,
alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally
halogen-, alkyl- or alkoxy-substituted cycloalkyl which may be
interrupted by at least one heteroatom, in each case optionally
substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or
hetaryloxyalkyl, [0035] R.sup.2 represents in each case optionally
halogen-substituted alkyl, alkenyl, alk-oxyalkyl, polyalkoxyalkyl
or represents in each case optionally substituted cycloalkyl,
phenyl or benzyl, [0036] R.sup.3, R.sup.4 and R.sup.5 independently
of one another represent in each case optionally
halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino,
alkylthio, alkenylthio, cycloalkylthio and represent in each case
optionally substituted phenyl, benzyl, phenoxy or phenylthio,
[0037] R.sup.6 and R.sup.7 independently of one another represent
hydrogen, in each case optionally halogen-substituted alkyl,
cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent optionally
substituted phenyl, represent optionally substituted benzyl, or
together with the N atom to which they are attached represent a
cycle which is optionally interrupted by oxygen or sulphur.
[0038] Depending inter alia on the nature of the substituents, the
compounds of the formula (I) can be present as geometrical and/or
optical isomers or isomer mixtures of varying composition which, if
appropriate, can be separated in a customary manner. The present
invention provides both the pure isomers and the isomer mixtures,
their preparation and use and compositions comprising them.
However, for the sake of simplicity, hereinbelow only compounds of
the formula (I) are referred to, although what is meant is both the
pure compounds and, if appropriate, mixtures having various
proportions of isomeric compounds.
[0039] Taking into consideration the meanings (1) to (8) of the
group CKE, the following principle structures (I-1) to (I -8)
result:
##STR00005##
in which A, B, D, G, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5,
Q.sup.6, W, X, Y and Z are as defined above.
[0040] Taking into consideration the different meanings (a), (b),
(c), (d), (e), (f) and (g) of the group G, the following principle
structures (I-1-a) to (I-1-g) result if CKE represents the group
(1)
##STR00006## ##STR00007##
in which A, B, D, E, L, M, W, 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 are as defined above.
[0041] Taking into consideration the different meanings (a), (b),
(c), (d), (e), (f) and (g) of the group G, the following principle
structures (I-2-a) to (I-2-g) result if CKE represents the group
(2)
##STR00008## ##STR00009##
in which A, B, E, L, M, W, 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 are as defined above.
[0042] Taking into consideration the different meanings (a), (b),
(c), (d), (e), (f) and (g) of the group G, the following principle
structures (I-3-a) to (I-3-g) result if CKE represents the group
(3)
##STR00010## ##STR00011##
in which A, B, E, L, M, W, 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 are as defined above.
[0043] Depending on the position of the substituent G, the
compounds of the formula (I-4) can be present in the two isomeric
forms of the formulae (I-4-A) and (I-4-B)
##STR00012##
which is meant to be indicated by the broken line in formula
(I-4).
[0044] The compounds of the formulae (I-4-A) and (I-4-B) can be
present both as mixtures and in the form of their pure isomers.
Mixtures of the compounds of the formulae (I-4-A) and (I-4-B) can,
if appropriate, be separated in a manner known per se by physical
methods, for example by chromatographic methods.
[0045] For reasons of clarity, hereinbelow only one of the possible
isomers is shown in each case. This does not exclude that the
compounds may, if appropriate, be present in the form of the isomer
mixtures or in the respective other isomeric form.
[0046] Taking into consideration the different meanings (a), (b),
(c), (d), (e), (f) and (g) of the group G, the following principle
structures (I-4-a) to (I-4-g) result if CKE represents the group
(4)
##STR00013## ##STR00014##
in which A, D, E, L, M, W, 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 are as defined above.
[0047] Taking into consideration the different meanings (a), (b),
(c), (d), (e), (f) and (g) of the group G, the following principle
structures (I-5-a) to (I-5-g) result if CKE represents the group
(5)
##STR00015## ##STR00016##
in which A, E, L, M, W, 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 are as defined above.
[0048] Depending on the position of the substituent G, the
compounds of the formula (I-6) can be present in the two isomeric
forms of the formulae (I-6-A) and (I-6-B)
##STR00017##
which is meant to be indicated by the broken line in formula
(I-6).
[0049] The compounds of the formulae (I-6-A) and (I-6-B) can be
present both as mixtures and in the form of their pure isomers.
Mixtures of the compounds of the formulae (I-6-A) and (I-6-B) can,
if appropriate, be separated by physical methods, for example by
chromatographic methods.
[0050] For reasons of clarity, hereinbelow only one of the possible
isomers is shown in each case. This does not exclude that the
compounds may, if appropriate, be present in the form of the isomer
mixtures or in the respective other isomeric form.
[0051] Taking into consideration the different meanings (a), (b),
(c), (d), (e), (f) and (g) of the group G, the following principle
structures (I-6-a) to (I-6-g) result:
##STR00018## ##STR00019##
in which A, B, Q.sup.1, Q.sup.2, E, L, M, W, 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 are as
defined above.
[0052] Depending on the position of the substituent G, the
compounds of the formula (I-7) can be present in the two isomeric
forms of the formulae (I-7-A) and (I-7-B), which is meant to be
indicated by the broken line in formula (I-7).
##STR00020##
[0053] The compounds of the formulae (I-7-A) and (I-7-B) can be
present both as mixtures and in the form of their pure isomers.
Mixtures of the compounds of the formulae (I-7-A) and (I-7-B) can,
if appropriate, be separated by physical methods, for example by
chromatographic methods.
[0054] For reasons of clarity, hereinbelow only one of the possible
isomers is shown in each case. This includes that the relevant
compound may, if appropriate, be present in the form of the isomer
mixture or in the respective other isomeric form.
[0055] Taking into consideration the different meanings (a), (b),
(c), (d), (e), (f) and (g) of the group G, the following principle
structures (I-7-a) to (I-7-g) result:
##STR00021## ##STR00022##
in which A, B, E, L, M, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, 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 are as defined above.
[0056] Depending on the position of the substituent G, the
compounds of the formula (I-8) can be present in the two isomeric
formulae (I-8-A) and (I-8-B)
##STR00023##
which is meant to be indicated by the broken line in formula
(I-8).
[0057] The compounds of the formulae (I-8-A) and (I-8-B) can be
present both as mixtures and in the form of their pure isomers.
Mixtures of the compounds of the formulae (I-8-A) and (I-8-B) can,
if appropriate, be separated in a manner known per se by physical
methods, for example by chromatographic methods.
[0058] For reasons of clarity, hereinbelow only one of the possible
isomers is shown in each case. This does not exclude that the
compounds may, if appropriate, be present in the form of the isomer
mixtures or in the respective other isomeric form.
[0059] Taking into consideration the different meanings (a), (b),
(c), (d), (e), (f) and (g) of the group G, the following principle
structures (I-8-a) to (I-8-g) result if Het represents the group
(8):
##STR00024##
in which A, D, E, L, M, W, 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 are as defined above.
[0060] Furthermore, it has been found that the novel compounds of
the formula (I) are obtained by one of the processes described
below: [0061] (A) Substituted
3-(N-heterocyclyl)phenylpyrrolidine-2,4-diones or enols thereof of
the formula (I-1-a)
[0061] ##STR00025## [0062] in which [0063] A, B, D, W, X, Y and Z
are as defined above [0064] are obtained when [0065] N-acylamino
acid esters of the formula (II)
[0065] ##STR00026## [0066] in which [0067] A, B, D, W, X, Y and Z
are as defined above [0068] and [0069] R.sup.8 represents alkyl
(preferably C.sub.1-C.sub.6-alkyl) [0070] are condensed
intramolecularly in the presence of a diluent and in the presence
of a base. [0071] (B) Moreover, it has been found that substituted
3-(N-heterocyclyl)phenyl-4-hydroxy-.DELTA..sup.3-dihydrofuranone
derivatives of the formula (I-2-a)
[0071] ##STR00027## [0072] in which [0073] A, B, W, X, Y and Z are
as defined above [0074] are obtained when [0075] carboxylic esters
of the formula (III)
[0075] ##STR00028## [0076] in which [0077] A, B, W, X, Y, Z and
R.sup.8 are as defined above [0078] are condensed intramolecularly
in the presence of a diluent and in the presence of a base. [0079]
(C) Furthermore, it has been found that substituted
3-(N-heterocyclyl)phenyl-4-hydroxy-.DELTA..sup.3-dihydrothiophenone
derivatives of the formula (I-3-a)
[0079] ##STR00029## [0080] in which [0081] A, B, W, X, Y and Z are
as defined above [0082] are obtained when [0083]
.beta.-ketocarboxylic esters of the formula (IV)
[0083] ##STR00030## [0084] in which [0085] A, B, W, X, Y, Z and
R.sup.8 are as defined above and [0086] V represents hydrogen,
halogen, alkyl (preferably C.sub.1-C.sub.6-alkyl) or alkoxy
(preferably C.sub.1-C.sub.8-alkoxy) [0087] are cyclized
intramolecularly, if appropriate in the presence of a diluent and
in the presence of an acid. [0088] (D) Furthermore, it has been
found that the novel substituted 3-(N-heterocyclyl)phenylpyrone
derivatives of the formula (I-4-a)
[0088] ##STR00031## [0089] in which [0090] A, D, W, X, Y and Z are
as defined above [0091] are obtained when [0092] carbonyl compounds
of the formula (V)
[0092] ##STR00032## [0093] in which [0094] A and D are as defined
above [0095] or silylenol ethers thereof of the formula (Va)
[0095] ##STR00033## [0096] in which [0097] A, D and R.sup.8 are as
defined above [0098] are reacted with ketene acid halides of the
formula (VI)
[0098] ##STR00034## [0099] in which [0100] W, X, Y and Z are as
defined above and [0101] Hal represents halogen (preferably
chlorine or bromine), [0102] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid acceptor.
Furthermore, it has been found [0103] (E) that the novel
substituted 2-(N-heterocyclyl)phenyl-1,3-thiazine derivatives of
the formula (I-5-a)
[0103] ##STR00035## [0104] in which [0105] A, W, X, Y and Z are as
defined above [0106] are obtained when thioamides of the formula
(VII)
[0106] ##STR00036## [0107] in which [0108] A is as defined above
[0109] are reacted with ketene acid halides of the formula (VI)
[0109] ##STR00037## [0110] in which [0111] Hal, W, X, Y and Z are
as defined above, [0112] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid acceptor.
Furthermore, it has been found [0113] (F) that compounds of the
formula (I-6-a)
[0113] ##STR00038## [0114] in which [0115] A, B, Q.sup.1, Q.sup.2,
W, X, Y and Z are as defined above [0116] are obtained when [0117]
ketocarboxylic acid esters of the formula (VIII)
[0117] ##STR00039## [0118] in which [0119] A, B, Q.sup.1, Q.sup.2,
W, X, Y and Z are as defined above and [0120] R.sup.8 represents
alkyl (in particular C.sub.1-C.sub.8-alkyl) [0121] are cyclized
intramolecularly, if appropriate in the presence of a diluent and
if appropriate in the presence of a base. Moreover, it has been
found [0122] (G) that compounds of the formula (I-7-a)
[0122] ##STR00040## [0123] in which [0124] A, B, Q.sup.3, Q.sup.4,
Q.sup.S, Q.sup.6, W, X, Y and Z are as defined above [0125] are
obtained when [0126] 6-aryl-5-ketohexanoic esters of the formula
(IX)
[0126] ##STR00041## [0127] in which [0128] A, B, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, W, X, Y and Z are as defined above [0129] and
[0130] R.sup.8 represents alkyl (preferably C.sub.1-C.sub.6-alkyl)
[0131] are condensed intramolecularly in the presence of a diluent
and in the presence of a base. [0132] (H) Furthermore, it has been
found that the compounds of the formula (I-8-a)
[0132] ##STR00042## [0133] in which [0134] A, D, W, X, Y and Z are
as defined above [0135] are obtained when [0136] compounds of the
formula (X)
[0136] ##STR00043## [0137] in which [0138] A and D are as defined
above [0139] .alpha.) are reacted with compounds of the formula
(VI)
[0139] ##STR00044## [0140] in which [0141] Hal, W, X, Y and Z are
as defined above, [0142] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid acceptor, or
[0143] .beta.) are reacted with compounds of the formula (XI)
[0143] ##STR00045## [0144] in which [0145] W, X, Y and Z are as
defined above [0146] and U represents NH.sub.2 or O--R.sup.8,
[0147] where R.sup.8 is as defined above, [0148] if appropriate in
the presence of a diluent and if appropriate in the presence of a
base, or [0149] .gamma.) are reacted with compounds of the formula
(XII)
[0149] ##STR00046## [0150] in which [0151] A, D, W, X, Y, Z and
R.sup.8 are as defined above, [0152] if appropriate in the presence
of a diluent and if appropriate in the presence of a base.
Moreover, it has been found [0153] (I) that the compounds of the
formulae (I-1-b) to (I-8-b) shown above in which A, B, D, Q.sup.1,
Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, R.sup.1, W, X, Y and Z
are as defined above are obtained when compounds of the formulae
(I-1-a) to (I-8-a) shown above in which A, B, D, Q.sup.1, Q.sup.2,
Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are as defined
above are in each case [0154] (.alpha.) reacted with acid halides
of the formula (XIII)
[0154] ##STR00047## [0155] in which [0156] R.sup.1 is as defined
above and [0157] Hal represents halogen (in particular chlorine or
bromine) [0158] or [0159] (.beta.) reacted with carboxylic
anhydrides of the formula (XIV)
[0159] R.sup.1--CO--O--CO--R.sup.1 (XIV) [0160] in which [0161]
R.sup.1 is as defined above, [0162] if appropriate in the presence
of a diluent and if appropriate in the presence of an acid binder;
[0163] (J) that the compounds of the formulae (I-1-c) to (I-8-c)
shown above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.2, M, W, X, Y and Z are as defined above
and L represents oxygen are obtained when compounds of the formulae
(I-1-a) to (I-8-a) shown above in which A, B, D, Q.sup.1, Q.sup.2,
Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are as defined
above are in each case [0164] reacted with chloroformic esters or
chloroformic thioesters of the formula (XV)
[0164] R.sup.2-M-CO-Cl (XV) [0165] in which [0166] R.sup.2 and M
are as defined above [0167] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder;
[0168] (K) that compounds of the formulae (I-1-c) to (I-8-c) shown
above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.2, M, W, X, Y and Z are as defined above
and L represents sulphur are obtained when compounds of the
formulae (I-1-a) to (I-8-a) shown above in which A, B, D, Q.sup.1,
Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are as
defined above are in each case [0169] reacted with
chloromonothioformic esters or chlorodithioformic esters of the
formula (XVI)
[0169] ##STR00048## [0170] in which [0171] M and R.sup.2 are as
defined above, [0172] if appropriate in the presence of a diluent
and if appropriate in the presence of an acid binder [0173] and
[0174] (L) that compounds of the formulae (I-1-d) to (I-8-d) shown
above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.3, W, X, Y and Z are as defined above are
obtained when compounds of the formulae (I-1-a) to (I-8-a) shown
above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, W, X, Y and Z are as defined above are in each
case [0175] reacted with sulphonyl chlorides of the formula
(XVII)
[0175] R.sup.3--SO.sub.2--Cl (XVII) [0176] in which [0177] R.sup.3
is as defined above, [0178] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder,
[0179] (M) that compounds of the formulae (I-1-e) to (I-8-e) shown
above in which A, B, D, L, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.4, R.sup.5, W, X, Y and Z are as defined
above are obtained when compounds of the formulae (I-1-a) to
(I-8-a) shown above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3,
Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are as defined above are
in each case [0180] reacted with phosphorus compounds of the
formula (XVIII)
[0180] ##STR00049## [0181] in which [0182] L, R.sup.4 and R.sup.5
are as defined above and [0183] Hal represents halogen (in
particular chlorine or bromine), [0184] if appropriate in the
presence of a diluent and if appropriate in the presence of an acid
binder, [0185] (N) that compounds of the formulae (I-1-0 to (I-8-0
shown above in which A, B, D, E, Q.sup.1, Q.sup.2, Q.sup.3,
Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are as defined above are
obtained when compounds of the formulae (I-1-a) to (I-8-a) shown
above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, W, X, Y and Z are as defined above are in each
case [0186] reacted with metal compounds or amines of the formulae
(XIX) and (XX), respectively,
[0186] ##STR00050## [0187] in which [0188] Me represents a mono- or
divalent metal (preferably an alkali metal or alkaline earth metal,
such as lithium, sodium, potassium, magnesium or calcium), [0189] t
represents the number 1 or 2 and [0190] R.sup.10, R.sup.11,
R.sup.12 independently of one another represent hydrogen or alkyl
(preferably C.sub.1-C.sub.8-alkyl), [0191] if appropriate in the
presence of a diluent, [0192] (O) that compounds of the formulae
(I-1-g) to (I-8-g) shown above in which A, B, D, L, Q.sup.1,
Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, R.sup.6, R.sup.7, W,
X, Y and Z are as defined above are obtained when compounds of the
formulae (I-1-a) to (I-8-a) shown above in which A, B, D, Q.sup.1,
Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are as
defined above are in each case [0193] (.alpha.) reacted with
isocyanates or isothiocyanates of the formula (XXI)
[0193] R.sup.6--N.dbd.C=L (XXI) [0194] in which [0195] R.sup.6 and
L are as defined above, [0196] if appropriate in the presence of a
diluent and if appropriate in the presence of a catalyst, or [0197]
(.beta.) reacted with carbamoyl chlorides or thiocarbamoyl
chlorides of the formula (XXII)
[0197] ##STR00051## [0198] in which [0199] L, R.sup.6 and R.sup.7
are as defined above, [0200] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder,
[0201] (P) that compounds of the formulae (I-1) to (I-8) shown
above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, W, X, Y and Z are as defined above are obtained
when compounds of the formulae (I-1') to (I-8')
[0201] ##STR00052## ##STR00053## [0202] in which [0203] A, B, D, G,
Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X and Y
are as defined above and [0204] Z' represents chlorine, bromine,
iodine, preferably bromine, [0205] are reacted with NH-heterocycles
of the formula (XXIII)
[0205] H-Z (XXIII) [0206] in which [0207] Z is as defined above
[0208] in the presence of a solvent, a base and a catalyst,
suitable catalysts being in particular copper(I) salts.
[0209] Furthermore, it has been found that the novel compounds of
the formula (I) are highly active as pesticides, preferably as
insecticides and/or acaricides and/or herbicides and/or
fungicides.
[0210] Surprisingly, it has now also been found that certain
substituted cyclic ketoenols, when used jointly with the compounds
which improve crop plant tolerance (safeners/antidotes) described
hereinbelow, are extremely effective in preventing damage of the
crop plants and can be used especially advantageously as
combination products with a broad range of activity for the
selective control of undesired plants in crops of useful plants,
such as, for example, in cereals, but also in maize, soybeans and
rice.
[0211] The invention also relates to selectively herbicidal
compositions with an effective content of an active compound
combination comprising, as components, [0212] (a') at least one
substituted cyclic ketoenol of the formula (I) in which CKE, W, X,
Y and Z have the abovementioned meanings and [0213] (b') at least
one compound which improves crop plant tolerance and which is
selected from the following group of compounds:
[0214] 4-dichloroacetyl-1-oxa-4-aza-spiro[4.5]-decane (AD-67,
MON-4660),
1-dichloroacetyl-hexahydro-3,3,8a-trimethylpyrrolo[1,2-a]-pyrimidin-6(2H)-
-one (dicyclonon, BAS-145138),
4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine
(benoxacor), 1-methyl-hexyl 5-chloro-quinolin-8-oxy-acetate
(cloquintocet-mexyl--cf. also related compounds in EP-A-86750,
EP-A-94349, EP-A-191736, EP-A-492366),
3-(2-chloro-benzyl)-1-(1-methyl-1-phenyl-ethyl)-urea (cumyluron),
.alpha.-(cyanomethoximino)-phenylacetonitrile (cyometrinil),
2,4-dichloro-phenoxyacetic acid (2,4-D),
4-(2,4-dichloro-phenoxy)-butyric acid (2,4-DB),
1-(1-methyl-1-phenyl-ethyl)-3-(4-methyl-phenyl)-urea (daimuron,
dymron), 3,6-dichloro-2-methoxy-benzoic acid (dicamba),
S-1-methyl-1-phenyl-ethyl piperidine-1-thiocarboxylate
(dimepiperate),
2,2-dichloro-N-(2-oxo-2-(2-propenylamino)-ethyl)-N-(2-propenyl)-acetamide
(DKA-24), 2,2-dichloro-N,N-di-2-propenyl acetamide (dichlormid),
4,6-dichloro-2-phenyl-pyrimidine (fenclorim), ethyl
1-(2,4-dichloro-phenyl)-5-trichloro-methyl-1H-1,2,4-triazole-3-carboxylat-
e (fenchlorazole-ethyl--cf. also related compounds in EP-A-174562
and EP-A-346620), phenyl-methyl
2-chloro-4-trifluoromethyl-thiazole-5-carboxylate (flurazole),
4-chloro-N-(1,3-dioxolan-2-yl-methoxy)-.alpha.-trifluoro-acetophenone
oxime (fluxofenim),
3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyl-oxazolidine
(furilazole, MON-13900), ethyl
4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate
(isoxadifen-ethyl--cf. also related compounds in WO-A-95/07897),
1-(ethoxycarbonyl)-ethyl-3,6-dichloro-2-methoxybenzoate
(lactidichlor), (4-chloro-o-tolyloxy)-acetic acid (MCPA),
2-(4-chloro-o-tolyloxy)-propionic acid (mecoprop), diethyl
1-(2,4-dichloro-phenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylat-
e (mefenpyr-diethyl--cf. also related compounds in WO-A-91/07874),
2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),
2-propenyl-1-oxa-4-azaspiro[4.5]decane 4-carbodithioate (MG-838),
1,8-naphthalic anhydride,
.alpha.-(1,3-dioxolan-2-yl-methoximino)-phenylacetonitrile
(oxabetrinil),
2,2-dichloro-N-(1,3-dioxolan-2-yl-methyl)-N-(2-propenyl)-acetamide
(PPG-1292), 3-dichloroacetyl-2,2-dimethyl-oxazolidine (R-28725),
3-dichloroacetyl-2,2,5-trimethyl-oxazolidine (R-29148),
4-(4-chloro-o-tolyl)-butyric acid, 4-(4-chloro-phenoxy)-butyric
acid, diphenylmethoxyacetic acid, methyl diphenylmethoxyacetate,
ethyl diphenylmethoxyacetate, methyl
1-(2-chloro-phenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichloro-phenyl)-5-methyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichloro-phenyl)-5-isopropyl-1H-pyrazole-3-carboxylate,
ethyl
1-(2,4-dichloro-phenyl)-5-(1,1-dimethyl-ethyl)-1H-pyrazole-3-carboxylate,
ethyl 1-(2,4-dichloro-phenyl)-5-phenyl-1H-pyrazole-3-carboxylate
(cf. also related compounds in EP-A-269806 and EP-A-333131), ethyl
5-(2,4-dichloro-benzyl)-2-isoxazoline-3-carboxylate, ethyl
5-phenyl-2-isoxazoline-3-carboxylate, ethyl
5-(4-fluoro-phenyl)-5-phenyl-2-isoxazoline-3-carboxylate (cf. also
related compounds in WO-A-91/08202), 1,3-dimethyl-but-1-yl
5-chloro-quinolin-8-oxy-acetate, 4-allyloxy-butyl
5-chloro-quinolin-8-oxy-acetate, 1-allyloxy-prop-2-yl
5-chloro-quinolin-8-oxy-acetate, methyl
5-chloro-quinoxalin-8-oxy-acetate, ethyl
5-chloro-quinolin-8-oxy-acetate, allyl
5-chloro-quinoxalin-8-oxy-acetate, 2-oxo-prop-1-yl
5-chloro-quinolin-8-oxy-acetate, diethyl
5-chloro-quinolin-8-oxy-malonate, diallyl
5-chloro-quinoxalin-8-oxy-malonate, diethyl
5-chloro-quinolin-8-oxy-malonate (cf. also related compounds in
EP-A-582198), 4-carboxy-chroman-4-yl-acetic acid (AC-304415, cf.
EP-A-613618), 4-chloro-phenoxy-acetic acid,
3,3'-dimethyl-4-methoxy-benzophenone,
1-bromo-4-chloromethylsulphonyl-benzene,
1-[4-(N-2-methoxybenzoyl-sulphamoyl-phenyl]-3-methyl-urea (alias
N-(2-methoxy-benzoyl)-4-[(methylamino-carbonyl)-amino]-benzenesulphonamid-
e), 1-[4-(N-2-methoxybenzoylsulphamoyl-phenyl]-3,3-dimethyl-urea,
1-[4-(N-4,5-dimethylbenzoylsulphamoyl)-phenyl]-3-methyl-urea,
1-[4-(N-naphthylsulphamoyl)-phenyl]-3,3-dimethyl-urea,
N-(2-methoxy-5-methyl-benzoyl)-4-(cyclopropylaminocarbonyl)-benzenesulpho-
namide,
and/or one of the following compounds (defined by general formulae)
of the general formula (Ha)
##STR00054##
or of the general formula (IIb)
##STR00055##
or of the formula (IIc)
##STR00056##
where [0215] n represents a number of between 0 and 5, [0216]
A.sup.1 represents one of the divalent heterocyclic groups outlined
hereinbelow,
[0216] ##STR00057## [0217] n represents a number of between 0 and
5, [0218] A.sup.2 represents alkanediyl having 1 or 2 carbon atoms
which is optionally substituted by C.sub.1-C.sub.4-alkyl and/or
C.sub.1-C.sub.4-alkoxy-carbonyl, [0219] R.sup.21 represents
hydroxyl, mercapto, amino, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino or
di-(C.sub.1-C.sub.4-alkyl)amino, [0220] R.sup.22 represents
hydroxyl, mercapto, amino, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino or
di-(C.sub.1-C.sub.4-alkyl)amino, [0221] R.sup.23 represents
C.sub.1-C.sub.4-alkyl which is optionally substituted in each case
by fluorine, chlorine and/or bromine, [0222] R.sup.24 represents
hydrogen, or represents C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl or C.sub.2-C.sub.6-alkynyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl,
dioxolanyl-C.sub.1-C.sub.4-alkyl, furyl,
furyl-C.sub.1-C.sub.4-alkyl, thienyl, thiazolyl, piperidinyl, each
of which is optionally substituted by fluorine, chlorine and/or
bromine, or represents phenyl which is optionally substituted by
fluorine, chlorine and/or bromine or C.sub.1-C.sub.4-alkyl, [0223]
R.sup.25 represents hydrogen, or represents C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl or C.sub.2-C.sub.6-alkynyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl,
dioxolanyl-C.sub.1-C.sub.4-alkyl, furyl,
furyl-C.sub.1-C.sub.4-alkyl, thienyl, thiazolyl, piperidinyl, each
of which is optionally substituted by fluorine, chlorine and/or
bromine, or represents phenyl which is optionally substituted by
fluorine, chlorine and/or bromine or C.sub.1-C.sub.4-alkyl, or
together with R.sup.24 represents C.sub.3-C.sub.6-alkanediyl or
C.sub.2-C.sub.5-oxaalkanediyl, each of which is optionally
substituted by C.sub.1-C.sub.4-alkyl, phenyl, furyl, a fused
benzene ring or by two substituents which, together with the C atom
to which they are bonded, form a 5- or 6-membered carbocycle,
[0224] R.sup.26 represents hydrogen, cyano, halogen, or represents
C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl or phenyl, each
of which is optionally substituted by fluorine, chlorine and/or
bromine, [0225] R.sup.27 represents hydrogen, or represents
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or
tri(C.sub.1-C.sub.4-alkyl)silyl, optionally substituted by
hydroxyl, cyano, halogen or C.sub.1-C.sub.4-alkoxy, [0226] R.sup.28
represents hydrogen, cyano, halogen, or represents
C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl or phenyl, each
of which is optionally substituted by fluorine, chlorine and/or
bromine, [0227] X.sup.1 represents nitro, cyano, halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkoxy, [0228]
X.sup.2 represents hydrogen, cyano, nitro, halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkoxy, [0229]
X.sup.3 represents hydrogen, cyano, nitro, halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkoxy, and/or the
following compounds (defined by general formulae) of the general
formula (IId)
##STR00058##
[0229] or of the general formula (IIe)
##STR00059##
where [0230] n represents a number of between 0 and 5, [0231]
R.sup.29 represents hydrogen or C.sub.1-C.sub.4-alkyl, [0232]
R.sup.39 represents hydrogen or C.sub.1-C.sub.4-alkyl, [0233]
R.sup.31 represents hydrogen, or represents C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylamino or di-(C.sub.1-C.sub.4-alkyl)amino, each
of which is optionally substituted by cyano, halogen or
C.sub.1-C.sub.4-alkoxy, or represents C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkyloxy, C.sub.3-C.sub.6-cycloalkylthio or
C.sub.3-C.sub.6-cycloalkylamino, each of which is optionally
substituted by cyano, halogen or C.sub.1-C.sub.4-alkyl, [0234]
R.sup.32 represents hydrogen, or represents C.sub.1-C.sub.6-alkyl
which is optionally substituted by cyano, hydroxyl, halogen or
C.sub.1-C.sub.4-alkoxy, or represents C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkynyl, each of which is optionally substituted by
cyano or halogen, or represents C.sub.3-C.sub.6-cycloalkyl which is
optionally substituted by cyano, halogen or C.sub.1-C.sub.4-alkyl,
[0235] R.sup.33 represents hydrogen, or represents
C.sub.1-C.sub.6-alkyl which is optionally substituted by cyano,
hydroxyl, halogen or C.sub.1-C.sub.4-alkoxy, or represents
C.sub.3-C.sub.6-alkenyl or C.sub.3-C.sub.6-alkynyl, each of which
is optionally substituted by cyano or halogen, or represents
C.sub.3-C.sub.6-cycloalkyl which is optionally substituted by
cyano, halogen or C.sub.1-C.sub.4-alkyl, or represents phenyl which
is optionally substituted by nitro, cyano, halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkoxy, or together
with R.sup.32 represents C.sub.2-C.sub.6-alkanediyl or
C.sub.2-C.sub.5-oxaalkanediyl, each of which is optionally
substituted by C.sub.1-C.sub.4-alkyl, [0236] X.sup.4 represents
nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl,
amino, halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkoxy, and [0237]
X.sup.5 represents nitro, cyano, carboxyl, carbamoyl, formyl,
sulphamoyl, hydroxyl, amino, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-haloalkoxy.
[0238] Formula (I) provides a general definition of the compounds
according to the invention. Preferred substituents or ranges of the
radicals given in the formulae mentioned hereinabove and
hereinbelow are illustrated in the following text: [0239] X
preferably represents halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkenyl, C.sub.1-C.sub.6-alkynyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.6-alkenyloxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylsulphinyl, C.sub.1-C.sub.6-alkylsulphonyl,
C.sub.1-C.sub.6-haloalkoxy, C.sub.3-C.sub.6-haloalkenyloxy, nitro,
cyano or represents phenyl, phenoxy, phenylthio, benzyloxy or
benzylthio, each of which is optionally mono- or disubstituted by
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy, nitro or
cyano, [0240] W and Y independently of one another preferably
represent hydrogen, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkenyl, C.sub.1-C.sub.6-alkynyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkoxy, nitro or cyano, [0241] Z preferably
represents optionally substituted pyrazolyl, triazolyl, tetrazolyl,
pyrrolyl, indolyl, benzimidazolyl, benzpyrazolyl, benztriazolyl,
pyrrolidinyl, piperidinyl, piperazidinyl, morpholinyl or
thiomorpholinyl which is attached via a nitrogen atom to the phenyl
ring, [0242] CKE preferably represents one of the groups
[0242] ##STR00060## [0243] A preferably represents hydrogen or
represents C.sub.1-C.sub.12-alkyl, C.sub.3-C.sub.8-alkenyl,
C.sub.1-C.sub.10-alkoxy-C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.10-alkylthio-C.sub.1-C.sub.6-alkyl, each of which is
optionally mono- to pentasubstituted by halogen, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.2-haloalkyl or C.sub.1-C.sub.6-alkoxy and in which
optionally one or two not directly adjacent ring members are
replaced by oxygen and/or sulphur or represents phenyl, naphthyl,
hetaryl having 5 or 6 ring atoms (for example furanyl, pyridyl,
imidazolyl, triazolyl, pyrazolyl, pyrimidyl, thiazolyl or thienyl),
phenyl-C.sub.1-C.sub.6-alkyl or naphthyl-C.sub.1-C.sub.6-alkyl,
each of which is optionally mono- to trisubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, cyano or nitro,
[0244] 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 [0245] A, B and
the carbon atom to which they are attached preferably represent
saturated C.sub.3-C.sub.10-cycloalkyl or unsaturated
C.sub.5-C.sub.10-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur and which are optionally mono- or
disubstituted by C.sub.1-C.sub.8-alkyl,
C.sub.3-C.sub.10-cycloalkyl, C.sub.1-C.sub.8-haloalkyl,
C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-alkylthio, halogen or
phenyl or [0246] A, B and the carbon atom to which they are
attached preferably represent C.sub.3-C.sub.6-cycloalkyl which is
substituted by an alkylenediyl group which optionally contains one
or two not directly adjacent oxygen and/or sulphur atoms and which
is optionally mono- to tetrasubstituted by C.sub.1-C.sub.4-alkyl or
by an alkylenedioxyl or by an alkylenedithioyl group which,
together with the carbon atom to which it is attached, forms a
further five- to eight-member ring or [0247] A, B and the carbon
atom to which they are attached 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
attached represent C.sub.2-C.sub.6-alkanediyl,
C.sub.2-C.sub.6-alkenediyl or C.sub.4-C.sub.6-alkanediendiyl, each
of which is optionally mono- to disubstituted by
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy or halogen and in
which optionally one methylene group is replaced by oxygen or
sulphur, [0248] D preferably represents hydrogen, represents
C.sub.1-C.sub.12-alkyl, C.sub.3-C.sub.8-alkenyl,
C.sub.3-C.sub.8-alkynyl,
C.sub.1-C.sub.10-alkoxy-C.sub.1-C.sub.8-alkyl, each of which is
optionally mono- to pentasubstituted by halogen, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkyl and in which
optionally one ring member is replaced by oxygen or sulphur or
represents phenyl, hetaryl having 5 or 6 ring atoms (for example
furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl,
pyrrolyl, thienyl or triazolyl), phenyl-C.sub.1-C.sub.6-alkyl or
hetaryl-C.sub.1-C.sub.6-alkyl having 5 or 6 ring atoms (for example
furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl,
pyrrolyl, thienyl or triazolyl), each of which radicals is
optionally mono- to trisubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, cyano or nitro,
or [0249] A and D together preferably represent in each case
optionally mono- or disubstituted C.sub.3-C.sub.6-alkanediyl or
C.sub.3-C.sub.6-alkenediyl in which optionally one methylene group
is replaced by a carbonyl group, oxygen or sulphur, [0250] possible
substituents being in each case: [0251] halogen, hydroxyl, mercapto
or 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 mono- to trisubstituted by
halogen, or a further C.sub.3-C.sub.6-alkanediyl grouping,
C.sub.3-C.sub.6-alkenediyl grouping or butadienyl grouping which is
optionally substituted by C.sub.1-C.sub.6-alkyl or in which
optionally two adjacent substituents together with the carbon atoms
to which they are attached form a further saturated or unsaturated
cycle having 5 or 6 ring atoms (in the case of the compound of the
formula (I-1), A and D together with the atoms to which they are
attached then represent, for example, the groups mentioned further
below (AD-1 to AD-10)) which can contain oxygen or sulphur, or
which optionally contains one of the following groups
[0251] ##STR00061## [0252] or [0253] A and Q.sup.1 together
preferably represent C.sub.3-C.sub.6-alkanediyl or
C.sub.4-C.sub.6-alkenediyl, each of which is optionally mono- or
disubstituted by identical or different substituents from the group
consisting of halogen, hydroxyl, of 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, each of which is optionally mono- to
trisubstituted by identical or different halogen, and of benzyloxy
and phenyl, each of which is optionally mono- to trisubstituted by
identical or different substituents from the group consisting of
halogen, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-alkoxy, which
C.sub.3-C.sub.6-alkanediyl or C.sub.4-C.sub.6-alkenediyl moreover
optionally contains one of the groups below
[0253] ##STR00062## [0254] or is bridged by a
C.sub.1-C.sub.2-alkanediyl group or by an oxygen atom or [0255]
Q.sup.1 preferably represents hydrogen or C.sub.1-C.sub.4-alkyl,
[0256] Q.sup.2, Q.sup.4, Q.sup.5 and Q.sup.6 independently of one
another preferably represent hydrogen or C.sub.1-C.sub.4-alkyl,
[0257] Q.sup.3 preferably represents hydrogen, represents
C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to pentasubstituted by halogen, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally substituted by
C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy and in which
optionally one methylene group is replaced by oxygen or sulphur or
represents phenyl which is optionally mono- or disubstituted by
halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-haloalkyl, C.sub.1-C.sub.2-haloalkoxy, cyano or
nitro, or [0258] Q.sup.3 and Q.sup.4 together with the carbon atom
to which they are attached preferably represent a
C.sub.3-C.sub.7-ring which is optionally mono- to trisubstituted by
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.2-haloalkyl and in which optionally one ring member
is replaced by oxygen or sulphur, [0259] G preferably represents
hydrogen (a) or represents one of the groups
##STR00063##
[0259] in particular (a), (b), (c) or (g) [0260] in which [0261] E
represents a metal ion equivalent or an ammonium ion, [0262] L
represents oxygen or sulphur and [0263] M represents oxygen or
sulphur, [0264] 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,
poly-C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl, each of which is
optionally mono- to pentasubstituted by halogen, or represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy and in which optionally one or more
(preferably not more than two) not directly adjacent ring members
are replaced by oxygen and/or sulphur, [0265] preferably represents
phenyl which is optionally mono- to trisubstituted by halogen,
cyano, nitro, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-haloalkoxy,
C.sub.1-C.sub.6-alkylthio or C.sub.1-C.sub.6-alkylsulphonyl, [0266]
preferably represents phenyl-C.sub.1-C.sub.6-alkyl which is
optionally mono- to trisubstituted by halogen, nitro, cyano,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkyl or C.sub.1-C.sub.6-haloalkoxy, [0267]
preferably represents 5- or 6-membered hetaryl which is optionally
mono- or disubstituted by halogen or C.sub.1-C.sub.6-alkyl (for
example pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or
thienyl), [0268] preferably represents phenoxy
C.sub.1-C.sub.6-alkyl which is optionally mono- or disubstituted by
halogen or C.sub.1-C.sub.6-alkyl or [0269] preferably represents 5-
or 6-membered hetaryloxy C.sub.1-C.sub.6-alkyl which is optionally
mono- or disubstituted by halogen, amino or C.sub.1-C.sub.6-alkyl
(for example pyridyloxy-C.sub.1-C.sub.6-alkyl,
pyrimidyloxy-C.sub.1-C.sub.6-alkyl or
thiazolyloxy-C.sub.1-C.sub.6-alkyl), [0270] 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,
poly-C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, each of which is
optionally mono- to pentasubstituted by halogen, [0271] preferably
represents C.sub.3-C.sub.8-cycloalkyl which is optionally mono- or
disubstituted by halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy or [0272] preferably represents phenyl or
benzyl, each of which is optionally mono- to trisubstituted by
halogen, cyano, nitro, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkyl or
C.sub.1-C.sub.6-halo-alkoxy, [0273] R.sup.3 preferably represents
C.sub.1-C.sub.8-alkyl which is optionally mono- to nonasubstituted
by halogen or represents phenyl or benzyl, each of which is
optionally mono- to trisubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy, cyano or
nitro, [0274] 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, C.sub.2-C.sub.8-alkenylthio,
C.sub.3-C.sub.7-cyclo-alkylthio, each of which is optionally mono-
to pentasubstituted by halogen, or represent phenyl, phenoxy or
phenylthio, each of which is optionally mono- to trisubstituted by
halogen, nitro, cyano, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-haloalkoxy, C.sub.1-C.sub.4-alkylthio,
C.sub.1-C.sub.4-halo-alkylthio, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-haloalkyl, [0275] R.sup.6 and R.sup.7 independently
of one another preferably represent hydrogen, 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,
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl, each of which is
optionally mono- to pentasubstituted by halogen, represent phenyl
which is optionally mono- to trisubstituted by halogen,
C.sub.1-C.sub.8-haloalkyl, C.sub.1-C.sub.8-alkyl or
C.sub.1-C.sub.8-alkoxy, represent benzyl which is optionally mono-
to trisubstituted by halogen, C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-haloalkyl or C.sub.1-C.sub.8-alkoxy or together
represent a C.sub.3-C.sub.6-alkylene radical which is optionally
mono- or disubstituted by C.sub.1-C.sub.4-alkyl and in which
optionally one carbon atom is replaced by oxygen or sulphur, [0276]
R.sup.13 preferably represents hydrogen, preferably represents
C.sub.1-C.sub.8-alkyl or C.sub.1-C.sub.8-alkoxy, each of which is
optionally mono- to trisubstituted by halogen, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy and in which optionally one methylene group
is 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 mono- or disubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy, nitro or
cyano, [0277] R.sup.14 preferably represents hydrogen or
C.sub.1-C.sub.8-alkyl or [0278] R.sup.13 and R.sup.14 together
preferably represent C.sub.4-C.sub.6-alkanediyl, [0279] R.sup.15
and R.sup.16 are identical or different and preferably represent
C.sub.1-C.sub.6-alkyl or [0280] R.sup.15 and R.sup.16 together
preferably represent a C.sub.2-C.sub.4-alkanediyl radical which is
optionally mono- or disubstituted by C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl or by phenyl which is optionally mono- or
disubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-haloalkoxy, nitro or cyano, [0281] R.sup.17 and
R.sup.18 independently of one another preferably represent
hydrogen, represent optionally halogen-substituted
C.sub.1-C.sub.8-alkyl or represent phenyl which is optionally mono-
or disubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-halo-alkoxy, nitro or cyano or [0282] R.sup.17 and
R.sup.18 together with the carbon atom to which they are attached
preferably represent a carbonyl group or represent
C.sub.5-C.sub.7-cycloalkyl which is optionally mono- or
disubstituted by halogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy and in which optionally one methylene group
is replaced by oxygen or sulphur, [0283] R.sup.19 and R.sup.29
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.
[0284] In the radical definitions mentioned as being preferred,
halogen represents fluorine, chlorine, bromine and iodine, in
particular fluorine, chlorine and bromine. [0285] X particularly
preferably represents fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy, nitro or
cyano, [0286] W and Y independently of one another particularly
preferably represent hydrogen, fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, [0287] Z
particularly preferably represents one of the radicals
[0287] ##STR00064## [0288] V.sup.1 particularly preferably
represents hydrogen, fluorine, chlorine, bromine, iodine,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy, cyano or
nitro, [0289] V.sup.2 particularly preferably represents hydrogen,
fluorine, chlorine, bromine, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.2-haloalkyl, [0290] V.sup.1 and V.sup.2 together
particularly preferably represent C.sub.3-C.sub.4-alkanediyl which
is optionally mono- to tetrasubstituted by fluorine and which may
optionally be interrupted once or twice by oxygen or represent
butadienyl which is optionally mono- or disubstituted by fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-haloalkyl, C.sub.1-C.sub.2-haloalkoxy, cyano or
nitro, [0291] CKE particularly preferably represents one of the
groups
[0291] ##STR00065## [0292] A particularly preferably represents
hydrogen, represents C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine,
represents C.sub.3-C.sub.6-cycloalkyl which is optionally mono- or
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl,
trifluoromethyl or C.sub.1-C.sub.2-alkoxy or (but not in the case
of the compounds of the formulae (I-3), (I-4), (I-6) and (I-7))
represents phenyl or benzyl, each of which is optionally mono- or
disubstituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.2-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.2-haloalkoxy, cyano or nitro,
[0293] B particularly preferably represents hydrogen,
C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.2-alkoxyl-C.sub.1-C.sub.2-alkyl or [0294] A, B and
the carbon atom to which they are attached particularly preferably
represent saturated C.sub.3-C.sub.7-cycloalkyl or unsaturated
C.sub.5-C.sub.7-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur and which is optionally mono- or
disubstituted by C.sub.1-C.sub.6-alkyl, trifluoromethyl or
C.sub.1-C.sub.6-alkoxy, with the proviso that in this case Q.sup.3
particularly preferably represents hydrogen or methyl, or [0295] A,
B and the carbon atom to which they are attached particularly
preferably represent C.sub.5-C.sub.6-cycloalkyl which is
substituted by an alkylenediyl group which optionally contains one
or two not directly adjacent oxygen or sulphur atoms and which is
optionally mono- or disubstituted by methyl or ethyl, or by an
alkylenedioxyl or by an alkylenedithiol group which, together with
the carbon atom to which it is attached, forms a further five- or
six-membered ring, with the proviso that in this case Q.sup.3
particularly preferably represents hydrogen or methyl, [0296] A, B
and the carbon atom to which they are attached 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 attached represent
C.sub.2-C.sub.4-alkanediyl, C.sub.2-C.sub.4-alkenediyl or
butadienediyl, each of which is optionally substituted by
C.sub.1-C.sub.2-alkyl or C.sub.1-C.sub.2-alkoxy, with the proviso
that in this case Q.sup.3 particularly preferably represents
hydrogen or methyl, [0297] D particularly preferably represents
hydrogen, represents C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.3-alkyl, each of which is
optionally mono- to trisubstituted by fluorine, represents
C.sub.3-C.sub.6-cycloalkyl which is optionally mono- or
disubstituted by C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.2-haloalkyl and in which optionally one methylene
group is replaced by oxygen or (but not in the case of the
compounds of the formula (I-1)) represents phenyl or pyridyl, each
of which is optionally mono- or disubstituted by fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-halo-alkoxy, or [0298] A and D together
particularly preferably represent C.sub.3-C.sub.5-alkanediyl which
is optionally mono- or disubstituted and in which one methylene
group may be replaced by a carbonyl group, oxygen or sulphur,
possible substituents being C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy, or [0299] A and D (in the case of the
compounds of the formula (I-1)) together with the atoms to which
they are attached represent one of the groups AD-1 to AD-10:
[0299] ##STR00066## [0300] or [0301] A and Q.sup.1 together
particularly preferably represent C.sub.3-C.sub.4-alkanediyl or
C.sub.4-alkenediyl, each of which is optionally mono- or
disubstituted by identical or different substituents from the group
consisting of fluorine, chlorine, hydroxyl and
C.sub.1-C.sub.8-alkyl and C.sub.1-C.sub.4-alkoxy, each of which is
optionally mono- to trisubstituted by fluorine, or [0302] Q.sup.1
particularly preferably represents hydrogen, [0303] Q.sup.2
particularly preferably represents hydrogen, [0304] Q.sup.4,
Q.sup.5 and Q.sup.6 independently of one another particularly
preferably represent hydrogen or C.sub.1-C.sub.3-alkyl, [0305]
Q.sup.3 particularly preferably represents hydrogen,
C.sub.1-C.sub.4-alkyl, trifluoromethyl or represents
C.sub.3-C.sub.6-cycloalkyl which is optionally mono- or
disubstituted by methyl or methoxy, or [0306] Q.sup.3 and Q.sup.4
together with the carbon to which they are attached particularly
preferably represent a saturated C.sub.5-C.sub.6-ring which is
optionally mono- or disubstituted by C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy and in which optionally one ring member is
replaced by oxygen or sulphur, with the proviso that in this case A
particularly preferably represents hydrogen or methyl, or [0307] G
particularly preferably represents hydrogen (a) or represents one
of the groups
##STR00067##
[0307] in particular (a), (b), or (c) [0308] in which [0309] E
represents a metal ion equivalent or an ammonium ion, [0310] L
represents oxygen or sulphur and [0311] M represents oxygen or
sulphur, [0312] R.sup.1 particularly preferably represents
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents C.sub.3-C.sub.6-cycloalkyl which is optionally mono- or
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy and in which optionally one or two not
directly adjacent ring members are replaced by oxygen, [0313]
particularly preferably represents phenyl which is optionally mono-
or disubstituted 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.2-haloalkyl or C.sub.1-C.sub.2-haloalkoxy, [0314]
R.sup.2 particularly preferably represents C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.8-alkenyl or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by fluorine, [0315] particularly
preferably represents C.sub.3-C.sub.6-cycloalkyl which is
optionally monosubstituted by C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy or [0316] particularly preferably represents
phenyl or benzyl, each of which is optionally mono- or
disubstituted by fluorine, chlorine, bromine, cyano, nitro,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.3-alkoxy, trifluoromethyl or
trifluoromethoxy, [0317] R.sup.3 particularly preferably represents
C.sub.1-C.sub.6-alkyl which is optionally mono- to trisubstituted
by fluorine or represents phenyl or benzyl, each of which is
optionally monosubstituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, trifluoromethyl,
trifluoro-methoxy, cyano or nitro, [0318] R.sup.4 particularly
preferably represents 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,
C.sub.3-C.sub.4-alkenylthio, C.sub.3-C.sub.6-cycloalkylthio, each
of which is optionally mono- to trisubstituted by fluorine, or
represents phenyl, phenoxy or phenylthio, each of which is
optionally mono- or disubstituted by fluorine, chlorine, bromine,
nitro, cyano, C.sub.1-C.sub.3-alkoxy, C.sub.1-C.sub.3-haloalkoxy,
C.sub.1-C.sub.3-alkylthio, C.sub.1-C.sub.3-halo-alkylthio,
C.sub.1-C.sub.3-alkyl or trifluoromethyl, [0319] R.sup.5
particularly preferably represents C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.6-alkylthio, [0320] R.sup.6 particularly preferably
represents hydrogen, represents 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,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by fluorine, represents phenyl
which is optionally mono- or disubstituted by fluorine, chlorine,
bromine, trifluoromethyl, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy, represents benzyl which is optionally
monosubstituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, trifluoromethyl or C.sub.1-C.sub.4-alkoxy,
[0321] R.sup.7 particularly preferably represents
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl or
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, [0322] R.sup.6 and
R.sup.7 together particularly preferably represent a
C.sub.4-C.sub.5-alkylene radical which is optionally mono- or
disubstituted by methyl or ethyl and in which optionally a
methylene group is replaced by oxygen or sulphur.
[0323] In the radical definitions mentioned as being particularly
preferred, halogen represents fluorine, chlorine, bromine and
iodine, in particular fluorine, chlorine and bromine [0324] W very
particularly preferably represents hydrogen, methyl, ethyl or
chlorine, [0325] X very particularly preferably represents
chlorine, methyl, ethyl, propyl, methoxy, ethoxy, propoxy,
trifluoromethyl, difluoromethoxy or trifluoromethoxy, [0326] Y very
particularly preferably represents hydrogen or methyl, [0327] Z
very particularly preferably represents one of the radicals
[0327] ##STR00068## [0328] V.sup.1 very particularly preferably
represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl,
methoxy, ethoxy, trifluoromethyl or cyano, [0329] CKE very
particularly preferably represents one of the groups
[0329] ##STR00069## [0330] A very particularly preferably
represents hydrogen, represents C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to trisubstituted by fluorine, represents
cyclopropyl, cyclopentyl or cyclohexyl and, only in the case of the
compounds of the formula (I-5), represents phenyl which is
optionally mono- or disubstituted by fluorine, chlorine, bromine,
methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy,
trifluoromethyl, trifluoromethoxy, cyano or nitro, [0331] B very
particularly preferably represents hydrogen, methyl or ethyl or
[0332] A, B and the carbon atom to which they are attached very
particularly preferably represent saturated
C.sub.5-C.sub.6-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur and which is optionally
monosubstituted by methyl, ethyl, propyl, isopropyl,
trifluoromethyl, methoxy, ethoxy, propoxy, butoxy or isobutoxy,
with the proviso that in this case Q.sup.3 very particularly
preferably represents hydrogen, or [0333] A, B and the carbon atom
to which they are attached very particularly preferably represent
C.sub.6-cycloalkyl which is substituted by an alkylenedioxyl group
containing two not directly adjacent oxygen atoms, with the proviso
that in this case Q.sup.3 very particularly preferably represents
hydrogen, or [0334] A, B and the carbon atom to which they are
attached very particularly preferably represent
C.sub.5-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
attached represent C.sub.2-C.sub.4-alkanediyl or
C.sub.2-C.sub.4-alkenediyl or butadienediyl, with the proviso that
in this case Q.sup.3 very particularly preferably represents
hydrogen, [0335] D very particularly preferably represents
hydrogen, represents C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.4-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.3-alkyl, each of which is
optionally mono- to trisubstituted by fluorine, represents
cyclopropyl, cyclopentyl or cyclohexyl or (but not in the case of
the compounds of the formula (I-1)) represents pyridyl or phenyl
which is optionally monosubstituted by fluorine, chlorine, methyl,
ethyl, n-propyl, isopropyl, methoxy, ethoxy or trifluoromethyl,
[0336] or [0337] A and D together very particularly preferably
represent C.sub.3-C.sub.5-alkanediyl which is optionally mono- or
disubstituted by methyl or methoxy and in which optionally one
carbon atom is replaced by oxygen or sulphur or represent the group
AD-1
[0337] ##STR00070## [0338] A and Q.sup.1 together very particularly
preferably represent C.sub.3-C.sub.4-alkanediyl which is optionally
mono- or disubstituted by methyl or methoxy, or [0339] Q.sup.1 very
particularly preferably represents hydrogen, [0340] Q.sup.2 very
particularly preferably represents hydrogen, [0341] Q.sup.4,
Q.sup.5 and Q.sup.6 independently of one another very particularly
preferably represent hydrogen or methyl, [0342] Q.sup.3 very
particularly preferably represents hydrogen, methyl, ethyl, propyl
or isopropyl, or [0343] Q.sup.3 and Q.sup.4 together with the
carbon to which they are attached very particularly preferably
represent a saturated C.sub.5-C.sub.6-ring which is optionally
monosubstituted by methyl or methoxy, with the proviso that in this
case A very particularly preferably represents hydrogen, [0344] G
very particularly preferably represents hydrogen (a) or represents
one of the groups
[0344] ##STR00071## [0345] in particular (a), (b) or (c) [0346] in
which [0347] E represents a metal ion equivalent or an ammonium
ion, [0348] L represents oxygen or sulphur and [0349] M represents
oxygen or sulphur, [0350] R.sup.1 very particularly preferably
represents C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.2-alkoxy-C.sub.1-alkyl,
C.sub.1-C.sub.2-alkylthio-C.sub.1-alkyl, each of which is
optionally mono- to trisubstituted by fluorine, or represents
cyclopropyl or cyclohexyl, each of which is optionally
monosubstituted by fluorine, chlorine, methyl or methoxy, [0351]
very particularly preferably represents phenyl which is optionally
monosubstituted by fluorine, chlorine, bromine, cyano, nitro,
methyl, methoxy, trifluoromethyl or tri-fluoromethoxy, [0352]
R.sup.2 very particularly preferably represents
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.6-alkenyl or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.3-alkyl, each of which is
optionally monosubstituted by fluorine, [0353] or very particularly
preferably represents phenyl or benzyl, each of which is optionally
monosubstituted by fluorine, chlorine, cyano, nitro, methyl, ethyl,
n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or
trifluoromethoxy, [0354] R.sup.3 very particularly preferably
represents methyl, ethyl, n-propyl, isopropyl, each of which is
optionally mono- to trisubstituted by fluorine, or represents
phenyl or benzyl, each of which is optionally monosubstituted by
fluorine, chlorine, bromine, methyl, tert-butyl, methoxy,
trifluoromethyl, trifluoromethoxy, cyano or nitro, [0355] R.sup.4
very particularly preferably represents 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, C.sub.1-C.sub.4-alkylthio, each of
which is optionally mono- to trisubstituted by fluorine, or
represents phenyl, phenoxy or phenylthio, each of which is
optionally monosubstituted by fluorine, chlorine, bromine, nitro,
cyano, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-fluoroalkoxy,
C.sub.1-C.sub.2-alkylthio, C.sub.1-C.sub.2-fluoroalkylthio or
C.sub.1-C.sub.3-alkyl, [0356] R.sup.5 very particularly preferably
represents methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio,
propylthio or butylthio, [0357] R.sup.6 very particularly
preferably represents hydrogen, represents 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,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by fluorine, represents phenyl
which is optionally monosubstituted by fluorine, chlorine, bromine,
trifluoromethyl, methyl or methoxy, represents benzyl which is
optionally monosubstituted by fluorine, chlorine, bromine, methyl,
trifluoromethyl or methoxy, [0358] R.sup.7 very particularly
preferably represents methyl, ethyl, propyl, isopropyl, butyl,
isobutyl or allyl, [0359] R.sup.6 and R.sup.7 very particularly
preferably represent a C.sub.4-C.sub.5-alkylene radical in which
optionally one methylene group is replaced by oxygen or sulphur.
[0360] W most preferably represents hydrogen, methyl or ethyl,
[0361] X most preferably represents chlorine, methyl or ethyl,
[0362] Y most preferably represents hydrogen, [0363] Z most
preferably represents, in the 4- or 5-position, the radical
[0363] ##STR00072## [0364] V.sup.1 most preferably represents
chlorine or methoxy, [0365] CKE most preferably represents one of
the groups
[0365] ##STR00073## [0366] A most preferably represents hydrogen,
C.sub.1-C.sub.4-alkyl or cyclopropyl, [0367] B most preferably
represents hydrogen or methyl, or [0368] A, B and the carbon atom
to which they are attached most preferably represent saturated
C.sub.5-C.sub.6-cycloalkyl in which optionally one ring member is
replaced by oxygen and which is optionally monosubstituted by
methyl or methoxy, with the proviso that in this case Q.sup.3 most
preferably represents hydrogen, [0369] D most preferably represents
hydrogen, [0370] or [0371] A and D together most preferably
represent C.sub.3-C.sub.5-alkanediyl in which optionally one carbon
atom is replaced by oxygen, [0372] Q.sup.1 most preferably
represents hydrogen, [0373] Q.sup.2 most preferably represents
hydrogen, [0374] Q.sup.3 most preferably represents methyl, [0375]
Q.sup.4 most preferably represents methyl, or [0376] Q.sup.3 and
Q.sup.4 together with the carbon to which they are attached most
preferably represent a saturated C.sub.5-C.sub.6-ring, with the
proviso that in this case A most preferably represents hydrogen,
[0377] Q.sup.5 most preferably represents hydrogen, [0378] Q.sup.6
most preferably represents hydrogen, [0379] G most preferably
represents hydrogen (a) or represents one of the groups
[0379] ##STR00074## [0380] in which [0381] L represents oxygen and
[0382] M represents oxygen or sulphur, [0383] R.sup.1 most
preferably represents C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.2-alkoxy-C.sub.1-alkyl, [0384] R.sup.2 most
preferably represents C.sub.1-C.sub.8-alkyl or benzyl.
[0385] The general or preferred radical definitions or
illustrations given above can be combined with one another as
desired, i.e. including combinations between the respective ranges
and preferred ranges. They apply both to the end product and,
correspondingly, to precursors and intermediates.
[0386] Preference according to the invention is given to the
compounds of the formula (I) which contain a combination of the
meanings given above as being preferred (preferable).
[0387] Particular preference according to the invention is given to
the compounds of the formula (I) which contain a combination of the
meanings given above as being particularly preferred.
[0388] Very particular preference according to the invention is
given to the compounds of the formula (I) which contain a
combination of the meanings given above as being very particularly
preferred.
[0389] Most preference according to the invention is given to the
compounds of the formula (I) which contain a combination of the
meanings given above as being most preferred.
[0390] Saturated or unsaturated hydrocarbon radicals, such as alkyl
or alkenyl, can in each case be straight-chain or branched as far
as this is possible, including in combination with heteroatoms,
such as, for example, in alkoxy.
[0391] Optionally substituted radicals can, unless stated
otherwise, be mono- or polysubstituted, where in the case of
polysubstitution the substituents can be identical or
different.
[0392] In addition to the compounds mentioned in the Preparation
Examples, the following compounds of the formula (I-1-a) may be
specifically mentioned:
##STR00075##
TABLE-US-00001 TABLE 1 ##STR00076## 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
##STR00077## CH.sub.3 H ##STR00078## CH.sub.3 H ##STR00079##
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)-- H
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
--CH.sub.2--O--(CH.sub.2).sub.3-- 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.2H5--(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--CHOC.sub.4H.sub.9--(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 ##STR00080## H
##STR00081## H ##STR00082## H ##STR00083## H ##STR00084## H A D B
--(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--CHCH.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 ##STR00085## 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
##STR00086## H H ##STR00087## H H ##STR00088## 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 ##STR00089## H CH.sub.3 ##STR00090## H
CH.sub.3 ##STR00091## H C.sub.2H.sub.5 CH.sub.3 H C.sub.2H.sub.5
C.sub.2H.sub.5 H
[0393] Table 2: A, B and D are as shown in Table 1
##STR00092##
[0394] Table 3: A, B and D are as shown in Table 1
##STR00093##
[0395] Table 4: A, B and D are as shown in Table 1
##STR00094##
[0396] Table 5: A, B and D are as shown in Table 1
##STR00095##
[0397] Table 6: A, B and D are as shown in Table 1
##STR00096##
[0398] Table 7: A, B and D are as shown in Table 1
##STR00097##
[0399] In addition to the compounds mentioned in the Preparation
Examples, the following compounds of the formula (I-2-a) may be
specifically mentioned:
##STR00098##
TABLE-US-00002 TABLE 8 ##STR00099## 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
##STR00100## CH.sub.3 ##STR00101## CH.sub.3 ##STR00102## 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--O--(CH.sub.2).sub.3--
--(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--CHCH.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--CHOC.sub.4H.sub.9--(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-- ##STR00103##
##STR00104## ##STR00105## ##STR00106##
[0400] Table 9: A and B are as shown in Table 8
##STR00107##
[0401] Table 10: A and B are as shown in Table 8
##STR00108##
[0402] Table 11: A and B are as shown in Table 8
##STR00109##
[0403] Table 12: A and B are as shown in Table 8
##STR00110##
[0404] Table 13: A and B are as shown in Table 8
##STR00111##
[0405] Table 14: A and B are as shown in Table 8
##STR00112##
[0406] In addition to the compounds mentioned in the Preparation
Examples, the following compounds of the formula (I-8-a) may be
specifically mentioned:
##STR00113##
TABLE-US-00003 TABLE 15 W, X, Y and Z are as shown in Table 1. A D
CH.sub.3 CH.sub.3 CH.sub.3 --(CH.sub.2).sub.2OH-- CH.sub.3
--(CH.sub.2).sub.2OCH.sub.3-- CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--OCH.sub.3--
--(CH.sub.2).sub.2--O--CH.sub.3-- --(CH.sub.2).sub.2--O--CH.sub.3--
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--OCH.sub.3--
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--OCH.sub.3--
--(CH.sub.2).sub.3-- --(CH.sub.2).sub.4--
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- ##STR00114## ##STR00115##
##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120##
##STR00121## ##STR00122## ##STR00123##
[0407] Table 16: A and D are as shown in Table 15 [0408] W, X, Y
and Z are as shown in Table 2.
[0409] Table 17: A and D are as shown in Table 15 [0410] W, X, Y
and Z are as shown in Table 3.
[0411] Table 18: A and D are as shown in Table 15 [0412] W, X, Y
and Z are as shown in Table 4.
[0413] Table 19: A and D are as shown in Table 15 [0414] W, X, Y
and Z are as shown in Table 5.
[0415] Table 20: A and D are as shown in Table 15 [0416] W, X, Y
and Z are as shown in Table 6.
[0417] Table 21: A and D are as shown in Table 15 [0418] W, X, Y
and Z are as shown in Table 7.
[0419] Preferred meanings of the groups mentioned above in
connection with the compounds improving crop plant tolerance
("herbicide safeners") of the formulae (IIa), (IIb), (IIc), (IId)
and (Re) are defined hereinbelow. [0420] n preferably represents
the numbers 0, 1, 2, 3 or 4. [0421] A.sup.1 preferably represents
one of the divalent heterocyclic groups outlined hereinbelow
[0421] ##STR00124## [0422] A.sup.2 preferably represents methylene
or ethylene, each of which is optionally substituted by methyl,
ethyl, methoxycarbonyl or ethoxycarbonyl. [0423] R.sup.21
preferably represents hydroxyl, mercapto, amino, methoxy, ethoxy,
n- or i-propoxy, n-, s- or t-butoxy, methylthio, ethylthio, n- or
i-propylthio, n-, s- or t-butylthio, methylamino, ethylamino, n- or
i-propylamino, n-, s- or t-butylamino, dimethylamino or
diethylamino. [0424] R.sup.22 preferably represents hydroxyl,
mercapto, amino, methoxy, ethoxy, n- or i-propoxy, n-, s- or
t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, s- or
t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, s-
or t-butylamino, dimethylamino or diethylamino. [0425] R.sup.23
preferably represents methyl, ethyl, n- or i-propyl, each of which
is optionally substituted by fluorine, chlorine and/or bromine
[0426] R.sup.24 preferably represents hydrogen, or represents
methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, propenyl,
butenyl, propynyl or butynyl, methoxymethyl, ethoxymethyl,
methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furylmethyl,
thienyl, thiazolyl, piperidinyl, each of which is optionally
substituted by fluorine and/or chlorine, or represents phenyl which
is optionally substituted by fluorine, chlorine, methyl, ethyl, n-
or i-propyl, n-, s- or t-butyl. [0427] R.sup.25 preferably
represents hydrogen, or represents methyl, ethyl, n- or i-propyl,
n-, s- or t-butyl, propenyl, butenyl, propynyl or butynyl,
methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl,
dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl,
piperidinyl, each of which is optionally substituted by fluorine
and/or chlorine, or represents phenyl which is optionally
substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl,
n-, s- or t-butyl or together with R represents one of the radicals
--CH.sub.2--O--CH.sub.2--CH.sub.2-- and
--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2-- which are optionally
substituted by methyl, ethyl, furyl, phenyl, a fused benzene ring
or by two substituents which, together with the carbon atom to
which they are bonded, form a 5- or 6-membered carbocycle. [0428]
R.sup.26 preferably represents hydrogen, cyano, fluorine, chlorine,
bromine, or represents methyl, ethyl, n- or i-propyl, cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl or phenyl, each of which is
optionally substituted by fluorine, chlorine and/or bromine [0429]
R.sup.27 preferably represents hydrogen, or represents methyl,
ethyl, n- or i-propyl, n-, s- or t-butyl, optionally substituted by
hydroxyl, cyano, fluorine, chlorine, methoxy, ethoxy, n- or
i-propoxy. [0430] R.sup.28 preferably represents hydrogen, cyano,
fluorine, chlorine, bromine, or represents methyl, ethyl, n- or
i-propyl, n-, s- or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl or phenyl, each of which is optionally substituted by
fluorine, chlorine and/or bromine [0431] X.sup.1 preferably
represents nitro, cyano, fluorine, chlorine, bromine, methyl,
ethyl, n- or i-propyl, n-, s- or t-butyl, difluoromethyl,
dichloromethyl, trifluoromethyl, trichloromethyl,
chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or
i-propoxy, difluoromethoxy or trifluoromethoxy. [0432] X.sup.2
preferably represents hydrogen, nitro, cyano, fluorine, chlorine,
bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl,
difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl,
chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or
i-propoxy, difluoromethoxy or trifluoromethoxy. [0433] X.sup.3
preferably represents hydrogen, nitro, cyano, fluorine, chlorine,
bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl,
difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl,
chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or
i-propoxy, difluoromethoxy or trifluoromethoxy. [0434] R.sup.29
preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
[0435] R.sup.30 preferably represents hydrogen, methyl, ethyl, n-
or i-propyl. [0436] R.sup.31 preferably represents hydrogen, or
represents methyl, ethyl, n- or i-propyl, n-, s- or t-butyl,
methoxy, ethoxy, n- or i-propoxy, n-, s- or t-butoxy, methylthio,
ethylthio, n- or i-propylthio, n-, s- or t-butylthio, methylamino,
ethylamino, n- or i-propylamino, n-, s- or t-butylamino,
dimethylamino or diethylamino, each of which is optionally
substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or
i-propoxy, or represents cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio,
cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino
or cyclohexylamino, each of which is optionally substituted by
cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl.
[0437] R.sup.32 preferably represents hydrogen, or represents
methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, each of which is
optionally substituted by cyano, hydroxyl, fluorine, chlorine,
methoxy, ethoxy, n- or i-propoxy, or represents propenyl, butenyl,
propynyl or butynyl, each of which is optionally substituted by
cyano, fluorine, chlorine or bromine, or represents cyclopropyl,
cyclobutyl, cyclopentyl or cyclohexyl, each of which is optionally
substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl,
n- or i-propyl. [0438] R.sup.33 preferably represents hydrogen, or
represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, each
of which is optionally substituted by cyano, hydroxyl, fluorine,
chlorine, methoxy, ethoxy, n- or i-propoxy, or represents propenyl,
butenyl, propynyl or butynyl, each of which is optionally
substituted by cyano, fluorine, chlorine or bromine, or represents
cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which
is optionally substituted by cyano, fluorine, chlorine, bromine,
methyl, ethyl, n- or i-propyl, or represents phenyl which is
optionally substituted by nitro, cyano, fluorine, chlorine,
bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl,
trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy
or trifluoromethoxy, or together with R.sup.32 represents
butane-1,4-diyl(trimethylene), pentane-1,5-diyl,
1-oxabutane-1,4-diyl or 3-oxapentane-1,5-diyl, each of which is
optionally substituted by methyl or ethyl. [0439] X.sup.4
preferably represents nitro, cyano, carboxyl, carbamoyl, formyl,
sulphamoyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl,
ethyl, n- or i-propyl, n-, s- or t-butyl, trifluoromethyl, methoxy,
ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
[0440] X.sup.5 preferably represents nitro, cyano, carboxyl,
carbamoyl, formyl, sulphamoyl, hydroxyl, amino, fluorine, chlorine,
bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl,
trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy
or trifluoromethoxy.
[0441] Examples of the compounds of the formula (IIa) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table which follows.
TABLE-US-00004 TABLE Examples of the compounds of the formula (IIa)
(IIa) ##STR00125## Example (Positions) No. (X.sup.1).sub.n A.sup.1
R.sup.21 IIa-1 (2) Cl, (4) Cl ##STR00126## OCH.sub.3 IIa-2 (2) Cl,
(4) Cl ##STR00127## OCH.sub.3 IIa-3 (2) Cl, (4) Cl ##STR00128##
OC.sub.2H.sub.5 IIa-4 (2) Cl, (4) Cl ##STR00129## OC.sub.2H.sub.5
IIa-5 (2) Cl ##STR00130## OCH.sub.3 IIa-6 (2) Cl, (4) Cl
##STR00131## OCH.sub.3 IIa-7 (2) F ##STR00132## OCH.sub.3 IIa-8 (2)
F ##STR00133## OCH.sub.3 IIa-9 (2) Cl, (4) Cl ##STR00134##
OC.sub.2H.sub.5 IIa-10 (2) Cl, (4) CF.sub.3 ##STR00135## OCH.sub.3
IIa-11 (2) Cl ##STR00136## OCH.sub.3 IIa-12 -- ##STR00137##
OC.sub.2H.sub.5 IIa-13 (2) Cl, (4) Cl ##STR00138## OC.sub.2H.sub.5
IIa-14 (2) Cl, (4) Cl ##STR00139## OC.sub.2H.sub.5 IIa-15 (2) Cl,
(4) Cl ##STR00140## OC.sub.2H.sub.5 IIa-16 (2) Cl, (4) Cl
##STR00141## OC.sub.2H.sub.5 IIa-17 (2) Cl, (4) Cl ##STR00142##
OC.sub.2H.sub.5 IIa-18 -- ##STR00143## OH
[0442] Examples of the compounds of the formula (IIb) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table which follows.
##STR00144##
TABLE-US-00005 TABLE Examples of the compounds of the formula (IIb)
Example (Position) (Position) No. X.sup.2 X.sup.3 A.sup.2 R.sup.22
IIb-1 (5) Cl -- CH.sub.2 OH IIb-2 (5) Cl -- CH.sub.2 OCH.sub.3
IIb-3 (5) Cl -- CH.sub.2 OC.sub.2H.sub.3 IIb-4 (5) Cl -- CH.sub.2
OC.sub.3H.sub.7-n IIb-5 (5) Cl -- CH.sub.2 OC.sub.3H.sub.7-i IIb-6
(5) Cl -- CH.sub.2 OC.sub.4H.sub.9-n IIb-7 (5) Cl -- CH.sub.2
OCH(CH.sub.3)C.sub.5H.sub.11-n IIb-8 (5) Cl (2) F CH.sub.2 OH IIb-9
(5) Cl (2) Cl CH.sub.2 OH IIb-10 (5) Cl -- CH.sub.2
OCH.sub.2CH.dbd.CH.sub.2 IIb-11 (5) Cl -- CH.sub.2
OC.sub.4H.sub.9-i IIb-12 (5) Cl -- CH.sub.2 ##STR00145## IIb-13 (5)
Cl -- ##STR00146## OCH.sub.2CH.dbd.CH.sub.2 IIb-14 (5) Cl --
##STR00147## OC.sub.2H.sub.3 IIb-15 (5) Cl -- ##STR00148##
OCH.sub.3
[0443] Examples of the compounds of the formula (IIc) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table which follows.
##STR00149##
TABLE-US-00006 TABLE Examples of the compounds of the formula (IIc)
Example No. R.sup.23 N(R.sup.24,R.sup.25) IIc-1 CHCl.sub.2
N(CH.sub.2CH.dbd.CH.sub.2).sub.2 IIc-2 CHCl.sub.2 ##STR00150##
IIc-3 CHCl.sub.2 ##STR00151## IIc-4 CHCl.sub.2 ##STR00152## IIc-5
CHCl.sub.2 ##STR00153## IIc-6 CHCl.sub.2 ##STR00154## IIc-7
CHCl.sub.2 ##STR00155##
[0444] Examples of the compounds of the formula (Id) which are very
particularly preferred as herbicide safeners according to the
invention are listed in the table which follows.
##STR00156##
TABLE-US-00007 TABLE Examples of the compounds of the formula (IId)
Example (Positions) (Positions) No. R.sup.29 R.sup.30 R.sup.31
(X.sup.4).sub.n (X.sup.5).sub.n IId-1 H H CH.sub.3 (2) OCH.sub.3 --
IId-2 H H C.sub.2H.sub.5 (2) OCH.sub.3 -- IId-3 H H
C.sub.3H.sub.7-n (2) OCH.sub.3 -- IId-4 H H C.sub.3H.sub.7-i (2)
OCH.sub.3 -- IId-5 H H ##STR00157## (2) OCH.sub.3 -- IId-6 H H
CH.sub.3 (2) OCH.sub.3 -- (5) CH.sub.3 IId-7 H H C.sub.2H.sub.5 (2)
OCH.sub.3 -- (5) CH.sub.3 IId-8 H H C.sub.3H.sub.7-n (2) OCH.sub.3
-- (5) CH.sub.3 IId-9 H H C.sub.3H.sub.7-i (2) OCH.sub.3 -- (5)
CH.sub.3 IId-10 H H ##STR00158## (2) OCH.sub.3 (5) CH.sub.3 --
IId-11 H H OCH.sub.3 (2) OCH.sub.3 -- (5) CH.sub.3 IId- 12 H H
OC.sub.2H.sub.5 (2) OCH.sub.3 -- (5) CH.sub.3 IId-13 H H
OC.sub.3H.sub.7-i (2) OCH.sub.3 -- (5) CH.sub.3 IId-14 H H
SCH.sub.3 (2) OCH.sub.3 -- (5) CH.sub.3 IId-15 H H SC.sub.2H.sub.5
(2) OCH.sub.3 -- (5) CH.sub.3 IId- 16 H H SC.sub.3H.sub.7-i (2)
OCH.sub.3 -- (5) CH.sub.3 IId-17 H H NHCH.sub.3 (2) OCH.sub.3 --
(5) CH.sub.3 IId-18 H H NHC.sub.2H.sub.5 (2) OCH.sub.3 -- (5)
CH.sub.3 IId-19 H H NHC.sub.3H.sub.7-i (2) OCH.sub.3 -- (5)
CH.sub.3 IId-20 H H ##STR00159## (2) OCH.sub.3 (5) CH.sub.3 --
IId-21 H H NHCH.sub.3 (2) OCH.sub.3 -- IId-22 H H
NHC.sub.3H.sub.7-i (2) OCH.sub.3 -- IId-23 H H N(CH.sub.3).sub.2
(2) OCH.sub.3 -- IId-24 H H N(CH.sub.3).sub.2 (3) CH.sub.3 -- (4)
CH.sub.3 IId-25 H H CH.sub.2--O--CH.sub.3 (2) OCH.sub.3 --
[0445] Examples of the compounds of the formula (Ile) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table which follows.
##STR00160##
TABLE-US-00008 TABLE Examples of the compounds of the formula (IIe)
Example (Positions) (Positions) No. R.sup.29 R.sup.32 R.sup.33
(X.sup.4).sub.n (X.sup.5).sub.n IIe-1 H H CH.sub.3 (2) OCH.sub.3 --
IIe-2 H H C.sub.2H.sub.5 (2) OCH.sub.3 -- IIe-3 H H
C.sub.3H.sub.7-n (2) OCH.sub.3 -- IIe-4 H H C.sub.3H.sub.7-i (2)
OCH.sub.3 -- IIe-5 H H ##STR00161## (2) OCH.sub.3 -- IIe-6 H
CH.sub.3 CH.sub.3 (2) OCH.sub.3 -- IIe-7 H H CH.sub.3 (2) OCH.sub.3
-- (5) CH.sub.3 IIe-8 H H C.sub.2H.sub.5 (2) OCH.sub.3 -- (5)
CH.sub.3 IIe-9 H H C.sub.3H.sub.7-n (2) OCH.sub.3 -- (5) CH.sub.3
IIe-10 H H C.sub.3H.sub.7-i (2) OCH.sub.3 -- (5) CH.sub.3 IIe-11 H
H ##STR00162## (2) OCH.sub.3 (5) CH.sub.3 -- IIe-12 H CH.sub.3
CH.sub.3 (2) OCH.sub.3 -- (5) CH.sub.3
[0446] Cloquintocet-mexyl, fenchlorazol-ethyl, isoxadifen-ethyl,
mefenpyr-diethyl, furilazole, fenclorim, cumyluron, dymron,
dimepiperate and the compounds Ile-5 and Ile-11 are most preferred
as the compound which improves crop plant tolerance [component
(b')], with cloquintocet-mexyl and mefenpyr-diethyl being
especially preferred.
[0447] The compounds of the general formula (Ha) to be used in
accordance with the invention as safeners are known and/or can be
prepared by methods known per se (cf. WO-A-91/07874,
WO-A-95/07897).
[0448] The compounds of the general formula (IIb) to be used in
accordance with the invention as safeners are known and/or can be
prepared by methods known per se (cf. EP-A-191736).
[0449] The compounds of the general formula (IIc) to be used in
accordance with the invention as safeners are known and/or can be
prepared by methods known per se (cf. DE-A-2218097,
DE-A-2350547).
[0450] The compounds of the general formula (IId) to be used in
accordance with the invention as safeners are known and/or can be
prepared by methods known per se (cf. DE-A-19621522/U.S. Pat. No.
6,235,680).
[0451] The compounds of the general formula (IIe) to be used in
accordance with the invention as safeners are known and can be
prepared by methods known per se (cf. WO-A-99/66795/U.S. Pat. No.
6,251,827).
[0452] Examples of the selectively herbicidal combinations
according to the invention of in each case one active compound of
the formula (I) and in each case one of the above-defined safeners
are listed in the table which follows.
TABLE-US-00009 TABLE Examples of the combinations according to the
invention Active compounds of the formula (I) Safener I-1
cloquintocet-mexyl I-1 fenchlorazole-ethyl I-1 isoxadifen-ethyl I-1
mefenpyr-diethyl I-1 furilazole I-1 fenclorim I-1 cumyluron I-1
daimuron/dymron I-1 dimepiperate I-1 IIe-11 I-1 IIe-5 I-2
cloquintocet-mexyl I-2 fenchlorazole-ethyl I-2 isoxadifen-ethyl I-2
mefenpyr-diethyl I-2 furilazole I-2 fenclorim I-2 cumyluron I-2
daimuron/dymron I-2 dimepiperate I-2 IIe-11 I-2 IIe-5 I-3
cloquintocet-mexyl I-3 fenchlorazole-ethyl I-3 isoxadifen-ethyl I-3
mefenpyr-diethyl I-3 furilazole I-3 fenclorim I-3 cumyluron I-3
daimuron/dymron I-3 dimepiperate I-3 IIe-5 I-3 IIe-11 I-4
cloquintocet-mexyl I-4 fenchlorazole-ethyl I-4 isoxadifen-ethyl I-4
mefenpyr-diethyl I-4 furilazole I-4 fenclorim I-4 cumyluron I-4
daimuron/dymron I-4 dimepiperate I-4 IIe-11 I-4 IIe-5 I-5
cloquintocet-mexyl I-5 fenchlorazole-ethyl I-5 isoxadifen-ethyl I-5
mefenpyr-diethyl I-5 furilazole I-5 fenclorim I-5 cumyluron I-5
daimuron/dymron I-5 dimepiperate I-5 IIe-5 I-5 IIe-11 I-6
cloquintocet-mexyl I-6 fenchlorazole-ethyl I-6 isoxadifen-ethyl I-6
mefenpyr-diethyl I-6 furilazole I-6 fenclorim I-6 cumyluron I-6
daimuron/dymron I-6 dimepiperate I-6 IIe-5 I-6 IIe-11 I-7
cloquintocet-mexyl I-7 fenchlorazole-ethyl I-7 isoxadifen-ethyl I-7
mefenpyr-diethyl I-7 furilazole I-7 fenclorim I-7 cumyluron I-7
daimuron/dymron I-7 dimepiperate I-7 IIe-5 I-7 IIe-11 I-8
cloquintocet-mexyl I-8 fenchlorazole-ethyl I-8 isoxadifen-ethyl I-8
mefenpyr-diethyl I-8 furilazole I-8 fenclorim I-8 cumyluron I-8
daimuron/dymron I-8 dimepiperate I-8 IIe-5 I-8 IIe-11
[0453] Surprisingly, it has now been found that the above-defined
active compound combinations of N-heterocyclylphenyl-substituted
cyclic ketoenols of the general formula (I) and safeners
(antidotes) from the above group (b') are not only very well
tolerated by useful plants, but also have a particularly high
herbicidal activity and can be used in a variety of crops, in
particular in cereals (mainly wheat), but also in soybeans,
potatoes, maize and rice, for the selective control of weeds.
[0454] It must be considered as surprising that, from a
multiplicity of known safeners or antidotes which are capable of
antagonizing the damaging effect of a herbicide on the crop plants,
it is precisely the abovementioned compounds of group (b') which
are capable of virtually completely compensating for the harmful
effect of N-heterocyclylphenyl-substituted cyclic ketoenols on the
crop plants without adversely affecting the herbicidal activity
towards the weeds to a substantial degree.
[0455] What must be emphasized in this context is the particularly
advantageous activity of the particularly and most preferred
components from group (b'), in particular with regard to leaving
cereal plants, such as, for example, wheat, barley and rye, but
also maize and rice, as crop plants unharmed.
[0456] Using, for example, according to process (A) ethyl
N-[6-methyl-3-(N-4-chloropyrazolyl)-phenylacetyl]-1-aminocyclohexanecarbo-
xylate as starting material, the course of the process according to
the invention can be represented by the following equation:
##STR00163##
[0457] Using, for example, according to process (B) ethyl
O--[2-chloro-5-(N-4-chloropyrazolyl)-phenylacetyl]-2-hydroxyisobutyrate,
the course of the process according to the invention can be
represented by the following equation:
##STR00164##
[0458] Using, for example, according to process (C) ethyl
2-[6-methyl-3-(N-4-chloropyrazolyl)-phenyl]-4-(4-methoxy)benzylmercapto-4-
-methyl-3-oxovalerate, the course of the process according to the
invention can be represented by the following equation:
##STR00165##
[0459] Using, for example, according to process (D) chlorocarbonyl
2-[2,6-dimethyl-4-(N-4-chloropyrazolyl)phenyl]ketene and acetone as
starting materials, the course of the process according to the
invention can be represented by the following equation:
##STR00166##
[0460] Using, for example, according to process (E) chlorocarbonyl
2-[2,6-dimethyl-4-(N-4-chloropyrazolyl)phenyl]ketene and
thiobenzamide as starting materials, the course of the process
according to the invention can be represented by the following
equation:
##STR00167##
[0461] Using, for example, according to process (F) ethyl
5-[2,6-dimethyl-(N-4-chloropyrazolyl-phenyl)]-2,3-tetramethylene-4-oxoval-
erate, the course of the process according to the invention can be
represented by the following equation:
##STR00168##
[0462] Using, for example, according to process (G) ethyl
5-[2,6-dimethyl-4-(N-4-chloro-pyrazolyl)phenyl]-2,2-dimethyl-5-oxohexanoa-
te, the course of the process according to the invention can be
represented by the following equation:
##STR00169##
[0463] Using, for example, according to process (H.alpha.)
hexahydropyridazine and chlorocarbonyl
2-[2,6-dimethyl-4-(N-4-chloropyrazolyl)phenyl]ketene as starting
materials, the course of the reaction of the process according to
the invention can be represented by the following equation:
##STR00170##
[0464] Using, for example, according to process (H.beta.)
hexahydropyridazine and dimethyl
2,6-dimethyl-4-(N-4-chloropyrazolyl)phenylmalonate as starting
materials, the course of the process according to the invention can
be represented by the following equation:
##STR00171##
[0465] Using, for example, according to process (H.gamma.)
1-ethoxycarbonyl-2-[2,6-dimethyl-4-(N-4-chloropyrazolyl)phenylacetyl]hexa-
hydropyridazine as starting material, the course of the reaction
can be represented by the following equation:
##STR00172##
[0466] Using, for example, according to process (I.alpha.)
3-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-phenyl]-5,5-dimethylpyrrolidine-2-
,4-dione and pivaloyl chloride as starting materials, the course of
the process according to the invention can be represented by the
following equation:
##STR00173##
[0467] Using, for example, according to process (I) (variant
.beta.)
3-[2,6-dimethyl-4-(N-4-chloro-pyrazolyl)phenyl]-4-hydroxy-5-phenyl-.DELTA-
..sup.3-dihydrofuran-2-one and acetic anhydride as starting
materials, the course of the process according to the invention can
be represented by the following equation:
##STR00174##
[0468] Using, for example, according to process (J)
8-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-phenyl]-1,6-diazabicyclo-(4,3,0.s-
up.1,6)-nonane-7,9-dione and ethoxyethyl chloroformate as starting
materials, the course of the process according to the invention can
be represented by the following equation:
##STR00175##
[0469] Using, for example, according to process (K)
3-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-phenyl]-4-hydroxy-5-methyl-6-(3-p-
yridyl)pyrone and methyl chloromonothioformate as starting
materials, the course of the reaction can be represented by the
following equation:
##STR00176##
[0470] Using, for example, according to process (L)
2-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-phenyl]-5,5-pentamethylenepyrroli-
dine-2,4-dione and methanesulphonyl chloride as starting materials,
the course of the reaction can be represented by the following
equation:
##STR00177##
[0471] Using, for example, according to process (M)
2-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-phenyl]-4-hydroxy-5,5-dimethyl-.D-
ELTA..sup.3-dihydrofuran-2-one and 2,2,2-trifluoroethyl
methane-thiophosphonyl chloride as starting materials, the course
of the reaction can be represented by the following equation:
##STR00178##
[0472] Using, for example, according to process (N)
3-[2-chloro-5-(N-4-chloropyrazolyl)phenyl]-5-cyclopropyl-5-methylpyrrolid-
ine-2,4-dione and NaOH as components, the course of the process
according to the invention can be represented by the following
equation:
##STR00179##
[0473] Using, for example, according to process (O) (variant
.alpha.)
3-[6-methyl-3-(N-4-chloropyrazolyl)phenyl]-4-hydroxy-5-tetramethylene-.DE-
LTA..sup.3-dihydrofuran-2-one and ethyl iso-cyanate as starting
materials, the course of the reaction can be represented by the
following equation:
##STR00180##
[0474] Using, for example, according to process (O) (variant
.beta.)
3-[2-chloro-5-(N-4-chloro-pyrazolyl)phenyl]-5-methylpyrrolidine-2,4-dione
and dimethylcarbamoyl chloride as starting materials, the course of
the reaction can be represented by the following equation:
##STR00181##
[0475] Using, for example, according to process (P)
3-[(2,6-dimethyl-4-bromo)phenyl]-4,4-(penta-methylene)pyrrolidine-2,4-dio-
ne and 4-chloropyrazole as starting materials, the course of the
reaction can be represented by the following equation:
##STR00182##
[0476] The compounds, required as starting materials in the process
(a) according to the invention, of the formula (II)
##STR00183##
in which A, B, D, W, X, Y, Z and R.sup.8 are as defined above are
novel.
[0477] The acylamino acid esters of the formula (H) are obtained,
for example, when amino acid derivatives of the formula (XXIV)
##STR00184##
in which A, B, R.sup.8 and D are as defined above are acylated with
substituted phenylacetic acid derivatives of the formula (XXV)
##STR00185##
in which [0478] W, X, Y and Z are as defined above and [0479] T
represents a leaving group introduced by reagents that activate
carboxylic acids, such as carbonyldiimidazole, carbodiimides (such
as, for example, dicyclohexylcarbodiimide), phosphorylating
reagents (such as, for example, POCl.sub.3, BOP-Cl), halogenating
agents, for example thionyl chloride, oxalyl chloride, phosgene,
sulphonyl chlorides (for example toluenesulphonyl chloride) or
chloroformic esters, (Chem. Reviews 52, 237-416 (1953);
Bhattacharya, Indian J. Chem. 6, 341-5, 1968) or when acylamino
acids of the formula (XXVI)
##STR00186##
[0479] in which A, B, D, W, X, Y and Z are as defined above are
esterified (Chem. Ind. (London) 1568 (1968)). The compounds of the
formula (XXVI)
##STR00187##
in which A, B, D, W, X, Y and Z are as defined above are novel.
[0480] The compounds of the formula (XXVI) are obtained when amino
acids of the formula (XXVII)
##STR00188##
in which A, B and D are as defined above are acylated with
substituted phenylacetic acid derivatives of the formula (XXV)
##STR00189##
in which W, X, Y and Z are as defined above and T is as defined
above, for example according to Schotten-Baumann (Organikum, VEB
Deutscher Verlag der Wissenschaften, Berlin 1977, p. 505).
[0481] The compounds of the formula (XXV) are novel. They can be
prepared by processes known in principle and as shown in the
Preparation Examples (see, for example, H. Henecka, Houben-Weyl,
Methoden der Organischen Chemie [Methods of Organic Chemistry],
Vol. 8, pp. 467-469 (1952)).
[0482] The compounds of the formula (XXV) are obtained, for
example, by reacting substituted phenylacetic acids of the formula
(XXVIII)
##STR00190##
in which W, X, Y and Z are as defined above with halogenating
agents (for example thionyl chloride, thionyl bromide, oxalyl
chloride, phosgene, phosphorus trichloride, phosphorus tribromide
or phosphorus pentachloride), phosphorylating reagents (such as,
for example, POCl.sub.3, BOP-Cl), carbonyldiimidazole,
carbodiimides (for example dicyclohexylcarbodiimide), if
appropriate in the presence of a diluent (for example, optionally
chlorinated aliphatic or aromatic hydrocarbons, such as toluene or
methylene chloride, or ethers, for example tetrahydrofuran,
dioxane, methyl tert-butyl ether), at temperatures of from
-20.degree. C. to 150.degree. C., preferably from -10.degree. C. to
100.degree. C.
[0483] Some of the compounds of the formulae (XXIV) and (XXVII) are
known and/or can be prepared by known processes (see, for example,
Compagnon, Miocque Ann. Chim (Paris) [14] 5, p. 11-22, 23-27
(1970)).
[0484] The substituted cyclic aminocarboxylic acids of the formula
(XXVII) in which A and B form a ring are generally obtained by
means of a Bucherer-Bergs synthesis or a Strecker synthesis, where
they are obtained in each case in different isomeric forms. Thus,
the conditions of the Bucherer-Bergs synthesis give predominantly
the isomers (for simplicity reasons referred to as B hereinbelow)
in which the radicals R and the carboxyl group are in equatorial
positions, while the conditions of the Strecker synthesis give
predominantly the isomers (for simplicity reasons referred to as a
hereinbelow) where the amino group and the radical R are in
equatorial positions.
##STR00191##
[0485] (L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C.
Jitrangeri, Can. J. Chem. 53, 3339 (1975).
[0486] Furthermore, the starting materials, used in process (A)
above, of the formula (II)
##STR00192##
in which A, B, D, W, X, Y, Z and R.sup.8 are as defined above can
be prepared by reacting aminonitriles of the formula (XXIX)
##STR00193##
in which A, B and D are as defined above with substituted
phenylacetic acid derivatives of the formula (XXV)
##STR00194##
in which T, W, X, Y and Z are as defined above to give compounds of
the formula (XXX)
##STR00195##
in which A, B, D, W, X, Y and Z are as defined above which are then
subjected to an acidic alcoholysis.
[0487] The compounds of the formula (XXX) are also novel.
[0488] The compounds, required as starting materials for the
process (B) according to the invention, of the formula (III)
##STR00196##
in which A, B, W, X, Y, Z and R.sup.8 are as defined above are
novel.
[0489] They can be prepared by methods known in principle.
[0490] Thus, the compounds of the formula (III) are obtained, for
example, when
[0491] 2-hydroxycarboxylic esters of the formula (XXXI-A)
##STR00197##
in which A, B and R.sup.8 are as defined above are acylated with
substituted phenylacetic acid derivatives of the formula (XXV)
##STR00198##
in which T, W, X, Y and Z are as defined above (Chem. Reviews 52,
237-416 (1953)).
[0492] Furthermore, compounds of the formula (III) are obtained
when substituted phenylacetic acids of the formula (XXVIII)
##STR00199##
in which W, X, Y and Z are as defined above are alkylated with
.alpha.-halocarboxylic esters of the formula (XXXI-B)
##STR00200##
in which A, B and R.sup.8 are as defined above and Hal represents
chlorine or bromine
[0493] The compounds of the formula (XXVIII) are novel.
[0494] The compounds of the formula (XXXI-B) are commercially
available.
[0495] The compounds of the formula (XXVIII)
##STR00201##
in which W, X, Y and Z are as defined above are obtained, for
example, when phenylacetic esters of the formula (XXXII)
##STR00202##
in which W, X, Y, Z and R.sup.8 are as defined above are hydrolyzed
in the presence of acids or bases in the presence of a solvent
under generally known standard conditions.
[0496] The compounds of the formula (XXXII) are novel.
[0497] The compounds of the formula (XXXII)
##STR00203##
in which W, X, Y, Z and R.sup.8 are as defined above are obtained,
for example, by the process (Q) described in the examples when
phenylacetic esters of the formula (XXXII-a)
##STR00204##
in which R.sup.8, W, X and Y are as defined above and Z' represents
halogen (in particular bromine) are reacted in the presence of an
HN-containing heterocycle of the formula (XXIII) in which Z is as
defined above in the presence of a base and, if appropriate, in the
presence of a catalyst (preferably copper salts, such as, for
example, copper(I) iodide) (S. Buchwald et. al. JACS 123, 7727,
2001).
[0498] Some of the phenylacetic esters of the formula (XXXII-a) are
known from the applications WO 96/35 664 and WO 97/02 243, or they
can be prepared by the processes described therein.
[0499] The compounds, required as starting materials in the above
process (C), of the formula (IV)
##STR00205##
in which A, B, V, W, X, Y, Z and R.sup.8 are as defined above are
novel.
[0500] They can be prepared by methods known in principle.
The compounds of the formula (IV) are obtained, for example, when
substituted phenylacetic esters of the formula (XXXII)
##STR00206##
in which W, X, Y, Z and R.sup.8 are as defined above are acylated
with 2-benzylthiocarbonyl halides of the formula (XXXIII)
##STR00207##
in which A, B and V are as defined above and Hal represents halogen
(in particular chlorine or bromine) in the presence of strong bases
(see, for example, M. S. Chambers, E. J. Thomas, D. J. Williams, J.
Chem. Soc. Chem. Commun, (1987), 1228).
[0501] Some of the benzylthiocarbonyl halides of the formula
(XXXIII) are known, and/or they can be prepared by known processes
(J. Antibiotics (1983), 26, 1589).
[0502] The halocarbonyl ketenes of the formula (VI) required as
starting materials for the above processes (D), (E) and (H-.alpha.)
are novel. They can be prepared in a simple manner by methods known
in principle (cf., for example, Org. Prep. Proced. Int., 7, (4),
155-158, 1975 and DE 1 945 703). Thus, for example, the compounds
of the formula (VI)
##STR00208##
in which W, X, Y and Z are as defined above and Hal represents
chlorine or bromine are obtained when substituted phenylmalonic
acids of the formula (XXXIV)
##STR00209##
in which W, X, Y and Z are as defined above are reacted with acid
halides, such as, for example, thionyl chloride, phosphorus(V)
chloride, phosphorus(III) chloride, oxalyl chloride, phosgene or
thionyl bromide, if appropriate in the presence of catalysts, such
as, for example, diethylformamide, methyl-steryl formamide or
triphenylphosphine and, if appropriate, in the presence of bases,
such as, for example, pyridine or triethylamine.
[0503] The substituted phenylmalonic acids of the formula (XXXIV)
are novel. They can be prepared in a simple manner by known
processes (cf., for example, Organikum, VEB Deutscher Verlag der
Wissenschaften, Berlin 1977, p. 517 ff, EP-A-528 156, WO 96/35 664,
WO 97/02 243, WO 97/01535, WO 97/36868 and WO 98/05638).
[0504] Thus, phenylmalonic acids of the formula (XXXIV)
##STR00210##
in which W, X, Y and Z are as defined above are obtained when
phenylmalonic acid derivatives of the formula (XI) where
U.dbd.OR.sup.8
##STR00211##
in which U, W, X, Y and Z are as defined above are initially
hydrolyzed in the presence of a base and a solvent and then
carefully acidified (EP-A-528 156, WO 96/35 664, WO 97/02 243).
[0505] The malonic esters of the formula (X.sup.1) where
U.dbd.OR.sup.8
##STR00212##
in which U, W, X, Y and Z are as defined above are novel.
[0506] They can be prepared by generally known methods of organic
chemistry (cf., for example, Tetrahedron Lett. 27, 2763 (1986),
Organikum VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p.
587 ff., WO 96/35664, WO 97/02243, WO 97/01535, WO 97/36868, WO
98/05638 and WO 99/47525).
[0507] The carbonyl compounds, required as starting materials for
the process (D) according to the invention, of the formula (V)
##STR00213##
in which A and D are as defined above or their silyl enol ethers of
the formula (Va)
##STR00214##
in which A, D and R.sup.8 are as defined above are compounds which
are commercially available, generally known or obtainable by known
processes.
[0508] The preparation of the ketene acid chlorides of the formula
(VI) required as starting materials for carrying out the process
(E) according to the invention has already been described above.
The thioamides, required for carrying out the process (E) according
to the invention, of the formula (VII)
##STR00215##
in which A is as defined above are compounds which are generally
known in organic chemistry.
[0509] The compounds, required as starting materials for the above
process (F), of the formula (VIII)
##STR00216##
in which A, B, Q.sup.1, Q.sup.2, W, X, Y, Z and R.sup.8 are as
defined above are novel.
[0510] They can be prepared by methods known in principle.
[0511] The 5-aryl-4-ketocarboxylic esters of the formula (VIII) are
obtained, for example, when 5-aryl-4-ketocarboxylic acids of the
formula (XXXV)
##STR00217##
in which W, X, Y, Z, A, B, Q.sup.1 and Q.sup.2 are as defined above
are esterified (cf., for example, Organikum, 15th Edition, Berlin,
1977, page 499) or alkylated (see Preparation Example).
[0512] The 5-aryl-4-ketocarboxylic acids of the formula (XXXV)
##STR00218##
in which A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are as defined above
are novel, but can be prepared by methods known in principle (WO
96/01 798, WO 97/14667, WO 98/39281).
[0513] The 5-aryl-4-ketocarboxylic acids of the formula (XXXV) are
obtained, for example, when 2-phenyl-3-oxoadipic esters of the
formula (XXXVI)
##STR00219##
in which A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are as defined above
and R.sup.8 and R.sup.8' represent alkyl (in particular
C.sub.1-C.sub.8-alkyl) and when the compound of the formula
(XXXVIR) is used, R.sup.8 represents hydrogen, are decarboxylated,
if appropriate in the presence of a diluent and if appropriate in
the presence of a base or an acid (cf., for example, Organikum,
15th Edition, Berlin, 1977, pages 519 to 521).
[0514] The compounds of the formula (XXXVI)
##STR00220##
in which A, B, Q.sup.1, Q.sup.2, W, X, Y, Z, R.sup.8, R.sup.8' are
as defined above and in which if the compound of the formula
(XXXVIR) is used, R.sup.8 also represents hydrogen, are novel.
[0515] The compounds of the formula (XXXVI) are obtained, for
example,
when dicarboxylic semiester chlorides of the formula (XXXVII),
##STR00221##
in which A, B, Q.sup.1, Q.sup.2 and R.sup.8 are as defined above
and Hal represents chlorine or bromine or carboxylic anhydrides of
the formula (XXXVIII)
##STR00222##
in which A, B, Q.sup.1 and Q.sup.2 are as defined above are
acylated with a phenylacetic ester of the formula (XXXII)
##STR00223##
in which W, X, Y, Z and R.sup.8' are as defined above in the
presence of a diluent and in the presence of a base (cf., for
example, M. S. Chambers, E. J. Thomas, D. J. Williams, J. Chem.
Soc. Chem. Commun, (1987), 1228, cf. also the Preparation
Examples).
[0516] Some of the compounds of the formulae (XXXVII) and (XXXVIII)
are known compounds of organic chemistry, and/or they can be
prepared in a simple manner by methods known in principle.
[0517] The compounds, required as starting materials for the above
process (G), of the formula (IX)
##STR00224##
in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y, Z and
R.sup.8 are as defined above are novel.
[0518] They can be prepared by methods known in principle.
[0519] The 6-aryl-5-ketocarboxylic esters of the formula (IX) are
obtained, for example, when 6-aryl-5-ketocarboxylic acids of the
formula (XXXIX)
##STR00225##
in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z
are as defined above are esterified (cf., for example, Organikum,
15th Edition, Berlin, 1977, page 499).
[0520] The 6-aryl-5-ketocarboxylic acids of the formula (XXXIX)
##STR00226##
in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z
are as defined above are novel. They can be prepared by methods
known in principle (WO 99/43649, WO 99/48869), for example by
hydrolyzing and decarboxylating substituted
2-phenyl-3-oxoheptanedioic esters of the formula (XL)
##STR00227##
in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z
are as defined above and R.sup.8 and R.sup.8' represent alkyl
(preferably C.sub.1-C.sub.6-alkyl) and, if the compound of the
formula (XLII) is used, R.sup.8 represents hydrogen, if appropriate
in the presence of a diluent and if appropriate in the presence of
a base or an acid (cf., for example, Organikum, 15th Edition,
Berlin, 1977, pages 519 to 521).
[0521] The compounds of the formula (XL)
##STR00228##
in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y, Z,
R.sup.8 and R.sup.8' are as defined above are novel and can be
obtained by condensing dicarboxylic esters of the formula
(XLI),
##STR00229##
in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6 and R.sup.8 are
as defined above or carboxylic anhydrides of the formula (XLII)
##STR00230##
in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6 are as defined
above with a substituted phenylacetic ester of the formula
(XXXII)
##STR00231##
in which W, X, Y, Z and R.sup.8 are as defined above in the
presence of a diluent and in the presence of a base.
[0522] Some of the compounds of the formulae (XLI) and (XLII) are
known, and/or they can be prepared by known processes.
[0523] Some of the hydrazines, required as starting materials for
the processes (H-.alpha.) and (H-.beta.) according to the
invention, of the formula (X)
A-NH--NH-D (X)
in which A and D are as defined above are known, and/or they can be
prepared by methods known from literature (cf., for example,
Liebigs Ann. Chem. 585, 6 (1954); Reaktionen der organischen
Synthese [Reaction of organic synthesis], C. Ferri, pages 212, 513;
Georg Thieme Verlag Stuttgart, 1978; Liebigs Ann. Chem. 443, 242
(1925); Chem. Ber. 98, 2551 (1965), EP-A-508 126, WO 92/16510, WO
99/47 525, WO 01/17 972).
[0524] The compounds, required for the process (H-.gamma.)
according to the invention, of the formula (XII)
##STR00232##
in which A, D, W, X, Y, Z and R.sup.8 are as defined above are
novel.
[0525] The acylcarbazates of the formula (XII) are obtained, for
example, when carbazates of the formula (XLIII)
##STR00233##
in which A, R.sup.8 and D are as defined above are acylated with
substituted phenylacetic acid derivatives of the formula (XXV)
##STR00234##
in which T, W, X, Y and Z are as defined above (Chem. Reviews 52,
237-416 (1953); Bhattacharya, Indian J. Chem. 6, 341-5, 1968).
[0526] Some of the carbazates of the formula (XLIII) are
commercially available and some are known compounds, or they can be
prepared by processes of organic chemistry known in principle.
[0527] Some of the compounds, required as starting materials for
the above process (P), of the formulae (I-1') to (I-8') in which A,
B, D, G, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X
and Y are as defined above and Z' represents chlorine or bromine,
preferably bromine, are known from the patent applications cited at
the outset (for example WO 96/35 664, WO 97/02 243), or they can be
prepared by the processes described therein.
[0528] Some of the compounds of the formula (XXIII)
H-Z (XXIII)
in which Z is as defined above are commercially available, or they
can be prepared by general processes known in principle.
[0529] The acid halides of the formula (XIII), carboxylic
anhydrides of the formula (XIV), chloroformic esters or
chloroformic thioesters of the formula (XV), chloromonothioformic
esters or chlorodithioformic esters of the formula (XVI), sulphonyl
chlorides of the formula (XVII), phosphorus compounds of the
formula (XVIII) and metal hydroxides, metal alkoxides or amines of
the formulae (XIX) and (XX) and isocyanates of the formula (XXI)
and carbamoyl chlorides of the formula (XXII) furthermore required
as starting materials for carrying out the processes (I), (J), (K),
(L), (M), (N) and (O) according to the invention are generally
known compounds of organic or inorganic chemistry.
[0530] In addition, the compounds of the formulae (V), (VII),
(XIII) to (XXII), (XXIV), (XXVII), (XXIX), (XXXI-A), (XXXI-B),
(XXXIII), (XXXVII), (XXXVIII), (XLI) and (XLII) are known from the
patent applications cited at the outset, and/or they can be
prepared by the methods given therein.
[0531] The process (A) is characterized in that compounds of the
formula (II) in which A, B, D, W, X, Y, Z and R.sup.8 are as
defined above are, in the presence of a base, subjected to an
intramolecular condensation.
[0532] Suitable diluents for the process (A) according to the
invention are all inert organic solvents. Preference is given to
using 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,
dimethylacetamide and N-methylpyrrolidone, and also alcohols, such
as methanol, ethanol, propanol, isopropanol, butanol, isobutanol
and tert-butanol.
[0533] Suitable bases (deprotonating agents) for carrying out the
process (A) according to the invention are all customary proton
acceptors. Preference is given to using alkali metal and alkaline
earth metal oxides, hydroxides and carbonates, such as sodium
hydroxide, potassium hydroxide, magnesium oxide, calcium oxide,
sodium carbonate, potassium carbonate and calcium carbonate, which
can also be used 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). It is furthermore possible to use
alkali metals such as sodium or potassium. Also suitable are alkali
metal and alkaline earth metal amides and hydrides, such as sodium
amide, sodium hydride and calcium hydride, and additionally also
alkali metal alkoxides, such as sodium methoxide, sodium ethoxide
and potassium tert-butoxide.
[0534] When carrying out the process (A) according to the
invention, the reaction temperatures can be varied within a
relatively large 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.
[0535] The process (A) according to the invention is generally
carried out under atmospheric pressure.
[0536] When carrying out the process (A) according to the
invention, the reaction components of the formula (II) and the
deprotonating bases are generally employed in approximately doubly
equimolar amounts. However, it is also possible to use a relatively
large excess (up to 3 mol) of one component or the other.
[0537] The process (B) is characterized in that compounds of the
formula (III) in which A, B, W, X, Y, Z and R.sup.8 are as defined
above are, in the presence of a diluent and in the presence of a
base, subjected to an intramolecular condensation.
[0538] Suitable diluents for the process (B) according to the
invention are all inert organic solvents. Preference is given to
using 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-methylpyrrolidone. It is furthermore possible to use alcohols,
such as methanol, ethanol, propanol, isopropanol, butanol,
isobutanol and tert-butanol.
[0539] Suitable bases (deprotonating agents) for carrying out the
process (B) according to the invention are all customary proton
acceptors. Preference is given to using alkali metal and alkaline
earth metal oxides, hydroxides and carbonates, such as sodium
hydroxide, potassium hydroxide, magnesium oxide, calcium oxide,
sodium carbonate, potassium carbonate and calcium carbonate, which
can also be used 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) It is furthermore possible to use
alkali metals, such as sodium or potassium. Also suitable are
alkali metal and alkaline earth metal amides and hydrides, such as
sodium amide, sodium hydride and calcium hydride, and additionally
also alkali metal alkoxides, such as sodium methoxide, sodium
ethoxide and potassium tert-butoxide.
[0540] When carrying out the process (B) according to the
invention, the reaction temperatures can be varied within a
relatively wide 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.
[0541] The process (B) according to the invention is generally
carried out under atmospheric pressure.
[0542] When carrying out the process (B) according to the
invention, the reaction components of the formula (III) and the
deprotonating bases are generally employed in approximately
equimolar amounts. However, it is also possible to use a relatively
large excess (up to 3 mol) of one component or the other.
[0543] The process (C) is characterized in that compounds of the
formula (IV) in which A, B, V, W, X, Y, Z and R.sup.8 are as
defined above are, in the presence of an acid and, if appropriate,
in the presence of a diluent, subjected to intramolecular
cyclization.
[0544] Suitable diluents for the process (C) according to the
invention are all inert organic solvents. Preference is given to
using 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-methylpyrrolidone. It is furthermore
possible to use alcohols, such as methanol, ethanol, propanol,
isopropanol, butanol, isobutanol, tert-butanol.
[0545] If appropriate, the acid used can also serve as diluent.
[0546] Suitable acids for the 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, in particular halogenated alkylcarboxylic
acids, such as, for example, trifluoroacetic acid.
[0547] When carrying out the process (C) according to the
invention, the reaction temperatures can be varied within a
relatively wide 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.
[0548] The process (C) according to the invention is generally
carried out under atmospheric pressure.
[0549] When carrying out the process (C) according to the
invention, the reaction components of the formula (IV) and the
acids are employed, for example, in equimolar amounts. However, it
is, if appropriate, also possible to use the acid as solvent or as
catalyst.
[0550] The process (D) according to the invention is characterized
in that carbonyl compounds of the formula (V) or enol ethers
thereof of the formula (V-a) are reacted with ketene acid halides
of the formula (VI) in the presence of a diluent and, if
appropriate, in the presence of an acid acceptor.
[0551] Suitable diluents for the process (D) according to the
invention are all inert organic solvents. Preference is given to
using optionally halogenated hydrocarbons, such as toluene, xylene,
mesitylene, chlorobenzene and dichlorobenzene, furthermore ethers,
such as dibutyl ether, glycol dimethyl ether, diglycol dimethyl
ether and diphenyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide or
N-methylpyrrolidone.
[0552] Suitable acid acceptors for carrying out the process variant
(D) according to the invention are all customary acid
acceptors.
[0553] Preference is given to using tertiary amines, such as
triethylamine, pyridine, diaza-bicyclooctane (DABCO),
diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethylaniline.
[0554] When carrying out the process variant (D) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. The process variant is expediently carried
out at temperatures between 0.degree. C. and 250.degree. C.,
preferably between 50.degree. C. and 220.degree. C.
[0555] The process (D) according to the invention is expediently
carried out under atmospheric pressure.
[0556] When carrying out the process (D) according to the
invention, the reaction components of the formulae (V) and (VI) in
which A, D, W, X, Y and Z are as defined above and Hal represents
halogen and, if appropriate, the acid acceptors are generally
employed in approximately equimolar amounts. However, it is also
possible to use a relatively large excess (up to 5 mol) of one
component or the other.
[0557] The process (E) according to the invention is characterized
in that thioamides of the formula (VII) are reacted with ketene
acid halides of the formula (VI) in the presence of a diluent and,
if appropriate, in the presence of an acid acceptor.
[0558] Suitable diluents for the process variant (E) according to
the invention are all inert organic solvents. Preference is given
to using hydrocarbons, such as 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 and
N-methylpyrrolidone.
[0559] Suitable acid acceptors for carrying out the process (E)
according to the invention are all customary acid acceptors.
[0560] Preference is given to using tertiary amines, such as
triethylamine, pyridine, diazabicyclo-octane (DABCO),
diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethylaniline.
[0561] When carrying out the process (E) according to the
invention, the reaction temperatures can be varied within a
relatively wide 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.
[0562] The process (E) according to the invention is expediently
carried out under atmospheric pressure.
[0563] When carrying out the process (E) according to the
invention, the reaction components of the formulae (VII) and (VI)
in which A, W, X, Y and Z are as defined above and Hal represents
halogen and, if appropriate, the acid acceptors are generally
employed in approximately equimolar amounts. However, it is also
possible to use a relatively large excess (up to 5 mol) of one
component or the other.
[0564] The process (F) is characterized in that compounds of the
formula (VIII) in which A, B, Q.sup.1, Q.sup.2, W, X, Y, Z and
R.sup.8 are as defined above are, in the presence of a base,
subjected to an intramolecular condensation.
[0565] Suitable diluents for the process (F) according to the
invention are all organic solvents which are inert towards the
reactants. Preference is given to using 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-methylpyrrolidone.
It is furthermore possible to use alcohols, such as methanol,
ethanol, propanol, isopropanol, butanol, isobutanol,
tert-butanol.
[0566] Suitable bases (deprotonating agents) for carrying out the
process (F) according to the invention are all customary proton
acceptors. Preference is given to using alkali metal and alkaline
earth metal oxides, hydroxides and carbonates, such as sodium
hydroxide, potassium hydroxide, magnesium oxide, calcium oxide,
sodium carbonate, potassium carbonate and calcium carbonate, which
can also be used 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) It is furthermore possible to use
alkali metals, such as sodium or potassium. Also suitable are
alkali metal and alkaline earth metal amides and hydrides, such as
sodium amide, sodium hydride and calcium hydride, and additionally
also alkali metal alkoxides, such as sodium methoxide, sodium
ethoxide and potassium tert-butoxide.
[0567] When carrying out the process (F) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between -75.degree. C. and 250.degree. C., preferably
between -50.degree. C. and 150.degree. C.
[0568] The process (F) according to the invention is generally
carried out under atmospheric pressure.
[0569] When carrying out the process (F) according to the
invention, the reaction components of the formula (VIII) and the
deprotonating bases are generally employed in approximately
equimolar amounts. However, it is also possible to use a relatively
large excess (up to 3 mol) of one component or the other.
[0570] The process (G) is characterized in that compounds of the
formula (IX) in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W,
X, Y, Z and R.sup.8 are as defined above are, in the presence of
bases, subjected to an intramolecular condensation.
[0571] Suitable diluents for the process (G) according to the
invention are all organic solvents which are inert towards the
reactants. Preference is given to using 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-methylpyrrolidone.
It is furthermore possible to use alcohols, such as methanol,
ethanol, propanol, isopropanol, butanol, isobutanol,
tert-butanol.
[0572] Suitable bases (deprotonating agents) for carrying out the
process (G) according to the invention are all customary proton
acceptors.
[0573] Preference is given to using alkali metal and alkaline earth
metal oxides, hydroxides and carbonates, such as sodium hydroxide,
potassium hydroxide, magnesium oxide, calcium oxide, sodium
carbonate, potassium carbonate and calcium carbonate, which can
also be used 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). It is
furthermore possible to use alkali metals, such as sodium or
potassium. Also suitable are alkali metal and alkaline earth metal
amides and hydrides, such as sodium amide, sodium hydride and
calcium hydride, and additionally also alkali metal alkoxides, such
as sodium methoxide, sodium ethoxide and potassium
tert-butoxide.
[0574] When carrying out the process (G) according to the
invention, the reaction temperatures can be varied within a
relatively wide 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.
[0575] The process (G) according to the invention is generally
carried out under atmospheric pressure.
[0576] When carrying out the process (G) according to the
invention, the reaction components of the formula (IX) and the
deprotonating bases are generally employed in approximately
equi-molar amounts. However, it is also possible to use a
relatively large excess (up to 3 mol) of one component or the
other.
[0577] The process (H-.alpha.) according to the invention is
characterized in that hydrazines of the formula (X) or salts of
these compounds are reacted with ketene acid halides of the formula
(VI) in the presence of a diluent and, if appropriate, in the
presence of an acid acceptor.
[0578] Suitable diluents for the process (H-.alpha.) according to
the invention are all inert organic solvents. Preference is given
to using optionally chlorinated hydrocarbons, such as, for example,
mesitylene, chlorobenzene and dichlorobenzene, toluene, xylene,
furthermore ethers, such as dibutyl ether, glycol dimethyl ether,
diglycol dimethyl ether and diphenyl ether, moreover polar
solvents, such as dimethyl sulphoxide, sulpholane,
dimethylformamide or N-methylpyrrolidone.
[0579] Suitable acid acceptors for carrying out the process variant
(H-.alpha.) according to the invention are all customary acid
acceptors.
[0580] Preference is given to using tertiary amines, such as
triethylamine, pyridine, diazabicyclo-octane (DABCO),
diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethylaniline.
[0581] When carrying out the process variant (H-.alpha.) according
to the invention, the reaction temperatures can be varied within a
relatively wide range. The process variant is expediently carried
out at temperatures between 0.degree. C. and 250.degree. C.,
preferably between 50.degree. C. and 220.degree. C.
[0582] The process (H-.alpha.) according to the invention is
expediently carried out under atmospheric pressure.
[0583] When carrying out the process (H-.alpha.) according to the
invention, the reaction components of the formulae (VI) and (X) in
which A, D, W, X, Y and Z are as defined above and Hal represents
halogen and, if appropriate, the acid acceptors are generally
employed in approximately equimolar amounts. However, it is also
possible to use a relatively large excess (up to 5 mol) of one
component or the other.
[0584] The process (H-.beta.) is characterized in that hydrazines
of the formula (X) or salts of this compound in which A and D are
as defined above are, in the presence of a base, subjected to a
condensation with malonic esters or malonamides of the formula (XI)
in which U, W, X, Y, Z and R.sup.8 are as defined above.
[0585] Suitable diluents for the process (H-.beta.) according to
the invention are all inert organic solvents. Preference is given
to using optionally halogenated hydrocarbons, such as toluene,
xylene, mesitylene, chlorobenzene and dichlorobenzene, furthermore
ethers, such as dibutyl ether, tetrahydrofuran, dioxane, diphenyl
ether, glycol dimethyl ether and diglycol dimethyl ether, moreover
polar solvents, such as dimethyl sulphoxide, sulpholane,
dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and
also alcohols, such as methanol, ethanol, propanol, isopropanol,
butanol, isobutanol and tert-butanol.
[0586] Suitable bases (deprotonating agents) for carrying out the
process (H-.beta.) according to the invention are all customary
proton acceptors. Preference is given to using alkali metal and
alkaline earth metal oxides, hydroxides and carbonates, such as
sodium hydroxide, potassium hydroxide, magnesium oxide, calcium
oxide, sodium carbonate, potassium carbonate and calcium carbonate,
and which can also be used in the presence of phase transfer
catalysts, such as, for example, triethylbenzylammonium chloride,
tetrabutyl-ammonium bromide, Adogen 464
(=methyltrialkyl(C.sub.8-C.sub.10)ammonium chloride) or TDA 1
(=tris(methoxyethoxyethyl)amine). It is furthermore possible to use
alkali metals, such as sodium or potassium. Also suitable are
alkali metal and alkaline earth metal amides and hydrides, such as
sodium amide, sodium hydride and calcium hydride, and additionally
also alkali metal alkoxides, such as sodium methoxide, sodium
ethoxide and potassium tert-butoxide.
[0587] It is also possible to use tertiary amines, such as
triethylamine, pyridine, diazabicyclooctane (DABCO),
diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethylaniline.
[0588] When carrying out the process (H-.beta.) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between 0.degree. C. and 280.degree. C., preferably
between 50.degree. C. and 180.degree. C.
[0589] The process (H-.beta.) according to the invention is
generally carried out under atmospheric pressure.
[0590] When carrying out the process (H-.beta.) according to the
invention, the reaction components of the formulae (XI) and (X) are
generally employed in approximately equimolar amounts. However, it
is also possible to use a relatively large excess (up to 3 mol) of
one component or the other.
[0591] The process (H-.gamma.) is characterized in that compounds
of the formula (XII) in which A, D, W, X, Y, Z and R.sup.8 are as
defined above are, in the presence of a base, subjected to an
intramolecular condensation.
[0592] Suitable diluents for the process (H-.gamma.) according to
the invention are all inert organic solvents. Preference is given
to using 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-methylpyrrolidone, and also alcohols, such
as methanol, ethanol, propanol, isopropanol, butanol, isobutanol
and tert-butanol.
[0593] Suitable bases (deprotonating agents) for carrying out the
process (H-.gamma.) according to the invention are all customary
proton acceptors. Preference is given to using alkali metal and
alkaline earth metal oxides, hydroxides and carbonates, such as
sodium hydroxide, potassium hydroxide, magnesium oxide, calcium
oxide, sodium carbonate, potassium carbonate and calcium carbonate,
and which can also be used 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) It is furthermore possible to use
alkali metals, such as sodium or potassium. Also suitable are
alkali metal and alkaline earth metal amides and hydrides, such as
sodium amide, sodium hydride and calcium hydride, and additionally
also alkali metal alkoxides, such as sodium methoxide, sodium
ethoxide and potassium tert-butoxide.
[0594] When carrying out the process (H-.gamma.) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between -20.degree. C. and 250.degree. C., preferably
between 50.degree. C. and 150.degree. C.
[0595] The process (H-.gamma.) according to the invention is
generally carried out under atmospheric pressure.
[0596] When carrying out the process (H-.gamma.) according to the
invention, the reaction components of the formula (XII) and the
deprotonating bases are generally employed in approximately doubly
equimolar amounts. However, it is also possible to use a relatively
large excess (up to 3 mol) of one component or the other.
[0597] The process (I-.alpha.) is characterized in that compounds
of the formulae (I-1-a) to (I-8-a) are in each case reacted with
carbonyl halides of the formula (XIII), if appropriate in the
presence of a diluent and if appropriate in the presence of an acid
binder.
[0598] Suitable diluents for the process (I-.alpha.) according to
the invention are all solvents which are inert towards the acid
halides. Preference is given to using hydrocarbons, such as
benzine, benzene, toluene, xylene and tetraline, 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. The hydrolytic stability of the acid halide permitting,
the reaction can also be carried out in the presence of water.
[0599] Suitable acid binders for the reaction according to the
process (I-.alpha.) according to the invention are all customary
acid acceptors. Preference is given to using tertiary amines, such
as triethylamine, pyridine, diazabicyclooctane (DABCO),
diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethylaniline, furthermore alkaline earth metal oxides,
such as magnesium oxide and calcium oxide, moreover alkali metal
and alkaline earth metal carbonates, such as sodium carbonate,
potassium carbonate and calcium carbonate, and also alkali metal
hydroxides, such as sodium hydroxide and potassium hydroxide.
[0600] In the process (I-.alpha.) according to the invention, the
reaction temperatures can be varied within a relatively wide 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.
[0601] When carrying out the process (I-.alpha.) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-8-a) and the carbonyl halide of the formula (XIII) are generally
each employed in approximately equivalent amounts. However, it is
also possible to use a relatively large excess (up to 5 mol) of the
carbonyl halide. Work-up is carried out by customary methods.
[0602] The process (I-.beta.) is characterized in that compounds of
the formulae (I-1-a) to (I-8-a) are reacted with carboxylic
anhydrides of the formula (XIV), if appropriate in the presence of
a diluent and if appropriate in the presence of an acid binder.
[0603] Suitable diluents for the process (I-.beta.) according to
the invention are, preferably, those diluents which are also
preferred when using acid halides. Besides, it may also be possible
for excess carboxylic anhydride to act simultaneously as
diluent.
[0604] In process (I-.beta.), suitable acid binders, which are
added, if appropriate, are preferably those acid binders which are
also preferred when using acid halides.
[0605] The reaction temperatures in the process (I-.beta.)
according to the invention can be varied within a relatively wide
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.
[0606] When carrying out the process (I-.beta.) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-8-a) and the carboxylic anhydride of the formula (XIV) are
generally each employed in approximately equivalent amounts.
However, it is also possible to use a relatively large excess (up
to 5 mol) of the carboxylic anhydride. Work-up is carried out by
customary methods.
[0607] In general, diluent and excess carboxylic anhydride and the
carboxylic acid formed are removed by distillation or by washing
with an organic solvent or with water.
[0608] The process (J) is characterized in that compounds of the
formulae (I-1-a) to (I-8-a) are in each case reacted with
chloroformic esters or chloroformic thioesters of the formula (XV),
if appropriate in the presence of a diluent and if appropriate in
the presence of an acid binder.
[0609] Suitable acid binders for the reaction according to the
process (J) according to the invention are all customary acid
acceptors. Preference is given to using tertiary amines, such as
tri-ethylamine, pyridine, DABCO, DBU, DBA, Hunig base and
N,N-dimethylaniline, furthermore alkaline earth metal oxides, such
as magnesium oxide and calcium oxide, moreover alkali metal and
alkaline earth metal carbonates, such as sodium carbonate,
potassium carbonate and calcium carbonate, and also alkali metal
hydroxides, such as sodium hydroxide and potassium hydroxide.
[0610] Suitable diluents for the process (J) according to the
invention are all solvents which are inert towards the chloroformic
esters or chloroformic thioesters. Preference is given to using
hydrocarbons, such as benzine, benzene, toluene, xylene and
tetraline, 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.
[0611] When carrying out the process (J) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. If the process is carried out in the
presence of a diluent and an acid binder, the reaction temperatures
are generally between -20.degree. C. and +100.degree. C.,
preferably between 0.degree. C. and 50.degree. C.
[0612] The process (J) according to the invention is generally
carried out under atmospheric pressure.
[0613] When carrying out the process (J) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-8-a) and the appropriate chloroformic ester or chloroformic
thioester of the formula (XIII) are generally each employed in
approximately equivalent amounts. However, it is also possible to
use a relatively large excess (up to 2 mol) of one component or the
other. Work-up is carried out by customary methods. In general,
precipitated salts are removed and the reaction mixture that
remains is concentrated by removing the diluent under reduced
pressure.
[0614] The process (K) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-8-a) are in each
case reacted with compounds of the formula (XVI), in the presence
of a diluent and, if appropriate, in the presence of an acid
binder.
[0615] In Preparation Process (K), about 1 mol of
chloromonothioformic ester or chlorodithio-formic ester of the
formula (XVI) is reacted per mole of starting material of the
formulae (I-1-a) to (I-8-a), at from 0 to 120.degree. C.,
preferably from 20 to 60.degree. C.
[0616] Suitable diluents, which are added, if appropriate, are all
inert polar organic solvents, such as ethers, amides, sulphones,
sulphoxides, and also halogenated alkanes.
[0617] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide or methylene chloride.
[0618] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-8-a) is prepared by the addition of strong
deprotonating agents, such as, for example, sodium hydride or
potassium tert-butoxide, the further addition of acid binders can
be dispensed with.
[0619] If acid binders are used, these are customary inorganic or
organic bases, for example sodium hydroxide, sodium carbonate,
potassium carbonate, pyridine, triethylamine.
[0620] The reaction can be carried out under atmospheric pressure
or under elevated pressure and is preferably carried out under
atmospheric pressure. Work-up is carried out by customary
methods.
[0621] The process (L) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-8-a) are in each
case reacted with sulphonyl chlorides of the formula (XVII), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0622] In the Preparation Process (L), about 1 mol of sulphonyl
chloride of the formula (XVII) is reacted per mole of starting
material of the formula (I-1-a to I-8-a), at from -20 to
150.degree. C., preferably from 20 to 70.degree. C.
[0623] Suitable diluents, which are added, if appropriate, are all
inert polar organic solvents, such as ethers, amides, nitriles,
sulphones, sulphoxides or halogenated hydrocarbons, such as
methylene chloride.
[0624] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide, methylene chloride.
[0625] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-8-a) is prepared by adding strong
deprotonating agents (such as, for example, sodium hydride or
potassium tert-butoxide), the further addition of acid binders can
be dispensed with.
[0626] If acid binders are used, these are customary inorganic or
organic bases, for example sodium hydroxide, sodium carbonate,
potassium carbonate, pyridine, triethylamine.
[0627] The reaction can be carried out under atmospheric pressure
or under elevated pressure and is preferably carried out under
atmospheric pressure. Work-up is carried out by customary
methods.
[0628] The process (M) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-8-a) are in each
case reacted with phosphorus compounds of the formula (XVIII), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0629] In the Preparation Process (M), to obtain compounds of the
formulae (I-1-e) to (I-8-e), 1 to 2, preferably 1 to 1.3 mol of the
phosphorus compound of the formula (XVIII) are reacted to 1 mol of
the compounds (I-1-a) to (I-8-a), at temperatures between
-40.degree. C. and 150.degree. C., preferably between -10 and
110.degree. C.
[0630] Suitable diluents, which are added, if appropriate, are all
inert polar organic solvents, such as ethers, amides, nitriles,
alcohols, sulphides, sulphones, sulphoxides, etc.
[0631] Preference is given to using acetonitrile, dimethyl
sulphoxide, tetrahydrofuran, dimethyl-formamide, methylene
chloride.
[0632] Suitable acid binders, which are added, if appropriate, are
customary inorganic or organic bases, such as hydroxides,
carbonates or amines. Examples are sodium hydroxide, sodium
carbonate, potassium carbonate, pyridine, triethylamine
[0633] The reaction can be carried out under atmospheric pressure
or under elevated pressure and is preferably carried out under
atmospheric pressure. Work-up is carried out by customary methods
of organic chemistry. The end products obtained are preferably
purified by crystallization, chromatographic purification or by
"incipient distillation", i.e. removal of the volatile components
under reduced pressure.
[0634] The process (N) is characterized in that compounds of the
formulae (I-1-a) to (I-8-a) are reacted with metal hydroxides or
metal alkoxides of the formula (XIX) or amines of the formula (XX),
if appropriate in the presence of a diluent.
[0635] Suitable diluents for the process (N) according to the
invention are, preferably, ethers, such as tetrahydrofuran,
dioxane, diethyl ether, or else alcohols, such as methanol,
ethanol, isopropanol, and also water.
[0636] The process (N) according to the invention is generally
carried out under atmospheric pressure.
[0637] The reaction temperatures are generally between -20.degree.
C. and 100.degree. C., preferably between 0.degree. C. and
50.degree. C.
[0638] The process (O) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-8-a) are in each
case reacted with (O-.alpha.) compounds of the formula (XXI), if
appropriate in the presence of a diluent and if appropriate in the
presence of a catalyst, or with (O-.beta.) compounds of the formula
(XXII), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0639] In Preparation Process (O-.alpha.), about 1 mol of
isocyanate of the formula (XXI) is reacted per mole of starting
material of the formulae (I-1-a) to (I-8-a), at from 0 to
100.degree. C., preferably at from 20 to 50.degree. C.
[0640] Suitable diluents, which are added, if appropriate, are all
inert organic solvents, such as ethers, amides, nitriles,
sulphones, sulphoxides.
[0641] If appropriate, catalysts may be added to accelerate the
reaction. Suitable catalysts are, very advantageously, organotin
compounds, such as, for example, dibutyltin dilaurate. The reaction
is preferably carried out under atmospheric pressure.
[0642] In the Preparation Process (O-.beta.), about 1 mol of
carbamoyl chloride of the formula (XXII) is reacted per mole of
starting material of the formulae (I-1-a) to (I-8-a), at from -20
to 150.degree. C., preferably from 0 to 70.degree. C.
[0643] Suitable diluents, which are added, if appropriate, are all
inert polar organic solvents, such as ethers, amides, sulphones,
sulphoxides or halogenated hydrocarbons.
[0644] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide or methylene chloride.
[0645] If, in a preferred embodiment, the enolate salt of the
compound (I-1-a) to (I-8-a) is prepared by adding strong
deprotonating agents (such as, for example, sodium hydride or
potassium tert-butoxide), the further addition of acid binders can
be dispensed with.
[0646] If acid binders are used, these are customary inorganic or
organic bases, for example sodium hydroxide, sodium carbonate,
potassium carbonate, triethylamine or pyridine.
[0647] The reaction can be carried out under atmospheric pressure
or under elevated pressure and is preferably carried out under
atmospheric pressure. Work-up is carried out by customary
methods.
[0648] The process (P) is characterized in that compounds of the
formula (I-1') to (I-8') in which A, B, D, Q.sup.1, Q.sup.2,
Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W X, Y, R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as defined above
and Z' represents halogen, particularly preferably bromine, are, in
the presence of a copper salt and in the presence of a base,
subjected to a coupling reaction with HN-heterocycles of the
formula (XXIII) in which Z is as defined above (J. Am. Chem. Soc.
2001, 123, 7729-29; WO 02-85 838; Synlett 2002, 3, 423-30).
[0649] Suitable solvents for the process (P) according to the
invention are, for example, optionally halogenated aliphatic,
alicyclic or aromatic hydrocarbons, such as, for example, benzine,
benzene, toluene, xylene, petroleum ether, hexane, cyclohexane,
chlorobenzene, dichlorobenzene, ethers, such as diethyl ether,
diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol
dimethyl ether or ethylene glycol diethyl ether; amides, such as,
for example, N,N-dimethylformamide, N,N-dimethylacetamide,
N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric
triamide; esters, such as methyl acetate or ethyl acetate, or
mixtures of such solvents. Preference is given to using
N,N-dimethylformamide.
[0650] Suitable bases for the process (P) according to the
invention are alkali metal and/or alkaline earth metal carbonates,
alkoxides, phosphates, fluorides and/or hydroxides, and particular
preference is given to potassium carbonate, sodium carbonate,
caesium carbonate, caesium bicarbonate, sodium methoxide, potassium
tert-butoxide, potassium amylate, caesium fluoride, potassium
phosphate and barium hydroxide. Especially preferred are potassium
carbonate, sodium carbonate, caesium carbonate and/or caesium
bicarbonate. Potassium carbonate is very especially preferred.
[0651] The bases can also be employed in the presence of phase
transfer catalysts, such as, for example, triethylbenzylammonium
chloride, tetrabutylammonium bromide or TDA 1
(=tris(methoxy-ethoxyethyl)amine).
[0652] The copper salts used in the process (P) according to the
invention are copper(I) salts, such as, for example, CuI.
[0653] The process (P) can furthermore also be carried out in the
presence of additional auxiliary bases, such as diamines, such as,
for example, ethylenediamine, propylenediamine,
1,2-diaminocyclohexane.
[0654] When carrying out the process (P), the reaction temperatures
can be varied within a relatively wide range. In general, the
process is carried out at temperatures of from 0 to 250.degree. C.,
preferably from 30 to 200.degree. C.; with very particular
preference from 50 to 150.degree. C.
[0655] The process (P) according to the invention is generally
carried out under atmospheric pressure.
[0656] When carrying out the process (P) according to the
invention, the reaction components of the formulae (I-1') to (I-8')
and (XXIII) are generally employed in equimolar amounts. However,
it is also possible to use a relatively large excess (up to 3 mol)
of one component or the other. The bases are generally employed in
a molar ratio of from 1:1 to 10:1, preferably from 2:1 to 5:1. The
copper salts are generally employed in a molar ratio of from 0.01:1
to 1:1, preferably from 0.05:1 to 0.5:1.
[0657] The process Q is characterized in that compounds of the
formula (XXXII-a) in which W, X, Y and R.sup.8 are as defined above
and Z' represents halogen, particularly preferably bromine, are, in
the presence of a base and in the presence of a copper salt,
subjected to a coupling reaction with HN-containing heterocycles of
the formula (XXIII) in which Z is as defined above (J. Am. Chem.
Soc. 2001, 123, 7727-29; WO O.sub.2-85 838, Synlett 2002, 3,
427-30).
[0658] Suitable solvents for the process (Q) according to the
invention are optionally halogenated aliphatic, alicyclic or
aromatic hydrocarbons, such as, for example, benzine, benzene,
toluene, xylene, petroleum ether, hexane, cyclohexane,
chlorobenzene, dichlorobenzene, ethers, such as diethyl ether,
diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol
dimethyl ether or ethylene glycol diethyl ether; amides, such as,
for example, N,N-dimethyl-formamide, N,N-dimethylacetamide,
N-methylformanilide, N-methylpyrrolidone or hexa-methylphosphoric
triamide; esters, such as methyl acetate or ethyl acetate, or
mixtures of such solvents. Preference is given to using
N,N-dimethylformamide.
[0659] Suitable bases for the process (Q) according to the
invention are alkali metal and/or alkaline earth metal carbonates,
alkoxides, phosphates, fluorides and/or hydroxides, and particular
preference is given to potassium carbonate, sodium carbonate,
caesium carbonate, caesium bicarbonate, sodium methoxide, potassium
tert-butoxide, potassium amylate, caesium fluoride, potassium
phosphate and barium hydroxide. Especially preferred are potassium
carbonate, sodium carbonate, caesium carbonate and/or caesium
bicarbonate. Potassium carbonate is very especially preferred.
[0660] The bases can also be employed in the presence of
phase-transfer catalysts, such as, for example,
triethylbenzylammonium chloride, tetrabutylammonium bromide or TDA
1 (=tris(methoxy-ethoxyethyl)amine).
[0661] The copper salts in the process (O) according to the
invention are copper(I) salts, such as, for example, CuI.
[0662] The process (Q) can furthermore also be carried out in the
presence of additional auxiliary bases, such as diamines, such as,
for example, ethylenediamine, propylenediamine,
1,2-diaminocyclohexane.
[0663] When carrying out the process (Q), the reaction temperatures
can be varied within a relatively wide range. In general, the
process is carried out at temperatures of from 0 to 250.degree. C.,
preferably from 30 to 200.degree. C.; very particularly preferably
from 50 to 150.degree. C.
[0664] The process (Q) according to the invention is generally
carried out under atmospheric pressure.
[0665] When carrying out the process (Q) according to the
invention, the reaction components of the formulae (XXXII-a) and
(XXIII) are generally employed in equimolar amounts. However, it is
also possible to use a relatively large excess (up to 3 mol) of one
component or the other. The bases are generally employed in a molar
ratio of from 1:1 to 10:1, preferably from 2:1 to 5:1. The copper
salts are generally employed in a molar ratio of from 0.001:1 to
1:1, preferably from 0.05:1 to 0.5:1.
[0666] The active compounds are well tolerated by plants and have
advantageous toxicity to warm-blooded species; they can be employed
for controlling animal pests, in particular insects, arachnids and
nematodes encountered in agriculture, forests, in the protection of
stored products and materials and in the hygiene sector. They are
preferably used as crop protection agents. They are active against
normally sensitive and resistant species and against all or some
stages of development. The abovementioned pests include:
[0667] From the order of the Isopoda, for example, Oniscus asellus,
Armadillidium vulgare and Porcellio scaber.
[0668] From the order of the Diplopoda, for example, Blaniulus
guttulatus.
[0669] From the order of the Chilopoda, for example, Geophilus
carpophagus and Scutigera spp.
[0670] From the order of the Symphyla, for example, Scutigerella
immaculata.
[0671] From the order of the Thysanura, for example, Lepisma
saccharina.
[0672] From the order of the Collembola, for example, Onychiurus
armatus.
[0673] From the order of the Orthoptera, for example, Acheta
domesticus, Gryllotalpa spp., Locusta migratoria migratorioides,
Melanoplus spp. and Schistocerca gregaria.
[0674] From the order of the Blattaria, for example, Blatta
orientalis, Periplaneta americana, Leucophaea maderae and Blattella
germanica.
[0675] From the order of the Dermaptera, for example, Forficula
auricularia.
[0676] From the order of the Isoptera, for example, Reticulitermes
spp.
[0677] From the order of the Phthiraptera, for example, Pediculus
humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes
spp., Damalinia spp.
[0678] From the order of the Thysanoptera, for example,
Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella
occidentalis.
[0679] From the order of the Heteroptera, for example, Eurygaster
spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius,
Rhodnius prolixus and Triatoma spp.
[0680] From the order of the Homoptera, for example, Aleurodes
brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis
gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae,
Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera
vastatrix, Pemphigus spp., 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.
[0681] From the order of the Lepidoptera, for example, Pectinophora
gossypiella, Bupalus piniarius, Chematobia brumata, Lithocolletis
blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma
neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix
thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp.,
Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae,
Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa
pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia
kuehniella, Galleria mellonella, Tineola bisselliella, Tinea
pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua
reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona
magnanima, Tortrix viridana, Cnaphalocerus spp. and Oulema
oryzae.
[0682] From the order of the Coleoptera, for example, Anobium
punctatum, Rhizopertha dominica, Bruchidius obtectus,
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, Costelytra zealandica and
Lissorphoptrus oryzophilus.
[0683] From the order of the Hymenoptera, for example, Diprion
spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa
spp.
[0684] 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 fit, Phorbia spp., Pegomyia hyoscyami,
Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp. and
Liriomyza spp.
[0685] From the order of the Siphonaptera, for example, Xenopsylla
cheopis and Ceratophyllus spp.
[0686] From the order of the Arachnida, for example, Scorpio
maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros
spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta
oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp.,
Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp.,
Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus
spp., Tetranychus spp., Hemitarsonemus spp. and Brevipalpus
spp.
[0687] The plant-parasitic nematodes include, for example,
Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci,
Tylenchulus semipenetrans, Heterodera spp., Globodera spp.,
Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema
spp., Trichodorus spp. and Bursaphelenchus spp.
[0688] If appropriate, the compounds or active compound
combinations according to the invention may also be used in certain
concentrations or application rates to act as herbicides. If
appropriate, they can also be employed as intermediates or
precursors for the synthesis of further active compounds.
[0689] All plants and plant parts can be treated in accordance with
the invention. Plants are to be understood as meaning in the
present context all plants and plant populations such as desired
and undesired wild plants or crop plants (including naturally
occurring crop plants). Crop plants can be plants which can be
obtained by conventional plant breeding and optimization methods or
by biotechnological and recombinant methods or by combinations of
these methods, including the transgenic plants and inclusive of the
plant cultivars protectable or not protectable by plant breeders'
rights. Plant parts are to be understood as meaning all parts and
organs of plants above and below the ground, such as shoot, leaf,
flower and root, examples which may be mentioned being leaves,
needles, stalks, stems, flowers, fruit bodies, fruits, seeds,
roots, tubers and rhizomes. The plant parts also include harvested
material, and vegetative and generative propagation material, for
example cuttings, tubers, rhizomes, offsets and seeds.
[0690] The treatment according to the invention of the plants and
plant parts with the active compounds or active compound
combinations is carried out directly or by allowing the compounds
to act on the surroundings, environment or storage space by the
customary treatment methods, for example by immersion, spraying,
evaporation, fogging, scattering, painting on or injection and, in
the case of propagation material, in particular in the case of
seeds, also by applying one or more coats.
[0691] The active compounds or active compound combinations 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 microencapsulations in polymeric materials.
[0692] 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
surfactants, that is, emulsifiers and/or dispersants, and/or foam
formers.
[0693] If the extender used is water, it is also possible, for
example, to use organic solvents as cosolvents. The following are
essentially suitable as liquid solvents: aromatics such as xylene,
toluene or alkylnaphthalenes, chlorinated aromatics or 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 and their ethers and
esters, ketones such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohexanone, strongly polar solvents such as
dimethylformamide and dimethyl sulphoxide, or else water.
Suitable solid carriers are:
[0694] for example ammonium salts and ground natural minerals such
as kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, and ground synthetic
materials such as highly-disperse silica, alumina and silicates;
suitable solid carriers for granules are: for example crushed and
fractionated natural rocks such as calcite, marble, pumice,
sepiolite and dolomite, or else synthetic granules of inorganic and
organic meals, and granules of organic material such as sawdust,
coconut shells, maize cobs and tobacco stalks; suitable emulsifiers
and/or foam formers are: for example nonionic and anionic
emulsifiers such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates, or else protein hydrolysates; suitable dispersants
are: for example lignin-sulphite waste liquors and
methylcellulose.
[0695] Tackifiers 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, or
else natural phospholipids such as cephalins and lecithins and
synthetic phospholipids can be used in the formulations. Other
additives can be mineral and vegetable oils.
[0696] It is possible to use colorants such as inorganic pigments,
for example iron oxide, titanium oxide and Prussian Blue, and
organic colorants such as alizarin colorants, azo colorants and
metal phthalocyanine colorants, and trace nutrients such as salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[0697] The formulations generally comprise between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90%.
[0698] The active compounds according to the invention, as such or
in their formulations, can also be used as a mixture with known
fungicides, bactericides, acaricides, nematicides or insecticides,
for example in order to widen the spectrum of action or to prevent
the development of resistances in this way. In many cases,
synergistic effects result, i.e. the activity of the mixture
exceeds the activity of the individual components.
[0699] Compounds which are suitable as components in the mixtures
are, for example, the following:
Fungicides:
[0700] 2-phenylphenol; 8-hydroxyquinoline sulphate;
acibenzolar-5-methyl; aldimorph; amido-flumet; ampropylfos;
ampropylfos-potassium; andoprim; anilazine; azaconazole;
azoxystrobin; benalaxyl; benodanil; benomyl;
benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl;
bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S;
bromuconazole; bupirimate; buthiobate; butylamine; calcium
polysulphide; capsimycin; captafol; captan; carbendazim; carboxin;
carpropamid; carvone; quinomethionate; chlobenthiazone;
chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon;
cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil;
cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone;
dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb;
difenoconazole; diflumetorim; dimethirimol; dimethomorph;
dimoxystrobin; diniconazole; diniconazole-M; dinocap;
diphenylamine; dipyrithione; ditalimfos; dithianon; dodine;
drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol;
etridiazole; famoxadone; fenamidone; fenapanil; fenarimol;
fenbuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil;
fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam;
flubenzimine; fludioxonil; flumetover; flumorph; fluoromide;
fluoxastrobin; fluquinconazole; flurprimidol; flusilazole;
flusulfamide; flutolanil; flutriafol; folpet; fosetyl-Al;
fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil;
furmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazol;
imazalil; imibenconazole; iminoctadine triacetate; iminoctadine
tris(albesilate); iodocarb; ipconazole; iprobenfos; iprodione;
iprovalicarb; irumamycin; isoprothiolane; isovaledione;
kasugamycin; kresoxim-methyl; mancozeb; maneb; meferimzone;
mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole;
methasulfocarb; methfuroxam; metiram; metominostrobin; metsulfovax;
mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen;
nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin;
oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin;
paclobutrazol; pefurazoate; penconazole; pencycuron; phosdiphen;
phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim;
probenazole; prochloraz; procymidone; propamocarb;
propanosine-sodium; propiconazole; propineb; pro-quinazid;
prothioconazole; pyraclostrobin; pyrazophos; pyrifenox;
pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrin; quinconazole;
quinoxyfen; quintozene; simeconazole; spiroxamine; sulphur;
tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole;
thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram;
tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol;
triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph;
trifloxystrobin; triflumizole; triforine; triticonazole;
uniconazole; validamycin A; vinclozolin; zineb; ziram; zoxamide;
(2S)--N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-
-3-methyl-2-[(methylsulphonyl)amino]-butanamide;
1-(1-naphthalenyl)-1H-pyrrole-2,5-dione;
2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine;
2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide;
2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxam-
ide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; Actinovate;
cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazole-1-yl)-cycloheptanol;
methyl
1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate;
monopotassium carbonate;
N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide;
N-butyl-8-(1,1-dimethylethyl)-1-oxaspiro[4.5]decan-3-amine; sodium
tetrathiocarbonate;
and copper salts and preparations such as Bordeaux mixture; copper
hydroxide; copper naphthenate; copper oxychloride; copper sulphate;
cufraneb; cuprous oxide; mancopper; oxine-copper.
Bactericides:
[0701] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
Insecticides/Acaricides/Nematicides:
[0702] abamectin, ABG-9008, acephate, acequinocyl, acetamiprid,
acetoprole, acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb,
aldicarb, aldoxycarb, allethrin, alpha-cypermethrin (alphamethrin),
amidoflumet, aminocarb, amitraz, avermectin, AZ-60541,
azadirachtin, aza-methiphos, azinphos-methyl, azinphos-ethyl,
azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus
subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain
EG-2348, Bacillus thuringiensis strain GC-91, Bacillus
thuringiensis strain NCTC-11821, baculoviruses, Beauveria bassiana,
Beauveria tenella, benclothiaz, bendiocarb, benfuracarb, bensultap,
benzoximate, beta-cyfluthrin, beta-cypermethrin, bifenazate,
bifenthrin, binapacryl, bioallethrin, bioallethrin S-cyclopentyl
isomer, bioethanomethrin, biopermethrin, bioresmethrin,
bistrifluoron, BPMC, brofenprox, bromophos-ethyl, bromopropylate,
bromfenvinfos (-methyl), BTG-504, BTG-505, bufencarb, buprofezin,
butathiofos, butocarboxim, butoxycarboxim, butylpyridaben,
cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion,
carbosulfan, cartap, CGA-50439, quinomethionate, chlordane,
chlordimeform, chloethocarb, chlorethoxyfos, chlorfenapyr,
chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate,
chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos
(-ethyl), chlovaporthrin, chromafenozide, cis-cypermethrin,
cis-resmethrin, cis-permethrin, clocythrin, cloethocarb,
clofentezine, clothianidin, clothiazoben, codlemone, coumaphos,
cyanofenphos, cyanophos, cycloprene, cycloprothrin, Cydia
pomonella, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,
cyphenothrin (1R-trans isomer), cyromazine, DDT, deltamethrin,
demeton-5-methyl, demeton-5-methylsulphone, diafenthiuron,
dialifos, diazinon, dichlofenthion, dichlorvos, dicofol,
dicrotophos, dicyclanil, diflubenzuron, dimefluthrin, dimethoate,
dimethylvinphos, dinobuton, dinocap, dinotefuran, diofenolan,
disulfoton, docusate-sodium, dofenapyn, DOWCO-439, eflusilanate,
emamectin, emamectin benzoate, empenthrin (1R isomer), endosulfan,
Entomo-phthora spp., EPN, esfenvalerate, ethiofencarb, ethiprole,
ethion, ethoprophos, etofenprox, etoxazole, etrimfos, famphur,
fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin,
fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb,
fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate,
fensulfothion, fenthion, fentrifanil, fenvalerate, fipronil,
flonicamid, fluacrypyrim, fluazuron, flubenzimine,
flubrocythrinate, flucycloxuron, flucythrinate, flufenerim,
flufenoxuron, flufenprox, flumethrin, flupyrazofos, flutenzin
(flufenzine), fluvalinate, fonofos, formetanate, formothion,
fosmethilan, fosthiazate, fubfenprox (fluproxyfen), furathiocarb,
gamma-cyhalothrin, gamma-HCH, gossyplure, grandlure, granulosis
viruses, halfenprox, halofenozide, HCH, HCN-801, heptenophos,
hexaflumuron, hexythiazox, hydra-methylnone, hydroprene, IKA-2002,
imidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobenfos,
isazofos, isofen-phos, isoprocarb, isoxathion, ivermectin,
japonilure, kadethrin, nuclear polyhedrosis viruses, kinoprene,
lambda-cyhalothrin, lindane, lufenuron, malathion, mecarbam,
mesulfenfos, metaldehyde, metam-sodium, methacrifos, methamidophos,
Metarhizium anisopliae, Metarhizium flavoviride, methidathion,
methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide,
metofluthrin, metolcarb, metoxadiazone, mevinphos, milbemectin,
milbemycin, MKI-245, MON-45700, monocrotophos, moxidectin, MTI-800,
naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide,
nicotine, nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250,
NNI-9768, novaluron, noviflumuron, OK-5101, OK-5201, OK-9601,
OK-9602, OK-9701, OK-9802, omethoate, oxamyl, oxydemeton-methyl,
Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl),
permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R-trans
isomer), phenthoate, phorate, phosalone, phosmet, phosphamidon,
phosphocarb, phoxim, piperonyl butoxide, pirimicarb,
pirimiphos-methyl, pirimiphos-ethyl, potassium oleate, prallethrin,
profenofos, profluthrin, promecarb, propaphos, propargite,
propetamphos, propoxur, prothiofos, prothoate, protrifenbute,
pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben,
pyridalyl, pyridaphenthion, pyridathion, pyrimidifen, pyriproxyfen,
quinalphos, resmethrin, RH-5849, ribavirin, RU-12457, RU-15525,
S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad,
spirodiclofen, spiromesifen, sulfluramid, sulfotep, sulprofos,
SZI-121, tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos,
teflubenzuron, tefluthrin, temephos, Temivinphos, Terbam, Terbufos,
Tetrachlorvinphos, Tetradifon, Tetramethrin, Tetramethrin (1R
isomer), tetrasul, theta-cypermethrin, thiacloprid, thiamethoxam,
thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb,
thiofanox, thiometon, thiosultap-sodium, thuringiensin,
tolfenpyrad, tralocythrin, tralomethrin, transfluthrin,
triarathene, triazamate, triazophos, triazuron, trichlophenidine,
trichlorfon, Trichoderma atroviride, triflumuron, trimethacarb,
vamidothion, vaniliprole, verbutin, Verticillium lecanii,
WL-108477, WL-40027,
YI-5201, YI-5301, YI-5302,
[0703] XMC, xylylcarb, ZA-3274, zeta-cypermethrin, zolaprofos,
ZXI-8901, the compound 3-methylphenyl propylcarbamate (Tsumacide
Z), the compound
3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octa-
ne-3-carbonitrile (CAS Reg. No. 185982-80-3) and the corresponding
3-endo isomer (CAS Reg. No. 185984-60-5) (cf. WO 96/37494, WO
98/25923), and preparations which contain insecticidally active
plant extracts, nematodes, fungi or viruses.
[0704] A mixture with other known active compounds, such as
herbicides, or with fertilizers and growth regulators is also
possible.
[0705] When used as insecticides in their commercially available
formulations and in the use forms prepared with these formulations,
the active compounds according to the invention can furthermore
exist in the form of a mixture with synergists. Synergists are
compounds by which the activity of the active compounds is
increased without it being necessary for the synergist added to be
active itself.
[0706] The active compound content of the use forms prepared from
the commercially available formulations can vary within broad
ranges. 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.
[0707] They are applied in a customary manner adapted to suit the
use forms.
[0708] When used against hygiene pests and pests of stored
products, the active compound or active compound combination is
distinguished by excellent residual action on wood and clay as well
as good stability to alkali on limed substrates.
[0709] As already mentioned above, it is possible to treat all
plants or their parts in accordance with the invention. In a
preferred embodiment, wild plant species or plant varieties and
plant cultivars which have been obtained by traditional biological
breeding methods, such as hybridization or protoplast fusion, and
the parts of these varieties and cultivars are treated. In a
further preferred embodiment, transgenic plants and plant cultivars
which have been obtained by recombinant methods, if appropriate in
combination with conventional methods (genetically modified
organisms), and their parts are treated. The term "parts" or "parts
of plants" or "plant parts" has been explained above.
[0710] Plants which are treated particularly preferably in
accordance with the invention are those of the plant cultivars
which are in each case commercially available or in use. Plant
cultivars are understood as meaning plants with new traits which
have been bred either by conventional breeding, by mutagenesis or
by recombinant DNA techniques. They may take the form of cultivars,
biotypes and genotypes.
[0711] Depending on the plant species or plant cultivars, their
location and growth conditions (soils, climate, vegetation period,
nutrition), the treatment according to the invention may also
result in superadditive ("synergistic") effects. Thus, for example,
reduced application rates and/or a widened activity spectrum and/or
an increase in the activity of the substances and compositions
which can be used in accordance with the invention, better plant
growth, increased tolerance to high or low temperatures, increased
tolerance to drought or to salinity in the water or soil, increased
flowering performance, facilitated harvesting, accelerated
maturation, higher yields, higher quality and/or better nutritional
value of the harvested products, better storage characteristics
and/or processability of the harvested products are possible which
exceed the effects which were actually to be expected.
[0712] The preferred transgenic plants or plant cultivars (those
obtained by recombinant methods) to be treated in accordance with
the invention include all those plants which, owing to the process
of recombinant modification, were given genetic material which
confers particular, advantageous, valuable traits to these plants.
Examples of such properties are better plant growth, increased
tolerance to high or low temperatures, increased tolerance to
drought or to salinity in the water or soil, increased flowering
performance, facilitated harvesting, accelerated maturation, higher
yields, higher quality and/or higher nutritional value of the
harvested products, better storage characteristics and/or better
processability of the harvested products. Further examples of such
traits, examples which must be mentioned especially, are better
defence of the plants against animal and microbial pests, such as
against insects, mites, phytopathogenic fungi, bacteria and/or
viruses and an increased tolerance of the plants to certain
herbicidal active compounds. Examples of transgenic plants which
may be mentioned are the important crop plants, such as cereals
(wheat, rice), maize, soybeans, potato, cotton, oilseed rape, beet,
sugar cane and fruit plants (with the fruits apples, pears, citrus
fruits and grapes), with particular emphasis on maize, soybeans,
potatoes, cotton and oilseed rape. Traits which are especially
emphasized are the increased defence of the plants against insects,
owing to toxins being formed in the plants, in particular toxins
which are generated in the plants by the genetic material of
Bacillus thuringiensis (for example by the genes CryIA(a),
CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb
and CryII.sup.2 and their combinations; hereinbelow "Bt plants").
Other traits which are particularly emphasized are the increased
defence of plants against fungi, bacteria and viruses by the
systemic acquired resistance (SAR), systemin, phytoalexins,
elicitors and resistance genes and correspondingly expressed
proteins and toxins. Other traits which are especially emphasized
are the increased tolerance of the plants to certain herbicidal
active compounds, for example imidazolinones, sulphonylureas,
glyphosate or phosphinotricin (for example "PAT" gene). The genes
which confer the desired traits in each case may also be present in
the transgenic plants in combination with one another. Examples of
"Bt plants" which may be mentioned are maize cultivars, cotton
cultivars, soybean cultivars and potato cultivars which are
commercially available under the trade names YIELD GARD.RTM. (for
example maize, cotton, soybeans), KnockOut.RTM. (for example
maize), StarLink.RTM. (for example maize), Bollgard.RTM. (cotton),
Nucotn.RTM. (cotton) and NewLeaf.RTM. (potato). Examples of
herbicide-tolerant plants which may be mentioned are maize
cultivars, cotton cultivars and soybean cultivars which are
commercially available under the trade names Roundup Ready.RTM.
(tolerance to glyphosate, for example maize, cotton, soybean),
Liberty Link.RTM. (tolerance to phosphinotricin, for example
oilseed rape), IMI.RTM. (tolerance to imidazolinones) and STS.RTM.
(tolerance to sulphonylureas, for example maize)
Herbicide-resistant plants (plants bred in a conventional manner
for herbicide tolerance) which may be mentioned include also the
varieties commercially available under the name Clearfield.RTM.
(for example maize). Naturally, these statements also apply to
plant cultivars having these genetic traits or genetic traits still
to be developed, which plant cultivars will be developed and/or
marketed in the future.
[0713] The plants listed can be treated particularly advantageously
with the compounds according to the invention or the active
compound mixtures according to the invention. The preferred ranges
stated above for the active compounds and mixtures also apply to
the treatment of these plants. Particular emphasis may be given to
the treatment of plants with the compounds or mixtures specifically
mentioned in the present text.
[0714] The active compounds or active compound combinations
according to the invention are not only active against plant,
hygiene and stored-product pests, but also, in the veterinary
medicine sector, against animal parasites (ectoparasites), such as
ixodid ticks, argasid ticks, scab mites, trombi-culid mites, flies
(stinging and sucking), parasitic fly larvae, lice, hair lice, bird
lice and fleas. These parasites include:
[0715] From the order of the Anoplurida, for example, Haematopinus
spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes
spp.
[0716] 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.
[0717] From the order of the 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. and Melophagus spp.
[0718] From the order of the Siphonapterida, for example, Pulex
spp., Ctenocephalides spp., Xenopyslla spp. and Ceratophyllus
spp.
[0719] From the order of the Heteropterida, for example, Cimex
spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
[0720] From the order of the Blattarida, for example, Blatta
orientalis, Periplaneta americana, Blattella germanica and Supella
spp.
[0721] From the sub-class of the Acaria (Acarida) and the orders of
the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus
spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,
Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus
spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp.,
Sternostoma spp. and Varroa spp.
[0722] From the order of the Actinedida (Prostigmata) and Acaridida
(Astigmata), for example, Acarapis spp., Cheyletiella spp.,
Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,
Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,
Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes
spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres
spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
[0723] The active compounds or active compound combinations
according to the invention are also suitable for controlling
arthropods which attack agricultural livestock, such as, for
example, cattle, sheep, goats, horses, pigs, donkeys, camels,
buffaloes, rabbits, chickens, turkeys, ducks, geese, honeybees,
other domestic animals, such as, for example, dogs, cats, cage
birds, aquarium fish, and so-called experimental animals, such as,
for example, hamsters, guinea-pigs, rats and mice. By combating
these arthropods, it is intended to reduce deaths and decreased
performances (in meat, milk, wool, hides, eggs, honey and the
like), so that more economical and simpler animal keeping is made
possible by using the active compounds according to the
invention.
[0724] In the veterinary sector, the active compounds or active
compound combinations according to the invention are used in a
known manner by enteral administration, for example in the form of
tablets, capsules, drinks, drenches, granules, pastes, boli, the
feed-through method, suppositories, by parenteral administration,
such as, for example, by means of injections (intramuscular,
subcutaneous, intravenous, intraperitoneal and the like), implants,
by nasal application, by dermal administration, for example in the
form of dipping or bathing, spraying, pouring-on and spotting-on,
washing, dusting, and with the aid of shaped articles which
comprise active compound, such as collars, ear tags, tail marks,
limb bands, halters, marking devices and the like.
[0725] When administered to livestock, poultry, domestic animals
and the like, the active compounds or active compound combinations
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 in the form of a chemical bath.
[0726] Furthermore, it has been found that the compounds or active
compound combinations according to the invention have a potent
insecticidal action against insects which destroy industrial
materials.
[0727] The following insects may be mentioned by way of example and
as being preferred, but without any limitation:
Beetles, such as
[0728] Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,
Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex,
Ernobius 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.
[0729] Dermapterans, such as Sirex juvencus, Urocerus gigas,
Urocerus gigas taignus, Urocerus augur.
[0730] Termites, such as Kalotermes flavicollis, Cryptotermes
brevis, Heterotermes indicola, Reticulitermes flavipes,
Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes
darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
[0731] Bristletails, such as Lepisma saccharina.
[0732] Industrial materials are to be understood as meaning, in the
present context, non-live materials, such as, preferably, synthetic
materials, glues, sizes, paper and board, leather, wood and timber
products, and paint. The materials to be very particularly
preferably protected against attack by insects are wood and timber
products.
[0733] Wood and timber products which can be protected by the
composition according to the invention or mixtures comprising such
a composition 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 cladding, windows and doors made of wood,
plywood, particle board, joiner's articles, or wood products which,
quite generally, are used in the construction of houses or in
joinery.
[0734] The active compounds or active compound combinations can be
used as such, in the form of concentrates or generally customary
formulations, such as powders, granules, solutions, suspensions,
emulsions or pastes.
[0735] The formulations mentioned 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 repellent, if appropriate desiccants and UV
stabilizers and, if appropriate, colorants and pigments and other
processing auxiliaries. The insecticidal compositions or
concentrates used for the protection of wood and wooden materials
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.
[0736] The amount of the compositions or concentrates employed
depends on the species and the occurrence of the insects and on the
medium. The optimum rate of application can be determined upon use
in each case by a 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.
[0737] The solvent and/or diluent used is an organochemical solvent
or solvent mixture and/or an oily or oil-type 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.
[0738] Organochemical solvents which are preferably employed are
oily or oil-type solvents having an evaporation number of above 35
and a flashpoint of above 30.degree. C., preferably above
45.degree. C. Substances which are used as such oily and oil-type
solvents which have low volatility and are insoluble in water are
suitable mineral oils or their aromatic fractions, or
mineral-oil-containing solvent mixtures, preferably white spirit,
petroleum and/or alkylbenzene.
[0739] Substances which are advantageously used are 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
range of 250 to 350.degree. C., petroleum or aromatics of boiling
range 160 to 280.degree. C., essence of terpentine and the
like.
[0740] In a preferred embodiment, 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,
are used.
[0741] The organic oily or oil-type solvents of low volatility
having an evaporation number of above 35 and a flashpoint of above
30.degree. C., preferably above 45.degree. C., can be partially
replaced 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.
[0742] In a preferred embodiment, part of the organochemical
solvent or solvent mixture is replaced by an aliphatic polar
organochemical solvent or solvent mixture. Substances which are
preferably used are aliphatic organochemical solvents having
hydroxyl and/or ester and/or ether groups, such as, for example,
glycol ethers, esters and the like.
[0743] The organochemical binders used within the scope of the
present invention are the synthetic resins and/or binding drying
oils which are known per se and can be diluted with water and/or
are soluble or 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/cumarone resin, silicone
resin, drying vegetable and/or drying oils and/or physically drying
binders based on a natural and/or synthetic resin.
[0744] The synthetic resin used as the binder can be employed in
the form of an emulsion, dispersion or solution. Up to 10% by
weight of bitumen or bituminous substances can also be used as
binders. In addition, colorants, pigments, water repellents,
odour-masking substances and inhibitors or anticorrosives known per
se and the like can also be employed.
[0745] The composition or the 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. Preferably used according to the invention are alkyd resins
with an oil content of over 45% by weight, preferably 50 to 68% by
weight.
[0746] 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 and
crystallization or precipitation. They preferably replace 0.01 to
30% of the binder (based on 100% of binder employed).
[0747] The plasticizers are from the chemical classes of the
phthalic esters, such as dibutyl phthalate, dioctyl phthalate or
benzyl butyl phthalate, the phosphoric esters, such as tributyl
phosphate, the adipic esters, such as di-(2-ethylhexyl) adipate,
the stearates, such as butyl stearate or amyl stearate, the
oleates, such as butyl oleate, the glycerol ethers or relatively
high-molecular-weight glycol ethers, glycerol esters and
p-toluenesulphonic esters.
[0748] Fixatives are chemically based on polyvinyl alkyl ethers,
such as, for example, polyvinyl methyl ether, or ketones, such as
benzophenone or ethylenebenzophenone.
[0749] Particularly suitable as a solvent or diluent is also water,
if appropriate as a mixture with one or more of the abovementioned
organochemical solvents or diluents, emulsifiers and
dispersants.
[0750] Particularly effective protection of wood is achieved by
large-scale industrial impregnation processes, for example vacuum,
double-vacuum or pressure processes.
[0751] If appropriate, the ready-to-use compositions can
additionally comprise other insecticides and, if appropriate,
additionally one or more fungicides.
[0752] Suitable additional components which may be admixed are,
preferably, the insecticides and fungicides mentioned in WO 94/29
268. The compounds mentioned in that document are expressly part of
the present application.
[0753] Very particularly preferred components which may be admixed
are insecticides, such as chlorpyriphos, phoxim, silafluofin,
alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin,
imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin,
thiacloprid, methoxyphenoxid and triflumuron,
and fungicides, such as epoxyconazole, hexaconazole, azaconazole,
propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,
dichlofluanid, tolylfluanid, 3-iodo-2-propynylbutyl carbamate,
N-octyl-isothiazolin-3-one and
4,5-dichloro-N-octylisothiazolin-3-one.
[0754] The compounds or active compound combinations according to
the invention can at the same time be employed for protecting
objects which come into contact with salt water or brackish water,
in particular hulls, screens, nets, buildings, moorings and
signalling systems, against fouling.
[0755] Fouling by sessile Oligochaeta, such as Serpulidae, and by
shells and species from the Ledamorpha group (goose barnacles),
such as various Lepas and Scalpellum species, or by species from
the Balanomorpha group (acorn barnacles), such as Balanus or
Pollicipes species, increases the frictional drag of ships and, as
a consequence, leads to a marked increase in operation costs owing
to higher energy consumption and additionally frequent residence in
the dry dock.
[0756] Apart from fouling by algae, for example Ectocarpus sp. and
Ceramium sp., fouling by sessile Entomostraka groups, which come
under the generic term Cirripedia (cirriped crustaceans), is of
particular importance.
[0757] Surprisingly, it has now been found that the compounds
according to the invention, alone or in combination with other
active compounds, have an outstanding antifouling action.
[0758] Using the compounds according to the invention, alone or in
combination with other active compounds, allows the use of heavy
metals such as, for example, in bis(trialkyltin) sulphides,
tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) oxide,
triethyltin chloride, tri-n-butyl-(2-phenyl-4-chlorophenoxy)tin,
tributyltin oxide, molybdenum disulphide, antimony oxide, polymeric
butyl titanate, phenyl-(bispyridine)-bismuth chloride,
tri-n-butyltin fluoride, manganese ethylenebisthiocarbamate, zinc
dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts
and copper salts of 2-pyridinethiol 1-oxide,
bis-dimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zinc
oxide, copper(I) ethylene-bis-dithiocarbamate, copper thiocyanate,
copper naphthenate and tributyltin halides to be dispensed with, or
the concentration of these compounds to be substantially
reduced.
[0759] If appropriate, the ready-to-use antifouling paints can
additionally comprise other active compounds, preferably algicides,
fungicides, herbicides, molluscicides, or other antifouling active
compounds.
[0760] Preferably suitable components in combination with the
antifouling compositions according to the invention are:
algicides such as
2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,
dichlorophen, diuron, endothal, fentin acetate, isoproturon,
methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
fungicides such as benzo[b]thiophenecarboxylic acid cyclohexylamide
S,S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propinyl
butylcarbamate, tolylfluanid and azoles such as azaconazole,
cyproconazole, epoxyconazole, hexaconazole, metconazole,
propiconazole and tebuconazole; molluscicides such as fentin
acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and
trimethacarb; Fe chelates; or conventional antifouling active
compounds such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one,
diiodomethylparatryl sulphone,
2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium,
copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,
pyridine-triphenylborane, tetrabutyldistannoxane,
2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,
2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide
and 2,4,6-trichlorophenylmaleimide.
[0761] The antifouling compositions used comprise the active
compound according to the invention of the compounds according to
the invention in a concentration of 0.001 to 50% by weight, in
particular 0.01 to 20% by weight.
[0762] Moreover, the antifouling compositions according to the
invention comprise the customary components such as, for example,
those described in Ungerer, Chem. Ind. 1985, 37, 730-732 and
Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
[0763] Besides the algicidal, fungicidal, molluscicidal active
compounds and insecticidal active compounds according to the
invention, antifouling paints comprise, in particular, binders.
[0764] Examples of recognized binders are polyvinyl chloride in a
solvent system, chlorinated rubber in a solvent system, acrylic
resins in a solvent system, in particular in an aqueous system,
vinyl chloride/vinyl acetate copolymer systems in the form of
aqueous dispersions or in the form of organic solvent systems,
butadiene/styrene/acrylonitrile rubbers, drying oils such as
linseed oil, resin esters or modified hardened resins in
combination with tar or bitumens, asphalt and epoxy compounds,
small amounts of chlorine rubber, chlorinated polypropylene and
vinyl resins.
[0765] If appropriate, paints also comprise inorganic pigments,
organic pigments or colorants which are preferably insoluble in
salt water. Paints may furthermore comprise materials such as rosin
to allow controlled release of the active compounds. Furthermore,
the paints may comprise plasticizers, modifiers which affect the
rheological properties and other conventional constituents. The
compounds according to the invention or the abovementioned mixtures
may also be incorporated into self-polishing antifouling
systems.
[0766] The active compounds or active compound combinations are
also suitable for controlling animal pests, in particular insects,
arachnids and mites, which are found in enclosed spaces such as,
for example, dwellings, factory halls, offices, vehicle cabins and
the like. They can be employed in domestic insecticide products for
controlling these pests alone or in combination with other active
compounds and auxiliaries. They are active against sensitive and
resistant species and against all development stages. These pests
include:
[0767] From the order of the Scorpionidea, for example, Buthus
occitanus.
[0768] From the order of the Acarina, for example, Argas persicus,
Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus
domesticus, Ornithodorus moubat, Rhipicephalus sanguineus,
Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides
pteronissimus, Dermatophagoides forinae.
[0769] From the order of the Araneae, for example, Aviculariidae,
Araneidae.
[0770] From the order of the Opiliones, for example,
Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones
phalangium.
[0771] From the order of the Isopoda, for example, Oniscus asellus,
Porcellio scaber.
[0772] From the order of the Diplopoda, for example, Blaniulus
guttulatus, Polydesmus spp.
[0773] From the order of the Chilopoda, for example, Geophilus
spp.
[0774] From the order of the Zygentoma, for example, Ctenolepisma
spp., Lepisma saccharina, Lepismodes inquilinus.
[0775] From the order of the Blattaria, for example, Blatta
orientalis, Blattella germanica, Blattella asahinai, Leucophaea
maderae, Panchlora spp., Parcoblatta spp., Periplaneta
australasiae, Periplaneta americana, Periplaneta brunnea,
Periplaneta fuliginosa, Supella longipalpa.
[0776] From the order of the Saltatoria, for example, Acheta
domesticus.
[0777] From the order of the Dermaptera, for example, Forficula
auricularia.
[0778] From the order of the Isoptera, for example, Kalotermes
spp., Reticulitermes spp.
[0779] From the order of the Psocoptera, for example, Lepinatus
spp., Liposcelis spp.
[0780] From the order of the Coleptera, for example, Anthrenus
spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia
spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius,
Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
[0781] From the order of the Diptera, for example, Aedes aegypti,
Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora
erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex
pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca
domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,
Stomoxys calcitrans, Tipula paludosa.
[0782] From the order of the Lepidoptera, for example, Achroia
grisella, Galleria mellonella, Plodia interpunctella, Tinea
cloacella, Tinea pellionella, Tineola bisselliella.
[0783] From the order of the Siphonaptera, for example,
Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga
penetrans, Xenopsylla cheopis.
[0784] From the order of the Hymenoptera, for example, Camponotus
herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,
Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
[0785] From the order of the Anoplura, for example, Pediculus
humanus capitis, Pediculus humanus corporis, Phthirus pubis.
[0786] From the order of the Heteroptera, for example, Cimex
hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma
infestans.
[0787] They are used in the household insecticides sector alone or
in combination with other suitable active compounds such as
phosphoric esters, carbamates, pyrethroids, growth regulators or
active compounds from other known classes of insecticides.
[0788] They are used in aerosols, pressure-free spray products, for
example pump and atomizer sprays, automatic fogging systems,
foggers, foams, gels, evaporator products with evaporator tablets
made of cellulose or polymer, liquid evaporators, gel and membrane
evaporators, propeller-driven evaporators, energy-free, or passive,
evaporation systems, moth papers, moth bags and moth gels, as
granules or dusts, in baits for spreading or in bait stations.
[0789] The active compounds or active compound combinations
according to the invention can also be used as defoliants,
desiccants, haulm killers and, in particular, as weed killers.
Weeds in the broadest sense are understood as meaning all plants
which grow at locations where they are undesired. Whether the
substances according to the invention act as nonselective or
selective herbicides depends essentially on the application
rate.
[0790] The active compounds or active compound combinations
according to the invention can be used for example in the following
plants:
[0791] Dicotyledonous weeds of the genera: Abutilon, Amaranthus,
Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bettis, Bidens,
Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium,
Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia,
Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium,
Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo,
Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca,
Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio,
Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria,
Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola,
Xanthium.
[0792] Dicotyledonous crops of the genera: Arachis, Beta, Brassica,
Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium,
Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum,
Solanum, Vicia.
[0793] Monocotyledonous weeds of the genera: Aegilops, Agropyron,
Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus,
Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria,
Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca,
Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa,
Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa,
Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
[0794] Monocotyledonous crops of the genera: Allium, Ananas,
Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale,
Sorghum, Triticale, Triticum, Zea.
[0795] However, the use of the active compounds or active compound
combinations according to the invention is in no way restricted to
these genera, but extends in the same manner to other plants.
[0796] Depending on the concentration, the active compounds or
active compound combinations according to the invention are
suitable for the nonselective weed control on, for example,
industrial terrains and railway tracks and on paths and locations
with and without trees. Likewise the active compounds according to
the invention can be employed for controlling weeds in perennial
crops, for example forests, ornamental 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 hop
fields, on lawns, turf and pastureland, and for the selective
control of weeds in annual crops.
[0797] The compounds or active compound combinations according to
the invention have strong herbicidal activity and a broad activity
spectrum when used on the soil and on aerial plant parts. To a
certain extent, they are also suitable for the selective control of
monocotyledonous and dicotyledonous weeds in monocotyledonous and
dicotyledonous crops, both pre- and post-emergence.
[0798] At certain concentrations or application rates, the active
compounds or active compound combinations according to the
invention can also be employed for controlling animal pests and
fungal or bacterial plant diseases. If appropriate, they can also
be used as intermediates or precursors for the synthesis of other
active compounds.
[0799] The active compounds or active compound combinations can be
converted into the customary formulations, such as solutions,
emulsions, wettable powders, suspensions, powders, dusting agents,
pastes, soluble powders, granules, suspoemulsion concentrates,
natural and synthetic materials impregnated with active compound,
and very fine capsules in polymeric substances.
[0800] 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
surfactants, that is emulsifiers and/or dispersants and/or
foam-formers.
[0801] If the extender used is water, it is also possible to use,
for example, organic solvents as auxiliary solvents. Suitable
liquid solvents are essentially: 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 petroleum fractions, mineral and vegetable
oils, alcohols, such as butanol or glycol, and also 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, and also water.
[0802] Suitable solid carriers are: 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 finely divided silica, alumina
and silicates, suitable solid carriers for granules are: for
example crushed and fractionated natural rocks such as calcite,
marble, pumice, sepiolite and dolomite, and also synthetic granules
of inorganic and organic meals, and granules of organic material
such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam-formers are: 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,
arylsulpho-nates and protein hydrolysates; suitable dispersants
are: for example lignosulphite waste liquors and
methylcellulose.
[0803] Tackifiers 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, and
also natural phospholipids, such as cephalins and lecithins, and
synthetic phospholipids, can be used in the formulations. Other
possible additives are mineral and vegetable oils.
[0804] 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.
[0805] The formulations generally comprise between 0.1 and 95
percent by weight of active compound, preferably between 0.5 and
90%.
[0806] The active compounds according to the invention, as such or
in their formulations, can also be used for weed control purposes
as a mixture with known herbicides and/or with substances which
improve crop plant tolerance ("safeners"), ready mixes or tank
mixes being possible. Mixtures with herbicide products which
contain one or more known herbicides and a safener are hence also
possible.
[0807] Herbicides which are suitable for the mixtures are known
herbicides, for example
[0808] acetochlor, acifluorfen (-sodium), aclonifen, alachlor,
alloxydim (-sodium), ametryne, ami-carbazone, amidochlor,
amidosulfuron, anilofos, asulam, atrazine, azafenidin,
azimsulfuron, beflubutamid, benazolin (-ethyl), benfuresate,
bensulfuron (-methyl), bentazone, benzfendizone, benzobicyclon,
benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac
(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor,
butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim,
carbetamide, carfentrazone (-ethyl), chlo-methoxyfen, chloramben,
chloridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron,
chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron,
clefoxydim, clethodim, clodinafop (-propargyl), clomazone,
clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam
(-methyl), cumyluron, cyanazine, cybutryne, cycloate,
cyclosulfamuron, cycloxydim, cy-halofop (-butyl), 2,4-D, 2,4-DB,
desmedipham, diallate, dicamba, dichlorprop (--P), diclofop
(-methyl), diclosulam, diethatyl (-ethyl), difenzoquat,
diflufenican, diflufenzopyr, dimef-uron, dimepiperate,
dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine,
diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC,
esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate,
ethoxyfen, ethoxysulfuron, etobenzanid, fenoxa-prop (--P-ethyl),
fentrazamide, flamprop (-isopropyl, -isopropyl-L, -methyl),
flazasulfuron, florasulam, fluazifop (--P-butyl), fluazolate,
flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac
(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron,
fluoro-chloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil,
flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone,
fluoroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone,
fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron,
glufosinate (-ammonium), glyphosate (-isopropylammonium),
halosafen, haloxyfop (-ethoxyethyl, --P-methyl), hexazinone,
imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic,
imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron
(-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron,
isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lacto-fen,
lenacil, linuron, MCPA, mecoprop, mefenacet, mesosulfurone,
mesotrione, metamitron, metazachlor, methabenzthiazuron,
metobenzuron, metobromuron, (alpha-) metolachlor, metosulam,
metoxuron, metribuzin, metsulfuron (-methyl), molinate,
monolinuron, napro-anilide, napropamide, neburon, nicosulfuron,
norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon,
oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic
acid, pen-dimethalin, pendralin, pentoxazone, phenmedipham,
picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron
(-methyl), profluazol, prometryn, propachlor, propanil,
propa-quizafop, propisochlor, propoxycarbazone (-sodium),
propyzamide, prosulfocarb, prosulf-uron, pyraflufen (-ethyl),
pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen,
pyri-benzoxim, pyributicarb, pyridate, pyridatol, pyriftalide,
pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac,
quinmerac, quinoclamine, quizalofop (--P-ethyl, --P-tefuryl),
rimsulf-uron, sethoxydim, simazine, simetryn, sulcotrione,
sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron,
tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn,
thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron
(-methyl), thiobencarb, tio-carbazil, tralkoxydim, triallate,
triasulfuron, tribenuron (-methyl), triclopyr, tridiphane,
trifluralin, trifloxysulfuron, triflusulfuron (-methyl),
tritosulfuron.
[0809] A mixture with other known active compounds, such as
fungicides, insectides, acaricides, nematicides, bird repellents,
plant nutrients and soil conditioners, is also possible.
[0810] The active compounds or active compound combinations can be
applied as such, in the form of their formulations or the use forms
prepared therefrom by further dilution, such as ready-to-use
solutions, suspensions, emulsions, powders, pastes and granules.
They are applied in the customary manner, for example by pouring,
spraying, atomizing, spreading.
[0811] The active compounds or active compound combinations
according to the invention can be applied both before and after
plant emergence. They can also be incorporated into the soil prior
to planting.
[0812] The application rate of active compound can vary within a
substantial range. Essentially, it depends on the nature of the
desired effect. In general, the application rates are between 1 g
and 10 kg of active compound per hectare of soil area, preferably
between 5 g and 5 kg per ha.
[0813] The advantageous effect of the compatibility with crop
plants of the active compound combinations according to the
invention is particularly pronounced at certain concentration
ratios. However, the weight ratios of the active compounds in the
active compound combinations can be varied within relatively wide
ranges. In general, from 0.001 to 1000 parts by weight, preferably
from 0.01 to 100 parts by weight, particularly preferably 0.05 to
20 parts by weight, of one of the compounds which improves crop
plant compatibility (antidotes/safeners) mentioned above under (b')
are present per part by weight of active compound of the formula
(I).
[0814] The active compound combinations according to the invention
are generally applied in the form of finished formulations.
However, the active compounds contained in the active compound
combinations can, as individual formulations, also be mixed during
use, i.e. be applied in the form of tank mixes.
[0815] For certain applications, in particular by the
post-emergence method, it may furthermore be advantageous to
include, as further additive in the formulations, mineral or
vegetable oils which are tolerated by plants (for example
commercial preparation "Rako Binol"), or ammonium salts, such as,
for example, ammonium sulphate or ammonium thiocyanate.
[0816] The novel active compound combinations can be used as such,
in the form of their formulations or the use forms prepared
therefrom by further dilution, such as ready-to-use solutions,
suspensions, emulsions, powders, pastes and granules. Application
is in the customary manner, for example by watering, spraying,
atomizing, dusting or scattering.
[0817] The application rates of the active compound combinations
according to the invention can be varied within a certain range;
they depend, inter alia, on the weather and on soil factors. In
general, the application rates are between 0.001 and 5 kg per ha,
preferably between 0.005 and 2 kg per ha, particularly preferably
between 0.01 and 0.5 kg per ha.
[0818] The active compound combinations according to the invention
can be applied before and after emergence of the plants, that is to
say by the pre-emergence and post-emergence method.
[0819] Depending on their properties, the safeners to be used
according to the invention can be used for pretreating the seed of
the crop plant (seed dressing) or can be introduced into the seed
furrows prior to sowing or be used separately prior to the
herbicide or together with the herbicide, before or after emergence
of the plants.
[0820] Examples of plants which may be mentioned are important crop
plants, such as cereals (wheat, rice), maize, soybeans, potatoes,
cotton, oil seed rape, beet, sugarcane and also fruit plants (with
the fruits apples, pears, citrus fruits and grapevines), greater
emphasis being given to maize, soybeans, potatoes, cotton and oil
seed rape.
[0821] The substances according to the invention have potent
microbicidal activity and can be employed for controlling unwanted
microorganisms, such as fungi and bacteria, in crop protection and
in the protection of materials.
[0822] Fungicides can be employed in crop protection for
controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes,
Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
[0823] Bactericides can be employed in crop protection for
controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae,
Corynebacteriaceae and Streptomycetaceae.
[0824] Some pathogens causing fungal and bacterial diseases which
come under the generic names listed above may be mentioned as
examples, but not by way of limitation:
[0825] Xanthomonas species, such as, for example, Xanthomonas
campestris pv. oryzae;
[0826] Pseudomonas species, such as, for example, Pseudomonas
syringae pv. lachrymans;
[0827] Erwinia species, such as, for example, Erwinia
amylovora;
[0828] Pythium species, such as, for example, Pythium ultimum;
[0829] Phytophthora species, such as, for example, Phytophthora
infestans;
[0830] Pseudoperonospora species, such as, for example,
Pseudoperonospora humuli or Pseudoperonospora cubensis;
[0831] Plasmopara species, such as, for example, Plasmopara
viticola; Bremia species, such as, for example, Bremia
lactucae;
[0832] Peronospora species, such as, for example, Peronospora pisi
or P. brassicae;
[0833] Erysiphe species, such as, for example, Erysiphe
graminis;
[0834] Sphaerotheca species, such as, for example, Sphaerotheca
fuliginea;
[0835] Podosphaera species, such as, for example, Podosphaera
leucotricha;
[0836] Venturia species, such as, for example, Venturia
inaequalis;
[0837] Pyrenophora species, such as, for example, Pyrenophora teres
or P. graminea
[0838] (conidia form: Drechslera, syn: Helminthosporium);
[0839] Cochliobolus species, such as, for example, Cochliobolus
sativus
[0840] (conidia form: Drechslera, syn: Helminthosporium);
[0841] Uromyces species, such as, for example, Uromyces
appendiculatus;
[0842] Puccinia species, such as, for example, Puccinia
recondita;
[0843] Sclerotinia species, such as, for example, Sclerotinia
sclerotiorum;
[0844] Tilletia species, such as, for example, Tilletia caries;
[0845] Ustilago species, such as, for example, Ustilago nuda or
Ustilago avenae;
[0846] Pellicularia species, such as, for example, Pellicularia
sasakii;
[0847] Pyricularia species, such as, for example, Pyricularia
oryzae;
[0848] Fusarium species, such as, for example, Fusarium
culmorum;
[0849] Botrytis species, such as, for example, Botrytis
cinerea;
[0850] Septoria species, such as, for example, Septoria
nodorum;
[0851] Leptosphaeria species, such as, for example, Leptosphaeria
nodorum;
[0852] Cercospora species, such as, for example, Cercospora
canescens;
[0853] Alternaria species, such as, for example, Alternaria
brassicae; and
[0854] Pseudocercosporella species, such as, for example,
Pseudocercosporella herpotrichoides.
[0855] The active compounds according to the invention also have
very good fortifying action in plants. Accordingly, they can be
used for mobilizing the defences of the plant against attack by
unwanted microorganisms.
[0856] In the present context, plant-fortifying
(resistance-inducing) substances are to be understood as meaning
those substances which are capable of stimulating the defence
system of plants such that, when the treated plants are
subsequently inoculated with unwanted microorganisms, they show
substantial resistance against these microorganisms.
[0857] In the present case, undesirable microorganisms are to be
understood as meaning phytopathogenic fungi, bacteria and viruses.
Accordingly, the substances according to the invention can be used
to protect plants for a certain period after the treatment against
attack by the pathogens mentioned. The period for which protection
is provided generally extends over 1 to 10 days, preferably 1 to 7
days, after the treatment of the plants with the active
compounds.
[0858] The fact that the active compounds are well tolerated by
plants at the concentrations required for controlling plant
diseases permits the treatment of above-ground parts of plants, of
propagation stock and seeds, and of the soil.
[0859] The active compounds according to the invention are also
suitable for increasing the yield of crops. In addition, they show
reduced toxicity and are well tolerated by plants.
[0860] At certain concentrations and application rates, the active
compounds according to the invention can also be used as
herbicides, for influencing plant growth and for controlling animal
pests. If appropriate, they can also be used as intermediates and
precursors for the synthesis of further active compounds.
[0861] In the protection of materials, the compounds according to
the invention can be employed for protecting industrial materials
against infection with, and destruction by, unwanted
microorganisms.
[0862] Industrial materials in the present context are understood
as meaning non-living materials which have been prepared for use in
industry. For example, industrial materials which are intended to
be protected by active compounds according to the invention from
microbial change or destruction can be adhesives, sizes, paper and
board, textiles, leather, wood, paints and plastic articles,
cooling lubricants and other materials which can be infected with,
or destroyed by, microorganisms. Parts of production plants, for
example cooling-water circuits, which may be impaired by the
proliferation of microorganisms may also be mentioned within the
scope of the materials to be protected. Industrial materials which
may be mentioned within the scope of the present invention are
preferably adhesives, sizes, paper and board, leather, wood,
paints, cooling lubricants and heat-transfer liquids, particularly
preferably wood.
[0863] Microorganisms capable of degrading or changing the
industrial materials which may be mentioned are, for example,
bacteria, fungi, yeasts, algae and slime organisms. The active
compounds according to the invention preferably act against fungi,
in particular moulds, wood-discolouring and wood-destroying fungi
(Basidiomycetes), and against slime organisms and algae.
[0864] Microorganisms of the following genera may be mentioned as
examples:
[0865] Alternaria, such as Alternaria tenuis,
[0866] Aspergillus, such as Aspergillus niger,
[0867] Chaetomium, such as Chaetomium globosum,
[0868] Coniophora, such as Coniophora puetana,
[0869] Lentinus, such as Lentinus tigrinus,
[0870] Penicillium, such as Penicillium glaucum, Polyporus, such as
Polyporus versicolor,
[0871] Aureobasidium, such as Aureobasidium pullulans, Sclerophoma,
such as Sclerophoma pityophila, Trichoderma, such as Trichoderma
viride,
[0872] Escherichia, such as Escherichia coli,
[0873] Pseudomonas, such as Pseudomonas aeruginosa, and
[0874] Staphylococcus, such as Staphylococcus aureus.
[0875] Depending on their particular physical and/or chemical
properties, the active compounds can be converted into the
customary formulations, such as solutions, emulsions, suspensions,
powders, foams, pastes, granules, aerosols and microencapsulations
in polymeric substances and in coating compositions for seeds, and
ULV cool and warm fogging formulations.
[0876] These formulations are produced in a known manner, for
example by mixing the active compounds with extenders, that is
liquid solvents, liquefied gases under pressure, and/or solid
carriers, optionally with the use of surfactants, that is
emulsifiers and/or dispersants, and/or foam formers. If the
extender used is water, it is also possible to employ, for example,
organic solvents as auxiliary solvents. Essentially, suitable
liquid solvents are: aromatics such as xylene, toluene or
alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic
hydrocarbons such as chlorobenzenes, chloroethylenes or methylene
chloride, aliphatic hydrocarbons such as cyclohexane or paraffins,
for example petroleum fractions, alcohols such as butanol or glycol
and their ethers and esters, ketones such as acetone, methyl ethyl
ketone, methyl isobutyl ketone or cyclohexanone, strongly polar
solvents such as dimethylformamide and dimethyl sulphoxide, or else
water. Liquefied gaseous extenders or carriers are to be understood
as meaning liquids which are gaseous at standard temperature and
under atmospheric pressure, for example aerosol propellants such as
halogenated hydrocarbons, or else butane, propane, nitrogen and
carbon dioxide. Suitable solid carriers are: for example ground
natural minerals such as kaolins, clays, talc, chalk, quartz,
attapulgite, montmorillonite or diatomaceous earth, and ground
synthetic minerals such as finely divided silica, alumina and
silicates. Suitable solid carriers for granules are: for example
crushed and fractionated natural rocks such as calcite, marble,
pumice, sepiolite and dolomite, or else synthetic granules of
inorganic and organic meals, and granules of organic material such
as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable
emulsifiers and/or foam formers are: for example nonionic and
anionic emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates, or else protein hydrolysates. Suitable dispersants
are: for example lignosulphite waste liquors and
methylcellulose.
[0877] Tackifiers 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, or
else natural phospholipids such as cephalins and lecithins and
synthetic phospholipids can be used in the formulations. Other
possible additives are mineral and vegetable oils.
[0878] 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.
[0879] The formulations generally comprise between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90%.
[0880] The active compounds according to the invention can be used
as such or in their formulations, also in a mixture with known
fungicides, bactericides, acaricides, nematicides or insecticides,
to broaden, for example, the activity spectrum or to prevent
development of resistance. In many cases, synergistic effects are
obtained, i.e. the activity of the mixture is greater than the
activity of the individual components.
[0881] Examples of suitable mixing components are the
following:
Fungicides:
[0882] 2-phenylphenol; 8-hydroxyquinoline sulphate;
acibenzolar-5-methyl; aldimorph; amidoflumet; ampropylfos;
ampropylfos-potassium; andoprim; anilazine; azaconazole;
azoxystrobin; benalaxyl; benodanil; benomyl;
benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl;
bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S;
bromuconazole; bupirimate; buthiobate; butylamine; calcium
polysulphide; capsimycin; captafol; captan; carbendazim; carboxin;
carpropamid; carvone; chinomethionat; chlobenthiazone;
chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon;
cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil;
cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone;
dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb;
difenoconazole; diflumetorim; dimethirimol; dimethomorph;
dimoxystrobin; diniconazole; diniconazole-M; dinocap;
diphenylamine; dipyrithione; ditalimfos; dithianon; dodine;
drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol;
etridiazole; famoxadone; fenamidone; fenapanil; fenarimol;
fenbuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil;
fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam;
flubenzimine; fludioxonil; flumetover; flumorph; fluoromide;
fluoxastrobin; fluquinconazole; flurprimidol; flusilazole;
flusulfamide; flutolanil; flutriafol; folpet; fosetyl-Al;
fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil;
furmecyclox; guazatine; hexachlorobenzene; hexaconazole;
hymexazole; imazalil; imibenconazole; iminoctadine triacetate;
iminoctadine tris(albesil); iodocarb; ipconazole; iprobenfos;
iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione;
kasugamycin; kresoxim-methyl; mancozeb; maneb; meferimzone;
mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole;
methasulfocarb; methfuroxam; metiram; metominostrobin; metsulfovax;
mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen;
nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin;
oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin;
paclobutrazole; pefurazoate; penconazole; pencycuron; phosdiphen;
phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim;
probenazole; prochloraz; procymidone; propamocarb;
propanosine-sodium; propiconazole; propineb; proquinazid;
prothioconazole; pyraclostrobin; pyrazophos; pyrifenox;
pyrimethanil; pyroquilon; pyroxyfur; pyrrolenitrine; quinconazole;
quinoxyfen; quintozene; simeconazole; spiroxamine; sulphur;
tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole;
thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram;
tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol;
triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph;
trifloxystrobin; triflumizole; triforine; triticonazole;
uniconazole; validamycin A; vinclozolin; zineb; ziram; zoxamide;
(2S)--N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-
-3-methyl-2-[(methylsulphonyl)amino]butanamide;
1-(1-naphthalenyl)-1H-pyrrole-2,5-dione;
2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine;
2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide;
2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxam-
ide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; actinovate;
cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol;
methyl
1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-S-carboxylate;
monopotassium carbonate;
N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide;
N-butyl-8-(1,1-dimethylethyl)-1-oxaspiro[4.5]decane-3-amine; sodium
tetrathiocarbonate; and copper salts and preparations, such as
Bordeaux mixture; copper hydroxide; copper naphthenate; copper
oxychloride; copper sulphate; cufraneb; cuprous oxide; mancopper;
oxine-copper.
Bactericides:
[0883] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
Insecticides/Acaricides/Nematicides:
[0884] abamectin, ABG-9008, acephate, acequinocyl, acetamiprid,
acetoprole, acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb,
aldicarb, aldoxycarb, allethrin, allethrin 1R-isomers,
alpha-cypermethrin (alphamethrin), amidoflumet, aminocarb, amitraz,
avermectin, AZ-60541, azadirachtin, azamethiphos, azinphos-methyl,
azinphos-ethyl, azocyclotin,
[0885] Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis,
Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348,
Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain
NCTC-11821, baculoviruses, Beauveria bassiana, Beauveria tenella,
benclothiaz, bendiocarb, benfuracarb, bensultap, benzoximate,
beta-cyfluthrin, beta-cypermethrin, bifenazate, bifenthrin,
binapacryl, bioallethrin, bioallethrin-5-cyclopentyl-isomer,
bioethanomethrin, biopermethrin, bioresmethrin, bistrifluoron,
BPMC, brofenprox, bromophos-ethyl, bromopropylate, bromfenvinfos
(-methyl), BTG-504, BTG-505, bufencarb, buprofezin, butathiofos,
butocarboxim, butoxycarboxim, butylpyridaben,
cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion,
carbosulfan, cartap, CGA-50439, chinomethionat, chlordane,
chlordimeform, chloethocarb, chlorethoxyfos, chlorfenapyr,
chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate,
chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos
(-ethyl), chlovaporthrin, chromafenozide, cis-cypermethrin,
cis-resmethrin, cis-permethrin, clocythrin, cloethocarb,
clofentezine, clothianidin, clothiazoben, codlemone, coumaphos,
cyanofenphos, cyanophos, cycloprene, cycloprothrin, Cydia
pomonella, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,
cyphenothrin (1R-trans-isomer), cyromazine, DDT, deltamethrin,
demeton-5-methyl, demeton-5-methylsulphone, diafenthiuron,
dialifos, diazinon, dichlofenthion, dichlorvos, dicofol,
dicrotophos, dicyclanil, diflubenzuron, dimeflurhrin, dimethoate,
dimethylvinphos, dinobuton, dinocap, dinotefuran, diofenolan,
disulfoton, docusat-sodium, dofenapyn, DOWCO-439, eflusilanate,
emamectin, emamectin-benzoate, empenthrin (1R-isomer), endosulfan,
Entomopthora spp., EPN, esfenvalerate, ethiofencarb, ethiprole,
ethion, ethoprophos, etofenprox, etoxazole, etrimfos, famphur,
fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin,
fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb,
fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate,
fensulfothion, fenthion, fentrifanil, fenvalerate, fipronil,
flonicamid, fluacrypyrim, fluazuron, flubenzimine,
flubrocythrinate, flucycloxuron, flucythrinate, flufenerim,
flufenoxuron, flufenprox, flumethrin, flupyrazofos, flutenzin
(flufenzine), fluvalinate, fonofos, formetanate, formothion,
fosmethilan, fosthiazate, fubfenprox (fluproxyfen), furathiocarb,
gamma-cyhalothrin, gamma-HCH, gossyplure, grandlure, granulosis
viruses, halfenprox, halofenozide, HCH, HCN-801, heptenophos,
hexaflumuron, hexythiazox, hydramethylnone, hydroprene, IKA-2002,
imidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobenfos,
isazofos, isofenphos, isoprocarb, isoxathion, ivermectin,
japonilure, kadethrin, nuclear polyhedrosis viruses, kinoprene,
lambda-cyhalothrin, lindane, lufenuron, malathion, mecarbam,
mesulfenfos, metaldehyde, metam-sodium, methacrifos, methamidophos,
Metharhizium anisopliae, Metharhizium flavoviride, methidathion,
methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide,
metofluthrin, metolcarb, metoxadiazone, mevinphos, milbemectin,
milbemycin, MKI-245, MON-45700, monocrotophos, moxidectin, MTI-800,
naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide,
nicotine, nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250,
NNI-9768, novaluron, noviflumuron, OK-5101, OK-5201, OK-9601,
OK-9602, OK-9701, OK-9802, omethoate, oxamyl, oxydemeton-methyl,
Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl),
permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R-trans
isomer), phenthoate, phorate, phosalone, phosmet, phosphamidon,
phosphocarb, phoxim, piperonyl butoxide, pirimicarb,
pirimiphos-methyl, pirimiphos-ethyl, potassium oleate, prallethrin,
profenofos, profluthrin, promecarb, propaphos, propargite,
propetamphos, propoxur, prothiofos, prothoate, protrifenbute,
pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben,
pyridalyl, pyridaphenthion, pyridathion, pyrimidifen, pyriproxyfen,
quinalphos, resmethrin, RH-5849, ribavirin, RU-12457, RU-15525,
S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad,
spirodiclofen, spiromesifen, sulfluramid, sulfotep, sulprofos,
SZI-121, tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos,
teflubenzuron, tefluthrin, temephos, temivinphos, terbam, terbufos,
tetrachlorvinphos, tetradifon, tetramethrin, tetramethrin
(1R-isomer), tetrasul, theta-cypermethrin, thiacloprid,
thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate,
thiodicarb, thiofanox, thiometon, thiosultap-sodium, thuringiensin,
tolfenpyrad, tralocythrin, tralomethrin, transfluthrin,
triarathene, triazamate, triazophos, triazuron, trichlophenidine,
trichlorfon, trichoderma atroviride, triflumuron, trimethacarb,
vamidothion, vaniliprole, verbutin, Verticillium lecanii,
WL-108477, WL-40027,
[0886] YI-5201, YI-5301, YI-5302, XMC, xylylcarb, ZA-3274,
zeta-cypermethrin, zolaprofos, ZX.sup.1-8901, the compound
3-methylphenyl propylcarbamate (tsumacide Z), the compound
3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octa-
ne-3-carbonitrile (CAS-Reg. No. 185982-80-3) and the corresponding
3-endo-isomer (CAS-Reg. No. 185984-60-5) (cf. WO-96/37494,
WO-98/25923), and preparations which comprise insecticidally active
plant extracts, nematodes, fungi or viruses.
[0887] A mixture with other known active compounds, such as
herbicides, or with fertilizers and growth regulators, is also
possible.
[0888] In addition, the compounds of the formula (I) according to
the invention also have very good antimycotic activity. They have a
very broad antimycotic activity spectrum in particular against
dermatophytes and yeasts, moulds and diphasic fungi (for example
against Candida species, such as Candida albicans, Candida
glabrata), and Epidermophyton floccosum, Aspergillus species, such
as Aspergillus niger and Aspergillus fumigatus, Trichophyton
species, such as Trichophyton mentagrophytes,
[0889] Microsporon species such as Microsporon canis and audouinii.
The list of these fungi by no means limits the mycotic spectrum
covered, but is only for illustration.
[0890] The active compounds can be used as such, in the form of
their formulations or the use forms prepared therefrom, such as
ready-to-use solutions, suspensions, wettable powders, pastes,
soluble powders, dusts and granules. Application is carried out in
a customary manner, for example by watering, spraying, atomizing,
broadcasting, dusting, foaming, spreading, etc. It is furthermore
possible to apply the active compounds by the ultra-low-volume
method, or to inject the active compound preparation or the active
compound itself into the soil. It is also possible to treat the
seeds of the plants.
[0891] When using the active compounds according to the invention
as fungicides, the application rates can be varied within a
relatively wide range, depending on the kind of application. For
the treatment of parts of plants, the active compound application
rates are generally between 0.1 and 10,000 g/ha, preferably between
10 and 1000 g/ha. For seed dressing, the active compound
application rates are generally between 0.001 and 50 g per kilogram
of seed, preferably between 0.01 and 10 g per kilogram of seed. For
the treatment of the soil, the active compound application rates
are generally between 0.1 and 10,000 g/ha, preferably between 1 and
5000 g/ha.
[0892] The preparation and the use of the active compounds
according to the invention is illustrated by the examples
below.
PREPARATION EXAMPLES
Example I-1-a-1
##STR00235##
[0894] At 40-50.degree. C., 3.15 g of the compound of Example II-1
in 7 ml of anhydrous dimethylformamide (DMF) are added to 1.95 g
(0.042 mol) of potassium tert-butoxide in 6 ml of anhydrous DMF,
and the mixture is stirred at 60.degree. C. for 1 hour.
[0895] The reaction mixture is stirred into ice-water and, at
0-10.degree. C., acidified to pH 4 using concentrated hydrochloric
acid. The precipitate is washed with ice-water and dried. This is
followed by column-chromatographic purification on silica gel
(dichloromethane:methanol, 20:1).
[0896] Yield: 190 mg (6% of theory). M.p.: 265.degree. C.
[0897] Analogously to Example (I-1-a-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (I-1-a) are obtained
TABLE-US-00010 (I-1-a) ##STR00236## Ex. No. W X Y Z D A B m.p.
.degree. C. isomer I-1-a-2 CH.sub.3 CH.sub.3 H ##STR00237## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- 277 .beta.
I-1-a-3 H CH.sub.3 H ##STR00238## H --(CH.sub.2).sub.5-- 286 --
I-1-a-4 CH.sub.3 CH.sub.3 H ##STR00239## H CH.sub.3 CH.sub.3 308 --
I-1-a-5 CH.sub.3 CH.sub.3 H ##STR00240## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- 291 .beta.
I-1-a-6 CH.sub.3 C.sub.2H.sub.5 H ##STR00241## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- 284 .beta.
I-1-a-7 CH.sub.3 C.sub.2H.sub.5 H ##STR00242## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- 318 .beta.
I-1-a-8 C.sub.2H.sub.5 C.sub.2H.sub.5 H ##STR00243## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- 278 .beta.
I-1-a-9 CH.sub.3 CH.sub.3 Cl ##STR00244## H CH.sub.3 CH.sub.3 305
-- I-1-a-10 H C.sub.2H.sub.5 H ##STR00245## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- 167 .beta.
I-1-a-11 C.sub.2H.sub.5 Cl H ##STR00246## H CH.sub.3 CH.sub.3 294
-- I-1-a-12 C.sub.2H.sub.5 Cl H ##STR00247## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- 272 .beta.
I-1-a-13 CH.sub.3 C.sub.2H.sub.5 H ##STR00248## H
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- 269 -- I-1-a-14 CH.sub.3
C.sub.2H.sub.5 H ##STR00249## H CH.sub.3 CH.sub.3 306 -- I-1-a-15 H
Cl H ##STR00250## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- *7.57-7.77 (m,
3H, Ar--H), 7.87, 8.18 (2 s, 2H Pyr--H) -- I-1-a-16 CH.sub.3
C.sub.2H.sub.5 H ##STR00251## H ##STR00252## CH.sub.3 171-172 --
*.sup.1H-NMR (400 MHz, d.sub.6-DMSO): Shift .delta. in ppm.
Example I-1-b-1
##STR00253##
[0899] Under argon, 0.6 g of the compound of Example I-1-a-1 is
initially charged in 30 ml of anhydrous ethyl acetate and 0.15 g of
triethylamine (1.5 mmol)=0.21 ml. The reaction is catalyzed using
10 mg of Steglich base, 0.16 g (0.0015 mol) of isobutyl chloride in
2 ml of anhydrous dichloro-methane is added under reflux. The
reaction is monitored by thin-layer chromatography. The solvent is
evaporated and the residue is chromatographed on silica gel using
the mobile phase dichloromethane/ethyl acetate 3:1.
[0900] Yield: 0.25 g (34% of theory), m.p. 217.degree. C.
[0901] Analogously to Example (I-1-b-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (I-1-b) are obtained
TABLE-US-00011 (I-1-b) ##STR00254## Ex. No. W X Y Z D A B R.sup.1
m.p. .degree. C. isomer I-1-b-2 CH.sub.3 CH.sub.3 H ##STR00255## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
i-C.sub.3H.sub.7 247 .beta. I-1-b-3 CH.sub.3 CH.sub.3 H
##STR00256## H --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
H.sub.3C--O--CH.sub.2-- 237 .beta. I-1-b-4 CH.sub.3 C.sub.2H.sub.5
H ##STR00257## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
i-C.sub.3H.sub.7 221 .beta. I-1-b-5 H C.sub.2H.sub.5 H ##STR00258##
H --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
i-C.sub.3H.sub.7 *3.21 (m, 1H, CH OCH.sub.3), 1.05 (d, 6H,
CH(CH.sub.3).sub.2) .beta. I-1-b-6 CH.sub.3 C.sub.2H.sub.5 H
##STR00259## H CH.sub.3 CH.sub.3 i-C.sub.3H.sub.7 140-141 --
*.sup.1H-NMR (400 MHz, CDCl.sub.3): Shift .delta. in ppm.
Example I-1-c-1
##STR00260##
[0903] At 10-20.degree. C., 0.14 ml (1 mmol) of triethylamine and
0.1 ml (1 mmol) of ethyl chloroformate in 5 ml of anhydrous
dichloromethane are added to 0.48 g of the compound of Example
I-1-a-1 in 10 ml of anhydrous dichloromethane.
[0904] The mixture is stirred at room temperature and the reaction
is monitored by thin-layer chromatography.
[0905] The solvent is distilled off and the residue is taken up in
dichloromethane, washed twice with 5 ml of 0.5 N NaOH solution and
dried. The solvent is distilled off. The product is then purified
by column chromatography on silica gel (dichloromethane:ethyl
acetate 3:1).
[0906] Yield: 0.3 g (65% of theory), m.p. 240.degree. C.
[0907] Analogously to Example (I-1-c-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (I-1-c) are obtained
TABLE-US-00012 (I-1-c) ##STR00261## Ex. No. W X Y Z D A B M R.sup.2
m.p. .degree. C. isomer I-1-c-2 CH.sub.3 CH.sub.3 H ##STR00262## H
CH.sub.3 CH.sub.3 O C.sub.2H.sub.5 159 -- I-1-c-3 CH.sub.3 CH.sub.3
H ##STR00263## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- O
C.sub.2H.sub.5 209-212 .beta. I-1-c-4 H C.sub.2H.sub.5 H
##STR00264## H --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
O C.sub.2H.sub.5 192-197 .beta. I-1-c-5 CH.sub.3 CH.sub.3 H
##STR00265## H --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
O C.sub.2H.sub.5 *1.13 (t, 3H, CH.sub.2--CH.sub.3) 2.28 (s, 6H,
Ar--CH.sub.3) 7.62, 7.88 (2s, 2H, Pyr--H) .beta. I-1-c-6 CH.sub.3
C.sub.2H.sub.5 H ##STR00266## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- O
C.sub.2H.sub.5 220 .beta. I-1-c-7 CH.sub.3 C.sub.2H.sub.5 H
##STR00267## H --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
O C.sub.2H.sub.5 197 .beta. I-1-c-8 C.sub.2H.sub.5 Cl H
##STR00268## H CH.sub.3 CH.sub.3 O C.sub.2H.sub.5 178 -- I-1-c-9
C.sub.2H.sub.5 Cl H ##STR00269## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- O
C.sub.2H.sub.5 196 .beta. I-1-c-10 C.sub.2H.sub.5 C.sub.2H.sub.5 H
##STR00270## H --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
O C.sub.2H.sub.5 190 .beta. I-1-c-11 CH.sub.3 C.sub.2H.sub.5 H
##STR00271## H CH.sub.3 CH.sub.3 O C.sub.2H.sub.5 149-151 --
I-1-c-12 CH.sub.3 C.sub.2H.sub.5 H ##STR00272## H ##STR00273##
CH.sub.3 O C.sub.2H.sub.5 -- -- *.sup.1H-NMR (400 MHz, CDCl.sub.3):
Shift .delta. in ppm.
Example 11-16
##STR00274##
[0909] 1.29 g of the compound of Example XXX-1 in 10 ml of
dichloromethane are added to 1 ml of sulphuric acid. The mixture is
stirred at 35.degree. C. for 2 h. 6 ml of methanol are added. The
mixture is stirred at 60.degree. C. for 6 h. The mixture is
extracted with dichloromethane, the extract is dried over magnesium
sulphate and the solvent is distilled off. The product is purified
by column chromatography on silica gel (ethyl acetate/n-heptane:
1/4.fwdarw.1/1).
[0910] Yield: 1 g (69% of theory), m.p. 136-137.degree. C.
Example II-1
##STR00275##
[0912] 4 ml of triethylamine are added to 3.04 g of methyl
1-amino-4-methoxycyclohexanecarboxylate.times.HCl in 40 ml of
anhydrous tetrahydrofuran (THF), and the mixture is stirred for 5
minutes. 2.51 g of 2-methyl-5-[1-(4-chloro)pyrazolyl]phenylacetic
acid are then added, and the mixture is stirred at room temperature
for 15 minutes. 2.2 ml of triethylamine are then added, followed
immediately by the dropwise addition of 0.56 ml of phosphorus
oxychloride such that the solution boils gently. The mixture is
stirred under reflux for 30 minutes.
[0913] The reaction solution is poured into 200 ml of ice-water,
made alkaline using 3.5 ml of triethylamine and extracted with
dichloromethane, and the extract is dried. The solvent is then
distilled off and the product is purified by column chromatography
on silica gel (dichloromethane:ethyl acetate 3:1).
[0914] Yield: 3.15 g (75% of theory). m.p.: 153.degree. C.
[0915] Analogously to Example (II-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (II) are obtained
TABLE-US-00013 TABLE II (II) ##STR00276## Ex. No. W X Y Z D A B
m.p. .degree. C. isomer II-2 CH.sub.3 CH.sub.3 H ##STR00277## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- 176 .beta. II-3
H CH.sub.3 H ##STR00278## H --(CH.sub.2).sub.5-- 146 -- II-4
CH.sub.3 CH.sub.3 H ##STR00279## H CH.sub.3 CH.sub.3 194 -- Ex. No.
W X Y Z D A B R8 m.p. .degree. C. isomer II-5 CH.sub.3 CH.sub.3 H
##STR00280## H --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
CH.sub.3 314 .beta. II-6 CH.sub.3 C.sub.2H.sub.5 H ##STR00281## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- CH.sub.3 128
.beta. II-7 CH.sub.3 C.sub.2H.sub.5 H ##STR00282## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- CH.sub.3 101
.beta. II-8 C.sub.2H.sub.5 C.sub.2H.sub.5 H ##STR00283## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- CH.sub.3 135
.beta. II-10 H C.sub.2H.sub.5 H ##STR00284## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- CH.sub.3 134
.beta. II-11 C.sub.2H.sub.5 Cl H ##STR00285## H CH.sub.3 CH.sub.3
CH.sub.3 179 -- II-12 C.sub.2H.sub.5 Cl H ##STR00286## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- CH.sub.3 163
.beta. II-13 CH.sub.3 C.sub.2H.sub.5 H ##STR00287## H
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- CH.sub.3 172 -- II-14
CH.sub.3 C.sub.2H.sub.5 H ##STR00288## H CH.sub.3 CH.sub.3 CH.sub.3
171 -- II-15 H Cl H ##STR00289## H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- CH.sub.3 91
.beta. II-9 CH.sub.3 C.sub.2H.sub.5 H ##STR00290## H ##STR00291##
CH.sub.3 CH.sub.3 136-137 --
Example XXX-1
##STR00292##
[0917] 0.38 g of 2-amino-2-cyclopropylpropionitrile and 0.48 ml of
triethylamine are initially charged in 20 ml of tetrahydrofuran. At
0.degree. C., 0.97 g of
4-(4-chloro-pyrazolyl)-2-ethyl-6-methylphenylacetyl chloride in 20
ml of tetrahydrofuran is added dropwise over a period of 1 h. The
mixture is stirred at room temperature for another 6 h. The
reaction solution is filtered off with suction through a frit and
washed, and the solvent is distilled off. The product is purified
by column chromatography on silica gel (ethyl
acetate/n-heptane=1/4.fwdarw.1/1).
[0918] Yield: 910 mg (62% of theory) m.p. 65-70.degree. C.
Example I-2-a-1
##STR00293##
[0920] 1 g of KOtBu is initially charged in 10 ml of DMF and cooled
to 0.degree. C., and 2.1 g of the compound of Example III-1 are
dissolved in DMF and added dropwise at 0-10.degree. C. The mixture
is stirred at room temperature for 8 h. The solvent is distilled
off and the residue is taken up in water. The mixture is extracted
with ethyl acetate. The aqueous phase is acidified with HCl, the
precipitate is filtered off with suction and the filtrate is
dried.
[0921] Yield 0.25 g (10% of theory)
[0922] .sup.1H-NMR (400 MHz, d.sub.6-DMSO): .delta.=1.50 (s, 6H,
C(CH.sub.3).sub.2), 7.5-8.9 (m, 5H, Ar--H, pyrazole-H) ppm
[0923] Analogously to Example (I-2-a-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (I-2-a) are obtained
TABLE-US-00014 TABLE I-2-a (I-2-a) ##STR00294## Ex. No. W X Y Z A B
m.p. .degree. C. I-2-a-2 H Cl H ##STR00295##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- *3.3-3.5 (2 m,
1H, CHOCH.sub.3) 3.3 (s, 3H, OCH.sub.3) 7.73, 7.88 (2 s, 2H, Ar--H)
7.90, 8.76 (2 s, 2H, Pyr--H) I-2-a-3 C.sub.2H.sub.5 Cl H
##STR00296## CH.sub.3 CH.sub.3 *7.72, 7.82 (2 s, 2H, Ar--H) 7.90,
8.87 (2 s, 2H, Pyr--H) I-2-a-4 C.sub.2H.sub.5 Cl H ##STR00297##
--(CH.sub.2).sub.4 *7.58, 7.67 (2 s, 2H, Ar--H) 7.68, 8.23 (2 s,
2H, Pyr--H) I-2-a-5 C.sub.2H.sub.5 Cl H ##STR00298##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- trans-isomer
.sup.1) *3.27 (s, 3H, O--CH.sub.3) 7.71, 7.82 (2 s, 2H, Ar--H)
7.90, 8.86 (2 s, 2H, Pyr--H) I-2-a-6 C.sub.2H.sub.5 Cl H
##STR00299## --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
cis-isomer .sup.1) *3.29 (s, 3H, O--CH.sub.3) 7.72, 7.82 (2 s, 2H,
Ar--H) 7.90, 8.87 (2 s, 2H, Pyr--H) I-2-a-7 CH.sub.3 C.sub.2H.sub.5
H ##STR00300## --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- *7.48,
7.54 (2 s, 2H, Ar--H) 7.84, 7.95 (2 s, 2H, Pyr--H) I-2-a-8 CH.sub.3
C.sub.2H.sub.5 H ##STR00301##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- *7.53, 7.55 (2
s, 2H, Ar--H) 7.84, 7.95 (2 s, 2H, Pyr--H) I-2-a-9 CH.sub.3
C.sub.2H.sub.5 H ##STR00302## --(CH.sub.2).sub.5-- *7.53, 7.55 (2
s, 2H, Ar--H) 7.83, 7.95 (2 s, 2H, Pyr--H) I-2-a-10 CH.sub.3
C.sub.2H.sub.5 H ##STR00303## CH.sub.3 CH.sub.3 *7.53, 7.55 (2 s,
2H, Ar--H) 7.84, 7.95 (2 s, 2H, Pyr--H) *.sup.1H--NMR (400 MHz,
d.sub.6-DMSO): .delta. in ppm .sup.1) separation by column
chromatography on silica gel using the mobile phase methylene
chloride
Example I-2-b-1
##STR00304##
[0925] 0.12 g of the compound of Example 1-2-a-1 is initially
charged in 10 ml of dichloromethane and 0.05 ml of triethylamine,
and 0.04 g of isobutyl chloride is added with ice-cooling. The
mixture is stirred at room temperature for 8 h. The mixture is then
washed with 10% strength citric acid, and the phases are separated.
The organic phase is dried and the solvent is distilled off.
[0926] Yield: 0.04 g (28% of theory), m.p. 150-152.degree. C.
[0927] .sup.1H-NMR (CD.sub.3CN): .delta.=1.1 (d, 6H), 1.5 (s, 6H),
2.8 (m, 1H), 7.5-8.2 (m, 5H) ppm.
[0928] Analogously to Example (I-2-b-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (I-2-b) are obtained
TABLE-US-00015 TABLE I-2-b (I-2-b) ##STR00305## Ex. No. W X Y Z A B
R.sup.1 m.p. .degree. C. I-2-b-2 C.sub.2H.sub.5 Cl H ##STR00306##
CH.sub.3 CH.sub.3 i-C.sub.3H.sub.7 *7.64, 7.70 (2 s, 2H, Ar--H)
7.71, 8.27 (2 s, 2H, Pyr--H) I-2-b-3 C.sub.2H.sub.5 Cl H
##STR00307## --(CH.sub.2).sub.4-- i-C.sub.3H.sub.7 *7.63, 7.70 (2
s, 2H, Ar--H) 7.71, 8.27 (2 s, 2H, Pyr--H) I-2-b-4 C.sub.2H.sub.5
Cl H ##STR00308##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
i-C.sub.3H.sub.7 trans-isomer .sup.1) *3.31 (s, 3H, O--CH.sub.3)
7.63, 7.70 (2 s, 2H, Ar--H) 7.71, 8.27 (2 s, 2H, Pyr--H) I-2-b-5
C.sub.2H.sub.5 Cl H ##STR00309##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
i-C.sub.3H.sub.7 cis-isomer .sup.1) *3.34 (s, 3H, O--CH.sub.3)
7.63, 7.70 (2 s, 2H, Ar--H) 7.21, 8.27 (2 s, 2H, Pyr--H) I-2-b-6
CH.sub.3 C.sub.2H.sub.5 H ##STR00310## CH.sub.3 CH.sub.3
i-C.sub.3H.sub.7 *7.48, 7.49 (2 s, 2H, Ar--H) 7.67, 8.23 (2 s, 2H,
Pyr--H) I-2-b-7 CH.sub.3 C.sub.2H.sub.5 H ##STR00311##
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- i-C.sub.3H.sub.7 *7.48,
7.50 (2 s, 2H, Ar--H) 7.67, 8.23 (2 s, 2H, Pyr--H) I-2-b-8 CH.sub.3
C.sub.2H.sub.5 H ##STR00312## --(CH.sub.2).sub.5-- i-C.sub.3H.sub.7
*7.47, 7.48 (2 s, 2H, Ar--H) 7.67, 8.22 (2 s, 2H, Pyr--H) I-2-b-9
CH.sub.3 C.sub.2H.sub.5 H ##STR00313##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
i-C.sub.3H.sub.7 trans-isomer .sup.1) *3.30 (s, 3H, O--CH.sub.3)
7.48, 7.50 (2 s, 2H, Ar--H) 7.67, 8.23 (2 s, 2H, Pyr--H) I-2-b-10
CH.sub.3 C.sub.2H.sub.5 H ##STR00314##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
--C.sub.3H.sub.7 cis-isomer .sup.1) *7.48 7.49 (2 s 2H, Ar--H)
7.67, 8.22 (2 s, 2H, Pyr--H) *.sup.1H--NMR (400 MHz, d.sub.6-DMSO):
.delta. in ppm .sup.1) separation by column chromatography on
silica gel using the mobile phase methylene chloride
Example III-1
##STR00315##
[0930] 0.9 g of ethyl hydroxyisobutyrate and 2 g of
2-chloro-5-N-(4-chloropyrazolyl)phenylacetyl chloride are stirred
in 20 ml of toluene under reflux for 8 h. The solvent is distilled
off and the residue is dried.
[0931] Yield: 2.2 g (83% of theory)
[0932] .sup.1H-NMR (400 MHz, d.sub.6 DMSO): 8=1.15 (t, 3H,
CH.sub.2--CH.sub.3), 1.50 (s, 6H, C(CH.sub.3).sub.2, 4.05 (q, 2H,
O--CH.sub.2--CH.sub.3), 7.3-8.8 (m, 5H) ppm.
[0933] Analogously to Example (III-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (III) are obtained
TABLE-US-00016 TABLE III (III) ##STR00316## Ex. No. W X Y Z A B
R.sup.8 m.p. .degree. C. III-2 H Cl H ##STR00317##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- C.sub.2H.sub.2
*7.18, 7.25 (2 s, 2H, Ar--H) 7.88, 8.75 (2 s, 2H, Pyr--H) III-3
C.sub.2H.sub.5 Cl H ##STR00318## CH.sub.3 CH.sub.3 C.sub.2H.sub.5
*7.57, 7.67 (2 s, 2H, Ar--H) 7.69, 8.23 (2 s, 2H, Pyr--H) III-4
C.sub.2H.sub.5 Cl H ##STR00319## --(CH.sub.2).sub.4--
C.sub.2H.sub.5 *7.58, 7.67 (2 s, 2H, Ar--H) 7.69, 8.24 (2 s, 2H,
Pyr--H) III-5 C.sub.2H.sub.5 Cl H ##STR00320##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- C.sub.2H.sub.5
*7.58, 7.67 (2 s, 2H, Ar--H) 7.69, 8.24 (2 s, 2H, Pyr--H) III-6
CH.sub.3 C.sub.2H.sub.5 H ##STR00321##
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- C.sub.2H.sub.5 *7.44,
7.45 (2 s, 2H, Ar--H) 7.66, 8.19 (2 s, 2H, Pyr--H) III-7 CH.sub.3
C.sub.2H.sub.5 H ##STR00322##
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- C.sub.2H.sub.5
*7.43, 7.44 (2 s, 2H, Ar--H) 7.65, 8.19 (2 s, 2H, Pyr--H) III-8
CH.sub.3 C.sub.2H.sub.5 H ##STR00323## --(CH.sub.2).sub.5--
C.sub.2H.sub.5 *7.43, 7.45 (2 s, 2H, Ar--H) 7.65, 8.19 (2 s, 2H,
Pyr--H) III-9 CH.sub.3 C.sub.2H.sub.5 H ##STR00324## CH.sub.3
CH.sub.3 C.sub.2H.sub.5 *7.42, 7.43 (2 s, 2H, Ar--H) 7.65, 8.19 (2
s, 2H, Pyr--H)
Example XXV-1
##STR00325##
[0935] At room temperature, 2.3 g of oxayl chloride are added
dropwise to 4 g of 2-chloro-5-N-(4-chloropyrazolyl)phenylacetic
acid in 100 ml of dichloromethane. The mixture is stirred at room
temperature for 8 h. The mixture is then boiled under reflux until
the evolution of gas has ceased. The solvent is distilled off and
the residue is degassed.
[0936] Yield: 4.25 g (99% of theory), GC/MS: M.sup.+285 m/e.
Example I-6-a-1
##STR00326##
[0938] 1.73 g (15.4 mmol) of potassium tert-butoxide are initially
charged in 20 ml of DMF, and 3.0 g (7.7 mmol) of the compound of
Example VIII-1 in 10 ml of DMF are added. The mixture is stirred at
50.degree. C. for 3 hours. The reaction solution is cooled and put
into 600 ml of cooled 1 N HCl and the precipitate is filtered off
with suction and dried.
[0939] Yield: 2.4 g (87% of theory). m.p.: >250.degree. C.
[0940] Analogously to Example (I-6-a-1) and in accordance with the
general statements on the preparation, the following compound of
the formula (I-6-a) is obtained
TABLE-US-00017 (I-6-a) ##STR00327## Ex. No. W X Y Z A B Q.sup.1
Q.sup.2 m.p. .degree. C. I-6-a-2 CH.sub.3 CH.sub.3 H ##STR00328##
--(CH.sub.2).sub.5-- H H 223-230
Example I-6-e-1
##STR00329##
[0942] 300 mg of the compound of Example I-6-a-1 are initially
charged in 5 ml of anhydrous acetone, and 0.174 g of potassium
carbonate is added. 0.119 g of ethyl chloroformate is then added.
The mixture is stirred at 50.degree. C. for 3 hours.
[0943] The reaction solution is concentrated, taken up in 10 ml of
CH.sub.2Cl.sub.2 and washed with 10 ml of H.sub.2O. The organic
phase is separated off and the solvent is distilled off.
[0944] Yield: 0.36 g (96% of theory). m.p.: 132.degree. C.
[0945] Analogously to Example (I-6-c-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (I-6-c) are obtained
TABLE-US-00018 (I-6-c) ##STR00330## Ex. No. W X Y Z A B Q.sup.1
Q.sup.2 M R.sup.2 m.p. .degree. C. I-6-c-2 H CH.sub.3 H
##STR00331## --(CH.sub.2).sub.5-- H H O i-C.sub.3H.sub.7 Wax *1.19,
(d, 6H, CH(CH.sub.3).sub.2), 4.77 (m, 1H, O--CH) I-6-c-3 H CH.sub.3
H ##STR00332## --(CH.sub.2).sub.5-- H H S i-C.sub.4H.sub.9 Wax
*2.09, (s, 3H, Ar--CH.sub.3) 8.75 (s, 1H, Pyr--H) I-6-c-4 H
CH.sub.3 H ##STR00333## --(CH.sub.2).sub.5-- H H O
C.sub.6H.sub.5--CH.sub.2 Wax *2.05, (s, 3H, Ar--CH.sub.3) 5.10 (s,
2H, O--CH.sub.2) 7.29-7.37 (m, 6H, Ar--H) *.sup.1H--NMR (400 MHz,
CDCl.sub.3): .delta. in ppm
Example VIII-1
##STR00334##
[0947] 3.2 g (22.9 mmol) of potassium carbonate and 8.1 g (57.3
mmol)=3.6 ml of methyl iodide are added to 8.6 g (22.9 mmol) of
crude product of Example XXXV-1 in 100 ml of anhydrous acetone. The
mixture is stirred under reflux for 16 hours.
[0948] The reaction solution is cooled and the precipitate is
filtered off with suction and washed with acetone.
[0949] The product is purified by column chromatography on silica
gel (dichloromethane:petroleum ether,
2:1.fwdarw.4:1.fwdarw.8:1.fwdarw.dichloromethane).
[0950] Yield: 3 g (34% of theory).
[0951] .sup.1H-NMR (400 MHz, d.sub.6-DMSO): .delta.=1.30-1.78 (m,
10H, cyclohexyl-H), 2.10 (s, 3H, CH.sub.3-aryl), 3.51 (s, 3H,
CO.sub.2Me), 7.28 (d, 1H, aryl-H), 7.54-7.60 (m, 2H, aryl-H), 7.82,
8.72 (2s, 1H each, 2 pyrazolyl-H) ppm
[0952] Analogously to Example (VIII-1) and in accordance with the
general statements on the preparation, the following compound of
the formula (VIII) is obtained
TABLE-US-00019 ##STR00335## Ex. No. W X Y Z A B Q.sup.1 Q.sup.2
m.p. .degree. C. VIII-2 CH.sub.3 CH.sub.3 H ##STR00336##
--(CH.sub.2).sub.5-- H H
Example XXXV-1
##STR00337##
[0954] At -15.degree. C., a solution of 5.0 g (18.9 mmol) of methyl
2-methyl-5-[1-(4-chloropyrazolyflphenyl]acetate in 10 ml of THF is
added dropwise to a solution of 9.44 ml of a solution (2 molar) of
LDA in 30 ml of anhydrous THF, and the mixture is stirred at
0.degree. C. for 60 minutes.
[0955] At -15.degree. C., a solution of 4.13 g (18.9 mmol) of
methyl 3,3-pentamethylenesuccinyl chloride in 10 ml of anhydrous
THF and simultaneously 14.2 ml of LDA solution (2.0 molar; 1.5 eq)
are then added dropwise. The mixture is stirred at room temperature
for two hours and then poured into 150 ml of ice-cold 10% strength
ammonium chloride solution.
[0956] The intermediate is extracted with MTB ether and the
solvents are distilled off. The residue is boiled under reflux with
10 g of KOH and 100 ml of water for 3 hours.
[0957] The reaction solution is cooled, acidified with concentrated
HCl and extracted with 200 ml of CH.sub.2Cl.sub.2, the extract is
dried and the solvent is distilled off.
[0958] Yield: 8.6 g (66.8% of theory).
[0959] Analogously to Example (XXXV-1) and in accordance with the
general statements on the preparation, the following compound of
the formula (XXXV) is obtained
TABLE-US-00020 (XXXV) ##STR00338## Ex. No. W X Y Z A B Q.sup.1
Q.sup.2 m.p. .degree. C. XXXV-2 CH.sub.3 CH.sub.3 H ##STR00339##
--(CH.sub.2).sub.5-- H H * * Was converted directly, as crude
product, into the compound of the formula (VIII-2)
Example I-7-a-1
##STR00340##
[0961] 0.80 g (2.2 mmol) of the compound of Example IX-1 in 2 ml of
DMF is added to 0.49 g (4 4 mmol, 2.0 eq) of potassium
tert-butoxide in 5 ml of DMF.
[0962] The mixture is stirred at 50.degree. C. for 3 hours. 20 ml
of ice-water are added, cooled 1 N HCl solution is added to make a
volume of 250 ml and the mixture is extracted with dichloromethane.
The organic phase is dried and concentrated.
[0963] The residue is purified by column chromatography on silica
gel (petroleum ether:ethyl acetate 2:1).
[0964] Yield: 0.15 g (21% of theory). m.p.: 172.degree. C.
[0965] Analogously to Example (I-7-a-1) and in accordance with the
general statements on the preparation, the following compound of
the formula (I-7-a) is obtained
TABLE-US-00021 (I-7-a) ##STR00341## Ex. No. W X Y Z A B Q.sup.3
Q.sup.4 Q.sup.5 Q.sup.6 m.p. .degree. C. I-7-a-2 H CH.sub.3 H
##STR00342## H H --(CH.sub.2).sub.4-- H H 241
Example IX-1
##STR00343##
[0967] 1.58 g of potassium carbonate and 4.07 g (2.5 eq)=1.79 ml of
methyl iodide are added to 4.0 g of the crude product of Example
XXXIX-1 in 50 ml of anhydrous acetone. The mixture is stirred under
reflux for 16 hours. The reaction solution is cooled and the
precipitate is filtered off with suction and washed with
acetone.
[0968] The product is purified by column chromatography on silica
gel using a gradient (methylene chloride:ethyl acetate
50:1.fwdarw.5:1).
[0969] Yield: 0.8 g (15% of theory).
[0970] .sup.1H-NMR (400 MHz, d.sub.6-DMSO): .delta.=1.03 (s, 6H,
CH.sub.3), 2.18 (s, 3H, CH.sub.3-aryl), 3.57 (s, 3H, CO.sub.2Me),
7.30 (d, 1H, aryl-H), 7.57-7.61 (m, 2H, aryl-H), 7.83, 8.72 (2s, 1H
each, 2 pyrazolyl-H) ppm
[0971] Analogously to Example (IX-1) and in accordance with the
general statements on the preparation, the following compound of
the formula (IX) is obtained
TABLE-US-00022 (IX) ##STR00344## Ex. No. W X Y Z A B Q.sup.3
Q.sup.4 Q.sup.5 Q.sup.6 R.sup.8 m.p. .degree. C. IX-2 H CH.sub.3 H
##STR00345## H H --(CH.sub.2).sub.4-- H H CH.sub.3 * *1H--NMR
(.delta..sub.6-400 MHz DMSO): .delta. = 1.05-1.50 (m, 8H,
cyclopentyl-H), 2.13 (s, 3H, CH.sub.3-aryl), 3.52 (s, 3H,
CO.sub.2Me), 7.28 (d, 1H, aryl-H), 7.82, 8.70 (2 s, 1H each, 2
pyrazolyl-H) ppm
Example XXXIX-1
##STR00346##
[0973] A solution of 3.0 g (11 3 mmol; 1 eq) of methyl
2-methyl-5-[1-(4-chloropyrazolyl)phenyl]acetate in 5 ml of
anhydrous THF, is, at -15.degree. C., added dropwise to a solution
of 5.7 ml of LDA solution (2 molar; 1.0 eq) in 20 ml of anhydrous
THF, and the mixture is stirred at 0.degree. C. for 60 minutes.
[0974] At -15.degree. C., a solution of 1.61 g (11.3 mmol; 1.0 eq)
of 3,3-dimethylglutaric anhydride in 10 ml of anhydrous THF and
simultaneously 8.52 ml of LDA solution (2.0 molar; 1.5 eq) are then
added dropwise. The mixture is stirred at room temperature for 2
hours and then poured into 150 ml of ice-cold 10% strength ammonium
chloride solution. The mixture is acidified with concentrated
HCl.
[0975] The intermediate is extracted with MTBE and the solvents are
distilled off. The residue is boiled under reflux with 7 g of KOH
and 70 ml of water for 4 hours.
[0976] The reaction solution is cooled, acidified with concentrated
HCl and extracted with 200 ml of MTBE, and the extract is dried and
the solvent is distilled off.
[0977] Yield: 4 g.
[0978] Analogously to Example (XXXIX-1) and in accordance with the
general statements on the preparation, the following compound of
the formula (XXXIX) is obtained
TABLE-US-00023 ##STR00347## Ex. No. W X Y Z A B Q.sup.3 Q.sup.4
Q.sup.5 Q.sup.6 m.p. .degree. C. XXXIX-2 H CH.sub.3 H ##STR00348##
H H --(CH.sub.2).sub.4-- H H * * The compound was used as crude
product for preparing Ex. No. IX-2
Example I-8-a-1
##STR00349##
[0980] 0.85 g of potassium tert-butoxide is initially charged in 36
ml of N,N-dimethylacetamide, 1.6 g of the compound of Example
(XII-1) in N,N-dimethylacetamide are slowly added dropwise at
60.degree. C. and the mixture is stirred for 1 hour. After cooling,
the solution is added dropwise to ice-cooled hydrochloric acid, and
the precipitate is filtered off with suction.
[0981] Yield: 1.1 g (81% of theory). m.p. 258.degree. C.
[0982] Analogously to Example (I-8-a-1) and in accordance with the
general statements on the preparation, the following compound of
the formula (I-8-a) is obtained
TABLE-US-00024 (I-8-a) ##STR00350## Ex. No. W X Y Z A D m.p.
.degree. C. I-8-a-2 CH.sub.3 C.sub.2H.sub.5 H ##STR00351##
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- >300
Example I-8-b-7
##STR00352##
[0984] 0.2 g of the compound of Example I-8-a-1 is initially
charged in 30 ml of dichloromethane, 0.067 g of triethylamine is
added, followed by 0.054 g of 2-methylpropionyl chloride, and the
mixture is stirred for 3 h.
[0985] The mixture is diluted with water and extracted. The organic
phase is dried and the solvent is distilled off. n-Heptane and a
little dichloromethane are added to the residue. The product
crystallizes out and is filtered off with suction.
[0986] Yield: 0.19 g (81% of theory), m.p.: 161.4.degree. C.
[0987] Analogously to Example (I-8-b-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (I-8-b) are obtained
TABLE-US-00025 (I-8-b) ##STR00353## Ex. No. W X Y Z A D R.sup.1
m.p. .degree. C. I-8-b-2 CH.sub.3 C.sub.2H.sub.5 H ##STR00354##
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- i-C.sub.3H.sub.7 138.4
I-8-b-3 CH.sub.3 C.sub.2H.sub.5 H ##STR00355##
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2 CH.sub.2--OCH.sub.3 252.6
I-8-b-4 CH.sub.3 C.sub.2H.sub.5 H ##STR00356##
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2 t-C.sub.4H.sub.9 119.1
I-8-b-5 CH.sub.3 C.sub.2H.sub.5 H ##STR00357## --(CH.sub.2).sub.4--
CH.sub.2--OCH.sub.3 259 I-8-b-6 CH.sub.3 C.sub.2H.sub.5 H
##STR00358## --(CH.sub.2).sub.4-- t-Bu 204.8
Example I-8-c-1
##STR00359##
[0989] 0.25 g of the compound of Example (I-8-a-1) is initially
charged in 36 ml of dichloromethane, 0.12 ml of triethylamine is
added, 0.06 ml of ethyl chloroformate, dissolved in
dichloromethane, is added dropwise at room temperature and the
mixture is stirred for 1 hour. The mixture is then diluted with
water and extracted. The organic phase is dried and the solvent is
distilled off. n-Heptane and a little dichloromethane are added to
the residue. The product crystallizes out and is filtered off with
suction.
[0990] Yield: 0.2 g (71% of theory). m.p. 172.degree. C.
[0991] Analogously to Example (I-8-b-1) and in accordance with the
general statements on the preparation, the following compound of
the formula (I-8-c-1) is obtained
TABLE-US-00026 (I-8-c) ##STR00360## Ex. No. W X Y Z A D M R.sup.2
m.p. .degree. C. I-8-c-2 CH.sub.3 C.sub.2H.sub.5 H ##STR00361##
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- O C.sub.2H.sub.5 230
Example (XII-1)
##STR00362##
[0993] 4-([4-Chloropyrazolyl)-2-ethyl-6-methylphenylacetic acid is
initially charged in 35 ml of dichloromethane, and 1.28 g of oxalyl
chloride is added. The mixture is stirred under reflux, and once
the evolution of gas ceases, 1 ml of dimethylformamide is added.
The mixture is stirred further under reflux and then cooled under
an atmosphere of protective gas. The solvent is distilled off. The
residue is taken up in dichloromethane and added dropwise to a
solution of 1.2 g of 1-ethoxycarbonylhexahydropyridazine in 35 ml
of dichloromethane and 1.6 ml of triethylamine. The mixture is
stirred at room temperature for 3 h and then extracted with water
and dichloromethane. The organic phase is separated off and dried,
and the solvent is distilled off.
[0994] Yield: 2 g (63% of theory).
[0995] .sup.1H-NMR-data (300 MHz, CDCl.sub.3): .delta.=2.6 (q, 2H,
Ar--CH.sub.2CH.sub.3), 4.3 (q, 2H, O--CH.sub.2CH.sub.3), 7.3, 7.35
(2s, 2H, ArH), 7.6, 7.9 (2s, 2H, Pyr H) ppm
[0996] Analogously to Example (XII-1) and in accordance with the
general statements on the preparation, the following compound of
the formula (XII) is obtained
TABLE-US-00027 (XII) ##STR00363## Ex. No. W X Y Z A D R.sup.8 m.p.
.degree. C. XII-2 CH.sub.3 C.sub.2H.sub.5 H ##STR00364##
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- C.sub.2H.sub.5 87
Examples according to process Q
Example XXXII-1
Methyl (4-N-[4-chloropyrazolyl]-2,6-dimethyl)phenylacetate
##STR00365##
[0998] Under an atmosphere of argon, 16.6 g (162 mmol) of
4-chloropyrazole, 10.3 g (54 mmol) of copper(I) iodide and 56 g
(405 mmol) of potassium carbonate (dry) are initially charged in
350 ml of absolute DMF, and the mixture is stirred for 5 minutes.
34.7 g (135 mmol) of methyl (4-bromo-2,6-dimethyl)phenylacetate are
then slowly added dropwise. The reaction mixture is stirred at
105.degree. C. for four days. During this time, the progress of the
reaction is monitored by GC, and in each case after 24 hours (three
times in total) 2.6 g (13.5 mmol) of copper(I) iodide and 4.15 g
(40.5 mmol) of 4-chloropyrazole are added. The reaction mixture is
allowed to cool and the solvent is then removed under reduced
pressure and the residue is filtered through a short frit with
silica gel and then purified chromatographically.
[0999] Yield: 17.2 g (46%).
[1000] .sup.1H-NMR {-400 MHz, CDCl.sub.3}: 2.38 (s, 6H, CH.sub.3);
3.70 (s, 3H, OCH.sub.3); 3.71 (s, 2H, CH.sub.2); 7.31 (s, 2H,
Ph-H); 7.61 (s, 1H, pyrazolyl-H); 7.88 (s, 1H, pyrazolyl-H).
[1001] Analogously to Example (XXXII-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (XXXII) are obtained.
Example XXXII-2
Methyl (2-ethyl-4-N-[4-methoxypyrazolyl]-6-methyl)phenylacetate
##STR00366##
[1003] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 1.15 (t,
.sup.3J.sub.HH=7 Hz, 3H, CH.sub.3); 2.28 (s, 3H, CH.sub.3); 2.64
(q, .sup.3J.sub.HH=7 Hz, 2H, CH.sub.2); 3.62 (s, 3H, OCH.sub.3);
3.73 (s, 2H, CH.sub.2); 3.76 (s, 3H, OCH.sub.3); 7.46 (m, 2H,
Ph-H); 7.50 (s, 1H, pyrazolyl-H); 8.24 (s, 1H, pyrazolyl-H).
[1004] MS/CI: 289 (M+1).
Example XXXII-3
Methyl (2,6-dimethyl-4-N-[4-methoxypyrazolyl])phenylacetate
##STR00367##
[1006] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 2.30 (s, 6H,
CH.sub.3); 3.62 (s, 3H, OCH.sub.3); 3.71 (s, 2H, CH.sub.2); 3.76
(s, 3H, OCH.sub.3); 7.46 (s, 2H, Ph-H); 7.50 (s, 1H, pyrazolyl-H);
8.22 (s, 1H, pyrazolyl-H).
[1007] MS/CI: 275 (M+1).
Example XXXII-4
Methyl (2,6-diethyl-4-N-[4-chloropyrazolyl])phenylacetate
##STR00368##
[1009] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 1.18 (t,
.sup.3J.sub.HH=7 Hz, 6H, CH.sub.3); 2.61 (q, .sup.3J.sub.HH=7 Hz,
4H, CH.sub.2); 3.57 (s, 3H, OCH.sub.3); 3.79 (s, 2H, CH.sub.2);
7.50 (m, 2H, Ph-H); 7.84 (s, 1H, pyrazolyl-H); 8.79 (s, 1H,
pyrazolyl-H).
[1010] MS/CI: 307(M+1).
Example XXXII-5
Methyl (2,6-dimethyl-4-N-[4-cyanopyrazolyl])phenylacetate
##STR00369##
[1012] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 2.31 (s, 6H,
CH.sub.3); 3.62 (s, 2H, CH.sub.2); 3.74 (s, 3H, OCH.sub.3); 7.52
(s, 2H, Ph-H); 8.05 (s, 1H, pyrazolyl-H); 8.82 (s, 1H,
pyrazolyl-H).
[1013] MS/CI: 270 (M+1).
Example XXXII-6
Methyl (2,6-dimethyl-4-N-[3-chlorotriazolyl])phenylacetate
##STR00370##
[1015] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 2.26 (s, 6H, CH.sub.3;
3.55 (s, 2H, CH.sub.2); 3.79 (s, 3H, OCH.sub.3); 7.44 (s, 2H,
Ph-H); 9.22 (s, 1H, triazolyl-H).
[1016] MS/CI: 280 (M+1).
Example XXXII-7
Methyl [(3-N-[4-chloropyrazolyl])-6-methyl]phenylacetate
##STR00371##
[1018] .sup.1H-NMR {-400 MHz, CDCl.sub.3}: 2.32 (s, 3H, CH.sub.3);
3.67 (s, 2H, CH.sub.2); 3.70 (s, 3H, OCH.sub.3); 7.22 (m, 1H,
Ph-H); 7.40 (m, 1H, Ph-H); 7.50 (m, 1H, Ph-H); 7.60 (s, 1H,
pyrazolyl-H); 7.95 (s, 1H, pyrazolyl-H).
[1019] GC-MS/CI: 265 (M+1).
Example XXXII-8
Methyl (2-chloro-6-ethyl-4-[4-chloropyrazolyl])phenylacetate
##STR00372##
[1021] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 1.18 (t,
.sup.3J.sub.HH=7 Hz, 3H, CH.sub.3); 2.72 (q, .sup.3J.sub.HH=7 Hz,
2H, CH.sub.2); 3.64 (s, 3H, OCH.sub.3); 3.89 (s, 2H, CH.sub.2);
7.69 (m, 1H, Ph-H); 7.81 (m, 1H, Ph-H); 7.89 (s, 1H, pyrazolyl-H);
8.88 (s, 1H, pyrazolyl-H).
[1022] MS/CI: 313 (M+1).
Example XXXII-9
Methyl (2-chloro-6-ethyl-4-[4-chloropyrazolyl])phenylacetate
##STR00373##
[1024] .sup.1H-NMR{-400 MHz, DMSO-d.sub.6}: 1.18 (t,
.sup.3J.sub.HH=7 Hz, 3H, CH.sub.3); 2.72 (q, .sup.3H.sub.HH=7 Hz,
2H, CH.sub.2); 3.64 (s, 3H, OCH.sub.3): 3.89 (s, 2H, CH.sub.2);
7.69 (m, 1H, Ph-H); 7.81 (m, 1H, Ph-H); 7.89 (s, 1H, pyrazolyl-H);
8.88 (s, 1H, pyrazolyl-H).
[1025] MS/CI: 313 (M+1).
Example XXXII-10
Methyl (2-ethyl-6-methyl-4-[4-chloropyrazolyl])phenylacetate
##STR00374##
[1027] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 1.18 (t,
.sup.3J.sub.HH=7 Hz, 3H, CH.sub.3): 2.59 (q, .sup.3J.sub.HH=7 Hz,
2H, CH.sub.2); 3.59 (s, 3H, OCH.sub.3); 3.72 (s, 2H, CH.sub.2);
7.51 (m, 2H, Ph-H); 7.89 (s, 1H, pyrazolyl-H); 8.78 (s, 1H,
pyrazolyl-H).
[1028] MS/CI: 313 (M+1).
Example XXVIII-1
(4-N-[4-Chloropyrazolyl]-2,6-dimethyl)phenylacetic acid
##STR00375##
[1030] 17.2 g (61 7 mmol) of
(4-[4-chloropyrazolyl]-2,6-dimethyl)phenylacetic acid are dissolved
in 160 ml of methanol and then, with 4.2 g (74 mmol) of potassium
hydroxide in 160 ml of water, heated at 80.degree. C. for 12 hours.
The methanol is removed using a rotary evaporator, the residue is
adjusted to pH 3 and the precipitated product is filtered off and
dried.
[1031] Yield: 16.2 g (99%)
[1032] .sup.1H-NMR {-400 MHz, CDCl.sub.3}: 2.38 (s, 6H, CH.sub.3);
3.73 (s, 2H, CH.sub.2); 7.32 (s, 2H, Ph-H); 7.61 (s, 1H,
pyrazolyl-H); 7.86 (s, 1H, pyrazolyl-H); acid-OH not detected.
[1033] Analogously to Example (XXVIII-1), the following compounds
of the formula (XXVIII) are obtained.
Example XXVIII-2
(2-Ethyl-4-N-[4-methoxypyrazolyl]-6-methyl)phenylacetic acid
##STR00376##
[1035] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 1.17 (t,
.sup.3J.sub.HH=7 Hz, 3H, CH.sub.3); 2.30 (s, 3H, CH.sub.3); 2.65
(q, .sup.3J.sub.HH=7 Hz, 2H, CH.sub.2); 3.63 (s, 2H, CH.sub.2);
3.77 (s, 3H, OCH.sub.3); 7.45 (m, 2H, Ph-H); 7.50 (s, 1H,
pyrazolyl-H); 8.23 (s, 1H, pyrazolyl-H); 12.5 (s, 1H, OH).
[1036] MS/CI: 275 (M+1).
Example XXVIII-3
(2,6-Dimethyl-4-N-[4-methoxypyrazolyl])phenylacetic acid
##STR00377##
[1038] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 2.30 (s, 6H,
CH.sub.3); 3.61 (s, 2H, CH.sub.2); 3.82 (s, 3H, OCH.sub.3); 7.44
(s, 2H, Ph-H); 7.50 (s, 1H, pyrazolyl-H); 8.21 (s, 1H,
pyrazolyl-H); 12.4 (s, 1H, OH).
[1039] MS/CI: 261 (M+1).
Example XXVIII-4
(2,6-Diethyl-4-N-[4-chloropyrazolyl])phenylacetic acid
##STR00378##
[1041] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 1.18 (t,
.sup.3J.sub.HH=8 Hz, 6H, CH.sub.3); 2.63 (q, .sup.3J.sub.HH=8 Hz,
4H, CH.sub.2); 3.67 (s, 2H, CH.sub.2); 7.50 (s, 2H, Ph-H); 7.85 (s,
1H, pyrazolyl-H); 8.79 (s, 1H, pyrazolyl-H); 12.5 (s, 1H, OH).
[1042] MS/CI: 293 (M+1).
Example XXVIII-5
(2,6-Dimethyl-4-N-[4-carboxylatopyrazolyl])phenylacetic acid
##STR00379##
[1044] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 2.32 (s, 6H,
CH.sub.3); 3.64 (s, 2H, CH.sub.2); 7.52 (s, 2H, Ph-H); 8.09 (s, 1H,
pyrazolyl-H); 8.87 (s, 1H, pyrazolyl-H); 12.3 (s, 2H, OH).
[1045] MS/CI: 275 (M+1).
Example XXVIII-6
(2,6-Dimethyl-4-N-[3-chlorotriazolyl])phenylacetic acid
##STR00380##
[1047] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 2.26 (s, 6H,
CH.sub.3); 3.56 (s, 2H, CH.sub.2); 7.44 (s, 2H, Ph-H); 9.22 (s, 1H,
triazolyl-H); 12.2 (s, 1H, OH).
[1048] MS/CI: 266 (M+1).
Example XXVIII-7
(3-N-[4-Chloropyrazolyl]-6-methyl)phenylacetic acid
##STR00381##
[1050] .sup.1H-NMR {-400 MHz, CDCl.sub.3}: 2.34 (s, 3H, CH.sub.3);
3.71 (s, 2H, CH.sub.2); 7.26 (m, 1H, Ph-H); 7.40 (m, 1H, Ph-H);
7.52 (m, 1H, Ph-H); 7.62 (s, 1H, pyrazolyl-H); 7.85 (s, 1H,
pyrazolyl-H); acid-OH not detected.
Example XXVIII-8
(2-Chloro-6-ethyl-4-[4-chloropyrazolyl])phenylacetic acid
##STR00382##
[1052] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 1.17 (t,
.sup.3J.sub.HH=7 Hz, 3H, CH.sub.3); 2.71 (q, .sup.3J.sub.HH=7 Hz,
2H, CH.sub.2); 3.79 (s, 2H, CH.sub.2); 7.69 (m, 1H, Ph-H); 7.79 (m,
1H, Ph-H); 7.91 (s, 1H, pyrazolyl-H); 8.88 (s, 1H, pyrazolyl-H);
12.6 (s, 1H, OH).
[1053] MS/CI: 299 (M+1).
Example XXVIII-9
[1054] (2-Chloro-6-ethyl-4-[4-chloropyrazolyl])phenylacetic
acid
##STR00383##
[1055] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 1.17 (t,
.sup.3J.sub.HH=7 Hz, 3H, CH.sub.3); 2.71 (q, .sup.3J.sub.HH=7 Hz,
2H, CH.sub.2); 3.79 (s, 2H, CH.sub.2); 7.69 (m, 1H, Ph-H); 7.79 (m,
1H, Ph-H); 7.91 (s, 1H, pyrazolyl-H); 8.88 (s, 1H, pyrazolyl-H);
12.6 (s, 1H, OH).
[1056] MS/CI: 299 (M+1).
Example XXVIII-10
(2-Ethyl-6-methyl-4-[4-chloropyrazolyl])phenylacetic acid
##STR00384##
[1058] .sup.1H-NMR {-400 MHz, DMSO-d.sub.6}: 1.19 (t,
.sup.3J.sub.HH=7 Hz, 3H, CH.sub.3); 2.60 (q, .sup.3J.sub.HH=7 Hz,
2H, CH.sub.2); 3.81 (s, 2H, CH.sub.2); 7.52 (m, 2H, Ph-H); 7.83 (s,
1H, pyrazolyl-H); 8.62 (s, 1H, pyrazolyl-H); OH not detected.
[1059] MS/CI: 279 (M+1).
Use Examples
Example A
Meloidogyne Test
TABLE-US-00028 [1060] Solvent: 7 parts by weight of
dimethylformamide Emulsifier: 2 parts by weight of alkylaryl
polyglycol ether
[1061] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
[1062] Containers are filled with sand, solution of active
compound, Meloidogyne incognita egg/larvae suspension and lettuce
seeds. The lettuce seeds germinate and the plants develop. On the
roots, galls are formed.
[1063] After the desired period of time, the nematicidal action is
determined in % by gall formation. 100% means that no galls are
formed; 0% means that the number of galls in the treated plants
corresponds to that of the untreated control.
[1064] In this test, for example, the following compounds of the
Preparation Examples show good activity:
TABLE-US-00029 TABLE A Plant-damaging nematodes Meloidogyne test
Concentration of active Efficacy Active compounds compound in ppm
in % after 14.sup.d Ex. I-1-a-2 20 100 Ex. I-6-a-2 20 100
Example B
Myzus Test
Spray Treatment
TABLE-US-00030 [1065] Solvents: 78 parts by weight of acetone 1.5
parts by weight of dimethylformamide Emulsifier: 0.5 part by weight
of alkylaryl polyglycol ether
[1066] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[1067] Discs of Chinese cabbage (Brassica pekinensis) infested by
the green peach aphid (Myzus persicae) are sprayed with a
preparation of active compound of the desired concentration.
[1068] After the desired period of time, the kill in % is
determined 100% means that all aphids have been killed; 0% means
that none of the aphids have been killed.
[1069] In this test, for example, the following compound of the
Preparation Examples shows good activity:
TABLE-US-00031 TABLE B Plant-damaging insects Myzus test
Concentration of active Kill rate Active compounds compound in g/ha
in % after 4.sup.d Ex. I-1-a-3 100 80
Example C
Phaedon Larvae Test
TABLE-US-00032 [1070] Solvent: 7 parts by weight of
dimethylformamide Emulsifier: 2 parts by weight of alkylaryl
polyglycol ether
[1071] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[1072] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are populated with larvae of the mustard beetle
(Phaedon cochleariae) while the leaves are still moist.
[1073] After the desired period of time, the kill in % is
determined 100% means that all beetle larvae have been killed; 0%
means that none of the beetle larvae have been killed.
[1074] In this test, for example, the following compounds of the
Preparation Examples show good activity:
TABLE-US-00033 TABLE C Plant-damaging insects Phaedon larvae test
Concentration of active Kill rate Active compounds compound in ppm
in % after 7.sup.d Ex. I-6-a-1 500 90 Ex. I-7-a-1 500 100 Ex.
I-7-a-2 500 100
Example D
Spodoptera frugiperda Test
TABLE-US-00034 [1075] Solvent: 7 parts by weight of
dimethylformamide Emulsifier: 2 parts by weight of alkylaryl
polyglycol ether
[1076] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[1077] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are populated with caterpillars of the army worm
(Spodoptera frugiperda) while the leaves are still moist.
[1078] After the desired period of time, the kill in % is
determined 100% means that all caterpillars have been killed; 0%
means that none of the caterpillars have been killed.
[1079] In this test, for example, the following compound of the
Preparation Examples shows good activity:
TABLE-US-00035 TABLE D Plant-damaging insects Spodoptera frugiperda
test Concentration of active Kill rate Active compounds compound in
ppm in % after 7.sup.d Ex. I-1-a-1 100 85
Example E
Tetranychus test (OP-Resistant/Spray Treatment)
TABLE-US-00036 [1080] Solvents: 78 parts by weight of acetone 1.5
parts by weight of dimethylformamide Emulsifier: 0.5 part by weight
of alkylaryl polyglycol ether
[1081] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[1082] Discs of bean leaves (Phaseolus vulgaris) infested by all
stages of the greenhouse red spider mite (Tetranychus urticae) are
sprayed with a preparation of active compound of the desired
concentration.
[1083] After the desired period of time, the effect in % is
determined 100% means that all spider mites have been killed; 0%
means that none of the spider mites have been killed.
[1084] In this test, for example, the following compound of the
Preparation Examples shows good activity:
TABLE-US-00037 TABLE E Plant-damaging mites Tetranychus test
(OP-resistant/spray treatment) Concentration of active Kill rate
Active compounds compound in ppm in % after 4.sup.d Ex. I-1-a-2 20
90
Example F
Sphaerotheca Test (Cucumber)/Protective
TABLE-US-00038 [1085] Solvents: 24.5 parts by weight of acetone
24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by
weight of alkylaryl polyglycol ether
[1086] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
[1087] To test for protective activity, the young plants are
sprayed with the preparation of active compound at the stated
application rate. After the spray coating has dried on, the plants
are inoculated with an aqueous spore suspension of Sphaerotheca
fuliginea. The plants are then placed in a greenhouse at about
23.degree. C. and a relative atmospheric humidity of about 70%.
[1088] Evaluation is carried out 7 days after the inoculation. 0%
means an efficacy which corresponds to that of the control, whereas
an efficacy of 100% means that no infection is observed.
TABLE-US-00039 TABLE F Sphaerotheca test (cucumber)/protective
Application rate of active compound in Active compound g/ha
Efficacy in % Ex. I-6-a-2 100 97
Example G
[1089] In vitro test for the ED.sub.50 determination in
microorganisms
[1090] A methanolic solution of the active compound to be tested,
mixed with Emulsifier PS16, is pipetted into the wells of
microtitre plates. After the solvent has evaporated, 200 .mu.l of
potato/dextrose medium are added to each well.
[1091] Beforehand, a suitable concentration of spores or mycelium
of the fungus to be tested was added to the medium.
[1092] The resulting concentrations of the active compound are 0.1,
1, 10 and 100 ppm. The resulting concentration of the emulsifier is
300 ppm.
[1093] The plates are then incubated on a shaker at a temperature
of 22.degree. C. for 3-5 days, until sufficient growth can be
observed in the untreated control.
[1094] Evaluation is carried out photometrically at a wavelength of
620 nm. The dose of active compound which causes 50% inhibition of
fungal growth compared to the untreated control (ED.sub.50) is
calculated from the data measured at different concentrations.
TABLE-US-00040 TABLE G In vitro test for the ED.sub.50
determination in microorganisms Active compound Microorganism
ED.sub.50 value Ex. I-6-a-2 Botrytis cinerea <0.1 Ex. I-6-c-1
Botrytis cinerea <0.1
Example H
Post-Emergence Test
TABLE-US-00041 [1095] Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
[1096] 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.
[1097] Test plants of a height of 5-15 cm are sprayed with the
preparation of active compound such that the particular amounts of
active compound desired are applied per unit area. The
concentration of the spray liquor is chosen such that the
particular amounts of active compound desired are applied in 10001
of water/ha.
[1098] After three weeks, the degree of damage to the plants is
rated in % damage in comparison to the development of the untreated
control.
[1099] The figures denote:
TABLE-US-00042 0% = no effect (like untreated control) 100% = total
destruction
Example I
Pre-Emergence Test
TABLE-US-00043 [1100] Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
[1101] 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.
[1102] Seeds of the test plants are sown in normal soil. After
about 24 hours, the soil is sprayed with the preparation of active
compound such that the particular amounts of active compound
desired are applied per unit area. The concentration of the spray
liquor is chosen such that the particular amounts of active
compound desired are applied in 1000 l of water/ha.
[1103] After three weeks, the degree of damage to the plants is
rated in % damage in comparison to the development of the untreated
control.
[1104] The figures denote:
TABLE-US-00044 0% = no effect (like untreated control) 100% = total
destruction
TABLE-US-00045 Greenhouse g of a.i./ha Alopecurus Avena fatua
Echinochloa Setaria Amaranthus Sinapis Pre-emergence Ex. I-1-a-2
250 100 100 100 100 100 80
J. Herbicidal Pre-Emergence Action
[1105] Seeds of monocotyledonous and dicotyledonous weed and crop
plants are placed into sandy loam in wood fibre pots and covered
with soil. The test compounds, formulated in the form of wettable
powders (WP) or emulsifiable concentrates (EC) are then, in various
dosages as aqueous suspension or emulsion with a water application
rate of 600 l/ha (converted), with 0.2% of wetting agent added,
applied to the surface of the covering soil.
[1106] After the treatment, the pots are placed in a greenhouse and
kept under good growth conditions for the test plants. The visual
assessment of the emergence damage on the test plants is carried
out after a trial period of 3 weeks by comparison with untreated
controls (herbicidal effect in percent (%): 100% effect=the plants
have died, 0% effect=like controlled plants).
K. Herbicidal Post-Emergence Action
[1107] Seeds of monocotyledonous and dicotyledonous weed and crop
plants are placed into sandy loam in wood fibre pots, covered with
soil and cultivated in a greenhouse under good growth conditions.
2-3 weeks after sowing, the test plants are treated at the one-leaf
stage. The test compounds, formulated as wettable powders (WP) or
emulsifiable concentrates (EC), are, in various dosages with a
water application rate of 600 l/ha (converted), with 0.2% of
wetting agent added, sprayed onto the green parts of the plants.
After the test plants were kept in a greenhouse under optimum
growth conditions for about 3 weeks, the effect of the preparations
is rated visually in comparison to untreated controls (herbicidal
effect in percent (%): 100% effect=the plants have died, 0%
effect=like controlled plants).
TABLE-US-00046 Greenhouse g of a.i./ha Sugar beet Echinochloa
Setaria Sorghum Post-emergence Ex. I-1-a-1 (EC) 320 0 100 100
90
Test Description for Profiling Tests
L. Herbicidal Post-Emergence Action
[1108] Seeds of monocotyledonous and dicotyledonous weed and crop
plants are placed into sandy loam in wood fibre pots or in plastic
pots, covered with soil and cultivated in a greenhouse and during
the vegetation period also outdoors, outside the greenhouse, under
good growth conditions. 2-3 weeks after sowing, the test plants are
treated in the one- to three-leaf stage. The test compounds,
formulated as wettable powders (WP) or liquid (EC), are, at various
dosages with a water application rate of 300 l/ha (converted), with
added wetting agent (0.2 to 0.3%), sprayed onto the plants and the
surface of the soil. 3 to 4 weeks after the treatment of the test
plants, the effect of the preparations is rated visually in
comparison to untreated controls (herbicidal effect in percent (%):
100% effect=the plants have died, 0% effect=like controlled
plants).
Use of Safeners
[1109] Prior to the application of the test substances, the crop
plants are sprayed with the safener using a certain application
rate per hectare (usually 1 day before the application of the test
substances).
[1110] By comparison with the effect of test substances on crop
plants treated with and without safener, it is possible to assess
the effect of the safener substance.
Container Trials with Cereals in the Greenhouse
TABLE-US-00047 TABLE Application rate Summer wheat g of a.i./ha
observed (%) I-1-a-2 25 50 I-1-a-2 + 25 + 100 10 mefenpyr
TABLE-US-00048 TABLE Application rate Summer wheat g of a.i./ha
observed (%) I-1-a-6 100 20 I-1-a-6 + 100 + 100 0 mefenpyr
TABLE-US-00049 TABLE Application rate Summer barley Summer wheat g
of a.i./ha observed (%) observed (%) I-1-a-7 25 95 60 I-1-a-7 + 25
+ 100 50 15 mefenpyr mefenpyr 1 day before the application of
herbicide
TABLE-US-00050 TABLE Application rate Summer barley Summer wheat g
of a.i./ha observed (%) observed (%) Ex. I-2-a-6 100 20 15 50 10 15
Ex. I-2-a-6 + 100 + 100 5 10 mefenpyr 50 + 100 0 10
TABLE-US-00051 TABLE Application rate Summer barley Summer wheat g
of a.i./ha observed (%) observed (%) Ex. I-2-a-5 100 20 40 50 15 20
Ex. I-2-a-5 + 100 + 100 0 10 mefenpyr 50 + 100 0 0
TABLE-US-00052 TABLE Application rate Summer barley Summer wheat g
of a.i./ha observed (%) observed (%) Ex. I-2-b-5 100 20 40 50 15 40
Ex. I-2-b-5 + 100 + 100 0 20 mefenpyr 50 + 100 0 10 mefenpyr 1 day
before the application of herbicide
Example L
Critical Concentration Test/Soil Insects-Treatment of Transgenic
Plants
TABLE-US-00053 [1111] Test insect: Diabrotica balteata - Larvae in
soil Solvent: 7 parts by weight of acetone Emulsifier: 1 part by
weight of alkylaryl polyglycol ether
[1112] 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.
[1113] The preparation of active compound is poured onto the soil.
Here, the concentration of active compound in the preparation is
virtually immaterial, only the amount by weight of active compound
per volume unit of soil, which is stated in ppm (mg/l), matters.
The soil is filled in to 0.25 l pots, and these are allowed to
stand at 20.degree. C.
[1114] Immediately after the preparation, 5 pregerminated maize
corns of the cultivar YIELD GUARD (trade mark of Monsanto Domp.,
USA) are placed into each pot. After 2 days, the appropriate test
insects are placed into the treated soil. After a further 7 days,
the efficacy of the active compound is determined by counting the
maize plants that emerged (1 plant=20% activity).
Example M
Heliothis virescens Test
Treatment of Transgenic Plants
TABLE-US-00054 [1115] Solvent: 7 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
[1116] 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.
[1117] Soybean shoots (Glycine max) of the cultivar Roundup Ready
(trade mark of Monsanto Comp. USA) are treated by being dipped into
the preparation of active compound of the desired concentration and
are populated with the tobacco budworm Heliothis virescens while
the leaves are still moist.
[1118] After the desired period of time, the kill of the insects is
determined.
* * * * *