U.S. patent application number 13/035293 was filed with the patent office on 2011-08-04 for spiroketal-substituted cyclic ketoenols.
This patent application is currently assigned to Bayer CropScience AG. Invention is credited to Christian Arnold, Thomas Auler, Thomas Bretschneider, Mark Wilhelm Drewes, Dieter Feucht, Reiner Fischer, Oliver Gaertzen, Waltraud Hempel, Martin Jeffrey Hills, Heinz Kehne, Stefan Lehr, Olga Malsam, Udo Reckmann, Christopher Hugh Rosinger, Erich Sanwald.
Application Number | 20110190493 13/035293 |
Document ID | / |
Family ID | 36685717 |
Filed Date | 2011-08-04 |
United States Patent
Application |
20110190493 |
Kind Code |
A1 |
Bretschneider; Thomas ; et
al. |
August 4, 2011 |
Spiroketal-Substituted Cyclic Ketoenols
Abstract
The invention relates to novel spiroketal-substituted cyclic
ketoenols of the formula (I) ##STR00001## in which A, B, Q.sup.1,
Q.sup.2, D, G, W, X, Y, and Z are as defined above, to processes
and intermediates for their preparation and to their use as
pesticides and/or microbicides and/or herbicides. Moreover, the
invention relates to selective herbicidal compositions comprising,
firstly, spiroketal-substituted cyclic ketoenols and, secondly, a
crop plant compatibility-improving compound.
Inventors: |
Bretschneider; Thomas;
(Lohmar, DE) ; Fischer; Reiner; (Monheim, DE)
; Gaertzen; Oliver; (Koln, DE) ; Lehr; Stefan;
(Liederbach, DE) ; Drewes; Mark Wilhelm;
(Langenfeld, DE) ; Feucht; Dieter; (Eschborn,
DE) ; Malsam; Olga; (Rosrath, DE) ; Reckmann;
Udo; (Koln, DE) ; Arnold; Christian;
(Langenfeld, DE) ; Auler; Thomas; (Leichlingen,
DE) ; Hempel; Waltraud; (Liederbach, DE) ;
Hills; Martin Jeffrey; (Idstein, DE) ; Kehne;
Heinz; (Hofheim, DE) ; Rosinger; Christopher
Hugh; (Hofheim, DE) ; Sanwald; Erich; (Kiel,
DE) |
Assignee: |
Bayer CropScience AG
Monheim
DE
|
Family ID: |
36685717 |
Appl. No.: |
13/035293 |
Filed: |
February 25, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11884887 |
Apr 3, 2008 |
7897543 |
|
|
PCT/EP2006/001089 |
Feb 8, 2006 |
|
|
|
13035293 |
|
|
|
|
Current U.S.
Class: |
544/142 ;
548/301.4; 548/408; 548/410; 549/265; 549/341; 560/109 |
Current CPC
Class: |
A01N 43/30 20130101;
A01N 43/24 20130101; A01N 43/38 20130101; A01N 43/32 20130101; C07D
491/10 20130101; C07D 493/10 20130101; A01N 47/06 20130101; A01N
43/12 20130101 |
Class at
Publication: |
544/142 ;
560/109; 549/265; 549/341; 548/301.4; 548/410; 548/408 |
International
Class: |
C07D 413/14 20060101
C07D413/14; C07C 69/612 20060101 C07C069/612; C07D 307/94 20060101
C07D307/94; C07D 317/72 20060101 C07D317/72; C07D 491/113 20060101
C07D491/113; C07D 209/54 20060101 C07D209/54 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 22, 2005 |
DE |
10 2005 008 021.9 |
Claims
1-18. (canceled)
19. A compound of the formula (II) ##STR00168## in which W
represents hydrogen, alkyl, alkenyl, alkynyl, halogen, alkoxy,
alkenyloxy, haloalkyl, haloalkoxy or cyano, X represents halogen,
alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro or cyano, Y and Z independently of one
another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy,
halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each
case optionally substituted aryl or heteroaryl, with the proviso
that at least one of the radicals W or Z is different from hydrogen
if X and Y represent methyl, A and B and the carbon atom to which
they are attached represent a five- to seven-membered ketal,
thioketal or dithioketal which is optionally interrupted by a
further heteroatom, each of which radicals is optionally
substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally
substituted phenyl, Q.sup.1 and Q.sup.2 independently of one
another represent hydrogen, alkyl, haloalkyl or alkoxy, and R.sup.8
represents alkyl.
20. A compound of the formula (III) ##STR00169## in which W
represents hydrogen, alkyl, alkenyl, alkynyl, halogen, alkoxy,
alkenyloxy, haloalkyl, haloalkoxy or cyano, X represents halogen,
alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro or cyano, Y and Z independently of one
another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy,
halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each
case optionally substituted aryl or heteroaryl, with the proviso
that at least one of the radicals W or Z is different from hydrogen
if X and Y represent methyl, A and B and the carbon atom to which
they are attached represent a five- to seven-membered ketal,
thioketal or dithioketal which is optionally interrupted by a
further heteroatom, each of which radicals is optionally
substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally
substituted phenyl, Q.sup.1 and Q.sup.2 independently of one
another represent hydrogen, alkyl, haloalkyl or alkoxy, and R.sup.8
represents alkyl.
21. A compound of the formula (XVIII) ##STR00170## in which W
represents hydrogen, alkyl, alkenyl, alkynyl, halogen, alkoxy,
alkenyloxy, haloalkyl, haloalkoxy or cyano, X represents halogen,
alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro or cyano, Y and Z independently of one
another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy,
halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each
case optionally substituted aryl or heteroaryl, with the proviso
that at least one of the radicals W or Z is different from hydrogen
if X and Y represent methyl, A and B and the carbon atom to which
they are attached represent a five- to seven-membered ketal,
thioketal or dithioketal which is optionally interrupted by a
further heteroatom, each of which radicals is optionally
substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally
substituted phenyl, and Q.sup.1 and Q.sup.2 independently of one
another represent hydrogen, alkyl, haloalkyl or alkoxy.
22. A compound of the formula (XXI) ##STR00171## in which W
represents hydrogen, alkyl, alkenyl, alkynyl, halogen, alkoxy,
alkenyloxy, haloalkyl, haloalkoxy or cyano, X represents halogen,
alkyl, alkenyl, alkenyl, alkoxy, alkenyloxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro or cyano, Y and Z independently of one
another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy,
halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each
case optionally substituted aryl or heteroaryl, with the proviso
that at least one of the radicals W or Z is different from hydrogen
if X and Y represent methyl, A and B and the carbon atom to which
they are attached represent a five- to seven-membered ketal,
thioketal or dithioketal which is optionally interrupted by a
further heteroatom, each of which radicals is optionally
substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally
substituted phenyl, and Q.sup.1 and Q.sup.2 independently of one
another represent hydrogen, alkyl, haloalkyl or alkoxy.
23. A compound of the formula (XXII) ##STR00172## in which A and B
and the carbon atom to which they are attached represent a five- to
seven-membered ketal, thioketal or dithioketal which is optionally
interrupted by a further heteroatom, each of which radicals is
optionally substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or
optionally substituted phenyl, Q.sup.1 and Q.sup.2 independently of
one another represent hydrogen, alkyl, haloalkyl or alkoxy, and
R.sup.8 represents alkyl.
24. A compound of the formula (XVI') ##STR00173## or a salt
thereof, in which Q.sup.3 represents C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, q represents 1, 2 or
3, and R.sup.8 is alkyl.
25. A compound of the formula (XVI'') ##STR00174## or a salt
thereof, in which Q.sup.3 represents C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, q represents 0, 1, 2
or 3, and R.sup.8 represents alkyl.
26. A compound of the formula (XVI''') ##STR00175## or a salt
thereof, in which Q.sup.3 represents C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, q represents 0, 1, 2
or 3, and R.sup.8 represents alkyl.
27. A compound of the formula (XIX') ##STR00176## in which Q.sup.3
represents C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.3-haloalkyl,
C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, and q represents 1, 2
or 3.
28. A compound of the formula (XIX'') ##STR00177## in which Q.sup.3
represents C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.3-haloalkyl,
C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, and q represents 0,
1, 2 or 3.
29. A compound of the formula (XIX''') ##STR00178## in which
Q.sup.3 represents C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, and q represents 0,
1, 2 or 3.
30. A compound of the formula (XXIII') ##STR00179## in which
Q.sup.3 represents C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, and q represents 1, 2
or 3.
31. A compound of the formula (XXIII'') ##STR00180## in which
Q.sup.3 represents C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, and q 0, 1, 2 or
3.
32. A compound of the formula (XXIII''') ##STR00181## in which
Q.sup.3 represents C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, and q represents 0,
1, 2 or 3.
33. A compound of the formula (XIV) ##STR00182## in which W
represents hydrogen, alkyl, alkenyl, alkynyl, alkoxy, halogen,
alkenyloxy, haloalkyl, haloalkoxy or cyano, X represents halogen,
alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro or cyano, Y and Z independently of one
another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy,
halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each
case optionally substituted aryl or heteroaryl, with the proviso
that at least one of the radicals W or Z is different from hydrogen
if X and Y represent methyl, D represents NH or oxygen, Q.sup.1 and
Q.sup.2 independently of one another represent hydrogen, alkyl,
haloalkyl or alkoxy, G represents hydrogen (a), or ##STR00183## in
which E represents a metal ion or an ammonium ion, L represents
oxygen or sulphur, M represents oxygen or sulphur, R.sup.1
represents in each case optionally halogen- or cyano-substituted
alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl, or
represents in each case optionally halogen-, alkyl- or
alkoxy-substituted cycloalkyl or heterocyclyl, or represents in
each case optionally substituted phenyl, phenylalkyl, heteroaryl,
phenoxyalkyl or heteroaryloxyalkyl, R.sup.2 represents in each case
optionally halogen- or cyano-substituted alkyl, alkenyl,
alkoxyalkyl or polyalkoxyalkyl, or represents in each case
optionally substituted cycloalkyl, phenyl or benzyl, 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 or cycloalkylthio, or
represent in each case optionally substituted phenyl, benzyl,
phenoxy or phenylthio, and R.sup.6 and R.sup.7 independently of one
another represent hydrogen, in each case optionally halogen- or
cyano-substituted alkyl, cycloalkyl, alkenyl, alkoxy, or
alkoxyalkyl, or represent in each case optionally substituted
phenyl or benzyl, or R.sup.6 and R.sup.7 together with the N atom
to which they are attached form an optionally substituted cycle
which optionally contains oxygen or sulphur.
Description
[0001] The present invention relates to novel
spiroketal-substituted cyclic ketoenols, to a plurality of
processes for their preparation and to their use as pesticides
and/or herbicides and/or microbicides. The invention also provides
selective herbicidal compositions comprising, firstly,
spiroketal-substituted cyclic ketoenols and, secondly, a crop plant
compatibility-improving compound.
[0002] Pharmaceutical properties of 3-acylpyrrolidine-2,4-diones
are described in the prior art (S. Suzuki et al. Chem. Pharm. Bull.
15 1120 (1967)). Furthermore, R. Schmierer and H. Mildenberger
(Liebigs Ann. Chem. 1985, 1095) synthesized
N-phenylpyrrolidine-2,4-diones. A biological activity of these
compounds has not been described.
[0003] EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a
similar structure (3-arylpyrrolidine-2,4-diones); however, a
herbicidal, insecticidal or acaricidal action of these compounds is
not known. Known to have a herbicidal, insecticidal or acaricidal
action are unsubstituted bicyclic 3-arylpyrrolidine-2,4-dione
derivatives (EP-A-355 599, EP-A-415 211 and JP-A-12-053 670), and
also substituted monocyclic 3-arylpyrrolidine-2,4-dione derivatives
(EP-A-377 893 and EP-A-442 077).
[0004] Also known are polycyclic 3-arylpyrrolidine-2,4-dione
derivatives (EP-A-442 073), and also 1H-arylpyrrolidine dione
derivatives (EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613
884, EP-A-613 885, WO 94/01 997, WO 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
99/24437, WO 99/43649, WO 99/48869 and WO 99/55673, WO 01/17972, WO
01/23354, WO 01/74770, WO 03/013249, WO 03/062244, WO 2004/007448,
WO 2004/024688, WO 04/065366, WO 04/080962, WO 04/111042, WO
05/044791, WO 05/044796, WO 05/048710, WO 05/049596, WO 05/066125,
WO 05/092897 and DE-A-04 030 753). Further well known are
ketal-substituted 1H-arylpyrrolidine-2,4-diones from WO 99/16748
and (spiro)-ketal-substituted N-alkoxyalkoxy-substituted
arylpyrrolidinediones from JP-A-14 205 984 and Ito M. et al.,
Bioscience, Biotechnology and Biochemistry 67, 1230-1238,
(2003).
[0005] 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 (such as, for example,
3-(2-methylphenyl)-4-hydroxy-5-(4-fluorophenyl)-.DELTA..sup.3-dihydrofura-
n-2-one) used as starting materials is also described in DE-A-4 014
420. Compounds of a similar structure with no stated insecticidal
and/or acaricidal activity are known from the publication Campbell
et al., J. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76.
Furthermore, 3-aryl-.DELTA..sup.3-dihydrofuranone derivatives
having herbicidal, acaricidal and insecticidal properties are 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 and WO 01/74770, WO 03/013 249,
WO 2004/024 688, WO 04/080962, WO 04/111042, WO 05/092897 and
DE-A-04 030 753.
[0006] However, the herbicidal and/or acaricidal and/or
insecticidal activity and/or activity spectrum and/or the plant
compatibility of the known compounds, in particular with respect to
crop plants, is/are not always satisfactory.
[0007] This invention now provides novel compounds of the formula
(I)
##STR00002##
in which [0008] W represents hydrogen, alkyl, alkenyl, alkynyl,
halogen, alkoxy, alkenyloxy, haloalkyl, haloalkoxy or cyano, [0009]
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy,
alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy,
haloalkenyloxy, nitro or cyano, [0010] Y and Z independently of one
another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy,
halogen, haloalkyl, haloalkoxy, cyano, nitro or in each case
optionally substituted aryl or hetaryl, [0011] with the proviso
that at least one of the radicals W or Z has to be different from
hydrogen if X and Y represent methyl, [0012] A and B and the carbon
atom to which they are attached represent five- to seven-membered
ketal, thioketal or dithioketal which may optionally be interrupted
by a further heteroatom, each of which radicals is optionally
substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally
substituted phenyl, [0013] D represents NH and oxygen, [0014]
Q.sup.1, Q.sup.2 independently of one another represent hydrogen,
alkyl, haloalkyl or alkoxy, [0015] G represents hydrogen (a) or
represents one of the groups
[0015] ##STR00003## [0016] in which [0017] E represents a metal ion
or an ammonium ion, [0018] L represents oxygen or sulphur, [0019] M
represents oxygen or sulphur, [0020] R.sup.1 represents in each
case optionally halogen- or cyano-substituted alkyl, alkenyl,
alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl or represents in
each case optionally halogen-, alkyl- or alkoxy-substituted
cycloalkyl or heterocyclyl or represents in each case optionally
substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or
hetaryloxyalkyl, [0021] R.sup.2 represents in each case optionally
halogen- or cyano-substituted alkyl, alkenyl, alkoxyalkyl or
polyalkoxyalkyl or represents in each case optionally substituted
cycloalkyl, phenyl or benzyl, [0022] 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 or cycloalkylthio or represent in each case
optionally substituted phenyl, benzyl, phenoxy or phenylthio,
[0023] R.sup.6 and R.sup.7 independently of one another represent
hydrogen, represent in each case optionally halogen- or
cyano-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl,
represent in each case optionally substituted phenyl or benzyl, or
together with the N atom to which they are attached form an
optionally substituted cycle which optionally contains oxygen or
sulphur.
[0024] Depending inter alia on the nature of the substituents, the
compounds of the formula (I) can be present as optical isomers or
isomer mixtures of varying composition which, if appropriate, may
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 are both the pure compounds
and, if appropriate, also mixtures having varying proportions of
isomeric compounds.
[0025] Including D for NH (1) and D for O (2), the following
principal structures (I-1) and (I-2) result:
##STR00004##
in which A, B, G, Q.sup.1, Q.sup.2, W, X, Y and Z are as defined
above.
[0026] Including the different meanings (a), (b), (c), (d), (e),
(f) and (g) of the group G, the following principal structures
(I-1-a) to (I-1-g) result if D represents NH (1)
##STR00005## ##STR00006##
in which A, B, E, L, M, Q.sup.1, Q.sup.2, 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.
[0027] Including the different meanings (a), (b), (c), (d), (e),
(f) and (g) of the group G, the following principal structures
(I-2-a) to (I-2-g) result if D represents O (2)
##STR00007## ##STR00008##
in which A, B, E, L, M, Q.sup.1, Q.sup.2, 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.
[0028] Furthermore, it has been found that the novel compounds of
the formula (I) are obtained by the processes described below:
[0029] (A) compounds of the formula (I-1-a)
[0029] ##STR00009## [0030] in which [0031] A, B, Q.sup.1, Q.sup.2,
W, X, Y and Z are as defined above [0032] are obtained when [0033]
compounds of the formula (II)
[0033] ##STR00010## [0034] in which [0035] A, B, Q.sup.1, Q.sup.2,
W, X, Y and Z are as defined above [0036] and [0037] R.sup.8
represents alkyl (preferably C.sub.1-C.sub.6-alkyl), [0038] are
condensed intramolecularly in the presence of a diluent and in the
presence of a base. [0039] (B) Moreover, it has been found that
compounds of the formula (I-2-a)
[0039] ##STR00011## [0040] in which [0041] A, B, Q.sup.1, Q.sup.2,
W, X, Y and Z are as defined above, are obtained when compounds of
the formula (III)
[0041] ##STR00012## [0042] in which [0043] A, B, Q.sup.1, Q.sup.2,
W, X, Y, Z and R.sup.8 are as defined above, [0044] are condensed
intramolecularly in the presence of a diluent and in the presence
of a base.
[0045] Moreover, it has been found [0046] (C) that the compounds of
the formulae (I-1-b) to (I-2-b) shown above in which R.sup.1, A, B,
Q.sup.1, Q.sup.2, W, X, Y and Z are as defined above are obtained
when compounds of the formulae (I-1-a) to (I-2-a) shown above in
which A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are as defined above
are in each case reacted [0047] .alpha.) with compounds of the
formula (IV)
[0047] ##STR00013## [0048] in which [0049] R.sup.1 is as defined
above and [0050] Hal represents halogen (in particular chlorine or
bromine) [0051] or [0052] .beta.) with carboxylic anhydrides of the
formula (V)
[0052] R.sup.1--CO--O--CO--R.sup.1 (V) [0053] in which [0054]
R.sup.1 is as defined above, [0055] if appropriate in the presence
of a diluent and if appropriate in the presence of an acid binder;
[0056] (D) that the compounds of the formulae (I-1-c) to (I-2-c)
shown above in which R.sup.2, A, B, Q.sup.1, Q.sup.2, W, M, X, Y
and Z are as defined above and L represents oxygen are obtained
when compounds of the formulae (I-1-a) to (I-2-a) shown above in
which A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are as defined above
are in each case reacted [0057] with chloroformic esters or
chloroformic thioesters of the formula (VI)
[0057] R.sup.2-M-CO--Cl (VI) [0058] in which [0059] R.sup.2 and M
are as defined above, [0060] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder;
[0061] (E) that compounds of the formulae (I-1-c) to (I-2-c) shown
above in which R.sup.2, A, B, Q.sup.1, Q.sup.2, W, M, X, Y and Z
are as defined above and L represents sulphur are obtained when
compounds of the formulae (I-1-a) to (I-2-a) shown above in which
A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are as defined above are in
each case reacted [0062] with chloromonothioformic esters or
chlorodithioformic esters of the formula (VII)
[0062] ##STR00014## [0063] in which [0064] M and R.sup.2 are as
defined above, [0065] if appropriate in the presence of a diluent
and if appropriate in the presence of an acid binder, [0066] (F)
that compounds of the formulae (I-1-d) to (I-2-d) shown above in
which R.sup.3, A, B, W, Q.sup.1, Q.sup.2, X, Y and Z are as defined
above are obtained when compounds of the formulae (I-1-a) to
(I-2-a) shown above in which A, B, Q.sup.1, Q.sup.2, W, X, Y and Z
are as defined above are in each case reacted [0067] with sulphonyl
chlorides of the formula (VIII)
[0067] R.sup.3--SO.sub.2--Cl (VIII) [0068] in which [0069] R.sup.3
is as defined above, [0070] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder,
[0071] (G) that compounds of the formulae (I-1-e) to (I-2-e) shown
above in which L, R.sup.4, R.sup.5, A, B, Q.sup.1, Q.sup.2, W, X, Y
and Z are as defined above are obtained when compounds of the
formulae (I-1-a) to (I-2-a) shown above in which A, B, Q.sup.1,
Q.sup.2, W, X, Y and Z are as defined above are in each case
reacted [0072] with phosphorus compounds of the formula (IX)
[0072] ##STR00015## [0073] in which [0074] L, R.sup.4 and R.sup.5
are as defined above and [0075] Hal represents halogen (in
particular chlorine or bromine), [0076] if appropriate in the
presence of a diluent and if appropriate in the presence of an acid
binder, [0077] (II) that compounds of the formulae (I-1-0 to (I-2-0
shown above in which E, A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are
as defined above are obtained when compounds of the formulae
(I-1-a) to (I-2-a) in which A, B, Q.sup.1, Q.sup.2, W, X, Y and Z
are as defined above are in each case reacted [0078] with metal
compounds or amines of the formula (X) or (X.sup.1)
[0078] ##STR00016## [0079] in which [0080] Me represents a mono- or
divalent metal (preferably an alkali metal or alkaline earth metal,
such as lithium, sodium, potassium, magnesium or calcium), [0081] t
represents the number 1 or 2 and [0082] 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), [0083] if appropriate in the
presence of a diluent, [0084] (I) that compounds of the formulae
(I-1-g) to (I-2-g) shown above in which L, R.sup.6, R.sup.7, A, B,
Q.sup.1, Q.sup.2, W, X, Y and Z are as defined above are obtained
when compounds of the formulae (I-1-a) to (I-2-a) shown above in
which A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are as defined above
are in each case [0085] .alpha.) reacted with isocyanates or
isothiocyanates of the formula (XII)
[0085] R.sup.6--N.dbd.C=L (XII) [0086] in which [0087] R.sup.6 and
L are as defined above, [0088] if appropriate in the presence of a
diluent and if appropriate in the presence of a catalyst, or [0089]
.beta.) reacted with carbamoyl chlorides or thiocarbamoyl chlorides
of the formula (XIII)
[0089] ##STR00017## [0090] in which [0091] L, R.sup.6 and R.sup.7
are as defined above, [0092] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder,
[0093] (J) that compounds of the formulae (I-1-a) to (I-1-g) and
(I-2-a) to (I-2-g) shown above in which A, B, D, G, Q.sup.1,
Q.sup.2, W, X, Y and Z are as defined above are obtained when
compounds of the formula (XIV)
[0093] ##STR00018## [0094] in which [0095] D, G, Q.sup.1, Q.sup.2,
W, X, Y and Z are as defined above, [0096] and A, B and the carbon
atom to which they are attached represent a
[0096] ##STR00019## [0097] are reacted, for example, with diols of
the formula (XV)
[0097] HO-A-B--OH (XV) [0098] in which [0099] A and B are as
defined above, [0100] if appropriate in the presence of a diluent,
in the presence of an acidic catalyst and under dehydrating
conditions.
[0101] The following compound of the formula (I-a) has been
disclosed in 1994 in the context of the European Patent Examination
of EP 596 298.
##STR00020##
[0102] Furthermore, it has been found that the novel compounds of
the formula (I) have good activity as pesticides, preferably as
insecticides and/or acaricides and/or fungicides and/or herbicides,
and are additionally frequently highly compatible with plants, in
particular with crop plants.
[0103] Surprisingly, it has now also been found that certain
substituted cyclic ketoenols, when employed together with the crop
plant compatibility-improving compounds (safeners/antidotes)
described later on, are extremely good at preventing damage to the
crop plants and can be used with particular advantage as
broad-spectrum combination products for the selective control of
unwanted plants in crops of useful plants, such as, for example, in
cereals, but also in maize, soy and rice.
[0104] The invention also provides selective herbicidal
compositions comprising an effective amount of an active compound
combination comprising, as components, [0105] (a') at least one
compound of the formula (I) in which A, B, D, G, Q.sup.1, Q.sup.2,
W, X, Y and Z are as defined above and [0106] (b') at least one
crop plant compatibility-improving compound from the following
group of compounds:
[0107] 4-dichloroacetyl-1-oxa-4-azaspiro[4.5]decane (AD-67,
MON-4660), 1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo
pyrimidin-6(2H)-one (dicyclonon, BAS-145138),
4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine
(benoxacor), 1-methylhexyl 5-chloroquinoline-8-oxyacetate
(cloquintocet-mexyl--cf. also related compounds in EP-A-86750,
EP-A-94349, EP-A-191736, EP-A-492366),
3-(2-chlorobenzyl)-1-(1-methyl-1-phenyl ethyl)urea (cumyluron),
.alpha.-(cyanomethoximino)phenylacetonitrile (cyometrinil),
2,4-dichlorophenoxyacetic acid (2,4-D),
4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
1-(1-methyl-1-phenylethyl)-3-(4-methylphenyl)urea (daimuron,
dymron), 3,6-dichloro-2-methoxybenzoic acid (dicamba),
S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate
(dimepiperate), 2,2-dichloro-N-(2-oxo-2-(2-propenyl
amino)ethyl)-N-(2-propenyl)acetamide (DKA-24),
2,2-dichloro-N,N-di-2-propenylacetamide (dichlormid),
4,6-dichloro-2-phenylpyrimidine (fenclorim), ethyl
1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate
(fenchlorazole-ethyl--cf. also related compounds in EP-A-174562 and
EP-A-346620), phenylmethyl
2-chloro-4-trifluoromethylthiazole-5-carboxylate (flurazole),
4-chloro-N-(1,3-dioxolan-2-ylmethoxy)-.alpha.-trifluoroacetophenone
oxime (fluxofenim),
3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine (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-dichorophenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylate
(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-ylmethoximino)phenylacetonitrile
(oxabetrinil),
2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide
(PPG-1292), 3-dichloroacetyl-2,2-dimethyloxazolidine (R-28725),
3-dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148),
4-(4-chloro-o-tolyl)butyric acid, 4-(4-chlorophenoxy)butyric acid,
diphenylmethoxyacetic acid, methyl diphenylmethoxyacetate, ethyl
diphenylmethoxyacetate, methyl
1-(2-chlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-methyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-isopropyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)-1H-pyrazole-3-carboxylate,
ethyl 1-(2,4-dichlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate
(cf. also related compounds in EP-A-269806 and EP-A-333131), ethyl
5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate, ethyl
5-phenyl-2-isoxazoline-3-carboxylate, ethyl
5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (cf. also
related compounds in WO-A-91/08202), 1,3-dimethylbut-1-yl
5-chloroquinoline-8-oxyacetate, 4-allyloxybutyl
5-chloroquinoline-8-oxyacetate, 1-allyloxyprop-2-yl
5-chloroquinoline-8-oxyacetate, methyl
5-chloroquinoxaline-8-oxyacetate, ethyl
5-chloroquinoline-8-oxyacetate, allyl
5-chloroquin-oxaline-8-oxyacetate, 2-oxoprop-1-yl
5-chloroquinoline-8-oxyacetate, diethyl
5-chloroquinoline-8-oxymalonate, diallyl
5-chloroquinoxaline-8-oxymalonate, diethyl
5-chloroquinoline-8-oxymalonate (cf. also related compounds in
EP-A-582198), 4-carboxychroman-4-ylacetic acid (AC-304415, cf.
EP-A-613618), 4-chlorophenoxyacetic acid,
3,3'-dimethyl-4-methoxy-benzophenone,
1-bromo-4-chloromethylsulphonylbenzene,
1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3-methylurea (also known
as
N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulphonamide),
1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3,3-dimethylurea,
1-[4-(N-4,5-dimethylbenzoyl sulphamoyl)phenyl]-3-methylurea,
1-[4-(N-naphthyl sulphamoyl)phenyl]-3,3-dimethylurea,
N-(2-methoxy-5-methylbenzoyl)-4-(cyclopropylaminocarbonyl)benzenesulphona-
mide,
and/or one of the following compounds, defined by general formulae,
of the general formula (IIa)
##STR00021##
or of the general formula (IIb)
##STR00022##
or of the formula (IIc)
##STR00023##
where [0108] m represents a number 0, 1, 2, 3, 4 or 5, [0109]
A.sup.1 represents one of the divalent heterocyclic groupings shown
below
[0109] ##STR00024## [0110] n represents a number 0, 1, 2, 3, 4 or
5, [0111] A.sup.2 represents optionally C.sub.1-C.sub.4-alkyl-
and/or C.sub.1-C.sub.4-alkoxy-carbonyl- and/or
C.sub.1-C.sub.4-alkenyloxycarbonyl-substituted alkanediyl having 1
or 2 carbon atoms, [0112] R.sup.14 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,
[0113] R.sup.15 represents hydroxyl, mercapto, amino,
C.sub.1-C.sub.7-alkoxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkenyloxy,
C.sub.1-C.sub.6-alkenyloxy-C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylamino or di(C.sub.1-C.sub.4-alkyl)-amino,
[0114] R.sup.16 represents optionally fluorine-, chlorine- and/or
bromine-substituted C.sub.1-C.sub.4-alkyl, [0115] R.sup.17
represents hydrogen, in each case optionally fluorine-, chlorine-
and/or bromine-substituted 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, or
optionally fluorine-, chlorine- and/or bromine- or
C.sub.1-C.sub.4-alkyl-substituted phenyl, [0116] R.sup.18
represents hydrogen, in each case optionally fluorine-, chlorine-
and/or bromine-substituted 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, or
optionally fluorine-, chlorine- and/or bromine- or
C.sub.1-C.sub.4-alkyl-substituted phenyl, R.sup.17 and R.sup.18
also together represent 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 attached, form a 5- or 6-membered carboxycle,
[0117] R.sup.19 represents hydrogen, cyano, halogen, or represents
in each case optionally fluorine-, chlorine- and/or
bromine-substituted C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.6-cycloalkyl or phenyl, [0118] R.sup.20 represents
hydrogen, in each case optionally hydroxyl-, cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-cycloalkyl or tri-(C.sub.1-C.sub.4-alkyl)-silyl,
[0119] R.sup.21 represents hydrogen, cyano, halogen, or represents
in each case optionally fluorine-, chlorine- and/or
bromine-substituted C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.6-cycloalkyl or phenyl, [0120] 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, [0121] 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, [0122] 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)
##STR00025##
[0122] or of the general formula (IIe)
##STR00026##
where [0123] t represents a number between 0 and 5, [0124] v
represents a number between 0 and 5, [0125] R.sup.22 represents
hydrogen or C.sub.1-C.sub.4-alkyl, [0126] R.sup.23 represents
hydrogen or C.sub.1-C.sub.4-alkyl, [0127] R.sup.24 represents
hydrogen, in each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted 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, or
in each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkyl-substituted 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, [0128] R.sup.25 represents
hydrogen, optionally cyano-, hydroxyl-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.1-C.sub.6-alkyl, in each
case optionally cyano- or halogen-substituted
C.sub.3-C.sub.6-alkenyl or C.sub.3-C.sub.6-alkynyl, or optionally
cyano-, halogen- or C.sub.1-C.sub.4-alkyl-substituted
C.sub.3-C.sub.6-cycloalkyl, [0129] R.sup.26 represents hydrogen,
optionally cyano-, hydroxyl-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.1-C.sub.6-alkyl, in each
case optionally cyano- or halogen-substituted
C.sub.3-C.sub.6-alkenyl or C.sub.3-C.sub.6-alkynyl, optionally
cyano-, halogen- or C.sub.1-C.sub.4-alkyl-substituted
C.sub.3-C.sub.6-cycloalkyl, or optionally 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-substituted
phenyl, or together with R.sup.25 represents in each case
optionally C.sub.1-C.sub.4-alkyl-substituted
C.sub.2-C.sub.6-alkanediyl or C.sub.2-C.sub.5-oxaalkanediyl, [0130]
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 [0131] 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.
[0132] The formula (I) provides a general definition of the
compounds according to the invention. Preferred substituents or
ranges of the radicals listed in the formulae given above and below
are illustrated below: [0133] W preferably represents hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, halogen, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy or cyano,
[0134] X preferably represents halogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-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
or cyano, [0135] Y and Z independently of one another preferably
represent hydrogen, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-haloalkoxy, cyano, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl or one of the (het)aryl radicals
##STR00027##
[0135] where in the case of (het)aryl only one of the radicals Y or
Z may represent (het)aryl, [0136] V.sup.1 preferably represents
hydrogen, halogen, C.sub.1-C.sub.12-alkyl, C.sub.1-C.sub.6-alkoxy,
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.4-haloalkyl,
C.sub.1-C.sub.4-haloalkoxy, nitro, cyano or represents phenyl,
phenoxy, phenoxy-C.sub.1-C.sub.4-alkyl,
phenyl-C.sub.1-C.sub.4-alkoxy, phenylthio-C.sub.1-C.sub.4-alkyl or
phenyl-C.sub.1-C.sub.4-alkylthio, each of which is optionally mono-
or polysubstituted 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, [0137] V.sup.2 and
V.sup.3 independently of one another preferably represent hydrogen,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-haloalkyl or C.sub.1-C.sub.4-haloalkoxy, [0138]
with the proviso that at least one of the radicals W or Z has to be
different from hydrogen if X and Y represent methyl, [0139] A and B
and the carbon atom to which they are attached preferably represent
five- to seven-membered ketal, thioketal, or dithioketal which may
optionally be interrupted by a further oxygen atom, sulphur atom or
by the group
##STR00028##
[0139] reach of which radicals is optionally mono- to
tetrasubstituted by C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, [0140] V.sup.4
preferably represents hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl, or represents the groups
--CO.sub.2V.sup.5, CO--NH--V.sup.5 or CO--NH--O--V.sup.5, [0141]
V.sup.5 preferably represents C.sub.1-C.sub.6-alkyl, [0142] D
preferably represents NH (1) or oxygen (2), [0143] Q.sup.1 and
Q.sup.2 independently of one another preferably represent hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.2-haloalkyl or
C.sub.1-C.sub.4-alkoxy, [0144] G preferably represents hydrogen (a)
or represents one of the groups
##STR00029##
[0144] in which [0145] E represents a metal ion or an ammonium ion,
[0146] L represents oxygen or sulphur and [0147] M represents
oxygen or sulphur, [0148] R.sup.1 preferably represents in each
case optionally halogen- or cyano-substituted
C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-alkylthio-C.sub.1-C.sub.8-alkyl or
poly-C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl or represents
optionally halogen-, C.sub.1-C.sub.6-alkyl- or
C.sub.1-C.sub.6-alkoxy-substituted C.sub.3-C.sub.8-cycloalkyl in
which optionally one or two not directly adjacent methylene groups
are replaced by oxygen and/or sulphur, [0149] represents optionally
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-substituted phenyl, [0150]
represents optionally 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-substituted
phenyl-C.sub.1-C.sub.6-alkyl, [0151] represents optionally halogen-
or C.sub.1-C.sub.6-alkyl-substituted 5- or 6-membered hetaryl
having one or two heteroatoms from the group consisting of oxygen,
sulphur and nitrogen, [0152] represents optionally halogen- or
C.sub.1-C.sub.6-alkyl-substituted phenoxy-C.sub.1-C.sub.6-alkyl or
[0153] represents optionally halogen-, amino- or
C.sub.1-C.sub.6-alkyl-substituted 5- or 6-membered
hetaryloxy-C.sub.1-C.sub.6-alkyl having one or two heteroatoms from
the group consisting of oxygen, sulphur and nitrogen, [0154]
R.sup.2 preferably represents in each case optionally halogen- or
cyano-substituted C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl or
poly-C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, [0155]
represents optionally halogen-, C.sub.1-C.sub.6-alkyl- or
C.sub.1-C.sub.6-alkoxy-substituted C.sub.3-C.sub.8-cycloalkyl or
[0156] represents in each case optionally 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-haloalkoxy-substituted phenyl or benzyl, [0157]
R.sup.3 preferably represents optionally halogen-substituted
C.sub.1-C.sub.8-alkyl or in each case optionally 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-substituted phenyl or benzyl, [0158] R.sup.4 and R.sup.5
independently of one another preferably represent in each case
optionally halogen-substituted C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-alkylamino,
di(C.sub.1-C.sub.8-alkyl)amino, C.sub.1-C.sub.8-alkylthio or
C.sub.3-C.sub.8-alkenylthio or represent in each case optionally
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-haloalkylthio-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-haloalkyl-substituted phenyl, phenoxy or
phenylthio, [0159] R.sup.6 and R.sup.7 independently of one another
preferably represent hydrogen, represent in each case optionally
halogen- or cyano-substituted C.sub.1-C.sub.8-alkyl,
C.sub.3-C.sub.8-cycloalkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.3-C.sub.8-alkenyl or
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, represent in each
case optionally halogen-, C.sub.1-C.sub.8-alkyl-,
C.sub.1-C.sub.8-haloalkyl- or C.sub.1-C.sub.8-alkoxy-substituted
phenyl or benzyl or together represent an optionally
C.sub.1-C.sub.6-alkyl-substituted C.sub.3-C.sub.6-alkylene radical
in which optionally one methylene group is replaced by oxygen or
sulphur.
[0160] In the radical definitions mentioned as being preferred,
halogen represents fluorine, chlorine, bromine and iodine, in
particular fluorine, chlorine and bromine. [0161] W particularly
preferably represents hydrogen, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-haloalkyl or C.sub.1-C.sub.2-haloalkoxy, [0162] X
particularly preferably represents chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy or cyano,
[0163] Y and Z independently of one another particularly preferably
represent hydrogen, fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy, cyano,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl or represent one
of the (het)aryl radicals
[0163] ##STR00030## [0164] where in the case of (het)aryl only one
of the radicals Y or Z may represent (het)aryl, [0165] V.sup.1
particularly preferably represents hydrogen, fluorine, chlorine,
bromine, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-haloalkyl, C.sub.1-C.sub.2-haloalkoxy, nitro, cyano
or represents phenyl 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, nitro or cyano, [0166] V.sup.2 and
V.sup.3 independently of one another particularly preferably
represent hydrogen, fluorine, chlorine, bromine,
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, [0167]
with the proviso that at least one of the radicals W or Z has to be
different from hydrogen if X and Y represent methyl, [0168] A and B
and the carbon atom to which they are attached particularly
preferably represent a five-, six- or seven-membered ketal which
may optionally be interrupted by a further oxygen atom and which is
optionally mono- to trisubstituted by C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, [0169] D particularly
preferably represents NH (1) or oxygen (2), [0170] Q.sup.1 and
Q.sup.2 independently of one another particularly preferably
represent hydrogen, methyl, ethyl, trifluoromethyl, methoxy or
ethoxy, [0171] G particularly preferably represents hydrogen (a) or
represents one of the groups
[0171] ##STR00031## [0172] in which [0173] E represents a metal ion
or an ammonium ion, [0174] L represents oxygen or sulphur and
[0175] M represents oxygen or sulphur, [0176] R.sup.1 particularly
preferably represents C.sub.1-C.sub.16-alkyl,
C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.4-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents C.sub.3-C.sub.7-cycloalkyl which is optionally mono- or
disubstituted by fluorine, chlorine, C.sub.1-C.sub.5-alkyl or
C.sub.1-C.sub.5-alkoxy and in which optionally one or two not
directly adjacent methylene groups are replaced by oxygen and/or
sulphur, [0177] represents phenyl which is optionally mono- to
trisubstituted by fluorine, chlorine, bromine, cyano, nitro,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.3-haloalkoxy,
C.sub.1-C.sub.4-alkylthio or C.sub.1-C.sub.4-alkylsulphonyl, [0178]
represents phenyl-C.sub.1-C.sub.4-alkyl 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.3-haloalkyl or C.sub.1-C.sub.3-haloalkoxy, [0179]
represents pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or
thienyl, each of which is optionally mono- or disubstituted by
fluorine, chlorine, bromine or C.sub.1-C.sub.4-alkyl, [0180]
represents phenoxy-C.sub.1-C.sub.5-alkyl which is optionally mono-
or disubstituted by fluorine, chlorine, bromine or
C.sub.1-C.sub.4-alkyl or [0181] represents
pyridyloxy-C.sub.1-C.sub.5 -alkyl,
pyrimidyloxy-C.sub.1-C.sub.5-alkyl or
thiazolyloxy-C.sub.1-C.sub.5-alkyl, each of which is optionally
mono- or disubstituted by fluorine, chlorine, bromine, amino or
C.sub.1-C.sub.4-alkyl, [0182] R.sup.2 particularly preferably
represents C.sub.1-C.sub.16-alkyl, C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, [0183]
represents C.sub.3-C.sub.7-cycloalkyl which is optionally mono- or
disubstituted by fluorine, chlorine, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy or [0184] represents phenyl or benzyl, each
of which is optionally mono- to trisubstituted by fluorine,
chlorine, bromine, cyano, nitro, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-alkoxy, C.sub.1-C.sub.3-haloalkyl or
C.sub.1-C.sub.3-haloalkoxy, [0185] R.sup.3 particularly preferably
represents C.sub.1-C.sub.6-alkyl which is optionally mono- to
trisubstituted by fluorine or chlorine or 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.4-alkoxy, C.sub.1-C.sub.2-haloalkoxy,
C.sub.1-C.sub.2-haloalkyl, cyano or nitro, [0186] R.sup.4 and
R.sup.5 independently of one another particularly preferably
represent C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylamino, di(C.sub.1-C.sub.6-alkyl)amino,
C.sub.1-C.sub.6-alkylthio or C.sub.3-C.sub.4-alkenylthio, each of
which is optionally mono- to trisubstituted by fluorine or
chlorine, or represent 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-haloalkylthio, C.sub.1-C.sub.3-alkyl or
C.sub.1-C.sub.3-haloalkyl, [0187] R.sup.6 and R.sup.7 independently
of one another particularly preferably represent hydrogen,
represent C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-alkenyl or
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine,
represent phenyl or benzyl, each of which is optionally mono- to
trisubstituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.5-haloalkyl, C.sub.1-C.sub.5-alkyl or
C.sub.1-C.sub.5-alkoxy, or together represent an optionally
C.sub.1-C.sub.4-alkyl-substituted C.sub.3-C.sub.6-alkylene radical
in which optionally one methylene group is replaced by oxygen or
sulphur.
[0188] In the radical definitions mentioned as being particularly
preferred, halogen represents fluorine, chlorine and bromine, in
particular fluorine and chlorine. [0189] W very particularly
preferably represents hydrogen, chlorine, bromine, methyl, ethyl,
vinyl, ethynyl, propynyl, methoxy, ethoxy or trifluoromethyl,
[0190] X very particularly preferably represents chlorine, bromine,
methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, propynyl,
methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy
or cyano, [0191] Y and Z independently of one another very
particularly preferably represent hydrogen, fluorine, chlorine,
bromine, methyl, ethyl, vinyl, ethynyl, propynyl, methoxy,
trifluoromethyl, trifluoromethoxy, cyano or a phenyl radical
[0191] ##STR00032## [0192] where in the case of phenyl only one of
the radicals Y or Z may represent phenyl, [0193] V.sup.1 very
particularly preferably represents hydrogen, fluorine, chlorine,
bromine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy,
ethoxy, n-propoxy, isopropoxy, trifluoromethyl or trifluoromethoxy,
[0194] V.sup.2 very particularly preferably represents hydrogen,
fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy,
ethoxy or trifluoromethyl, [0195] with the proviso that at least
one of the radicals W or Z has to be different from hydrogen if X
and Y represent methyl, [0196] A and B and the carbon atom to which
they are attached very particularly preferably represent a five-,
six- or seven-membered ketal which may optionally be interrupted by
a further oxygen atom and which is optionally mono- or
disubstituted by methyl, ethyl, propyl, trifluoromethyl,
monochloromethyl, methoxy, ethoxy, methoxymethyl or ethoxymethyl,
[0197] D very particularly preferably represents NH (1) or oxygen
(2), [0198] Q.sup.1 and Q.sup.2 very particularly preferably
represent hydrogen, [0199] G very particularly preferably
represents hydrogen (a) or represents one of the groups
[0199] ##STR00033## [0200] in which [0201] E represents a metal ion
or an ammonium ion, [0202] L represents oxygen or sulphur and
[0203] M represents oxygen or sulphur, [0204] R.sup.1 very
particularly preferably represents C.sub.1-C.sub.10-alkyl,
C.sub.2-C.sub.10-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
monosubstituted by fluorine, chlorine, methyl, ethyl or methoxy,
[0205] represents phenyl which is optionally mono- or disubstituted
by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl,
n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or
trifluoromethoxy, [0206] represents (uranyl, thienyl or pyridyl,
each of which is optionally monosubstituted by chlorine, bromine or
methyl, [0207] R.sup.2 very particularly preferably represents
C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-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 or chlorine, [0208]
represents cyclopentyl or cyclohexyl, [0209] or represents phenyl
or benzyl, each of which is optionally mono- or disubstituted by
fluorine, chlorine, cyano, nitro, methyl, ethyl, methoxy,
trifluoromethyl or trifluoromethoxy, [0210] R.sup.3 very
particularly preferably represents methyl, ethyl, propyl or
isopropyl, each of which is optionally mono- to trisubstituted by
fluorine or chlorine, or represents phenyl which is optionally
monosubstituted by fluorine, chlorine, bromine, methyl, ethyl,
isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy,
trifluoromethyl, trifluoromethoxy, cyano or nitro, [0211] R.sup.4
and R.sup.5 independently of one another very particularly
preferably represent C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkylthio or represent phenyl, phenoxy or
phenylthio, each of which is optionally monosubstituted by
fluorine, chlorine, bromine, nitro, cyano, methyl, methoxy,
trifluoromethyl or trifluoromethoxy, [0212] R.sup.6 and R.sup.7
independently of one another very particularly preferably represent
hydrogen, represent C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenyl or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, represent phenyl
which is optionally mono- or disubstituted by fluorine, chlorine,
bromine, methyl, methoxy or trifluoromethyl, or together represent
a C.sub.5-C.sub.6-alkylene radical in which optionally one
methylene group is replaced by oxygen or sulphur. [0213] W
especially preferably represents hydrogen, chlorine, bromine,
methyl, ethyl or methoxy, [0214] X especially preferably represents
chlorine, bromine, methyl, ethyl or methoxy, [0215] Y and Z
independently of one another especially preferably represent
hydrogen, chlorine, bromine, methyl or represent the radical
[0215] ##STR00034## [0216] where in this case only one of the
radicals Y or Z may represent
[0216] ##STR00035## [0217] with the proviso that at least one of
the radicals W or Z has to be different from hydrogen if X and Y
represent methyl, [0218] A and B and the carbon atom to which they
are attached especially preferably represent a five- or
six-membered ketal which is optionally mono- or disubstituted by
methyl, ethyl, propyl, monochloromethyl or methoxymethyl, [0219] D
especially preferably represents NH (1) or oxygen (2), [0220]
Q.sup.1 and Q.sup.2 especially preferably represent hydrogen,
[0221] G especially preferably represents hydrogen (a) or
represents one of the groups
[0221] ##STR00036## [0222] R.sup.1 especially preferably represents
C.sub.1-C.sub.10-alkyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.3-C.sub.6-cycloalkyl, [0223] represents phenyl which is
optionally monosubstituted by chlorine, or represents thienyl,
[0224] R.sup.2 especially preferably represents
C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl or benzyl, [0225]
R.sup.3 especially preferably represents methyl, [0226] R.sup.6 and
R.sup.7 together especially preferably represent a
C.sub.5-C.sub.6-alkylene radical in which optionally one methylene
group is replaced by oxygen or sulphur. [0227] 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 products and, correspondingly, to precursors and
intermediates.
[0228] 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).
[0229] 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.
[0230] 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.
[0231] Special 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 especially preferred.
[0232] Emphasis is given to compounds of the formula (I) in which G
represents hydrogen.
[0233] In the case of the compounds of the formula (I-1), the
phenyl ring is, with emphasis, substituted 3 times, resulting in
the following substitution patterns: 2,4,6-, 2,4,5- or
2,5,6-substitution. Moreover, in the case of the compounds of the
formula (I-1), the phenyl ring is, with emphasis, substituted 4
times, resulting in the following substitution pattern:
2,4,5,6-substitution. In the case of the compounds of the formula
(I-1), the phenyl ring is, with emphasis, also substituted 2 times
(2,5-position). In the case of the compounds of the formula (I-1),
the phenyl ring is, with emphasis, also monosubstituted (ortho
position). The other substituents W, X, Y, Z, G, A, B, Q.sup.1 and
Q.sup.2 are as defined in the text.
[0234] Moreover, in the case of the compounds of the formula (I-1)
in which the phenyl ring is substituted in the 2,4-position, the
substituent G represents, with emphasis, the group (b), but also
the group (c) or (d) or (e) or (f) or (g). In this case, G
represents especially the groups (a), (b) or (c). The other
substituents W, X, Y, Z, A, B, Q.sup.1 and Q.sup.2 are as defined
in the text. Furthermore, in the case of the compounds of the
formula (I-1) in which the phenyl ring is substituted in the
2,4-position, the substituents A and B are, with emphasis, in the
3'-position on the spirocycle. Furthermore, in the case of the
compounds of the formula (I-1) in which the phenyl ring is
substituted in the 2,4-position, the substituents A and B are, with
emphasis, in the 4'-position on the spirocycle.
[0235] Saturated or unsaturated hydrocarbon radicals, such as
alkyl, alkanediyl or alkenyl, may 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.
[0236] Unless indicated otherwise, optionally substituted radicals
may be mono- or polysubstituted, where in the case of
polysubstitution the substituents may be identical or
different.
[0237] In addition to the compounds mentioned in the Preparation
Examples, the following compounds of the formula (I-1-a) may be
specifically mentioned:
TABLE-US-00001 TABLE 1 (I-1-a) ##STR00037## A-B X W Y Z
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H H
--O--(CH.sub.2).sub.2--O-- Br H H H --O--(CH.sub.2).sub.2--O-- Cl H
H H --O--(CH.sub.2).sub.2--O-- CF.sub.3 H H H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 H H H
--O--(CH.sub.2).sub.2--O-- Br H Cl H --O--(CH.sub.2).sub.2--O-- Cl
H Br H --O--(CH.sub.2).sub.2--O-- Cl H Cl H
--O--(CH.sub.2).sub.2--O-- Cl H CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H Cl H
--O--(CH.sub.2).sub.2--O-- Cl Cl H H --O--(CH.sub.2).sub.2--O-- Cl
OCH.sub.3 H H --O--(CH.sub.2).sub.2--O-- Cl CH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- Cl OC.sub.2H.sub.5 H H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 OCH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 H H
--O--(CH.sub.2).sub.2--O-- Br CH.sub.3 Br H
--O--(CH.sub.2).sub.2--O-- Cl CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 Br CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- OC.sub.2H.sub.5 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- OC.sub.3H.sub.7 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Br Br CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Cl Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 Br H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 C.sub.2H.sub.5 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- OC.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3
H --O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 OCH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Br Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Br CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- Cl CH.sub.3 Br H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 C.sub.2H.sub.5 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5
C.sub.2H.sub.5 H --O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3
Cl H --O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 Cl H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 Br H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 Br H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Br CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Cl Cl H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Br Br H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Cl Br H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Br Cl H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 C.sub.2H.sub.5 Cl H
--O--(CH.sub.2).sub.2--O-- OC.sub.2H.sub.5 CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- OC.sub.2H.sub.5 C.sub.2H.sub.5 Cl H
--O--(CH.sub.2).sub.2--O-- Cl OCH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Cl OC.sub.2H.sub.5 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- Cl H Cl Cl --O--(CH.sub.2).sub.2--O--
CH.sub.3 H CH.sub.3 CH.sub.3 --O--(CH.sub.2).sub.2--O-- CH.sub.3 H
Cl CH.sub.3 --O--(CH.sub.2).sub.2--O-- Br H Cl CH.sub.3
--O--(CH.sub.2).sub.2--O-- Br H CH.sub.3 CH.sub.3
--O--(CH.sub.2).sub.2--O-- Cl H Br CH.sub.3
--O--(CH.sub.2).sub.2--O-- Cl H Cl CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H Br CH.sub.3
--O--(CH.sub.2).sub.2--O-- Cl H CH.sub.3 Cl
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H CH.sub.3
--O--(CH.sub.2).sub.2--O-- Cl H H CH.sub.3
--O--(CH.sub.2).sub.2--O-- Br H H CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H Cl
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H Br
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 F
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 Cl
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 Br
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H Cl
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H Br
--O--(CH.sub.2).sub.2--O-- Cl Cl H Br --O--(CH.sub.2).sub.2--O--
CH.sub.3 CH.sub.3 4-Cl--C.sub.6H.sub.4 H --O--(CH.sub.2).sub.2--O--
C.sub.2H.sub.5 CH.sub.3 4-Cl--C.sub.6H.sub.4 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5
4-Cl--C.sub.6H.sub.4 H --O--(CH.sub.2).sub.2--O-- Cl CH.sub.3
4-Cl--C.sub.6H.sub.4 H --O--(CH.sub.2).sub.2--O-- Cl C.sub.2H.sub.5
4-Cl--C.sub.6H.sub.4 H --O--(CH.sub.2).sub.2--O-- CH.sub.3 H H
4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H
4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- CH.sub.3 H CH.sub.3
4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3
CH.sub.3 4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- Cl H H
4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- I H H H
--O--(CH.sub.2).sub.2--O-- I H CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- I CH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- I C.sub.2H.sub.5 H H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H I
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H CH.sub.3 I
--O--(CH.sub.2).sub.2--O-- I CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- I C.sub.2H.sub.5 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- I CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- I C.sub.2H.sub.5 Cl H
--O--(CH.sub.2).sub.2--O-- I Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- I H CH.sub.3 CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H I H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 H I H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 I H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 I H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 I H
--O--(CH.sub.2).sub.2--O-- Cl CH.sub.3 I H
--O--(CH.sub.2).sub.2--O-- Cl C.sub.2H.sub.5 I H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H I CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H I
--O--(CH.sub.2).sub.2--O-- I H H CH.sub.3
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 H H H
[0238] Table 2: W, X, Y and Z as stated in Table 1
A-B=4'-O--CH.sub.2--CHCH.sub.3--O--
[0239] Table 3: W, X, Y and Z as stated in Table 1
A-B=4'-O--CHCH.sub.3--CHCH.sub.3--O--
[0240] Table 4: W, X, Y and Z as stated in Table 1
A-B=4'-O--(CH.sub.2).sub.3--O--
[0241] Table 5: W, X, Y and Z as stated in Table 1
A-B=4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O--
[0242] Table 6: W, X, Y and Z as stated in Table 1
A-B=4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O--
[0243] Table 7: W, X, Y and Z as stated in Table 1
A-B=-4'O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O--
[0244] Table 8: W, X, Y and Z as stated in Table 1
##STR00038##
[0245] Table 9: W, X, Y and Z as stated in Table 1
A-B=3'-O--(CH.sub.2).sub.2--O--
[0246] Table 10: W, X, Y and Z as stated in Table 1
A-B=3'-O--CH.sub.2--CHCH.sub.3--O--
[0247] Table 11: W, X, Y and Z as stated in Table 1
A-B=3'-O--CHCH.sub.3--CHCH.sub.3--O--
[0248] Table 12: W, X, Y and Z as stated in Table 1
A-B=3'-O--(CH.sub.2).sub.3--O--
[0249] Table 13: W, X, Y and Z as stated in Table 1
A-B=3'-O--CHCH.sub.3--(CH.sub.2).sub.2--O--
[0250] Table 14: W, X, Y and Z as stated in Table 1
A-B=3'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O--
[0251] Table 15: W, X, Y and Z as stated in Table 1
A-B=3'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O--
[0252] Table 16: W, X, Y and Z as stated in Table 1
##STR00039##
[0253] In addition to the compounds mentioned in the Preparation
Examples, the following compounds of the formula (I-2-a) may be
specifically mentioned:
TABLE-US-00002 TABLE 17 (I-2-a) ##STR00040## A-B X W Y Z
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H H
--O--(CH.sub.2).sub.2--O-- Br H H H --O--(CH.sub.2).sub.2--O-- Cl H
H H --O--(CH.sub.2).sub.2--O-- CF.sub.3 H H H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 H H H
--O--(CH.sub.2).sub.2--O-- Br H Cl H --O--(CH.sub.2).sub.2--O-- Cl
H Br H --O--(CH.sub.2).sub.2--O-- Cl H Cl H
--O--(CH.sub.2).sub.2--O-- Cl H CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H Cl H
--O--(CH.sub.2).sub.2--O-- Cl Cl H H --O--(CH.sub.2).sub.2--O-- Cl
OCH.sub.3 H H --O--(CH.sub.2).sub.2--O-- Cl CH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- Cl OC.sub.2H.sub.5 H H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 OCH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 H H
--O--(CH.sub.2).sub.2--O-- Br CH.sub.3 Br H
--O--(CH.sub.2).sub.2--O-- Cl CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 Br CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- OC.sub.2H.sub.5 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- OC.sub.3H.sub.7 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Br Br CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Cl Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 Br H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 C.sub.2H.sub.5 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- OC.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3
H --O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 OCH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Br Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Br CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- Cl CH.sub.3 Br H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 C.sub.2H.sub.5 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5
C.sub.2H.sub.5 H --O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3
Cl H --O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 Cl H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 Br H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 Br H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Br CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Cl Cl H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Br Br H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Cl Br H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 Br Cl H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- OCH.sub.3 C.sub.2H.sub.5 Cl H
--O--(CH.sub.2).sub.2--O-- OC.sub.2H.sub.5 CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- OC.sub.2H.sub.5 C.sub.2H.sub.5 Cl H
--O--(CH.sub.2).sub.2--O-- Cl OCH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- Cl OC.sub.2H.sub.5 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- Cl H Cl Cl --O--(CH.sub.2).sub.2--O--
CH.sub.3 H CH.sub.3 CH.sub.3 --O--(CH.sub.2).sub.2--O-- CH.sub.3 H
Cl CH.sub.3 --O--(CH.sub.2).sub.2--O-- Br H Cl CH.sub.3
--O--(CH.sub.2).sub.2--O-- Br H CH.sub.3 CH.sub.3
--O--(CH.sub.2).sub.2--O-- Cl H Br CH.sub.3
--O--(CH.sub.2).sub.2--O-- Cl H Cl CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H Br CH.sub.3
--O--(CH.sub.2).sub.2--O-- Cl H CH.sub.3 Cl
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H CH.sub.3
--O--(CH.sub.2).sub.2--O-- Cl H H CH.sub.3
--O--(CH.sub.2).sub.2--O-- Br H H CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H Cl
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H Br
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 F
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 Cl
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 CH.sub.3 Br
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H Cl
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H Br
--O--(CH.sub.2).sub.2--O-- Cl Cl H Br --O--(CH.sub.2).sub.2--O--
CH.sub.3 CH.sub.3 4-Cl--C.sub.6H.sub.4 H --O--(CH.sub.2).sub.2--O--
C.sub.2H.sub.5 CH.sub.3 4-Cl--C.sub.6H.sub.4 H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5
4-Cl--C.sub.6H.sub.4 H --O--(CH.sub.2).sub.2--O-- Cl CH.sub.3
4-Cl--C.sub.6H.sub.4 H --O--(CH.sub.2).sub.2--O-- Cl C.sub.2H.sub.5
4-Cl--C.sub.6H.sub.4 H --O--(CH.sub.2).sub.2--O-- CH.sub.3 H H
4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H
4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- CH.sub.3 H CH.sub.3
4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3
CH.sub.3 4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- Cl H H
4-Cl--C.sub.6H.sub.4 --O--(CH.sub.2).sub.2--O-- I H H H
--O--(CH.sub.2).sub.2--O-- I H CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- I CH.sub.3 H H
--O--(CH.sub.2).sub.2--O-- I C.sub.2H.sub.5 H H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H H I
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H CH.sub.3 I
--O--(CH.sub.2).sub.2--O-- I CH.sub.3 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- I C.sub.2H.sub.5 CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- I CH.sub.3 Cl H
--O--(CH.sub.2).sub.2--O-- I C.sub.2H.sub.5 Cl H
--O--(CH.sub.2).sub.2--O-- I Cl CH.sub.3 H
--O--(CH.sub.2).sub.2--O-- I H CH.sub.3 CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H I H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 H I H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 I H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 CH.sub.3 I H
--O--(CH.sub.2).sub.2--O-- C.sub.2H.sub.5 C.sub.2H.sub.5 I H
--O--(CH.sub.2).sub.2--O-- Cl CH.sub.3 I H
--O--(CH.sub.2).sub.2--O-- Cl C.sub.2H.sub.5 I H
--O--(CH.sub.2).sub.2--O-- CH.sub.3 H I CH.sub.3
--O--(CH.sub.2).sub.2--O-- CH.sub.3 CH.sub.3 H I
--O--(CH.sub.2).sub.2--O-- I H H CH.sub.3
[0254] Table 18: W, X, Y and Z as stated in Table 17
A-B=4'-O--CH.sub.2--CHCH.sub.3--O--
[0255] Table 19: W, X, Y and Z as stated in Table 17
A-B=4'-O--CHCH.sub.3--CHCH.sub.3--O--
[0256] Table 20: W, X, Y and Z as stated in Table 17
A-B=4'-O--(CH.sub.2).sub.3--O--
[0257] Table 21: W, X, Y and Z as stated in Table 17
A-B=4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O--
[0258] Table 22: W, X, Y and Z as stated in Table 17
A-B=4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O--
[0259] Table 23: W, X, Y and Z as stated in Table 17
A-B=4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O--
[0260] Table 24: W, X, Y and Z as stated in Table 17
##STR00041##
[0261] Table 25: W, X, Y and Z as stated in Table 17
A-B=3'-O--(CH.sub.2).sub.2--O--
[0262] Table 26: W, X, Y and Z as stated in Table 17
A-B=3'-O--CH.sub.2--CHCH.sub.3--O--
[0263] Table 27: W, X, Y and Z as stated in Table 17
A-B=3'-O--CHCH.sub.3--CHCH.sub.3--O--
[0264] Table 28: W, X, Y and Z as stated in Table 17
A-B=3'-O--(CH.sub.2).sub.3--O--
[0265] Table 29: W, X, Y and Z as stated in Table 17
A-B=3'-O--CHCH.sub.3--(CH.sub.2).sub.2--O--
[0266] Table 30: W, X, Y and Z as stated in Table 17
A-B=3'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O--
[0267] Table 31: W, X, Y and Z as stated in Table 17
A-B=3'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O--
[0268] Table 32: W, X, Y and Z as stated in Table 17
##STR00042##
[0269] Preferred definitions of the groups listed above in
connection with the crop plant compatibility-improving compounds
("herbicide safeners") of the formulae (IIa), (IIb), (IIc), (IId)
and (IIe) are defined below. [0270] m preferably represents the
numbers 0, 1, 2, 3 or 4. [0271] A.sup.1 preferably represents one
of the divalent heterocyclic groupings shown below
[0271] ##STR00043## [0272] n preferably represents the numbers 0,
1, 2, 3 or 4. [0273] A.sup.2 preferably represents in each case
optionally methyl-, ethyl-, methoxycarbonyl- or ethoxycarbonyl- or
allyloxycarbonyl-substituted methylene or ethylene. [0274] R.sup.14
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. [0275] R.sup.15 preferably represents hydroxyl,
mercapto, amino, methoxy, ethoxy, n- or i-propoxy, n-, s- or
t-butoxy, 1-methylhexyloxy, allyloxy, 1-allyloxymethylethoxy,
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. [0276] R.sup.16
preferably represents in each case optionally fluorine-, chlorine-,
and/or bromine-substituted methyl, ethyl, n- or i-propyl. [0277]
R.sup.17 preferably represents hydrogen, in each case optionally
fluorine- and/or chlorine-substituted 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, or optionally fluorine-, chlorine-, methyl-, ethyl-,
n- or i-propyl-, n-, s- or t-butyl-substituted phenyl. [0278]
R.sup.18 preferably represents hydrogen, in each case optionally
fluorine- and/or chlorine-substituted 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, or optionally fluorine-, chlorine-, methyl-, ethyl-,
n- or i-propyl-, n-, s- or t-butyl-substituted phenyl, or together
with R.sup.17 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 C atom to which
they are attached, form a 5- or 6-membered carbocycle. [0279]
R.sup.19 preferably represents hydrogen, cyano, fluorine, chlorine,
bromine, or represents in each case optionally fluorine-, chlorine-
and/or bromine-substituted methyl, ethyl, n- or i-propyl,
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl. [0280]
R.sup.20 preferably represents hydrogen, optionally hydroxyl-,
cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, s- or
t-butyl. [0281] R.sup.21 preferably represents hydrogen, cyano,
fluorine, chlorine, bromine, or represents in each case optionally
fluorine-, chlorine- and/or bromine-substituted methyl, ethyl, n-
or i-propyl, n-, s- or t-butyl, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl or phenyl. [0282] X.sup.1 preferably
represents nitro, cyano, fluorine, chlorine, bromine, methyl,
ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl,
dichloromethyl, trifluoromethyl, trichloromethyl,
chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or
i-propoxy, difluoromethoxy or trifluoromethoxy. [0283] 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. [0284] 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. [0285] t preferably
represents the numbers 0, 1, 2, 3 or 4. [0286] v preferably
represents the numbers 0, 1, 2, or 3. [0287] R.sup.22 preferably
represents hydrogen, methyl, ethyl, n- or i-propyl. [0288] R.sup.23
preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
[0289] R.sup.24 preferably represents hydrogen, in each case
optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted 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-, i-, s- or
t-butylamino, dimethylamino or diethylamino, or in each case
optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-,
n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio,
cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino
or cyclohexylamino. [0290] R.sup.25 preferably represents hydrogen,
in each case optionally cyano-, hydroxyl-, fluorine-, chlorine-,
methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or
i-propyl, n-, i- or s-butyl, in each case optionally cyano-,
fluorine-, chlorine- or bromine-substituted propenyl, butenyl,
propynyl or butynyl, or in each case optionally cyano-, fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted
cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. [0291] R.sup.26
preferably represents hydrogen, in each case optionally cyano-,
hydroxyl-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or
s-butyl, in each case optionally cyano-, fluorine-, chlorine- or
bromine-substituted propenyl, butenyl, propynyl or butynyl, in each
case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-,
ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl,
cyclopentyl or cyclohexyl, or optionally 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-substituted phenyl, or
together with R.sup.25 represents in each case optionally methyl-
or ethyl-substituted butane-1,4-diyl (trimethylene),
pentane-1,5-diyl, 1-oxabutane-1,4-diyl or 3-oxapentane-1,5-diyl.
[0292] 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. [0293] 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.
[0294] 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 below.
TABLE-US-00003 TABLE Examples of the compounds of the formula (IIa)
(IIa) ##STR00044## Example (Positions) No. (X.sup.1).sub.m A.sup.1
R.sup.14 IIa-1 (2) Cl, (4) Cl ##STR00045## OCH.sub.3 IIa-2 (2) Cl,
(4) Cl ##STR00046## OCH.sub.3 IIa-3 (2) Cl, (4) Cl ##STR00047##
OC.sub.2H.sub.5 IIa-4 (2) Cl, (4) Cl ##STR00048## OC.sub.2H.sub.5
IIa-5 (2) Cl ##STR00049## OCH.sub.3 IIa-6 (2) Cl, (4) Cl
##STR00050## OCH.sub.3 IIa-7 (2) F ##STR00051## OCH.sub.3 IIa-8 (2)
F ##STR00052## OCH.sub.3 IIa-9 (2) Cl, (4) Cl ##STR00053##
OC.sub.2H.sub.5 IIa-10 (2) Cl, (4) CF.sub.3 ##STR00054## OCH.sub.3
IIa-11 (2) Cl ##STR00055## OCH.sub.3 IIa-12 -- ##STR00056##
OC.sub.2H.sub.5 IIa-13 (2) Cl, (4) Cl ##STR00057## OC.sub.2H.sub.5
IIa-14 (2) Cl, (4) Cl ##STR00058## OC.sub.2H.sub.5 IIa-15 (2) Cl,
(4) Cl ##STR00059## OC.sub.2H.sub.5 IIa-16 (2) Cl, (4) Cl
##STR00060## OC.sub.2H.sub.5 IIa-17 (2) Cl, (4) Cl ##STR00061##
OC.sub.2H.sub.5 IIa-18 -- ##STR00062## OH
[0295] 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 below.
##STR00063##
TABLE-US-00004 TABLE Examples of the compounds of the formula (IIb)
Example (Position) (Position) No. X.sup.2 X.sup.3 A.sup.2 R.sup.15
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.5 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 ##STR00064## IIb-13 (5)
Cl -- ##STR00065## OCH.sub.2CH.dbd.CH.sub.2 IIb-14 (5) Cl --
##STR00066## OC.sub.2H.sub.5 IIb-15 (5) Cl -- ##STR00067##
OCH.sub.3
[0296] 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 below.
##STR00068##
TABLE-US-00005 TABLE Examples of the compounds of the formula (IIc)
Example No. R.sup.16 N(R.sup.17, R.sup.18) IIc-1 CHCl.sub.2
N(CH.sub.2CH.dbd.CH.sub.2).sub.2 IIc-2 CHCl.sub.2 ##STR00069##
IIc-3 CHCl.sub.2 ##STR00070## IIc-4 CHCl.sub.2 ##STR00071## IIc-5
CHCl.sub.2 ##STR00072## IIc-6 CHCl.sub.2 ##STR00073## IIc-7
CHCl.sub.2 ##STR00074##
[0297] Examples of the compounds of the formula (IId) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table below.
##STR00075##
TABLE-US-00006 TABLE Examples of the compounds of the formula (IId)
Example (Positions) (Positions) No. R.sup.22 R.sup.23 R.sup.24
(X.sup.4).sub.t (X.sup.5).sub.v 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 ##STR00076## (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 ##STR00077## (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 ##STR00078## (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 --
[0298] 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 below.
##STR00079##
TABLE-US-00007 TABLE Examples of the compounds of the formula (IIe)
Example (Positions) (Positions) No. R.sup.22 R.sup.25 R.sup.26
(X.sup.4).sub.t (X.sup.5).sub.v 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 ##STR00080## (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
##STR00081## (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
[0299] Most preferred as crop plant compatibility-improving
compound [component (b')] are cloquintocetmexyl,
fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl,
furilazole, fenclorim, cumyluron, dymron, dimepiperate and the
compounds IIe-5 and IIe-11, and particular emphasis is given to
cloquintocet-mexyl and mefenpyr-diethyl.
[0300] The compounds of the general formula (IIa) to be used as
safeners according to the invention are known and/or can be
prepared by processes known per se (cf. WO-A-91/07874,
WO-A-95/07897).
[0301] The compounds of the general formula (IIb) to be used as
safeners according to the invention are known and/or can be
prepared by processes known per se (cf. EP-A-191736).
[0302] The compounds of the general formula (IIc) to be used as
safeners according to the invention are known and/or can be
prepared by processes known per se (cf. DE-A-2218097,
DE-A-2350547).
[0303] The compounds of the general formula (IId) to be used as
safeners according to the invention are known and/or can be
prepared by processes known per se (cf. DE-A-19621522/U.S. Pat. No.
6,235,680).
[0304] The compounds of the general formula (IIe) to be used as
safeners according to the invention are known and can be prepared
by processes known per se (cf. WO-A-99/66795/U.S. Pat. No.
6,251,827).
[0305] Examples of the selective herbicidal combinations according
to the invention comprising in each case one active compound of the
formula (I) and one of the safeners defined above are listed in the
table below.
TABLE-US-00008 TABLE Examples of the combinations according to the
invention Active compounds of the formula (I) Safeners I-1-a
cloquintocet-mexyl I-1-a fenchlorazole-ethyl I-1-a isoxadifen-ethyl
I-1-a mefenpyr-diethyl I-1-a furilazole I-1-a fenclorim I-1-a
cumyluron I-1-a daimuron/dymron I-1-a dimepiperate I-1-a IIe-11
I-1-a IIe-5 I-1-b cloquintocet-mexyl I-1-b fenchlorazole-ethyl
I-1-b isoxadifen-ethyl I-1-b mefenpyr-diethyl I-1-b furilazole
I-1-b fenclorim I-1-b cumyluron I-1-b daimuron/dymron I-1-b
dimepiperate I-1-b IIe-11 I-1-b IIe-5 I-1-c cloquintocet-mexyl
I-1-c fenchlorazole-ethyl I-1-c isoxadifen-ethyl I-1-c
mefenpyr-diethyl I-1-c furilazole I-1-c fenclorim I-1-c cumyluron
I-1-c daimuron/dymron I-1-c dimepiperate I-1-c IIe-5 I-1-c IIe-11
I-1-d cloquintocet-mexyl I-1-d fenchlorazole-ethyl I-1-d
isoxadifen-ethyl I-1-d mefenpyr-diethyl I-1-d furilazole I-1-d
fenclorim I-1-d cumyluron I-1-d daimuron/dymron I-1-d dimepiperate
I-1-d IIe-11 I-1-d IIe-5 I-1-e cloquintocet-mexyl I-1-e
fenchlorazole-ethyl I-1-e isoxadifen-ethyl I-1-e mefenpyr-diethyl
I-1-e furilazole I-1-e fenclorim I-1-e cumyluron I-1-e
daimuron/dymron I-1-e dimepiperate I-1-e IIe-5 I-1-e IIe-11 I-1-f
cloquintocet-mexyl I-1-f fenchlorazole-ethyl I-1-f isoxadifen-ethyl
I-1-f mefenpyr-diethyl I-1-f furilazole I-1-f fenclorim I-1-f
cumyluron I-1-f daimuron/dymron I-1-f dimepiperate I-1-f IIe-5
I-1-f IIe-11 I-1-g cloquintocet-mexyl I-1-g fenchlorazole-ethyl
I-1-g isoxadifen-ethyl I-1-g mefenpyr-diethyl I-1-g furilazole
I-1-g fenclorim I-1-g cumyluron I-1-g daimuron/dymron I-1-g
dimepiperate I-1-g IIe-5 I-1-g IIe-11 I-2-a cloquintocet-mexyl
I-2-a fenchlorazole-ethyl I-2-a isoxadifen-ethyl I-2-a
mefenpyr-diethyl I-2-a furilazole I-2-a fenclorim I-2-a cumyluron
I-2-a daimuron/dymron I-2-a dimepiperate I-2-a IIe-5 I-2-a IIe-11
I-2-b cloquintocet-mexyl I-2-b fenchlorazole-ethyl I-2-b
isoxadifen-ethyl I-2-b mefenpyr-diethyl I-2-b furilazole I-2-b
fenclorim I-2-b cumyluron I-2-b daimuron/dymron I-2-b dimepiperate
I-2-b IIe-5 I-2-b IIe-11 I-2-c cloquintocet-mexyl I-2-c
fenchlorazole-ethyl I-2-c isoxadifen-ethyl I-2-c mefenpyr-diethyl
I-2-c furilazole I-2-c fenclorim I-2-c cumyluron I-2-c
daimuron/dymron I-2-c dimepiperate I-2-c IIe-5 I-2-c IIe-11 I-2-d
cloquintocet-mexyl I-2-d fenchlorazole-ethyl I-2-d isoxadifen-ethyl
I-2-d mefenpyr-diethyl I-2-d furilazole I-2-d fenclorim I-2-d
cumyluron I-2-d daimuron/dymron I-2-d dimepiperate I-2-d IIe-5
I-2-d IIe-11 I-2-e cloquintocet-mexyl I-2-e fenchlorazole-ethyl
I-2-e isoxadifen-ethyl I-2-e mefenpyr-diethyl I-2-e furilazole
I-2-e fenclorim I-2-e cumyluron I-2-e daimuron/dymron I-2-e
dimepiperate I-2-e IIe-5 I-2-e IIe-11 I-2-f cloquintocet-mexyl
I-2-f fenchlorazole-ethyl I-2-f isoxadifen-ethyl I-2-f
mefenpyr-diethyl I-2-f furilazole I-2-f fenclorim I-2-f cumyluron
I-2-f daimuron/dymron I-2-f dimepiperate I-2-f IIe-5 I-2-f IIe-11
I-2-g cloquintocet-mexyl I-2-g fenchlorazole-ethyl I-2-g
isoxadifen-ethyl I-2-g mefenpyr-diethyl I-2-g furilazole I-2-g
fenclorim I-2-g cumyluron I-2-g daimuron/dymron I-2-g dimepiperate
I-2-g IIe-5 I-2-g IIe-11
[0306] It has now surprisingly been found that the above-defined
active-compound combinations of compounds of the general formula
(I) and safeners (antidotes) from the group (b') set out above
combine very good useful plant tolerance with a high herbicidal
activity and can be used in various crops, in particular in cereals
(especially wheat), but also in soya, potatoes, maize and rice, for
selective weed control.
[0307] In this context it is considered surprising that, from a
multiplicity of known safeners or antidotes capable of antagonizing
the damaging effect of a herbicide on the crop plants, it is
specifically the compounds of group (b') set out above which are
suitable for compensating--almost completely--the damaging effect
of substituted cyclic ketoenols on the crop plants, without at the
same time having any critical adverse effect on the herbicidal
activity against the weeds.
[0308] Emphasis may be given here to the particularly advantageous
effect of the particularly preferred and most preferred combination
partners from group (b'), particularly with regard to the gentle
treatment of cereal plants, such as wheat, barley and rye, for
example, but also maize and rice, as crop plants.
[0309] Using, for example, according to process (A) ethyl
N-[(4-chloro-2,6-dimethyl)phenylacetyl]-1-amino-4,4'-propylenedioxycycloh-
exanecarboxylate as starting material, the course of the process
according to the invention can be represented by the reaction
scheme below:
##STR00082##
[0310] Using, for example, according to process (B) ethyl
O-[(2-chloro-6-methyl)phenylacetyl]-1-hydroxy-4,4'-ethylenedioxycyclohexa-
necarboxylate, the course of the process according to the invention
can be represented by the reaction scheme below:
##STR00083##
[0311] Using, for example, according to process (C.alpha.)
8,8'-ethylenedioxy-3-[(4-chloro-2,6-dimethyl)phenyl]-1-azaspiro[4,5]decan-
e-2,4-dione and pivaloyl chloride as starting materials, the course
of the process according to the invention can be represented by the
reaction scheme below:
##STR00084##
[0312] Using, for example, according to process (C) (variant
.beta.)
8,8'-propylenedioxy-3-[(2,4-dichloro)phenyl]-1-oxaspiro-[4,5]-decane-2,4--
dione and acetic anhydride as starting materials, the course of the
process according to the invention can be represented by the
reaction scheme below:
##STR00085##
[0313] Using, for example, according to process (D)
8,8'-propylenedioxy-3-[2,4-dichloro-6-methyl)phenyl]-1-azaspiro[4,5]decan-
e-2,4-dione and ethyl chloroformate as starting materials, the
course of the process according to the invention can be represented
by the reaction scheme below:
##STR00086##
[0314] Using, for example, according to process (E)
8,8'-ethylenedioxy-3-[(2,4,6-trimethyl)phenyl]-1-oxaspiro[4,5]decane-2,4--
dione and methyl chloromonothioformate as starting materials, the
course of the reaction can be represented as follows:
##STR00087##
[0315] Using, for example, according to process (F)
8,8'-propylenedioxy-3-[(2,4,6-trimethyl)phenyl]-1-azaspiro[4,5]decane-2,4-
-dione and methanesulphonyl chloride as starting materials, the
course of the reaction can be represented by the reaction scheme
below:
##STR00088##
[0316] Using, for example, according to process (G)
8,8'-propylenedioxy-3-[(2,4-dichloro-6-methyl)phenyl]-1-oxaspiro[4,5]deca-
ne-2,4-dione and 2,2,2-trifluoroethyl methanethiophosphonyl
chloride as starting materials, the course of the reaction can be
represented by the reaction scheme below:
##STR00089##
[0317] Using, for example, according to process (H)
8,8'-ethylenedioxy-3-[(2,3,4,6-tetramethyl)phenyl]-1-azaspiro[4,5]decane--
2,4-dione and NaOH as components, the course of the process
according to the invention can be represented by the reaction
scheme below:
##STR00090##
[0318] Using, for example, according to process (I) (variant
.alpha.)
8,8'-ethylenedioxy-3-[(2,4,5-trimethyl)phenyl]-1-oxaspiro[4,5]decane-2,4--
dione and ethyl isocyanate as starting materials, the course of the
reaction can be represented by the reaction scheme below:
##STR00091##
[0319] Using, for example, according to process (I) (variant
.beta.)
8,8'-ethylenedioxy-3-[(2,4,6-trimethyl)phenyl]-1-azaspiro[4,5]decane-2,4--
dione and dimethylcarbamoyl chloride as starting materials, the
course of the reaction can be represented by the scheme below:
##STR00092##
[0320] The compounds, required as starting materials in the process
(A) according to the invention, of the formula (II)
##STR00093##
in which [0321] A, B, Q.sup.1, Q.sup.2, W, X, Y, Z and R.sup.8 are
as defined above are novel.
[0322] The acylamino acid esters of the formula (II) are obtained,
for example, when amino acid derivatives of the formula (XVI)
##STR00094##
in which [0323] A, B, Q.sup.1 and Q.sup.2 and R.sup.8 are as
defined above are acylated with substituted phenylacetic acid
derivatives of the formula (XVII)
##STR00095##
[0323] in which [0324] W, X, Y and Z are as defined above and
[0325] U represents a leaving group introduced by reagents for
activating carboxylic acids, such as carbonyldiimidazole,
carbodiimides (such as, for example, dicyclohexylcarbodiimide),
phosphorylating agents (such as, for example, POCl.sub.3, BOP-Cl),
halogenating agents, such as, for example, thionyl chloride, oxalyl
chloride, phosgene or chloroformic esters (Chem. Reviews 52,
237-416 (1953); Bhattacharya, Indian J. Chem. 6, 341-5, 1968) or
when acylamino acids of the formula (XVIII)
##STR00096##
[0325] in which [0326] A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are as
defined above, are esterified (Chem. Ind. (London) 1568
(1968)).
[0327] The compounds of the formula (XVIII)
##STR00097##
in which [0328] A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are as
defined above, are novel.
[0329] The compounds of the formula (XVIII) are obtained, for
example, when 1-aminocyclohexane-carboxylic acids of the formula
(XIX)
##STR00098##
in which [0330] A, B, Q.sup.1 and Q.sup.2 are as defined above are
acylated with substituted phenylacetic acid derivatives of the
formula (XVII)
##STR00099##
[0330] in which [0331] U, W, X, Y and Z are as defined above, for
example according to Schotten-Baumann (Organikum, VEB Deutscher
Verlag der Wissen-schaften, Berlin 1977, p. 505).
[0332] Some of the compounds of the formula (XVII) are known,
and/or they can be prepared by the known processes described in the
laid-open publications cited at the outset.
[0333] Some of the compounds of the formulae (XVI) and (XIX) are
novel, and they can be prepared by known processes (see, for
example, Compagnon, Ann. Chim. (Paris) [14] 5, pp. 11-22, 23-27
(1970), L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C.
Jitrangeri, Can. J. Chem. 53, 3339 (1975)).
[0334] Furthermore, the starting materials, used in the above
process (A), of the formula (II)
##STR00100##
in which [0335] A, B, Q.sup.1, Q.sup.2, W, X, Y, Z and R.sup.8 are
as defined above, can be prepared by reacting
1-aminocyclohexanecarbonitriles of the formula (XX)
##STR00101##
[0335] in which [0336] A, B, Q.sup.1 and Q.sup.2 are as defined
above, with substituted phenylacetic acid derivatives of the
formula (XVII)
##STR00102##
[0336] in which [0337] U, W, X, Y and Z are as defined above, to
give compounds of the formula (XXI)
##STR00103##
[0337] in which [0338] A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are as
defined above, and then subjecting these to an acidic
alcoholysis.
[0339] The compounds of the formula (XXI) are likewise novel. Some
of the compounds of the formula (XX) are novel and can be prepared,
for example, as described in EP-A-595 130.
[0340] The compounds, required as starting materials in the process
(B) according to the invention, of the formula (III)
##STR00104##
in which [0341] A, B, Q.sup.1, Q.sup.2, W, X, Y, Z and R.sup.8 are
as defined above, are novel.
[0342] They can be prepared in a simple manner by methods known in
principle.
[0343] The compounds of the formula (III) obtained, for example,
when 1-hydroxycyclohexanecarboxylic esters of the formula
(XXII)
##STR00105##
in which [0344] A, B, Q.sup.1, Q.sup.2 and R.sup.8 are as defined
above, are acylated with substituted phenylacetic acid derivatives
of the formula (XVII)
##STR00106##
[0344] in which [0345] U, W, X, Y and Z are as defined above,
(Chem. Reviews 52, 237-416 (1953)).
[0346] The 1-hydroxy-3-alkoxycyclohexylcarboxylic esters of the
formula (XXII) are novel. They are obtained, for example, when
substituted 1-hydroxy-4,4'-alkylidenyldioxycyclohexanecarbonitriles
are reacted with alcohols in the presence of acids, for example
according to Pinner, and the 1-hydroxy-4-oxocyclohexanecarboxylic
esters formed, which are known from WO 99/16748 (Ex. XXI-1), are
re-ketalized with diols. The cyanohydrin is obtained, for example,
by reacting 4,4'-alkylidenyldioxycyclohexan-1-ones with hydrocyanic
acid (see WO 99/16748).
[0347] The acid halides of the formula (IV), carboxylic anhydrides
of the formula (V), chloroformic esters or chloroformic thioesters
of the formula (VI), chloromonothioformic esters or
chlorodithioformic esters of the formula (VII), sulphonyl chlorides
of the formula (VIII), phosphorus compounds of the formula (IX) and
metal hydroxides, metal alkoxides or amines of the formulae (X) and
(XI) and isocyanates of the formula (XII) and carbamoyl chlorides
of the formula (XIII) and diols of the formula (XV) furthermore
required as starting materials for carrying out the processes (C),
(D), (E), (F), (G), (H), (I) and (J) according to the invention are
generally known compounds of organic or inorganic chemistry. Some
of the compounds of the formula (XIV) are known from WO
99/16748.
[0348] Additionally, the compounds of the formula (XVII) are known
from the patent applications cited at the outset, and/or they can
be prepared by the methods given therein.
[0349] The process (A) is characterized in that compounds of the
formula (II) in which A, B, Q.sup.1, Q.sup.2, W, X, Y, Z and
R.sup.8 are as defined above are subjected to an intramolecular
condensation in the presence of a diluent and in the presence of a
base.
[0350] Suitable diluents for use in the process (A) according to
the invention are all organic solvents which are inert towards the
reaction participants. 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.
[0351] 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. Alkali metal or
alkaline earth metal amides and hydrides, such as sodium amide,
sodium hydride and calcium hydride, and additionally also alkali
metal alkoxides, such as sodium methoxide, sodium ethoxide and
potassium tert-butoxide, can be employed, too.
[0352] When carrying out the process (A) according to the
invention, the reaction temperature can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between -75.degree. C. and 200.degree. C., preferably
between -50.degree. C. and 150.degree. C.
[0353] The process (A) according to the invention is generally
carried out under atmospheric pressure.
[0354] When carrying out the process (A) according to the
invention, the reaction component of the formula (II) and the
deprotonating base are generally employed in equimolar to about
doubly equimolar amounts. However, it is also possible to use a
relatively large excess (up to 3 mol) of one component or the
other.
[0355] The process (B) is characterized in that compounds of the
formula (III) in which A, B, Q.sup.1, Q.sup.2, W, X, Y, Z and
R.sup.8 are as defined above are condensed intramolecularly in the
presence of a diluent and in the presence of a base.
[0356] Suitable diluents for use in the process (B) according to
the invention are all organic solvents which are inert towards the
reaction participants. 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.
[0357] 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. Alkali metal or
alkaline earth metal amides and hydrides, such as sodium amide,
sodium hydride and calcium hydride, and additionally also alkali
metal alkoxides, such as sodium methoxide, sodium ethoxide and
potassium tert-butoxide, can be employed, too.
[0358] When carrying out the process (B) according to the
invention, the reaction temperature can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between -75.degree. C. and 200.degree. C., preferably
between -50.degree. C. and 150.degree. C.
[0359] The process (B) according to the invention is generally
carried out under atmospheric pressure.
[0360] When carrying out the process (B) according to the
invention, the reaction component of the formula (II) and the
deprotonating base are generally employed in equimolar to about
doubly equimolar amounts. However, it is also possible to use a
relatively large excess (up to 3 mol) of one component or the
other.
[0361] The process (C.sub..alpha.) is characterized in that
compounds of the formulae (I-1-a) to (I-2-a) are in each case
reacted with carbonyl halides of the formula (IV), if appropriate
in the presence of a diluent and if appropriate in the presence of
an acid binder.
[0362] Suitable diluents for the process (C.sub..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 tetralin; furthermore
halogenated hydrocarbons, such as methylene chloride, chloroform,
carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover
ketones, such as acetone and methylisopropyl ketone, furthermore
ethers, such as diethyl ether, tetrahydrofuran and dioxane,
additionally carboxylic esters, such as ethyl acetate, and also
strongly polar solvents, such as dimethylformamide, dimethyl
sulphoxide and sulpholane. The hydrolytic stability of the acid
halide permitting, the reaction may also be carried out in the
presence of water.
[0363] Suitable acid binders for the reaction according to the
process (C.sub..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.
[0364] The reaction temperature in the process (C.sub..alpha.)
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.
[0365] When carrying out the process (C.sub..alpha.) according to
the invention, the starting materials of the formulae (I-1-a) to
(I-2-a) and the carbonyl halide of the formula (IV) are generally
each used in approximately equivalent amounts. However, it is also
possible to employ a relatively large excess (up to 5 mol) of the
carbonyl halide. Work-up is carried out by customary methods.
[0366] The process (C.sub..beta.) is characterized in that
compounds of the formulae (I-1-a) to (I-2-a) are in each case
reacted with carboxylic anhydrides of the formula (V), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0367] Suitable diluents for use in the process (C.sub..beta.)
according to the invention are preferably those diluents which are
also preferred when using acid halides. Besides, it is also
possible for excess carboxylic anhydride to act simultaneously as
diluent.
[0368] Suitable acid binders for the process (C.sub..beta.), which
are added, if appropriate, are preferably those acid binders which
are also preferred when using acid halides.
[0369] The reaction temperature in the process (C.sub..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.
[0370] When carrying out the process (C.sub..beta.) according to
the invention, the starting materials of the formulae (I-1-a) to
(I-2-a) and the carboxylic anhydride of the formula (V) 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.
[0371] 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.
[0372] The process (D) is characterized in that compounds of the
formulae (I-1-a) to (I-2-a) are in each case reacted with
chloroformic esters or chloroformic thioesters of the formula (VI),
if appropriate in the presence of a diluent and if appropriate in
the presence of an acid binder.
[0373] Suitable acid binders for the process (D) according to the
invention are all customary acid acceptors. Preference is given to
using tertiary amines, such as triethylamine, pyridine, DABCO, DBU,
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.
[0374] Suitable diluents for use in the process (D) 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 tetralin; furthermore halogenated hydrocarbons, such as
methylene chloride, chloroform, carbon tetrachloride, chlorobenzene
and o-dichlorobenzene, moreover ketones, such as acetone and methyl
isopropyl ketone, furthermore ethers, such as diethyl ether,
tetrahydrofuran and dioxane, additionally carboxylic esters, such
as ethyl acetate, moreover nitriles, such as acetonitrile, and also
strongly polar solvents, such as dimethylformamide, dimethyl
sulphoxide and sulpholane.
[0375] When carrying out the process (D) according to the
invention, the reaction temperature can be varied within a
relatively wide range. In general, the reaction temperature is
between -20.degree. C. and +100.degree. C., preferably between
0.degree. C. and 50.degree. C.
[0376] Process (D) according to the invention is generally carried
out under atmospheric pressure.
[0377] When carrying out the process (D) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-2-a) and the appropriate chloroformic ester or chloroformic
thioester of the formula (VI) 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.
[0378] The process (E) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-2-a) are in each
case reacted with compounds of the formula (VII) in the presence of
a diluent and, if appropriate, in the presence of an acid
binder.
[0379] In the preparation process (E), about 1 mol of
chloromonothioformic ester or chlorodithioformic ester of the
formula (VII) is employed per mole of starting material of the
formulae (I-1-a) to (I-2-a), at from 0 to 120.degree. C.,
preferably from 20 to 60.degree. C.
[0380] Suitable diluents which are added, if appropriate, are all
inert polar organic solvents, such as ethers, amides, sulphones,
sulphoxides, and also halogenated alkanes.
[0381] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide, ethyl acetate or methylene
chloride.
[0382] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-2-a) is prepared by adding strong
deprotonating agents, such as, for example, sodium hydride or
potassium tert-butoxide, the further addition of acid binders may
be dispensed with.
[0383] Suitable bases for use in the process (E) are all customary
proton acceptors. Preference is given to using alkali metal
hydrides, alkali metal alkoxides, alkali metal or alkaline earth
metal carbonates or bicarbonates or nitrogen bases. Sodium hydride,
sodium methoxide, sodium hydroxide, calcium hydroxide, potassium
carbonate, sodium bicarbonate, triethylamine, dibenzylamine,
diisopropylamine, pyridine, quinoline diazabicyclooctane (DABCO),
diazabicyclononene (DBN) and diazabicycloundecene (DBU) may be
mentioned by way of example.
[0384] The reaction can be carried out at atmospheric pressure or
under elevated pressure and is preferably carried out at
atmospheric pressure. Work-up is carried out by customary
methods.
[0385] The process (F) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-2-a) are in each
case reacted with sulphonyl chlorides of the formula (VIII), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0386] In the preparation process (F), about 1 mol of sulphonyl
chloride of the formula (VIII) is reacted per mole of starting
material of the formulae (I-1-a) to (I-2-a), at from -20 to
150.degree. C., preferably from 0 to 70.degree. C.
[0387] The process (F) is preferably carried out in the presence of
a diluent.
[0388] Suitable diluents are all inert polar organic solvents, such
as ethers, amides, ketones, carboxylic esters, nitriles, sulphones,
sulphoxides or halogenated hydrocarbons, such as methylene
chloride.
[0389] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide, ethyl acetate, methylene
chloride.
[0390] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-2-a) is prepared by adding strong
deprotonating agents (such as, for example, sodium hydride or
potassium tert-butoxide), the further addition of acid binders may
be dispensed with.
[0391] If acid binders are used, these may be customary inorganic
or organic bases, for example sodium hydride, sodium carbonate,
potassium carbonate, pyridine and triethylamine.
[0392] The reaction can be carried out at atmospheric pressure or
under elevated pressure and is preferably carried out at
atmospheric pressure. Work-up is carried out by customary
methods.
[0393] The process (G) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-2-a) are in each
case reacted with phosphorus compounds of the formula (IX), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0394] In the preparation process (G), to obtain compounds of the
formulae (I-1-e) to (I-2-e), from 1 to 2, preferably from 1 to 1.3,
mol of the phosphorus compound of the formula (IX) are employed per
mole of the compounds (I-1-a) to (I-2-a), at temperatures between
-40.degree. C. and 150.degree. C., preferably between -10 and
110.degree. C.
[0395] The process (G) is preferably carried out in the presence of
a diluent.
[0396] Suitable diluents are all inert polar organic solvents, such
as ethers, carboxylic esters, halogenated hydrocarbons, ketones,
amides, nitriles, sulphones, sulphoxides, etc.
[0397] Preference is given to using acetonitrile, dimethyl
sulphoxide, tetrahydrofuran, dimethylformamide, methylene
chloride.
[0398] Suitable acid binders, which are added, if appropriate, are
customary inorganic or organic bases, such as hydroxides,
carbonates or amines. Sodium hydroxide, sodium carbonate, potassium
carbonate, pyridine and triethylamine may be mentioned by way of
example.
[0399] The reaction can be carried out at atmospheric pressure or
under elevated pressure and is preferably carried out at
atmospheric pressure. Work-up is carried out by customary methods
of organic chemistry. The end products are preferably purified by
crystallization, chromatographic purification or "incipient
distillation", i.e. removal of the volatile components under
reduced pressure.
[0400] The process (H) is characterized in that compounds of the
formulae (I-1-a) to (I-2-a) are in each case reacted with metal
hydroxides or metal alkoxides of the formula (X) or amines of the
formula (XI), if appropriate in the presence of a diluent.
[0401] Suitable diluents for use in the process (H) according to
the invention are, preferably, ethers, such as tetrahydrofuran,
dioxane, diethyl ether, or else alcohols, such as methanol,
ethanol, isopropanol, and also water. The process (H) according to
the invention is generally carried out under atmospheric pressure.
The reaction temperature is generally between -20.degree. C. and
100.degree. C., preferably between 0.degree. C. and 50.degree.
C.
[0402] The process (I) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-2-a) are in each
case reacted with (I.alpha.) compounds of the formula (XII), if
appropriate in the presence of a diluent and if appropriate in the
presence of a catalyst, or (I.beta.) with compounds of the formula
(XIII), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0403] In the preparation process (I.alpha.), about 1 mol of
isocyanate of the formula (XII) is employed per mole of starting
material of the formulae (I-1-a) to (I-2-a) at from 0 to
100.degree. C., preferably from 20 to 50.degree. C.
[0404] The process (I.alpha.) is preferably carried out in the
presence of a diluent.
[0405] Suitable diluents are all inert organic solvents, such as
aromatic hydrocarbons, halogenated hydrocarbons, ethers, amides,
nitriles, sulphones or sulphoxides.
[0406] If appropriate, catalysts may be added to promote the
reaction. Suitable for use as catalysts are, very advantageously,
organotin compounds, such as, for example, dibutyltin
dilaurate.
[0407] The reaction is preferably carried out at atmospheric
pressure.
[0408] In the preparation process (I.beta.), about 1 mol of
carbamoyl chloride of the formula (XIII) is employed per mole of
starting material of the formulae (I-1-a) to (I-2-a), at from 0 to
150.degree. C., preferably from 20 to 70.degree. C.
[0409] Suitable diluents which are added, if appropriate, are all
inert polar organic solvents, such as ethers, carboxylic esters,
nitriles, ketones, amides, sulphones, sulphoxides or halogenated
hydrocarbons.
[0410] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylfoiniamide or methylene chloride.
[0411] If, in a preferred embodiment, the enolate salt of the
compound (I-1-a) to (I-2-a) is prepared by adding strong
deprotonating agents (such as, for example, sodium hydride or
potassium tert-butoxide), the further addition of acid binders may
be dispensed with.
[0412] If acid binders are used, these may be customary inorganic
or organic bases, for example sodium hydroxide, sodium carbonate,
potassium carbonate, triethylamine or pyridine.
[0413] The reaction can be carried out at atmospheric pressure or
under elevated pressure and is preferably carried out at
atmospheric pressure. Work-up is carried out by customary
methods.
[0414] In the preparation process (J), up to 50 mol of diol of the
formula (XVI), preferably from 1 to 10 mol, are employed per mole
of the starting materials (I-1-a) to (I-1-g) or (I-2-a) to (I-2-g),
at from -50 to 250.degree. C., preferably from 0 to 150.degree.
C.
[0415] Suitable diluents are all inert organic solvents, such as
aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters,
amides, nitriles, sulphones or sulphoxides.
[0416] If appropriate, catalysts may be added to promote the
reaction. Suitable for use as catalysts are, very advantageously,
acids, such as, for example, p-toluenesulphonic acid, concentrated
sulphuric acid, and also Lewis acids, such as, for example, boron
trifluoride etherate.
[0417] The reaction is preferably carried out at atmospheric
pressure.
[0418] The dehydrating conditions can be achieved both by
azeotropic removal of the water and by adding suitable dehydrating
agents, such as, for example, orthoformates, dimethoxypropane and
also molecular sieves.
[0419] Work-up is carried out by customary methods.
[0420] The active compounds/active compound combinations, in
combination with good plant tolerance and favourable toxicity to
warm-blooded animals and being tolerated well by the environment,
are suitable for protecting plants and plant organs, for increasing
the harvest yields, for improving the quality of the harvested
material and for controlling animal pests, in particular insects,
arachnids, helminths, nematodes and molluscs, which are encountered
in agriculture, in horticulture, in animal husbandry, in forests,
in gardens and leisure facilities, in the protection of stored
products and of materials, and in the hygiene sector. They may be
preferably employed as plant protection agents. They are active
against normally sensitive and resistant species and against all or
some stages of development. The abovementioned pests include:
[0421] From the order of the Anoplura (Phthiraptera), for example,
Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus
spp., Trichodectes spp.
[0422] From the class of the Arachnida, for example, Acarus siro,
Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas
spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa,
Chorioptes spp., Demianyssus gallinae, Eotetranychus spp.,
Epitrimerus pyri, Eutetranychus spp., Eriophyes spp.,
Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus
mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp.,
Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus
latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp.,
Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus
spp., Tetranychus spp., Vasates lycopersici.
[0423] From the class of the Bivalva, for example, Dreissena
spp.
[0424] From the order of the Chilopoda, for example, Geophilus
spp., Scutigera spp.
[0425] From the order of the Coleoptera, for example,
Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes
spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora
spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria
spp., Attagenus spp., Bruchidius obtectus, Bruchus spp.,
Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites
spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi,
Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae,
Gibbium psylloides, Heteronychus arator, Hylamorpha elegans,
Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna
consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus,
Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha,
Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus
hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis,
Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae,
Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes
chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha
dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp.,
Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma
spp., Tychius spp., Xylotrechus spp., Zabrus spp.
[0426] From the order of the Collembola, for example, Onychiurus
armatus.
[0427] From the order of the Dermaptera, for example, Forficula
auricularia.
[0428] From the order of the Diplopoda, for example, Blaniulus
guttulatus.
[0429] From the order of the Diptera, for example, Aedes spp.,
Anopheles spp., Bibio hortulanus, Calliphora erythrocephala,
Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia
anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia
hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia
spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia
spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit,
Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp.,
Tannia spp., Tipula paludosa.
[0430] From the class of the Gastropoda, for example, Anion spp.,
Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp.,
Lymnaea spp., Oncomelania spp., Succinea spp.
[0431] From the class of the helminths, for example, Ancylostoma
duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis,
Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi,
Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp.,
Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria,
Diphyllobothrium latum, Dracunculus medinensis, Echinococcus
granulosus, Echinococcus multilocularis, Enterobius veiinicularis,
Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana,
Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum
spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp.,
Paragonimus spp., Schistosomen spp, Strongyloides fuelleborni,
Strongyloides stercoralis, Stronyloides spp., Taenia saginata,
Taenia solium, Trichinella spiralis, Trichinella nativa,
Trichinella britovi, Trichinella nelsoni, Trichinella
pseudopsiralis, Trichostrongulus spp., Trichuris trichuria,
Wuchereria bancrofti.
[0432] It is furthermore possible to control Protozoa, such as
Eimeria.
[0433] From the order of the Heteroptera, for example, Anasa
tristis, Antestiopsis spp., Blissus spp., Calocoris spp.,
Campylomma livida, Cavelerius spp., Cimex spp., Creontiades
dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti,
Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp.,
Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus
spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp.,
Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus,
Pseudacysta persea, Rhodnius spp., Sahlbergella singularis,
Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma
spp.
[0434] From the order of the Homoptera, for example, Acyrthosipon
spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus
barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui,
Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis,
Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani,
Bemisia spp., Brachycaudus helichrysii, Brachycolus spp.,
Brevicoryne brassicae, Calligypona marginata, Cameocephala fulgida,
Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon
fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis
juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus
halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes
spp., Diaphorina spp., Diaspis spp., Drosicha spp., Dysaphis spp.,
Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp.,
Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata,
Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus
spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp.,
Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata,
Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum,
Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia
ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp.,
Orthezia praelonga, Parabemisia myricae, Paratrioza spp.,
Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus
spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp.,
Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria
pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla
spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada
gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp.,
Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus,
Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala
festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis
spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp.,
Typhlocyba spp., Unaspis spp., Viteus vitifolii.
[0435] From the order of the Hymenoptera, for example, Diprion
spp., Hoplocampa spp., Lasius spp., Monomorium pharaonic, Vespa
spp.
[0436] From the order of the Isopoda, for example, Armadillidium
vulgare, Oniscus asellus, Porcellio scaber.
[0437] From the order of the Isoptera, for example, Reticulitermes
spp.
[0438] From the order of the Lepidoptera, for example, Acronicta
major, Aedia leucomelas, Agrotis spp., Alabama argillacea,
Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella,
Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa
pomonella, Chematobia brumata, Chilo spp., Choristoneura
fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana,
Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia
spp., Galleria mellonella, Helicoverpa spp., Heliothis spp.,
Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta
padella, Laphygma spp., Lithocolletis blancardella, Lithophane
antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma
neustria, Mamestra brassicae, Mocis repanda, Mythimna separata,
Oria spp., Oulema oryzae, Panolis flammea, Pectinophora
gossypiella, Phyllocnistis citrella, Pieris spp., Plutella
xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia
includens, Pyrausta nubilalis, Spodoptera spp., Thermesia
gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix
viridana, Trichoplusia spp.
[0439] From the order of the Orthoptera, for example, Acheta
domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa
spp., Leucophaea maderae, Locusta spp., Melanoplus spp.,
Periplaneta americana, Schistocerca gregaria.
[0440] From the order of the Siphonaptera, for example,
Ceratophyllus spp., Xenopsylla cheopis.
[0441] From the order of the Symphyla, for example, Scutigerella
immaculata.
[0442] From the order of the Thysanoptera, for example, Baliothrips
biformis, Enneothrips flavens, Frankliniella spp., Heliothrips
spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus,
Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
[0443] From the order of the Thysanura, for example, Lepisma
saccharina.
[0444] The phytoparasitic nematodes include, for example,
Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus dipsaci,
Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp.,
Pratylenchus spp., Radopholus similis, Trichodorus spp.,
Tylenchulus semipenetrans, Xiphinema spp.
[0445] If appropriate, the compounds/active compound combinations
according to the invention can, at certain concentrations or
application rates, also be used as herbicides, safeners, growth
regulators or agents to improve plant properties, or as
microbicides, for example as fungicides, antimycotics,
bactericides, viricides (including agents against viroids) or as
agents against MLO (Mycoplasma-like organisms) and RLO
(Rickettsia-like organisms). If appropriate, they can also be
employed as intermediates or precursors for the synthesis of other
active compounds.
[0446] 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 genetic engineering methods or by
combinations of these methods, including the transgenic plants and
including 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, offshoots and
seeds.
[0447] Treatment according to the invention of the plants and plant
parts with the active compounds/active compound combinations is
carried out directly or by allowing the compounds to act on the
surroundings, habitat or storage space by the customary treatment
methods, for example by immersion, spraying, evaporation, fogging,
scattering, painting on, injection and, in the case of propagation
material, in particular in the case of seeds, also by applying one
or more coats.
[0448] The active compounds/active compound combinations can be
converted to the customary formulations, such as solutions,
emulsions, wettable powders, water- and oil-based suspensions,
powders, dusts, pastes, soluble powders, soluble granules, granules
for broadcasting, suspension-emulsion concentrates, natural
materials impregnated with active compound, synthetic materials
impregnated with active compound, fertilizers and
microencapsulations in polymeric substances.
[0449] These formulations are produced in a known manner, for
example by mixing the active compounds/active compound combinations
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.
[0450] If the extender used is water, it is also possible to use
organic solvents, for example, as auxiliary solvents. Suitable
liquid solvents are esentially 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, as well as their ethers
and esters, ketones, such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohexanone, strongly polar solvents, such as
dimethylformamide and dimethyl sulphoxide, and also water.
[0451] Suitable solid carriers are:
[0452] for example ammonium salts and ground natural minerals such
as kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, and ground synthetic
minerals such as highly disperse silica, alumina and silicates;
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.
[0453] 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.
[0454] 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.
[0455] The formulations generally comprise between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90%.
[0456] The active compound/active compound combinations according
to the invention can be present in their commercially available
formulations, as well as in the use forms prepared from these
formulations, in a mixture with other active compounds such as
insecticides, attractants, sterilizers, bactericides, acaricides,
nematicides, fungicides, growth-regulating substances, herbicides,
safeners, fertilizers or semiochemicals.
[0457] Compounds which are suitable as mixing partners are, for
example, the following:
Fungicides:
[0458] 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-A1;
fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil;
furmecyclox; guazatine; hexachlorobenzene; hexaconazole;
hymexazole; 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;
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-tri chloro-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-5-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:
[0459] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
Insecticides/Acaricides/Nematicides:
[0460] 1. Acetylcholine esterase (AChE) inhibitors
[0461] 1.1 Carbamates, [0462] for example alanycarb, aldicarb,
aldoxycarb, allyxycarb, aminocarb, bendiocarb, benfuracarb,
bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl,
carbofuran, carbosulfan, cloethocarb, dimetilan, ethiofencarb,
fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb,
metam-sodium, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb,
promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC,
xylylcarb, triazamate
[0463] 1.2 Organophosphates, [0464] for example acephate,
azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl,
bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion,
chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos
(-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos,
chlorfenvinphos, demeton-S-methyl, demeton-S-methylsulphon,
dialifos, diazinon, dichlofenthion, dichlorvos/DDVP, dicrotophos,
dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, EPN,
ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion,
fensulfothion, fenthion, flupyrazofos, fonofos, formothion,
fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos,
isazofos, isofenphos, isopropyl O-salicylate, isoxathion,
malathion, mecarbam, methacrifos, methamidophos, methidathion,
mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl,
parathion (-methyl/-ethyl), phenthoate, phorate, phosalone,
phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos
(-methyl/-ethyl), profenofos, propaphos, propetamphos, prothiofos,
prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos,
sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos,
tetrachlorvinphos, thiometon, triazophos, triclorfon,
vamidothion
[0465] 2. Sodium channel modulators/voltage-gated sodium channel
blockers
[0466] 2.1 Pyrethroids, [0467] for example acrinathrin, allethrin
(d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin,
bioallethrin-S cyclopentyl isomer, bioethanomethrin, biopermethrin,
bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin,
cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin,
cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin,
deltamethrin, empenthrin (1R isomer), esfenvalerate, etofenprox,
fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate,
flubrocythrinate, flucythrinate, flufenprox, flumethrin,
fluvalinate, fubfenprox, gamma-cyhalothrin, imiprothrin, kadethrin,
lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-),
phenothrin (1R trans-isomer), prallethrin, profluthrin,
protrifenbute, pyresmethrin, resmethrin, RU15525, silafluofen,
tau-fluvalinate, tefluthrin, terallethrin, tetramethrin (1R
isomer), tralomethrin, transfluthrin, ZXI 8901, pyrethrins
(pyrethrum) [0468] DDT
[0469] 2.2 Oxadiazines, [0470] for example indoxacarb
[0471] 2.3 Semicarbazones, [0472] for example metaflumizone (BAS
3201)
Acetylcholine Receptor Agonists-Antagonists
[0473] 3.1 Chloronicotinyls, [0474] for example acetamiprid,
clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine,
thiacloprid, thiamethoxam
[0475] 3.2 Nicotine, bensultap, cartap
Acetylcholine Receptor Modulators
[0476] 4.1 Spinosyns, [0477] for example spinosad [0478] GABA-gated
chloride channel antagonists
[0479] 5.1 Cyclodiene organochlorines, [0480] for example
camphechlor, chlordane, endosulfan, gamma-HCH, HCH, heptachlor,
lindane, methoxychlor
[0481] 5.2 Fiproles, [0482] for example acetoprole, ethiprole,
fipronil, pyrafluprole, pyripole, van liprole
Chloride Channel Activators
[0483] 6.1 Mectins, [0484] for example avermectin, emamectin,
emamectin-benzoate, ivermectin, milbemycin
Juvenile Bon Lone Mimetics,
[0484] [0485] for example diofenolan, epofenonane, fenoxycarb,
hydroprene, kinoprene, methoprene, pyriproxifen, triprene
Ecdyson Agonists/Disruptors
[0486] 8.1 Diacylhydrazines, [0487] for example chromafenozide,
halofenozide, methoxyfenozide, tebufenozide
Chitin Biosynthesis Inhibitors
[0488] 9.1 Benzoylureas, [0489] for example bistrifluoron,
chlofluazuron, diflubenzuron, fluazuron, flucycloxuron,
flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron,
penfluoron, teflubenzuron, triflumuron
[0490] 9.2 Buprofezin
[0491] 9.3 Cyromazine
Oxidative Phosphorylation Inhibitors, ATP Disruptors
[0492] 10.1 Diafenthiuron
[0493] 10.2 Organotins, [0494] for example azocyclotin, cyhexatin,
fenbutatin-oxide
[0495] Oxidative Phosphorylation Decouplers Acting by Interrupting
the H-Proton Gradient
[0496] 11.1 Pyrroles, [0497] for example chlorfenapyr
[0498] 11.2 Dinitrophenols, [0499] for example binapacyrl,
dinobuton, dinocap, DNOC
Electron Transport Inhibitors
[0500] 12.1 Site-I electron transport inhibitors [0501] from the
group of the [0502] METIs, [0503] for example fenazaquin,
fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad
and also [0504] Hydramethylnon [0505] Dicofol
[0506] 12.2 Site-II electron transport inhibitors [0507]
Rotenone
[0508] 12.3 Site-III electron transport inhibitors [0509]
Acequinocyl, fluacrypyrim
Microbial Disruptors of the Insect Gut Membrane
[0509] [0510] Bacillus thuringiensis strains
Fat Biosynthesis Inhibitors
[0511] 14.1 Tetronic acids, [0512] for example spirodiclofen,
spiromesifen
[0513] 14.2 Tetramic acids, [0514] for example spirotetramat
Carboxamides,
[0514] [0515] for example flonicamid
[0516] Octopaminergic agonists, [0517] for example amitraz
[0518] Inhibitors of magnesium-stimulated ATPase, [0519]
propargite
[0520] Ryanodine receptor effectors [0521] 18.1 Benzoic acid
dicarboxamides, [0522] for example flubendiamide [0523] 18.2
Anthranilamides, for example DPX E2 Y45
[0524] Nereistoxin analogues, [0525] for example thiocyclam
hydrogen oxalate, thiosultap-sodium
[0526] Biologicals, hormones or pheromones, [0527] azadirachtin,
Bacillus spec., Beauveria spec., codlemone, Metarrhizium spec.,
Paecilomyces spec., thuringiensin, Verticillium spec.
[0528] Active compounds with unknown or unspecific mechanisms of
action
[0529] 21.1 Fumigants, [0530] for example aluminium phosphide,
methyl bromide, sulphuryl fluoride
[0531] 21.2 Antifeedants, [0532] for example cryolite, flonicamid,
pymetrozine
[0533] 21.3 Mite growth inhibitors, [0534] for example
clofentezine, etoxazole, hexythiazox
[0535] 21.4 Amidoflumet, benclothiaz, benzoximate, bifenazate,
bromopropylate, buprofezin, chinomethionat, chlordimeform,
chlorobenzilate, chloropicrin, clothiazoben, cycloprene,
cyflumetofen, dicyclanil, fenoxacrim, fentrifanil, flubenzimine,
flufenerim, flutenzin, gossyplure, hydramethylnone, japonilure,
metoxadiazone, petroleum, piperonyl butoxide, potassium oleate,
pyridalyl, sulfluramid, tetradifon, tetrasul, triarathene,
verbutin
[0536] A mixture with other known active compounds, such as
herbicides, fertilizers, growth regulators, safeners,
semiochemicals, or else with agents which improve plant properties
is also possible.
[0537] When used as insecticides in their commercially available
formulations and in the use forms prepared with these formulations,
the active compounds/active compound combinations according to the
invention can furthermore be present 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.
[0538] When used as insecticides in their commercially available
formulations and in the use forms prepared with these formulations,
the active compounds/active compound combinations according to the
invention can furthermore be present in the form of a mixture with
inhibitors which reduce the degradation of the active compound
after application in the habitat of the plant, on the surface of
parts of plants or in plant tissues.
[0539] The active compound content of the use foams prepared from
the commercially available formulations can vary within broad
ranges. The active compound concentration of the use forms can be
from 0.00000001 up to 95% by weight of active compound and is
preferably between 0.00001 and 1% by weight.
[0540] Application is in a customary manner adapted to suit the use
forms.
[0541] As already mentioned above, it is possible to treat all
plants and 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.
[0542] 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.
[0543] 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.
[0544] 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, sugar beet, tomatoes, peas
and other vegetable varieties, cotton, tobacco, oilseed rape and
fruit plants (with the fruits apples, pears, citrus fruits and
grapes), with particular emphasis on maize, soybeans, potatoes,
cotton, tobacco, and oilseed rape. Traits which are especially
emphasized are the increased defence of the plants against insects,
arachnids, nematodes and slugs and snails, 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 CryIF 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),
systemins, 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 also include 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.
[0545] The plants listed can be treated particularly advantageously
according to the invention with the compounds of the general
formula I 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.
[0546] The active compounds/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 and endoparasites), 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:
[0547] From the order of the Anoplurida, for example, Haematopinus
spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes
spp.
[0548] 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.
[0549] 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.
[0550] From the order of the Siphonapterida, for example, Pulex
spp., Ctenocephalides spp., Xenopyslla spp. and Ceratophyllus
spp.
[0551] From the order of the Heteropterida, for example, Cimex
spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
[0552] From the order of the Blattarida, for example, Blatta
orientalis, Periplaneta americana, Blattela germanica and Supella
spp.
[0553] From the sub-class of the Acaria (Acarina) 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.
[0554] 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.
[0555] The active compounds/active compound combinations of the
formula (I) 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.
[0556] In the veterinary sector, the active compounds/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.
[0557] When administered to livestock, poultry, domestic animals
and the like, the active compounds of the formula (I) can be used
as formulations (for example powders, emulsions, flowables) which
comprise the active compounds in an amount of 1 to 80% by weight,
either directly or after dilution by a factor of 100 to 10 000, or
they may be used in the form of a chemical bath.
[0558] Furthermore, it has been found that the compounds/active
compound combinations according to the invention have a potent
insecticidal action against insects which destroy industrial
materials.
[0559] The following insects may be mentioned by way of example and
as being preferred, but without any limitation:
[0560] Beetles, such as 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.
[0561] Dermapterans, such as Sirex juvencus, Urocerus gigas,
Urocerus gigas taignus, Urocerus augur.
[0562] Termites, such as Kalotermes flavicollis, Cryptotermes
brevis, Heterotermes indicola, Reticulitermes flavipes,
Reticulitelines santonensis, Reticulitermes lucifugus, Mastotermes
darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
[0563] Bristletails, such as Lepisma saccharina.
[0564] 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.
[0565] The materials to be very particularly preferably protected
against attack by insects are wood and timber products.
[0566] 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:
[0567] 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.
[0568] The active compounds can be used as such, in the form of
concentrates or generally customary formulations, such as powders,
granules, solutions, suspensions, emulsions or pastes.
[0569] 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.
[0570] 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.
[0571] 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.
[0572] 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.
[0573] 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.
[0574] 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.
[0575] 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.
[0576] 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.
[0577] In a preferred embodiment, part of the organochemical
solvent or solvent mixture or an aliphatic polar organochemical
solvent or solvent mixture is replaced. 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.
[0578] 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.
[0579] 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.
[0580] 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.
[0581] 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).
[0582] 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.
[0583] Fixatives are chemically based on polyvinyl alkyl ethers,
such as, for example, polyvinyl methyl ether, or ketones, such as
benzophenone or ethylenebenzophenone.
[0584] 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.
[0585] Particularly effective protection of wood is achieved by
large-scale industrial impregnation processes, for example vacuum,
double-vacuum or pressure processes.
[0586] If appropriate, the ready-to-use compositions can
additionally comprise other insecticides and, if appropriate,
additionally one or more fungicides.
[0587] 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.
[0588] 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, triflumuron, chlothianidin, spinosad,
tefluthrin,
[0589] and fungicides, such as epoxyconazole, hexaconazole,
azaconazole, propiconazole, tebuconazole, cyproconazole,
metconazole, imazalil, dichlorfluanid, tolylfluanid,
3-iodo-2-propynylbutyl carbamate, N-octyl-isothiazolin-3-one and
4,5-dichloro-N-octylisothiazolin-3-one.
[0590] The compounds according to the invention can at the same
time be employed for protecting objects which come into contact
with saltwater or brackish water, in particular hulls, screens,
nets, buildings, moorings and signalling systems, against
fouling.
[0591] 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.
[0592] 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.
[0593] 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.
[0594] 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,
bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate, zinc
oxide, copper(I) ethylenebisdithiocarbamate, copper thiocyanate,
copper naphthenate and tributyltin halides to be dispensed with, or
the concentration of these compounds to be substantially
reduced.
[0595] If appropriate, the ready-to-use antifouling paints can
additionally comprise other active compounds, preferably algicides,
fungicides, herbicides, molluscicides, or other antifouling active
compounds.
[0596] Preferably suitable components in combination with the
antifouling compositions according to the invention are:
[0597] algicides such as
[0598]
2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,
dichlorophen, diuron, endothal, fentin acetate, isoproturon,
methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
[0599] fungicides such as
[0600] benzo[b]thiophenecarboxylic acid cyclohexylamide
S,S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propinyl
butylcarbamate, tolylfluanid and azoles such as
[0601] azaconazole, cyproconazole, epoxyconazole, hexaconazole,
metconazole, propiconazole and tebuconazole;
[0602] molluscicides such as
[0603] fentin acetate, metaldehyde, methiocarb, niclosamid,
thiodicarb and trimethacarb; Fe chelates;
[0604] or conventional antifouling active compounds such as
[0605] 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.
[0606] 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.
[0607] 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.
[0608] Besides the algicidal, fungicidal, molluscicidal active
compounds and insecticidal active compounds according to the
invention, antifouling paints comprise, in particular, binders.
[0609] 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.
[0610] If appropriate, paints also comprise inorganic pigments,
organic pigments or colorants which are preferably insoluble in
saltwater. 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.
[0611] The active compounds 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:
[0612] From the order of the Scorpionidea, for example, Buthus
occitanus.
[0613] 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.
[0614] From the order of the Araneae, for example, Aviculariidae,
Araneidae.
[0615] From the order of the Opiliones, for example,
Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones
phalangium.
[0616] From the order of the Isopoda, for example, Oniscus asellus,
Porcellio scaber.
[0617] From the order of the Diplopoda, for example, Blaniulus
guttulatus, Polydesmus spp.
[0618] From the order of the Chilopoda, for example, Geophilus
spp.
[0619] From the order of the Zygentoma, for example, Ctenolepisma
spp., Lepisma saccharina, Lepismodes inquilinus.
[0620] From the order of the Blattaria, for example, Blatta
orientalies, Blattella germanica, Blattella asahinai, Leucophaea
maderae, Panchlora spp., Parcoblatta spp., Periplaneta
australasiae, Periplaneta americana, Periplaneta brunnea,
Periplaneta fuliginosa, Supella longipalpa.
[0621] From the order of the Saltatoria, for example, Acheta
domesticus.
[0622] From the order of the Dermaptera, for example, Forficula
auricularia.
[0623] From the order of the Isoptera, for example, Kalotermes
spp., Reticulitermes spp.
[0624] From the order of the Psocoptera, for example, Lepinatus
spp., Liposcelis spp.
[0625] 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.
[0626] 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.
[0627] From the order of the Lepidoptera, for example, Achroia
grisella, Galleria mellonella, Plodia interpunctella, Tinea
cloacella, Tinea pellionella, Tineola bisselliella.
[0628] From the order of the Siphonaptera, for example,
Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga
penetrans, Xenopsylla cheopis.
[0629] From the order of the Hymenoptera, for example, Camponotus
herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,
Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
[0630] From the order of the Anoplura, for example, Pediculus
humanus capitis, Pediculus humanus corporis, Phthirus pubis.
[0631] From the order of the Heteroptera, for example, Cimex
hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma
infestans.
[0632] They are used in the household insecticides sector alone or
in combination with other suitable active compounds such as
phosphoric esters, carbamates, pyrethroids, neonicotinoids, growth
regulators or active compounds from other known classes of
insecticides.
[0633] 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.
[0634] The active compounds/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.
[0635] The active compounds/active compound combinations according
to the invention can be used, for example, in the following
plants:
[0636] Dicotyledonous weeds of the genera: Abutilon, Amaranthus,
Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens,
Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium,
Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia,
Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium,
Lepidium, Lindemia, 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.
[0637] Dicotyledonous crops of the genera: Arachis, Beta, Brassica,
Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium,
Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum,
Solanum, Vicia.
[0638] 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.
[0639] Monocotyledonous crops of the genera: Allium, Ananas,
Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale,
Sorghum, Triticale, Triticum, Zea.
[0640] However, the use of the active compounds/active compound
combinations according to the invention is in no way restricted to
these genera, but extends in the same manner to other plants.
[0641] Depending on the concentration, the active compounds/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 plantations and hop fields, on lawns, turf
and pastureland, and for the selective control of weeds in annual
crops.
[0642] The compounds of the formula (I)/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.
[0643] At certain concentrations or application rates, the active
compounds/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.
[0644] The active compounds/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.
[0645] 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.
[0646] 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.
[0647] 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 nonionic
and anionic emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates and protein hydrolysates; suitable dispersants are:
for example lignosulphite waste liquors and methylcellulose.
[0648] 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.
[0649] 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.
[0650] The formulations generally comprise between 0.1 and 95
percent by weight of active compound, preferably between 0.5 and
90%.
[0651] The active compounds/active compound combinations 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.
[0652] Herbicides which are suitable for the mixtures are known
herbicides, for example
[0653] acetochlor, acifluorfen (-sodium), aclonifen, alachlor,
alloxydim (-sodium), ametryne, amicarbazone, amidochlor,
amidosulfuron, aminopyralid, anilofos, asulam, atrazine,
azafenidin, azimsulfuron, beflubutamid, benazolin (-ethyl),
benfuresate, bensulfuron (-methyl), bentazone, bencarbazone,
benzfendizone, benzobicyclon, benzolenap, benzoylprop (-ethyl),
bialaphos, bifenox, bispyribac (-sodium), bromobutide,
bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl),
butroxydim, butylate, cafenstrole, caloxydim, carbetamide,
carfentrazone (-ethyl), chlomethoxyfen, 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,
cyhalofop (-butyl), 2,4-D, 2,4-DB, desmedipham, diallate, dicamba,
dichlorprop (--P), diclofop (-methyl), diclosulam, diethatyl
(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron,
dimepiperate, dimethachlor, dimethametryn, dimethenamid,
dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron,
dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron
(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid,
fenoxaprop (--P-ethyl), fentrazamide, flamprop (-isopropyl,
-iso-propyl-L, -methyl), flazasulfuron, florasulam, fluazifop
(--P-butyl), fluazolate, flucarbazone (-sodium), flufenacet,
flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn,
flumetsulam, fluometuron, fluorochloridone, 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, HOK-201, imazamethabenz
(-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin,
imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium),
ioxynil, isopropalin, isoproturon, isouron, isoxaben,
isoxachlortole, isoxaflutole, isoxapyrifop, KIH 485, lactofen,
lenacil, linuron, MCPA, mecoprop, mefenacet, mesosulfuron,
mesotrione, metamifop, metamitron, metazachlor, methabenzthiazuron,
metobenzuron, metobromuron, (alpha-) metolachlor, metosulam,
metoxuron, metribuzin, metsulfuron (-methyl), molinate,
monolinuron, naproanilide, napropamide, neburon, nicosulfuron,
norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl,
oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat,
pelargonic acid, pendimethalin, pendralin, penoxsulam, pentoxazone,
phenmedipham, picolinafen, pinoxaden, piperophos, pretilachlor,
primisulfuron (-methyl), profluazol, prometryn, propachlor,
propanil, propaquizafop, propisochlor, propoxycarbazone (-sodium),
propyzamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl),
pyrasulfotole, pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl),
pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol,
pyriftalide, pyriminobac (-methyl), pyrimisulfan, pyrithiobac
(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop
(--P-ethyl, --P-tefuryl), rimsulfuron, sethoxydim, simazine,
simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl),
sulfosate, sulfosulfuron, tebutam, tebuthiuron, tembotrione,
tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide,
thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb,
tiocarbazil, topramezone, tralkoxydim, triallate, triasulfuron,
tribenuron (-methyl), triclopyr, tridiphane, trifluralin,
trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron and
##STR00107##
[0654] A mixture with other known active compounds, such as
fungicides, insectides, acaricides, nematicides, bird repellents,
plant nutrients and soil conditioners, is also possible.
[0655] The active compounds/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.
[0656] The active compounds/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.
[0657] 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.
[0658] The substances/active compound combinations 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.
[0659] Fungicides can be employed in crop protection for
controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes,
Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
[0660] Bactericides can be employed in crop protection for
controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae,
Corynebacteriaceae and Streptomycetaceae.
[0661] 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:
[0662] Xanthomonas species, such as, for example, Xanthomonas
campestris pv. oryzae;
[0663] Pseudomonas species, such as, for example, Pseudomonas
syringae pv. lachrymans;
[0664] Erwinia species, such as, for example, Erwinia
amylovora;
[0665] Pythium species, such as, for example, Pythium ultimum;
[0666] Phytophthora species, such as, for example, Phytophthora
infestans;
[0667] Pseudoperonospora species, such as, for example,
Pseudoperonospora humuli or Pseudoperonospora cubensis;
[0668] Plasmopara species, such as, for example, Plasmopara
viticola;
[0669] Bremia species, such as, for example, Bremia lactucae;
[0670] Peronospora species, such as, for example, Peronospora pisi
or P. brassicae;
[0671] Erysiphe species, such as, for example, Erysiphe
graminis;
[0672] Sphaerotheca species, such as, for example, Sphaerotheca
fuliginea;
[0673] Podosphaera species, such as, for example, Podosphaera
leucotricha;
[0674] Venturia species, such as, for example, Venturia
inaequalis;
[0675] Pyrenophora species, such as, for example, Pyrenophora teres
or P. graminea
[0676] (conidia form: Drechslera, syn: Helminthosporium);
[0677] Cochliobolus species, such as, for example, Cochliobolus
sativus
[0678] (conidia form: Drechslera, syn: Helminthosporium);
[0679] Uromyces species, such as, for example, Uromyces
appendiculatus;
[0680] Puccinia species, such as, for example, Puccinia
recondita;
[0681] Sclerotinia species, such as, for example, Sclerotinia
sclerotiorum;
[0682] Tilletia species, such as, for example, Tilletia caries;
[0683] Ustilago species, such as, for example, Ustilago nuda or
Ustilago avenae;
[0684] Pellicularia species, such as, for example, Pellicularia
sasakii;
[0685] Pyricularia species, such as, for example, Pyricularia
oryzae;
[0686] Fusarium species, such as, for example, Fusarium
culmorum;
[0687] Botrytis species, such as, for example, Botrytis
cinerea;
[0688] Septoria species, such as, for example, Septoria
nodorum;
[0689] Leptosphaeria species, such as, for example, Leptosphaeria
nodorum;
[0690] Cercospora species, such as, for example, Cercospora
canescens;
[0691] Alternaria species, such as, for example, Alternaria
brassicae; and
[0692] Pseudocercosporella species, such as, for example,
Pseudocercosporella herpotrichoides.
[0693] The active compounds/active compound combinations 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.
[0694] 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.
[0695] In the present case, unwanted 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.
[0696] The fact that the active compounds/active compound
combinations 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.
[0697] The active compounds/active compound combinations 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.
[0698] At certain concentrations and application rates, the active
compounds/active compound combinations according to the invention
can if appropriate 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.
[0699] 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.
[0700] 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.
[0701] 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.
[0702] Microorganisms of the following genera may be mentioned as
examples:
[0703] Alternaria, such as Alternaria tenuis,
[0704] Aspergillus, such as Aspergillus niger,
[0705] Chaetomium, such as Chaetomium globosum,
[0706] Coniophora, such as Coniophora puetana,
[0707] Lentinus, such as Lentinus tigrinus,
[0708] Penicillium, such as Penicillium glaucum,
[0709] Polyporus, such as Polyporus versicolor,
[0710] Aureobasidium, such as Aureobasidium pullulans,
[0711] Sclerophoma, such as Sclerophoma pityophila,
[0712] Trichoderma, such as Trichoderma viride,
[0713] Escherichia, such as Escherichia coli,
[0714] Pseudomonas, such as Pseudomonas aeruginosa, and
[0715] Staphylococcus, such as Staphylococcus aureus.
[0716] Depending on their particular physical and/or chemical
properties, the active compounds/active compound combinations 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.
[0717] These formulations are produced in a known manner, for
example by mixing the active compounds/active compound combinations
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.
[0718] 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.
[0719] 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.
[0720] The formulations generally comprise between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90%.
[0721] 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.
Fungicides:
[0722] 2-phenylphenol; 8-hydroxyquinoline sulphate;
acibenzolar-S-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; 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-A1;
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; proquinazid;
prothioconazole; pyraclostrobin; pyrazophos; pyrifenox;
pyrimethanil; pyroquilon; pyroxyfur; pyrroInitrin; 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-5-carboxylate;
monopotassium carbonate;
N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide;
N-butyl-8-(1,1-dimethyl ethyl)-1-oxaspiro[4.5]decan-3-amine; sodium
tetrathiocarbonate;
[0723] and copper salts and preparations such as Bordeaux mixture;
copper hydroxide; copper naphthenate; copper oxychloride; copper
sulphate; cufraneb; cuprous oxide; mancopper; oxine-copper.
Bactericides:
[0724] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
insecticides/Acaricides/Nematicides:
[0725] abamectin, ABG-9008, acephate, acequinocyl, acetamiprid,
acetoprole, acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb,
aldicarb, aldoxycarb, allethrin 1R-isomers, alpha-cypermethrin
(alphamethrin), amidoflumet, aminocarb, amitraz, avermectin,
AZ-60541, azadirachtin, azamethiphos, azinphos-methyl,
azinphos-ethyl, azocyclotin,
[0726] 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,
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,
[0727] 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,
[0728] DDT, deltamethrin, demeton-S-methyl,
demeton-S-methylsulphone, diafenthiuron, dialifos, diazinon,
dichlofenthion, dichlorvos, dicofol, dicrotophos, dicyclanil,
diflubenzuron, dimethoate, dimethylvinphos, dinobuton, dinocap,
dinotefuran, diofenolan, disulfoton, docusate-sodium, dofenapyn,
DOWCO-439,
[0729] eflusilanate, emamectin, emamectin benzoate, empenthrin (1R
isomer), endosulfan, Entomophthora spp., EPN, esfenvalerate,
ethiofencarb, ethiprole, ethion, ethoprophos, etofenprox,
etoxazole, etrimfos,
[0730] 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,
[0731] gamma-HCH, gossyplure, grandlure, granulosis viruses,
[0732] halfenprox, halofenozide, HCH, HCN-801, heptenophos,
hexaflumuron, hexythiazox, hydramethylnone, hydroprene,
[0733] IKA-2002, imidacloprid, imiprothrin, indoxacarb,
iodofenphos, iprobenfos, isazofos, isofenphos, isoprocarb,
isoxathion, ivermectin, japonilure,
[0734] kadethrin, nuclear polyhedrosis viruses, kinoprene,
[0735] lambda-cyhalothrin, lindane, lufenuron,
[0736] malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium,
methacrifos, methamidophos, Metarhizium anisopliae, Metarhizium
flavoviride, methidathion, methiocarb, methomyl, methoprene,
methoxychlor, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,
milbemectin, milbemycin, MKI-245, MON-45700, monocrotophos,
moxidectin, MTI-800,
[0737] 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,
[0738] OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802,
omethoate, oxamyl, oxydemeton-methyl,
[0739] 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, prallethrin, profenofos,
promecarb, propaphos, propargite, propetamphos, propoxur,
prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos,
pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphenthion,
pyridathion, pyrimidifen, pyriproxyfen,
[0740] quinalphos,
[0741] resmethrin, RH-5849, ribavirin, RU-12457, RU-15525,
[0742] S-421, S-1833, salithion, sebufos, SI-0009, silafluofen,
spinosad, spirodiclofen, spiromesifen, sulfluramid, sulfotep,
sulprofos, SZI-121,
[0743] 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, triflumuron, trimethacarb,
[0744] vamidothion, vaniliprole, verbutin, Verticillium
lecanii,
[0745] WL-108477, WL-40027,
[0746] YI-5201, YI-5301, YI-5302,
[0747] XMC, xylylcarb,
[0748] ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901,
[0749] the compound 3-methylphenyl propylcarbamate (Tsumacide
Z),
[0750] 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),
[0751] and preparations which contain insecticidally active plant
extracts, nematodes, fungi or viruses.
[0752] A mixture with other known active compounds, such as
herbicides, or with fertilizers and growth regulators, is also
possible.
[0753] In addition, the compounds of the formula (I)/active
compound combinations 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,
[0754] Microsporon species such as Microsporon canis and audouinii.
The listing of these fungi by no means limits the mycotic spectrum
that can be covered, but is only for illustration.
[0755] The active compounds/active compound combinations 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 further 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.
[0756] When using the active compounds/active compound combinations
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.
[0757] The preparation and the use of the active compounds/active
compound combinations according to the invention are illustrated by
the examples below.
PREPARATION EXAMPLES
Example I-1-a-1
##STR00108##
[0759] 4.88 g (0.042 mol) of potassium tert-butoxide are initially
charged in 13 ml of anhydrous dimethylformamide (DMF), 6.82 g of
Example II-1 in 14 ml of anhydrous DMF are added dropwise at
60.degree. C. and the mixture is stirred at 80.degree. C. and
monitored by thin-layer chromatography.
[0760] After the reaction has ended, the reaction solution is
poured into 150 ml of ice-water and, at 0 to 10.degree. C.,
acidified to pH=2 using concentrated hydrochloric acid, and the
precipitate is filtered off with suction, washed with ice-water and
then dried. This is followed by purification by silica gel column
chromatography (dichloromethane/acetone=5:1).
[0761] Yield: 2.5 g (40% of theory), m.p. 233.degree. C.
Example I-1-a-8
##STR00109##
[0763] Under argon protective gas, 0.644 g (2 mmol) of the compound
of Example XIV-1-1 is initially charged in 30 ml of xylene, 2.083 g
(20 mmol) of 1,2-pentanediol and 0.059 g (0.29 mmol) of
p-toluenesulphonic acid are added at room temperature, 0.5 g of
molecular sieve 4 .ANG. (powder) is added and the mixture is
stirred under reflux for three days and monitored by thin-layer
chromatography.
[0764] After reaction has ended, the solvent is distilled off. The
product is purified by silica gel column chromatography
(dichloromethane/acetone=5:1).
[0765] Yield: 0.27 g ( 35% of theory), m.p. 273.degree. C.
[0766] The following compounds of the formula (I-1-a) are obtained
analogously to Example (I-1-a-1) and in accordance with the general
statements on the preparation
TABLE-US-00009 (I-1-a) ##STR00110## Ex. No. W X Y Z A B m.p.
.degree. C. Isomer I-1-a-2 CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- >220 -- I-1-a-3 CH.sub.3 CH.sub.3
CH.sub.3 CH.sub.3 4'-O--(CH.sub.2).sub.2--O-- >240 -- I-1-a-4
CH.sub.3 CH.sub.3 Cl H 4'-O--(CH.sub.2).sub.2--O-- >240 --
I-1-a-5 H CH.sub.3 CH.sub.3 CH.sub.3 4'-O--(CH.sub.2).sub.2--O--
240 -- I-1-a-6 CH.sub.3 Cl Cl H 4'-O--(CH.sub.2).sub.2--O-- >245
-- I-1-a-7 CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--CHCH.sub.3--CHCH.sub.3--O-- * mixture I-1-a-8 CH.sub.3
CH.sub.3 CH.sub.3 H 4'-O--CHC.sub.3H.sub.7--CH.sub.2--O-- 273 A
logP 2.73 I-1-a-9 CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--CHC.sub.3H.sub.7--CH.sub.2--O-- decomp. B logP 2.78 I-1-a-10
CH.sub.3 CH.sub.3 CH.sub.3 H 4'-O--CHCH.sub.3--CHCH.sub.3--O-- 275
mixture I-1-a-11 CH.sub.3 Cl Cl H 4'-O--(CH.sub.2).sub.3--O-- 262
-- I-1-a-12 H CH.sub.3 H CH.sub.3 4'-O--(CH.sub.2).sub.3--O-- 166
-- I-1-a-13 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
4'-O--(CH.sub.2).sub.3--O-- 263 -- I-1-a-14 CH.sub.3 CH.sub.3 Cl H
4'-O--(CH.sub.2).sub.3--O-- 312 -- I-1-a-15 H Cl H 4-Cl--Ph
4'-O--(CH.sub.2).sub.3--O-- 133 -- I-1-a-16 H CH.sub.3 H 4-Cl--Ph
4'-O--(CH.sub.2).sub.3--O-- 210 I-1-a-17 H CH.sub.3 CH.sub.3
CH.sub.3 4'-O--(CH.sub.2).sub.3--O-- 189 -- I-1-a-18 CH.sub.3
CH.sub.3 CH.sub.3 H 4'-O--(CH.sub.2).sub.3--O-- 229 -- I-1-a-19
CH.sub.3 CH.sub.3 Br H 4'-O--(CH.sub.2).sub.3--O-- 255 -- I-1-a-20
CH.sub.3 CH.sub.3 Cl H
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- 273 -- I-1-a-21
CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3-- 265 mixture I-1-a-22
CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--CHCH.sub.3--C(CH.sub.2).sub.2--O-- 230 mixture I-1-a-23
CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- 230 -- I-1-a-24
CH.sub.3 OCH.sub.3 CH.sub.3 H 4'-O--(CH.sub.2).sub.3--O-- 202 --
I-1-a-25 CH.sub.3 C.sub.2H.sub.5 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- decomp. -- I-1-a-26 CH.sub.3 CH.sub.3
Br H 4'-O--(CH.sub.2).sub.2--O-- 306 -- I-1-a-27 H CH.sub.3 H
5-(4-Cl--Ph) 4'-O--(CH.sub.2).sub.2--O-- 154 -- I-1-a-28 H CH.sub.3
H CH.sub.3 4'-O--CHCH.sub.3--CH.sub.2--O-- wax mixture I-1-a-29 H
CH.sub.3 H CH.sub.3 4'-O--CHCH.sub.3--CHCH.sub.3--O-- 84 mixture I-
I-a-30 CH.sub.3 CH.sub.3 Cl H 4'-O--CHCH.sub.3--CHCH.sub.3--O-- 268
mixture I-1-a-31 CH.sub.3 CH.sub.3 Cl H
-4'O--CHCH.sub.3--CH.sub.2--O-- 301 mixture I-1-a-32 CH.sub.3
CH.sub.3 Br H 4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- 171 mixture
I-1-a-33 CH.sub.3 CH.sub.3 Br H
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- 266 -- I-1-a-34
CH.sub.3 CH.sub.3 Cl H 4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O--
265 mixture I-1-a-35 CH.sub.3 CH.sub.3 Cl H
4'-O--CHCH.sub.3--(CH.sub.2).sub.2 --O-- 243 mixture I-1-a-36 H
CH.sub.3 H CH.sub.3 4'O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- 161
mixture I-1-a-37 H CH.sub.3 H CH.sub.3
4'-O--CHCH.sub.3--(CH.sub.2).sub.2 --O-- oil mixture I-1-a-38
CH.sub.3 CH.sub.3 Cl H 4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O--
276 mixture I-1-a-39 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--(CH.sub.2).sub.2--O-- 293 -- I-1-a-40 C.sub.2H.sub.5
C.sub.2H.sub.5 CH.sub.3 H 4'-O--(CH.sub.2).sub.2--O-- 269 --
I-1-a-41 H CH.sub.3 Cl CH.sub.3 4'-O--(CH.sub.2).sub.2--O-- 236 --
I-1-a-42 C.sub.2H.sub.5 OCH.sub.3 Cl H 4'-O--(CH.sub.2).sub.2--O--
234 -- I-1-a-43 CH.sub.3 OCH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- 237 -- I-1-a-44 C.sub.2H.sub.5 Cl Cl H
4'-O--(CH.sub.2).sub.2--O-- 305 -- I-1-a-45 C.sub.2H.sub.5 CH.sub.3
Br H 4'-O--CHCH.sub.3--CHCH.sub.3--O-- 148 mixture I-1-a-46
CH.sub.3 CH.sub.3 Br H 4'-O--CHCH.sub.3--CHCH.sub.3--O-- 275
mixture I-1-a-47 CH.sub.3 CH.sub.3 Br H
4'-O--CHCH.sub.3--CH.sub.2--O-- 292 mixture I-1-a-48 C.sub.2H.sub.5
Br CH.sub.3 H 4'-O--(CH.sub.2).sub.2--O-- 296 -- I-1-a-49 H Cl H
4-Cl--Ph 4'-O--(CH.sub.2).sub.2--O-- 257 -- I-1-a-50 CH.sub.3
CH.sub.3 Br H ##STR00111## 116 mixture I-1-a-51 CH.sub.3 CH.sub.3 H
4-Cl--Ph 4'-O--CHCH.sub.3--CH.sub.2--O-- 288 mixture I-1-a-52 H
CH.sub.3 H 4-Cl--Ph 4'-O--CHCH.sub.3--CH.sub.2--O-- 198 mixture
I-1-a-53 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--CH.sub.2--O-- 255 mixture I-1-a-54 H CH.sub.3 H
4-Cl--Ph 4'-O--CHCH.sub.3--CHCH.sub.3--O-- 213 mixture I-1-a-55 H
CH.sub.3 Cl CH.sub.3 4'-O--CHCH.sub.3--CH.sub.2--O-- 272 mixture
I-1-a-56 CH.sub.3 CH.sub.3 Br H
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- 262 mixture I-1-a-57 H
Cl Cl H 4'-O--(CH.sub.2).sub.3--O-- 237 -- I-1-a-58 CH.sub.3
CH.sub.3 Br H 4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- 80 mixture
I-1-a-59 CH.sub.3 Cl Cl H
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- 264 -- I-1-a-60
CH.sub.3 C.sub.2H.sub.5 Br H 4'-O--CHCH.sub.3--(CH.sub.2).sub.2
--O-- 190 mixture I-1-a-61 H CH.sub.3 H CH.sub.3
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- 240 -- I-1-a-62 H
CH.sub.3 H CH.sub.3 4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- 276
mixture I-1-a-63 CH.sub.3 C.sub.2H.sub.5 Br H
4'O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- >300 mixture I-1-a-64
H Cl H 4-Cl--Ph 4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O--
276 -- I-1-a-65 H Cl H 4-Cl--Ph
4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- 79 mixture I-1-a-66 H
CH.sub.3 H 4-Cl--Ph 4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- 67
mixture I-1-a-67 H CH.sub.3 H 4-Cl--Ph
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- 234 -- I-1-a-68 H
CH.sub.3 H CH.sub.3 3'-O--(CH.sub.2).sub.2--O-- 211 -- I-1-a-69
C.sub.2H.sub.5 Br CH.sub.3 H 3'-O--(CH.sub.2).sub.2--O-- decomp. --
I-1-a-70 CH.sub.3 CH.sub.3 Cl H 3'-O--(CH.sub.2).sub.2--O-- 260 --
I-1-a-71 CH.sub.3 CH.sub.3 CH.sub.3 H ##STR00112## oil mixture
I-1-a-72 C.sub.2H.sub.5 Br CH.sub.3 H ##STR00113## oil mixture
I-1-a-73 H CH.sub.3 H CH.sub.3 ##STR00114## oil mixture I-1-a-74
CH.sub.3 CH.sub.3 Cl H ##STR00115## 82 mixture I-1-a-75 CH.sub.3
CH.sub.3 Cl H ##STR00116## 67 mixture I-1-a-76 H Cl H 4-Cl--Ph
4'-O--CHCH.sub.3--CH.sub.2--O-- 68 mixture I-1-a-77 C.sub.2H.sub.5
Br CH.sub.3 H 4'-O--CHCH.sub.3--CH.sub.2--O-- 281 mixture I-1-a-78
H Cl H 4-Cl--Ph 4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- 232 mixture
I-1-a-79 H Cl H 4-Cl--Ph 4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O--
160 mixture I-1-a-80 H Cl H 4-Cl--Ph
4'O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- 268 mixture I-1-a-81 H
Cl H 4-Cl--Ph 4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- 151
-- I-1-a-82 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--(CH.sub.2).sub.3--O-- 244 -- I-1-a-83 CH.sub.3 CH.sub.3 Cl H
3'-O--CHCH.sub.3--CH.sub.2--O-- 167 mixture I-1-a-84 CH.sub.3
CH.sub.3 Cl H 3'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- 266
mixture I-1-a-85 CH.sub.3 CH.sub.3 Cl H 3'-O--(CH.sub.2).sub.3--O--
261 mixture I-1-a-86 CH.sub.3 C.sub.2H.sub.5 4-Cl--Ph H
4'-O--CHCH.sub.3--CH.sub.2--O-- 219-222 mixture *.sup.1H-NMR (400
MHz, d.sub.6-DMSO): .delta. = 1.05-1.09 (2d, 6H, 2xCHCH.sub.3);
4.18-4.23 (m, 2H, 2xCHCH.sub.3) ppm decomp. = decomposition
##STR00117##
Example I-1-b-1
##STR00118##
[0768] 1.82 g of the compound of Example I-1-a-4 are initially
charged in 50 ml of anhydrous ethyl acetate and 0.77 ml (5.5 mmol)
of triethylamine under reflux. 0.55 ml (0.0055 mol) of isobutyryl
chloride in 5 ml of anhydrous ethyl acetate is added, and the
mixture is stirred under reflux.
[0769] After the reaction has ended (monitored by thin-layer
chromatography) the solvent is distilled off and the residue is
taken up in dichloromethane. The mixture is washed twice with 30 ml
of 0.5 N NaOH and dried, and the solvent is distilled off.
[0770] The product is purified by silica gel column chromatography
(dichloromethane/ethyl acetate=3:1).
[0771] Yield: 0.3 g (14% of theory), m.p. 215.degree. C.
[0772] The following compounds of the formula (I-1-b) are obtained
analogously to Example (I-1-b-1) and in accordance with the general
statements on the preparation
TABLE-US-00010 (I-1-b) ##STR00119## Ex. No. W X Y Z A B R.sup.1
m.p. .degree. C. Isomer I-1-b-2 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--(CH.sub.2).sub.2--O-- H.sub.3CO--CH.sub.2-- *3.23 (s, 3H,
OCH.sub.3) -- 7.21 (s, 2H, --Ar--H) I-1-b-3 CH.sub.3 C.sub.2H.sub.5
Br H 4'-O--(CH.sub.2).sub.2--O-- i-C.sub.3H.sub.7 solidified foam
-- I-1-b-4 C.sub.2H.sub.5 Cl Cl H 4'-O--(CH.sub.2).sub.2--O--
i-C.sub.3H.sub.7 106-112 -- I-1-b-5 C.sub.2H.sub.5 Br CH.sub.3 H
4'-O--CHCH.sub.3--CHCH.sub.3--O-- i-C.sub.3H.sub.7 198-200 mixture
I-1-b-6 C.sub.2H.sub.5 Cl Cl H 4'-O--(CH.sub.2).sub.2--O--
H.sub.3CO--CH.sub.2-- *2.63(m, 2H, Ar--CH.sub.2) -- 3.29(s, 3H,
OCH.sub.3) I-1-b-7 C.sub.2H.sub.5 OCH.sub.3 Cl H
4'-O--(CH.sub.2).sub.2--O-- H.sub.3CO--CH.sub.2-- 170-175 --
I-1-b-8 C.sub.2H.sub.5 Br CH.sub.3 H 3'-O--(CH.sub.2).sub.2--O--
i-C.sub.3H.sub.7 solidified foam -- **1.07(m, 6H,
CHCH.sub.2).sub.2) 2.28(s,3H, ArCH.sub.3) I-1-b-9 C.sub.2H.sub.5 Br
CH.sub.3 H 3'-O--(CH.sub.2).sub.2--O-- H.sub.3CO--CH.sub.2--
*2.29(s, 3H, Ar--CH.sub.3) -- 3.26(s, 3H, OCH.sub.3) I-1-b-10
C.sub.2H.sub.5 Br CH.sub.3 H ##STR00120## i-C.sub.3H.sub.7 oil
**1.05(m, 6H, CHCH.sub.3).sub.2) 2.29(s,3H,ArCH.sub.3) mixture
I-1-b-11 C.sub.2H.sub.5 Br CH.sub.3 H ##STR00121##
H.sub.3CO--CH.sub.2-- oil **2.29(s, 3H, ArCH.sub.3) 3.26(s, 3H,
OCH.sub.3) mixture I-1-b-12 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- ##STR00122## 225
mixture I-1-b-13 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- 2-Cl--Ph 225 mixture
I-1-b-14 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--CHCH.sub.3--O-- ##STR00123## 246 mixture I-1-b-15
CH.sub.3 C.sub.2H.sub.5 Br H ##STR00124## t-C.sub.4H.sub.9
solidified foam mixture I-1-b-16 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--CH.sub.2--O-- i-C.sub.3H.sub.7 194 mixture
I-1-b-17 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- i-C.sub.3H.sub.7 *1.06(m,
6H, CH(CH.sub.3).sub.2) 7.21(s, 2H, ArH) mixture I-1-b-18
C.sub.2H.sub.5 CH.sub.3 Br H 4'-O--CHCH.sub.3--CHCH.sub.3--O--
H.sub.3CO--CH.sub.2 *3.24(s,3H, OCH.sub.3) mixture 7.21(s,2H,
Ar--H) I-1-b-19 C.sub.2H.sub.5 CH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- i-C.sub.3H.sub.7 *0.98 (dd, 6H, --
CH(CH.sub.3).sub.2) 3.98 (m, 4H, CH.sub.2O) 6.86 (s, 2H, Ar--H)
I-1-b-20 C.sub.2H.sub.5 CH.sub.3 Br H
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- i-C.sub.3H.sub.7 120
mixture *.sup.1H-NMR (400 MHz, CDCl.sub.3); shifts .delta. in ppm
**.sup.1H-NMR (300 MHz, CDC1.sub.3): shifts .delta. in ppm
Example I-1-c-1
##STR00125##
[0774] 1.82 g of the compound of Example I-1-a-4 are stirred at 10
to 20.degree. C. in 30 ml of anhydrous dichloromethane and 0.7 ml
of triethylamine. 0.5 ml of ethyl chloroformate in 2 ml of
anhydrous dichloromethane is added, and the mixture is stirred at
room temperature.
[0775] After the reaction has ended (monitored by thin-layer
chromatography), the mixture is washed twice with 10 ml of 0.5 N
NaOH and dried over magnesium sulphate. The solvent is then
distilled off.
[0776] The product is purified by silica gel column chromatography
(dichloromethane/ethanol=30:1).
[0777] Yield: 1.15 g (52% of theory), m.p. 198.degree. C.
[0778] The following compounds of the formula (I-1-c) are obtained
analogously to Example (I-1-c-1) and in accordance with the general
statements on the preparation:
TABLE-US-00011 (I-1 -C) ##STR00126## Ex. No. W X Y Z A B M R2 m.p.
.degree. C. Isomer I-1-c-2 CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 181 -- I-1-c-3 H
CH.sub.3 CH.sub.3 CH.sub.3 4'-O--(CH.sub.2).sub.2--O-- O
C.sub.2H.sub.5 221 -- I-1-c-4 CH.sub.3 Cl Cl H
4'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 233 -- I-1-c-5
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 4'-O--(CH.sub.2).sub.2--O-- O
C.sub.2H.sub.5 209 -- I-1-c-6 CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--CHCH.sub.3--CH.sub.2--O-- O C.sub.2H.sub.5 218 mixture
I-1-c-7 CH.sub.3 Cl Cl H 4'---O--(CH.sub.2).sub.3--O-- O
C.sub.2H.sub.5 235 -- I-1-c-8 CH.sub.3 CH.sub.3 Cl H
4'-O--(CH.sub.2).sub.3--O-- O C.sub.2H.sub.5 195 -- I-1-c-9 H
CH.sub.3 CH.sub.3 CH.sub.3 4'-O--(CH.sub.2).sub.3--O-- O
C.sub.2H.sub.5 235 -- I-1-c-10 CH.sub.3 CH.sub.3 Br H
4'-O--(CH.sub.2).sub.3--O-- O C.sub.2H.sub.5 234 -- I-1-c-11
CH.sub.3 CH.sub.3 CH.sub.3 H 4'-O--(CH.sub.2).sub.3--O-- O
C.sub.2H.sub.5 229 -- I-1-c-12 CH.sub.3 CH.sub.3 Cl H
4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- O C.sub.2H.sub.5 241
mixture I-1-c-13 CH.sub.3 CH.sub.3 Cl H
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- O C.sub.2H.sub.5
247 -- I-1-c-14 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 200-201 -- I-1-c-15
CH.sub.3 C.sub.2H.sub.5 CH.sub.3 H 4'-O--(CH.sub.2).sub.2--O-- O
C.sub.2H.sub.5 oil -- I-1-c-16 H CH.sub.3 H 4-Cl--Ph
4'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 197 -- I-1-c-17
CH.sub.3 CH.sub.3 Cl H 4'-O--CHCH.sub.3--CH.sub.2--O-- O
C.sub.2H.sub.5 223 mixture I-1-c-18 CH.sub.3 CH.sub.3 Cl H
4'-O--CHCH.sub.3--CHCH.sub.3--O-- O C.sub.2H.sub.5 232 mixture
I-1-c-19 H CH.sub.3 H CH.sub.3 4'-O--CHCH.sub.3--CH.sub.2--O-- O
C.sub.2H.sub.5 141 mixture I-1-c-20 CH.sub.3 CH.sub.3 Br H
4'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 222 -- I-1-c-21 H
CH.sub.3 Cl CH.sub.3 4'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5
187 -- I-1-c-22 H CH.sub.3 H CH.sub.3
4'-O--CHCH.sub.3--CHCH.sub.3--O-- O C.sub.2H.sub.5 180 mixture
I-1-c-23 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 179 -- I-1-c-24
CH.sub.3 O--CH.sub.3 CH.sub.3 H 4'-O--(CH.sub.2).sub.2--O-- O
C.sub.2H.sub.5 176 -- I-1-c-25 C.sub.2H.sub.5 O--CH.sub.3 Cl H
4'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 **1.16 -- (,,q'', 6H,
--Ar--CH.sub.2--CH.sub.3 and O--CH.sub.2--CH.sub.3) 3.79 (s, 3H,
Ar--OCH.sub.3) I-1-c-26 C.sub.2H.sub.5 Cl Cl H
4'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 175-183 -- I-1-c-27
CH.sub.3 C.sub.2H.sub.5 Br H 4'-O--CHCH.sub.3--CH.sub.2--O-- O
C.sub.2H.sub.5 181 mixture I-1-c-28 C.sub.2H.sub.5 Cl Cl H
4'-O--(CH.sub.2).sub.2--O-- O C.sub.6H.sub.5--CH.sub.2-- 173 --
I-1-c-29 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--CHCH.sub.3--O-- O CH.sub.2.dbd.CH--CH.sub.2-- 187
mixture I-1-c-30 CH.sub.3 CH.sub.3 Cl H
4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 229
mixture I-1-c-31 H CH.sub.3 H 4-Cl--Ph 4'-O--(CH.sub.2).sub.3--O--
O C.sub.2H.sub.5 207 -- I-1-c-32 CH.sub.3 CH.sub.3 Br H
4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- O C.sub.2H.sub.5 242
mixture I-1-c-33 CH.sub.3 CH.sub.3 Br H
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- O C.sub.2H.sub.5
250 -- I-1-c-34 CH.sub.3 O--CH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.3--O-- O C.sub.2H.sub.5 222 -- I-1-c-35 H
CH.sub.3 H CH.sub.3
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- O C.sub.2H.sub.5
194 -- I-1-c-36 H CH.sub.3 H CH.sub.3 4'-O--CH.sub.2--CHCH.sub.3
--CH.sub.2--O-- O C.sub.2H.sub.5 169 mixture I-1-c-37 CH.sub.3
C.sub.2H.sub.5 Br H 4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- O
C.sub.2H.sub.5 175-178 mixture I-1-c-38 CH.sub.3 C.sub.2H.sub.5 Br
H 4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 97
mixture I-1-c-39 H Cl H 4-Cl--Ph 4'-O--(CH.sub.2).sub.3--O-- O
C.sub.2H.sub.5 237 -- I-1-c-40 H CH.sub.3 H CH.sub.3
3'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 156 -- I-1-c-41
CH.sub.3 CH.sub.3 Cl H 3'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5
193 -- I-1-c-42 C.sub.2H.sub.5 Br CH.sub.3 H
3'-O--(CH.sub.2).sub.2--O-- O C.sub.2H.sub.5 **2.58 -- (m, 2H,
Ar--CH.sub.2--), 4.08 (q, 2H, OCH.sub.2--CH.sub.3) I-1-e-43
C.sub.2H.sub.5 Br CH.sub.3 H ##STR00127## O C.sub.2H.sub.5
oil**1.18 (,,q'', 6H, Ar--CH.sub.2--CH.sub.3 and
O--CH.sub.2--CH.sub.3) 2.32 (s, 3H, Ar--CH.sub.3) mixture I-1-c-44
C.sub.2H.sub.5 Br CH.sub.3 H 3'-O--(CH.sub.2).sub.2--O-- O
(H.sub.3C).sub.3 foam -- C--CH.sub.2-- **0.8 (s, 9H,
C(CH.sub.3).sub.3) 2.28 (s, 3H, Ar--CH.sub.3) I-1-c-45 H Cl H
4-Cl--Ph 4'-O--CHCH.sub.3--CH.sub.2--O-- O C.sub.2H.sub.5 219
mixture I-1-c-46 H Cl H 4-Cl--Ph 4'-O--(CH.sub.2).sub.2--O-- O
C.sub.2H.sub.5 239 -- *.sup.1H-NMR (400 MHz, CDCl.sub.3): shifts
.delta. in ppm **.sup.1H-NMR (300 MHz, CDCl.sub.3): shifts .delta.
in ppm
Example I-1-d-1
##STR00128##
[0780] 0.159 g of the compound of Example I-1-a-44 is initially
charged in 10 ml of trichloromethane, 0.098 ml of
diisopropylethylamine and 1.5 mg of DMAP are added at room
temperature, 0.037 ml of methanesulphonyl chloride is added and the
mixture is stirred for 20 hours, 5 ml of NaCl solution are added,
the mixture is stirred at room temperature for about 0.5 hours and
the organic phase is separated off, dried with sodium sulphate and
concentrated using a rotary evaporator. The resulting crude product
is purified by column chromatography on silica gel using an
n-heptane/ethyl acetate gradient of from 4:1 to 0:100.
[0781] Yield: 0.07 g (37% of theory), m.p.: 217.degree. C.
Example I-1-g-1
##STR00129##
[0783] 0.233 g of the compound of Example I-1-a-72 is initially
charged in 8 ml of chloroform, 0.098 ml of diisopropylethylamine
and 1.5 mg of DMAP are added, 0.056 ml of morpholinecarbonyl
chloride is then added, the mixture is stirred at room temperature
for 20 hours, 5 ml of 5% strength sodium bicarbonate solution are
added, the mixture is stirred for another 0.5 hours and the organic
phase is separated off, dried with sodium sulphate and concentrated
using a rotary evaporator. The crude product is purified by column
chromatography on silica gel using an n-heptane/ethyl acetate
gradient from 4:1 to 0:100.
[0784] Yield: 0.148 g (64% of theory), oil
[0785] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta.=2.31 (2, 3H,
Ar--CH.sub.3), 3.1, 3.2 (each m, 2H, CH.sub.2O) ppm.
Example II-1
##STR00130##
[0787] 9.56 g of 8-aminomethyl
1,4-dioxaspiro[4.5]decane-8-carboxylate hydrochloride are initially
charged in 38 ml of anhydrous acetonitrile, and 17.5 g (0.127 mol)
of ground potassium carbonate are added at from 5 to 10.degree. C.
6.94 g of 2,5-dimethylphenylacetyl chloride in 10 ml of anhydrous
acetonitrile are then added dropwise over a period of 12
minutes.
[0788] The mixture is stirred at room temperature for 3 h.
[0789] The reaction solution is poured into 250 ml of ice-water,
and the precipitate is filtered off with suction. The precipitate
is washed with water and taken up in dichloromethane, the mixture
is dried and the solvent is distilled off. The product is purified
by column chromatography on silica gel (dichloromethane/ethyl
acetate=3:1).
[0790] Yield: 6.82 g (49% of theory), m.p. 115.degree. C.
Example (II-2)
##STR00131##
[0792] 154.6 g (1.579 mol) of concentrated sulphuric acid are
initially charged, and at an internal temperature of from 30 to
40.degree. C., 107.9 g of the compound of Example (XXI-1) in 630 ml
of methylene chloride are added dropwise as a suspension. The
mixture is stirred at from 30 to 40.degree. C. for 2 h, and 220 ml
of anhydrous methanol are then added dropwise such that an internal
temperature of 40.degree. C. is obtained.
[0793] The mixture is stirred at an external temperature of 40 to
70.degree. C. for a further 6 h.
[0794] The reaction solution is poured onto 1.5 kg of ice,
extracted with dichloromethane and washed with NaHCO.sub.3
solution. The mixture is dried and the solvent is distilled
off.
[0795] The product is purified by column chromatography on silica
gel (toluene/ethyl acetate=1:1).
[0796] Yield: 11.4 g (10% of theory).
[0797] The following compounds of the formula (II) are obtained
analogously to Examples (II-1) and (II-2) and in accordance with
the general statements on the preparation
TABLE-US-00012 (II) ##STR00132## Ex. No. W X Y Z A B R.sup.8 m.p.
.degree. C. II-2 CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 log P 2.68 II-3 CH.sub.3
CH.sub.3 CH.sub.3 CH.sub.3 4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 141
II-4 CH.sub.3 CH.sub.3 Cl H 4'-O--(CH.sub.2).sub.2--O-- CH.sub.3
181 II-5 H CH.sub.3 CH.sub.3 CH.sub.3 4'-O--(CH.sub.2).sub.2--O--
CH.sub.3 129 II-6 CH.sub.3 Cl Cl H 4'-O--(CH.sub.2).sub.2--O--
CH.sub.3 159 II-7 CH.sub.3 CH.sub.3 Br H
4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 wax log P 2.81* II-8 CH.sub.3
C.sub.2H.sub.5 CH.sub.3 H 4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 wax
log P 2.95* II-9 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 wax log P 3.19* II-11 CH.sub.3
Cl Cl H 4'-O--(CH.sub.2).sub.3--O-- CH.sub.3 175 II-12 H CH.sub.3 H
CH.sub.3 4'-O--(CH.sub.2).sub.3--O-- CH.sub.3 144 II-13 CH.sub.3
CH.sub.3 CH.sub.3 CH.sub.3 4'-O--(CH.sub.2).sub.3--O-- CH.sub.3 148
II-14 CH.sub.3 CH.sub.3 Cl H 4'-O--(CH.sub.2).sub.3--O-- CH.sub.3
184 II-15 H Cl H 4-Cl--Ph 4'-O--(CH.sub.2).sub.3--O-- CH.sub.3 177
II-16 H CH.sub.3 H 4-Cl--Ph 4'-O--(CH.sub.2).sub.3--O-- CH.sub.3
181 II-17 H CH.sub.3 CH.sub.3 CH.sub.3 4'-O--(CH.sub.2).sub.3--O--
CH.sub.3 log P 2.59* II-18 CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.3--O-- CH.sub.3 143 II-19 CH.sub.3 CH.sub.3 Br
H 4'-O--(CH.sub.2).sub.3--O-- CH.sub.3 189 II-20 CH.sub.3 CH.sub.3
Cl H 4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- CH.sub.3 178
II-21 CH.sub.3 CH.sub.3 Cl H
4'-O--CH.sub.2-CHCH.sub.3--CH.sub.2--O-- CH.sub.3 170 II-22
CH.sub.3 CH.sub.3 Br H
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- CH.sub.3 181 II-23
CH.sub.3 CH.sub.3 Br H 4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O--
CH.sub.3 177 II-24 CH.sub.3 OCH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.3--O-- CH.sub.3 log P 2.49* II-25 CH.sub.3
CH.sub.3 Br H 4'-O--CHCH.sub.3--CHCH.sub.3--O-- CH.sub.3 189 II-26
CH.sub.3 CH.sub.3 Br H 4'-O--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 161
II-27 H CH.sub.3 H CH.sub.3 4'-O--CHCH.sub.3--CHCH.sub.3--O--
CH.sub.3 166 II-28 CH.sub.3 CH.sub.3 Cl H
4'-O--CHCH.sub.3--CHCH.sub.3--O-- CH.sub.3 183 II-29 CH.sub.3
CH.sub.3 Cl H 4'-O--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 170 II-30 H
CH.sub.3 H CH.sub.3 4'-O--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 141
II-31 H CH.sub.3 H 5-(4-Cl--Ph 4'-O--(CH.sub.2).sub.2--O-- CH.sub.3
log P 3.47* II-32 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 log P 3.28* II-33 CH.sub.3
OCH.sub.3 CH.sub.3 H 4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 139 II-34
H CH.sub.3 Cl CH.sub.3 4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 182
II-35 C.sub.2H.sub.5 OCH.sub.3 Cl H 4'-O--(CH.sub.2).sub.2--O--
CH.sub.3 153 II-36 C.sub.2H.sub.5 Br CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 log P 3.04* II-37 H CH.sub.3 H
CH.sub.3 4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- CH.sub.3 122
II-38 CH.sub.3 CH.sub.3 Cl H 4
'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- CH.sub.3 208 II-39 H
CH.sub.3 H CH.sub.3 4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O--
CH.sub.3 144 II-40 CH.sub.3 CH.sub.3 Cl H
4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- CH.sub.3 174 II-41 CH.sub.3
CH.sub.3 Br H 4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- CH.sub.3 175
II-42 CH.sub.3 CH.sub.3 Br H
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- CH.sub.3 202 II-43
CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- CH.sub.3 200 II-44 H
CH.sub.3 H CH.sub.3
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- CH.sub.3 157 II-45
H CH.sub.3 H CH.sub.3 4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O--
CH.sub.3 154 II-46 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- CH.sub.3 158 II-47 CH.sub.3
Cl Cl H 4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- CH.sub.3
197 II-48 CH.sub.3 Cl Cl H
4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 174 II-49 H Cl H
4-Cl--Ph 4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- CH.sub.3
205 II-50 H Cl H 4-Cl--Ph 4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O--
CH.sub.3 166 II-51 H CH.sub.3 H 4-Cl--Ph
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- CH.sub.3 184 II-52
H CH.sub.3 H 4-Cl--Ph 4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O--
CH.sub.3 163 II-53 H CH.sub.3 H 4-Cl--Ph
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- CH.sub.3 149 II-54
CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CH2--C(CH.sub.3).sub.2--CH.sub.2--O-- CH.sub.3 241 II-55
CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 147 II-56
CH.sub.3 C.sub.2H.sub.5 Br H 4'-O--CHCH.sub.3--CH.sub.2--O--
CH.sub.3 157 II-57 CH.sub.3 C.sub.2H.sub.5 Br H
4'-O--CHCH.sub.3--CHCH.sub.3--O-- CH.sub.3 167 II-58 C.sub.2H.sub.5
Cl Cl H 4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 281 II-59 H Cl H
4-Cl--Ph 4'-O--(CH.sub.2).sub.2--O-- CH.sub.3 II-60 CH.sub.3
CH.sub.3 H 4-Cl--Ph 4'-O--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 173
II-61 H CH.sub.3 Cl CH.sub.3 4'-O--CHCH.sub.3--CH.sub.2--O--
CH.sub.3 165 II-62 H CH.sub.3 H 4-Cl--Ph 4'-O--CHCH.sub.3--CH2--O--
CH.sub.3 174 II-63 H CH.sub.3 H 4-Cl--Ph
4'-O--CHCH.sub.3--CHCH.sub.3--O-- CH.sub.3 151 II-64 H Cl H
4-Cl--Ph 4'-O--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 181 II-65 H Cl H
4-Cl--Ph 4'-O--CHCH.sub.3--CHCH.sub.3--O-- CH.sub.3 182 II-66 H
CH.sub.3 H CH.sub.3 3'-O--(CH.sub.2).sub.2--O-- CH.sub.3 111 II-67
C.sub.2H.sub.5 Br CH.sub.3 H 3'-O--(CH.sub.2).sub.2--O-- CH.sub.3
174 II-68 CH.sub.3 CH.sub.3 Cl H 3'-O--(CH.sub.2).sub.2--O--
CH.sub.3 154 II-69 CH.sub.3 CH.sub.3 Cl H ##STR00133## CH.sub.3 oil
II-70 CH.sub.3 CH.sub.3 CH.sub.3 H ##STR00134## CH.sub.3 oil II-71
H CH.sub.3 H CH.sub.3 ##STR00135## CH.sub.3 oil II-72
C.sub.2H.sub.5 Br CH.sub.3 H ##STR00136## CH.sub.3 oil II-73
C.sub.2H.sub.5 Br CH.sub.3 H 4'-O--CHCH.sub.3--CH.sub.2--O--
CH.sub.3 143 II-74 H Cl H 4-Cl--Ph
4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 169 II-75
CH.sub.3 C.sub.2H.sub.5 Br H 4'-O--(CH.sub.2).sub.3--O-- CH.sub.3
165 II-76 H Cl H 4-Cl--Ph 4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O--
CH.sub.3 161 II-77 H Cl H 4-Cl--Ph
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- CH.sub.3 74 II-78
C.sub.2H.sub.5 Br CH.sub.3 H
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- CH.sub.3 84 *The log P
values given in the Preparation Examples and Tables above are
determined in accordance with EEC Directive 79/831 Annex V.A8 by
HPLC (High Performance Liquid Chromatography) on a reversed-phase
column (C 18). Temperature: 43.degree. C.
[0798] In the acidic range, the determination is carried out at pH
2.3 using 0.1% aqueous phosphoric acid and acetonitrile as mobile
phases; linear gradient from 10% acetonitrile to 95%
acetonitrile.
[0799] The determination by LC-MS in the acidic range is carried
out at pH 2.7 using 0.1% aqueous formic acid and acetonitrile
(comprises 0.1% formic acid) as mobile phases; linear gradient from
10% acetonitrile to 95% acetonitrile.
[0800] The determination by LC-MS in the neutral range is carried
out at pH 7.8 using 0.001 molar aqueous ammonium bicarbonate
solution and acetonitrile as mobile phases; linear gradient from
10% acetonitrile to 95% acetonitrile.
[0801] Calibration is carried out using unbranched alkan-2-ones
(having 3 to 16 carbon atoms) with known logP values (determination
of the logP values by the retention times using linear
interpolation between two successive alkanones).
[0802] The lambda-max values were determined in the maxima of the
chromatographic signals using the UV spectra from 200 nm to 400
nm.
Example (XXL-1)
##STR00137##
[0804] 49.4 ml of triethylamine are added to 65 g of
1,4-dioxaspiro[4.5]decane-8-amino-8-carbonitrile in 800 ml of
anhydrous tetrahydrofuran (THF). At 0 to 10.degree. C., 70.2 g of
mesitylene acetyl chloride in 80 ml of anhydrous THF are added
dropwise.
[0805] The mixture is stirred at room temperature.
[0806] After the reaction has ended (monitored by thin-layer
chromatography), the reaction solution is added with stirring to
1.2 l of ice-water, 200 ml of 1N HCl are added and the precipitate
is filtered off with suction. The latter is taken up in
dichloromethane, and the aqueous phase is removed. The organic
phase is dried, the solvent is distilled off and the residue is
recrystallized from 320 ml of toluene/640 ml of n-hexane.
[0807] Yield: 107.9 g (88% of theory), m.p. >220.degree. C.
Example XIV-1-1
##STR00138##
[0809] At room temperature, 20.6 g of the compound of Example
I-1-c-2 in 24 g of semiconcentrated aqueous sodium hydroxide
solution and about 100 ml of ethanol are stirred under argon
protective gas for one hour, and the ethanol is then evaporated
off. The solution is then acidified using hydrochloric acid, the
entire mixture is dissolved in methylene chloride and the organic
phase is separated off and concentrated by evaporation. The residue
is stirred at 60.degree. C. in 4 N hydrochloric acid for two
hours.
[0810] The precipitate is separated off and stirred in ethyl
acetate.
[0811] Yield: 6.67 g; m.p.: 293.9.degree. C.
Example XVI-1
##STR00139##
[0813] 46 g of 1,4-dioxa[4.5]decane-8-amino-8-carboxylic acid are
initially charged in 350 ml of anhydrous methanol, and 32.6 g
(0.275 mol) of thionyl chloride are added dropwise at from 0 to
5.degree. C. The mixture is stirred at 0.degree. C. for 30 minutes
(suspension) and then at 40.degree. C. overnight.
[0814] The mixture is cooled, the potassium chloride is filtered
off with suction and the solvent is distilled off. The residue is
triturated with MTB ether and filtered off with suction.
[0815] Yield: 48.63 g (83% of theory), m.p.: decomposition
[0816] The following novel compounds of the formula (XVI) are
obtained analogously to Example XVI-1
TABLE-US-00013 (XVI) ##STR00140## Ex. No. A B R.sup.8 m.p. .degree.
C. XVI-2 4'-O--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 * 1.18-1.19 (2d,
3H, CHCH.sub.3) 3.76 (2s, 3H, OCH.sub.3) XVI-3
4'-O--CHCH.sub.3--CHCH.sub.3--O-- CH.sub.3 * 3.76 (s, 3H,
OCH.sub.3) 4.18-4.23 (m, 2H, 2xCH--O) XVI
4'-O--(CH.sub.2).sub.3--O-- CH.sub.3 resin XVI-5
4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- CH.sub.3 * 1.07-1.08 (d,
3H, CHCH.sub.3) 3.77 (s, 3H, OCH.sub.3) XVI-6
--O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- CH.sub.3 * 0.77 (d, 3H,
CHCH.sub.3) 8.71 (3H, br, NH.sub.3+) XVI-7
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- CH.sub.3 * 1.07-1.15
(m, 6H, 2xCHCH.sub.3) 3.93-4.0 (m, 2H, O--CH) XVI-8
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- CH.sub.3 * 0.9 (s,
6H, C(CH.sub.3).sub.2) 3.76 (s, 3H, OCH.sub.3) XVI-9
3'-O--(CH).sub.2--O-- CH.sub.3 * 3.74, 3.75 (2s, 3H,
CO.sub.2CH.sub.3) 3.79-3.99 (m, 4H, --O--(CH.sub.2).sub.2--O--)
XVI-10 ##STR00141## CH.sub.3 * 3.28 (2s, 3H, OCH.sub.3) 3.73-3.75
(4s, 3H, CO.sub.2CH.sub.3) * .sup.1H-NMR (400 MHz, d.sub.6-DMSO):
shift .delta. in ppm
[0817] The substituted 1,4-dioxa[4,5]decane-8-amino-8-carboxylic
esters and their salts of the formula (XVI'), the optionally
substituted 1,4-dioxa[4,5]decane-7-amino-7-carboxylic esters and
their salts of the formula (XVI'') and the optionally substituted
1,5-dioxa[5,5]undecane-9-amino-9-carboxylic esters and their salts
of the formula (XVI'''), possible substituents being the
substituents mentioned at the outset in the definition of A, B, are
novel and form part of the subject-matter of the invention:
##STR00142##
in which [0818] Q.sup.3 represents C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, [0819] q represents
1, 2 or 3 and, in the case of the compounds of the formulae (XVI'')
and (XVI'''), may also represent 0, [0820] R.sup.8 is as defined
above.
Example XIX-1
##STR00143##
[0822] 112 g of the compound of Example are suspended in 710 ml of
30% strength KOH and, under reflux, stirred under an atmosphere of
nitrogen.
[0823] At from 0 to 20.degree. C., the mixture is acidified with
concentrated HCl to a pH of from 5.2 to 5.3 and filtered off with
suction, the filtrate is subjected to an azeotropic distillation
with methanol until a volume of about 0.5 l is obtained, the
potassium chloride is filtered off with suction and the filtrate is
concentrated using a rotary evaporator and dehydrated
azeotropically with methanol.
[0824] Yield: 46 g (46% of theory).
[0825] The following novel compounds of the formula (XIX) are
obtained analogously to Example XIX-1
TABLE-US-00014 (XIX) ##STR00144## Ex. No. A B XIX-2
4'-O--CHCH.sub.3--CH.sub.2--O-- XIX-3
4'-O--CHCH.sub.3--CHCH.sub.3--O-- XIX-4 4'-O--(CH.sub.2).sub.3--O--
XIX-5 4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- XIX-6
4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- XIX-7
4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- XIX-8
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- XIX-9
3'--O--(CH.sub.2).sub.2--O-- XIX-10 ##STR00145##
[0826] Without further purification, the amino acids were directly
esterified to give the compounds (XVI). These were characterized.
The substituted 1,4-dioxa[4,5]decane-8-amino-8-carboxylic acids
(XIX'), the optionally substituted
1,4-dioxa[4,5]decane-7-amino-7-carboxylic acids of the formula
(XIX'') and the optionally substituted
1,5-dioxa[5,5]undecane-9-aminocarboxylic acids of the formula
(XIX'''), possible substituents of which are the substituents
mentioned at the outset in the definition of the radicals A, B, are
novel and also form part of the subject-matter of the
invention:
##STR00146##
in which [0827] Q.sup.3 is as defined above and [0828] q represents
1, 2 or 3 and, in the case of the compounds of the formulae (XIX'')
and (XIX'''), also 0.
Example XXIII-1
##STR00147##
[0830] 16.4 g (335 mmol) of sodium cyanide and 128.7 g (1339 mmol)
of ammonium carbonate are initially charged in 600 ml of water and,
at room temperature, 57 g (335 mmol) of
1,4-dioxa[4,5]decane-2-methyl-8-one (XXIV-1), dissolved in 30 ml of
ethanol, are slowly added dropwise.
[0831] The mixture is stirred at from 55 to 60.degree. C. for about
12 to 15 hours.
[0832] The mixture is cooled to 0.degree. C., the solid is filtered
off with suction and resuspended in water, the suspension is
filtered off with suction and the product is washed with hexane and
dried.
[0833] Yield: 73.6 g (92% of theory). 2 Isomers 1:1.
[0834] The following novel compounds of the formula (XXIII) are
obtained analogously to Example (XXIII-1)
TABLE-US-00015 (XXIII) ##STR00148## Ex. No. A B .sup.1H-NMR (400
MHz) Shifts .delta. in ppm XXIII-1 4 '-O--CHCH.sub.3--CH.sub.2--O--
d.sub.6-DMSO 10.53 (s); 8.35 (s); 4.15 (m, 1H); 4.02 (m, 1H); 3.37
(m, 1H); 1.93-1.50 (6m, 8H); 1.18 (dd, J = 6.2 Hz, 6.5 Hz. 3H)
XXIII-2 4'-O--CHCH.sub.3--CHCH.sub.3--O-- d.sub.6-DMSO 10.52 (s);
8.35 (s); 4.18 (m) + 3.59 (m): .SIGMA.2H; 1.90-1.50 (bm,
.SIGMA.8H); 1.18 (dd, 2 diastereomers 2:1 J = 6.3Hz, 5.8 Hz) + 1.06
(dd, J = 6.1 Hz, 7.7 Hz): .SIGMA.6H XXIII-3
4'-O--(CH.sub.2).sub.3--O-- d.sub.6-DMSO 10.50 (s); 8.35 (s); 3.81
(m, 4H); 2.12 (m, 2H); 1.78 (m, 2H); 1.60 (m, 4H); 1.48 (m, 2H)
XXIII-4 4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- d.sub.6-DMSO 10.50
(s); 8.31/8.30 (each s.); 4.09-3.67 2 diastereomers (6m, 3H); 2.54
(m, 1H); 1.88 (m, 1H); 1.76-1.39 (6m, 8H); 1.08 (dd, J = 6 Hz)
XXIII-5 4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- d.sub.6-DMSO
10.51 (s); 8.34 (s); 3.73 (m,2H); 3.51 (dd, J = 9.7 Hz, 11.5 Hz,
1H); 3.43 (dd, J = 9.7 Hz, 11.5 Hz, 1H); 2.41 (m, 1H); 1.88-1.41
(bm, 8H); 0,76 (d, J = 6.8 Hz, 3H) XXIII-6 4
'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- d.sub.6-DMSO 10.53 (s);
8.28 (s); 4.02 + 3.92 (each m, 2 diastereomers 2:1 .SIGMA.2H); 1.95
(6m) + 1.75-1.40 (bm): .SIGMA.10H; 1.12 (dd, J = 6.3 Hz, 10,8 Hz) +
1,08 (dd, J = 6.1 Hz, 11.3 Hz): .SIGMA.6H XXIII-7
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- d.sub.6-DMSO 10.50
(s); 8.34 (s); 3.45 (s, 2H); 3.43 (s, 2H); 2.11 (m, 2H); 1.78 (m,
2H); 1.62 (m, 2H); 1.50 (m, 2H); 0.89 (s, 6H) XXIII-8
3'-O--(CH.sub.2).sub.2--O-- d.sub.6-DMSO 10.6 (bm, 1H), 7.32 (bm,
1H), 3.9 (m, 4H), 1.71 (m, 4H), 1.61 (m, 1H), 1.52 (m, 3H) XXIII-9
##STR00149## d.sub.6-DMSO isomer mixtures 10.5 (bm ), 7.16 (bm),
6.98 (bm), 6.87 (bm), 6.60 (bm), 4.22 (m), 4.01 (m), 3.64 (m), 3.34
(m), 3.27 (m), 3.17 (s), 2.40 (m), 2.22 (m), 2.01 (m), 1.90-1.60
(bm)
[0835] The compounds of the formulae (XXIII'), (XXIII'') and
(XXIII''')
##STR00150##
in which [0836] Q.sup.3 is as defined above and [0837] q represents
1, 2 or 3 and, in the case of the compounds of the formulae
(XXIII'') and (XXIII'''), may also represent 0, are novel and form
part of the subject-matter of the invention.
Example XXIV-1
##STR00151##
[0839] 53.7 g (423 mmol) of oxalyl chloride are initially charged
in 1000 ml of dichloromethane. At -70.degree. C., a solution of 60
ml of dimethyl sulphoxide in 100 ml of dichloromethane is added
dropwise, and the mixture is stirred for 20 min. 66 g (385 mmol) of
1,4-dioxa[4,5]decane-2-methyl-8-ol are dissolved in 300 ml of
dichloromethane and, at the same temperature, added dropwise over a
period of 1 h to the reaction solution. The mixture is stirred for
another hour, the ice bath is then removed and the mixture is
allowed to warm to -40.degree. C. over a period of 30 min. The
mixture is stirred at this temperature for 30 min, triethylamine
(140 ml) is then added and the mixture is allowed to warm to room
temperature (1 h) and stirred overnight.
[0840] The reaction is quenched with 500 ml of water and the
mixture is stirred for another 15 minutes.
[0841] The organic phase is separated off and the aqueous solution
is extracted 3.times. with 200 ml of dichloromethane. The combined
organic phases are dried with sodium sulphate and the solvent is
distilled off. Purification by chromatography on silica gel,
hexane/ethyl acetate 2:1.
[0842] Yield: 58 g (88% of theory)
[0843] .sup.1H-NMR (400 MHz, d.sub.6-DMSO): .delta.=4.24 (m, 1H),
3.46 (t, 1H), 4.10 (dd, 1H), 2.36 (m, 4H), 1.94 (m, 4H), 1.23 (d,
3H) ppm.
Example XXIV-7
##STR00152##
[0845] 50 g of cyclohexane-1,3-dione, 27.67 g of 1,2-ethanediol,
500 ml of toluene and 0.849 g of 4-toluenesulphonic acid
monohydrate are mixed and, on a water separator, boiled under
reflux for 3 to 4 h. The mixture is washed with 100 ml of sat.
NaHCO.sub.3 solution and 2.times. with sat. NaCl solution, dried
and concentrated using a rotary evaporator. The mixture is then
subjected to fractional distillation under high vacuum
(distillation of the product at 85.degree. C./1 mbar or
62-75.degree. C./0.15 mmHg).
[0846] Yield: 21.9 g (27% of theory)
[0847] .sup.1H-NMR (400 MHz, CD.sub.3CN): .delta.=3.9 (m, 4H), 2.52
(s, 2H), 2.27 (m, 2H), 1.87 (m, 2H), 1.79 (m, 2H) ppm.
[0848] The following novel compounds of the formula (XXIV) are
obtained analogously to Examples (XXIV-1) and (XXIV-7)
TABLE-US-00016 (XXIV) ##STR00153## 1H-NMR Ex. No. A B (400 MHz)
Shifts .delta. in ppm XXIV-1 4'-O--CHCH.sub.3--CH.sub.2--O--
d.sub.6-DMSO 4.24 (m, 1H); 3.46 (t, 1H, J = 7.7 Hz); 4.10 (dd, 1H,
J = 5.8 HZ, 7.9 Hz); 2.36 (m, 4H); 1.94 (m, 4H); 1.23 (d, J = 6
Hz/3H) XXIV-2 4'-O--CHCH.sub.3--CHCH.sub.3--O-- d.sub.6-DMSO
4.28/3.68 (each m, .SIGMA.2H); 2 isomers 2:1 2.35/1.94 (each m,
.SIGMA.8H); 1.22 (d.J = 5.7 Hz) + 1.10 (d, J = 6.1Hz); .SIGMA.6H
XXIV-3 4'-O--(CH.sub.2).sub.3--O-- d.sub.6-DMSO 3.88 (dd, J = 5.6
Hz, 4H); 2.25 (m, 4H); 2.08 (m, 4H); 1.64 (m, 2H) XXIV-4
4'-O--CHCH.sub.3--(CH.sub.2).sub.2--O-- in d.sub.6-DMSO 4.03 (m,
1H); 3.93 (m, 1H); 3.80 (m, 1H); 2.30 (m, 2H); 2.22 (m, 4H); 1.87
(m, 2H); 1.51 (m, 2H); 1.10 (d, 3H, J = 6.1 Hz) XXIV-5
4'-O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- d.sub.6-DMSO 3.81 (dd, J
= 4.7 Hz, 12.0 Hz, 1 isomer 2H); 3.52 (dd, 2H, J = 9.7 Hz); 2.28
(m, 2H); 2.21 (m, 4H); 1.95 (m, 2H); 1.91 (m, 1H); 0.80 (d, J = 6.8
Hz, 1H) XXIV-6 4'-O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O--
d.sub.6-DMSO 4.02 (m, 2H); 2.31/2.21/1.97/ 2 isomers = 45:55
1.87/1.61 (in each case m, .SIGMA.10H); 1.17 (d, 3H, J = 6.3 Hz);
1.12 (d, 3H, J = 6.1 Hz) XXIV-8 ##STR00154## CD.sub.3CN isomer
mixture 4.23 (m), 4.01 (m), 3.66 (m), 3.38 (m), 3.31 (s), 2.54 (s),
2.26 (m), 1.87 (m), 1.78 (m), 1.56 (m)
[0849] Some of the ketones of the formula (XXIV) are commercially
available, some are known (JACS 108, 2691-2699; 1986; JACS 109,
1363-1370, 1987) and some are novel.
Example XXV-1
##STR00155##
[0851] 114 g of 4-hydroxycyclohexanone, 80 g of 1,2 propanediol (77
ml) and 2 g of 4-toluenesulphonic acid dihydrate are added to 500
ml of toluene. The mixture is boiled on a water separtor until no
more water separates out. For work-up, 1 ml of triethylamine is
added, and the reaction solution is washed with 200 ml of water,
dried and concentrated using a rotary evaporator. The residue (104
g) is distilled under reduced pressure.
[0852] Yield: 76.3 g 44% of theory
[0853] The following novel compounds of the formula (XXIV) are
obtained analogously to Example (XXIV-1)
TABLE-US-00017 (XXIV) ##STR00156## Ex. No. A B 1H-NMR (400 MHz,
d.sub.6-DMSO) Shift .delta. in ppm XXV-1
--O--CHCH.sub.3--CH.sub.2--O-- 4.38 (dd, 1 H J = 4.2 Hz, 5.3 Hz);
4.12 (m, 1H); 3.97 (m, 1H); 3.54 (6s, 1H); 3.33 (m, 1H); 1.67 (m,
4H); 1.44 (m, 4H); 1.16 (dd, J = 6.1 HZ, 3H); XXV-2
--O--CHCH.sub.3--CHCH.sub.3--O-- 4.35 (m); 4.16 (m); 3.54 (m); 1.67
(m); 1.44 (m); 1.15 (dd, J = 5.7 Hz); 1.03 (dd, J = 6.1 Hz) XXV-3
--O--(CH.sub.2).sub.3--O-- 4.35 (OH); 3.77 (m, 4H); 3.52 (m, 1H);
1.96 (m, 2H); 1.57 (m, 4H); 1.50-128 (m, 4H) XXV-4
--O--CHCH.sub.3--(CH.sub.2).sub.2--O-- 4.34 (m, 1H); 3.95 (m, 1H);
3.87 (m, 1H); 3.67 (m, 1H); 3.53 (m, 1H); 2.25 (m, 1H); 2.66-2.20
(m, 10H); 1.06 (dd, J = 6.1 Hz, 3H) XXV-5
--O--CH.sub.2--CHCH.sub.3--CH.sub.2--O-- 4.41 (bs, OH); 3.69 (m) +
3.53 (m) + 3.43 (m) + 3.35 (m) + 3.25 (m): .SIGMA.5 H; 2.12 (m,
1H); 1.74 (m, 2H); 1.62-1.23 (m, 5H); 0.80 (d, J = 6.8 Hz) + 0.75
(d, J = 6.8 Hz): .SIGMA.3 H XXV-6
--O--CHCH.sub.3--CH.sub.2--CHCH.sub.3--O-- 4.34 (s,OH); 3.94 (m);
3,53 (m) 2.20 (m); 1.78 (m); 2.65-2.20 (bm); 1.10 (dd, J = 6.3 Hz);
1.05 (dd, J = 6 Hz)
[0854] Some of the compounds of the formula (XXV) are commercially
available, some are known (J. Med. Chem. 24, 341-346, 1981) and
some are novel.
Example I-2-a-1
##STR00157##
[0856] 0.32 g (1.00 mmol) of the compound of Example XIV-2-1, 0.62
g (10 mmol) of ethylene glycol and 50 mg of 4-toluenesulphonic acid
in 15 ml of toluene are heated under reflux overnight.
[0857] For work-up, the mixture is cooled and the solid is filtered
off with suction and dried.
[0858] Yield: 0.35 g (96% of theory), m.p. 267.degree. C.
[0859] The following compounds of the formula (I-2-a) are obtained
analogously to Example (I-2-a-1) and in accordance with the general
statements on the preparation:
TABLE-US-00018 (I-2-a) ##STR00158## Ex. No. W X Y Z A B m.p.
.degree. C. I-2-a-2 CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- >250 I-2-a-3 CH.sub.3 CH.sub.3 Cl H
4'-O--CHCH.sub.3--CH.sub.2--O-- 198 I-2-a-4 CH.sub.3 CH.sub.3 Cl H
4'-O--CHCH.sub.2Cl--CH.sub.2--O-- 248 I-2-a-5 CH.sub.3 CH.sub.3 Br
H 4'-O--(CH.sub.2).sub.2--O-- 266 I-2-a-6 CH.sub.3 CH.sub.3 Cl H
4'-O--(CH.sub.2).sub.3--O-- 227 I-2-a-7 CH.sub.3 CH.sub.3 Cl H
4'-O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O-- 270 I-2-a-8 H
CH.sub.3 H 4-Cl--Ph 4'-O--(CH.sub.2).sub.2--O-- * ##STR00159##
*.sup.1H-NMR (400 MHz, d.sub.6-DMSO): .delta. = 2.19 (s, 3H,
Ar--CH.sub.3), 3.92 (s, 4H, (O--CH.sub.2,-)2), 7.3 (m, 1H, Ar--H),
7.4 (m, 1H, Ar--H), 7.5 (m, 3H, Ar--H), 7.65 (m, 2H-Ar--H) ppm.
Example I-2-b-1
##STR00160##
[0861] 0.22 g (0.60 mmol) of the compound of Example (I-2-a-1) is
initially charged in 10 ml of dichloromethane, 0.067 g (0.66 mmol)
of triethylamine is added, 0.071 g (0.66 mmol) of isobutyryl
chloride is added dropwise with ice-cooling and the mixture is
stirred at room temperature overnight.
[0862] For work-up, the mixture is extracted with 10% strength
citric acid solution and saturated sodium bicarbonate solution and
the organic phase is dried with sodium sulphate and concentrated
using a rotary evaporator.
[0863] Yield: 0.22 g (77% of theory), m.p. 142.degree. C.
[0864] The following compounds of the formula (I-2-b) are obtained
analogously to Example (I-2-b-1) and in accordance with the general
statements on the preparation:
TABLE-US-00019 (I-2-b) ##STR00161## Ex. No. W X Y Z A B R.sup.1
m.p. .degree. C. I-2-b-2 CH.sub.3 CH.sub.3 CH.sub.3 H
4'-O--(CH.sub.2).sub.2--O-- t-C.sub.4H.sub.9 165-169 I-2-b-3
CH.sub.3 CH.sub.3 Cl H 4'-O--CHCH.sub.2Cl--CH.sub.2--O--
i-C.sub.3H.sub.7 240-243 I-2-b-4 CH.sub.3 CH.sub.3 Cl H
4'-O--CHCH.sub.3--CH.sub.2--O-- i-C.sub.3H.sub.7 232
Example XIV-2-1
##STR00162##
[0866] 4.59 g (40.89 mmol) of potassium tert-butoxide are initially
charged in 35 ml of dimethylformamide, with ice-cooling, a solution
of 10.00 g (27.26 mmol) of the compound of Example (III-A-1) in 15
ml of dimethylformamide is added dropwise at from 0 to 10.degree.
C. and the mixture is stirred at room temperature overnight.
[0867] For work-up, most of the DMF is distilled off using a rotary
evaporator, and the residue is partitioned between water and ethyl
acetate. The aqueous phase is acidified with hydrochloric acid and
the precipitated product is filtered off with suction, washed with
water and dried.
[0868] Further purification is carried out by preparative HPLC
(silica gel RP-18, mobile phase acetonitrile/water).
[0869] Yield: 2.20 g (25% of theory), m.p. 210.degree. C.
[0870] The following compounds of the formula (XIV-2) are obtained
analogously to Example (XIV-2-1) and in accordance with the general
statements on the preparation of compounds of the formula (XIV-2)
in WO 99/16 748:
TABLE-US-00020 (XIV-2) ##STR00163## Ex. No. W X Y Z A B m.p.
.degree. C. XIV-2-2 CH.sub.3 CH.sub.3 CH.sub.3 H ##STR00164##
187-190 XIV-2-3 CH.sub.3 CH.sub.3 Br H ##STR00165## 222
Example III-A-1
##STR00166##
[0872] 5.00 g (26.85 mmol) of ethyl
4-oxo-1-hydroxycyclohexanecarboxylate and 3.26 g (32.22 mmol) of
triethylamine are initially charged in 35 ml of dichloromethane,
with ice-cooling, a solution of 6.41 g (29.53 mmol) of
2,6-dimethyl-4-chlorophenylacetyl chloride in 15 ml of
dichloromethane is added at from 0 to 10.degree. C. and the mixture
is stirred at room temperature overnight.
[0873] For work-up, the mixture is extracted with 10% strength
citric acid solution and saturated sodium bicarbonate solution and
the organic phase is dried with sodium sulphate and concentrated
using a rotary evaporator.
[0874] Yield: 10.00 g of an oil (67% of theory).
[0875] The following compounds of the formula (III-A) are obtained
analogously to Example (III-A-1) and in accordance with the general
statements on the preparation:
TABLE-US-00021 (III-A) ##STR00167## Ex. No. W X Y Z R.sup.8 m.p.
.degree. C. III-A-2 CH.sub.3 CH.sub.3 CH.sub.3 H C.sub.2H.sub.5 oil
III-A-3 CH.sub.3 CH.sub.3 Br H C.sub.2H.sub.5 oil
[0876] The oils were used without further characterization for
synthesizing compounds of the formula (XIV-2).
Example A
Myzus persicae Test (7:1)
[0877] Solvent: 7 parts by weight of dimethylformamide
[0878] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0879] 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.
[0880] Cabbage leaves (Brassica oleracea) which are heavily
infested by the green peach aphid (Myzus persicae) are treated by
being dipped into the preparation of active compound of the desired
concentration.
[0881] 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.
[0882] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.80% at a
concentration of 1000 ppm: Ex. I-1-a-2, Ex. I-1-a-1, Ex. I-1-a-3,
Ex. I-1-a-4, Ex. I-1-b-1, Ex. I-1-c-3, Ex. I-1-c-4, Ex.
I-1-c-1.
Example B
Aphis gossypii Test (7:1)
[0883] Solvent: 7 parts by weight of dimethylformamide
[0884] Emulsifier: 1 parts by weight of alkylaryl polyglycol
ether
[0885] 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.
[0886] Cotton leaves (Gossypium hirsutum) which are heavily
infested by the cotton aphid (Aphis gossypii) are treated by being
dipped into the preparation of active compound of the desired
concentration.
[0887] 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.
[0888] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.80% at a
concentration of 200 ppm: Ex. I-1-a-2, Ex. I-1-a-3, Ex. I-1-a-4,
Ex. I-1-c-1.
Example C
Phaedon cochleariae-larvae Test (7:1)
[0889] Solvent: 7 parts by weight of dimethylformamide
[0890] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0891] 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.
[0892] 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.
[0893] 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.
[0894] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.90% at a
concentration of 1000 ppm: Ex. I-2-a-2, Ex. I-2-b-2, Ex. I-1-a-2,
Ex. I-1-a-1, Ex. I-1-a-3, Ex. I-1-a-4, Ex. I-1-c-3, Ex. I-1-c-4,
Ex. I-1-c-5, Ex. I-1-b-1, Ex. I-1-c-1.
Example D
Plutella Test (7:1)
[0895] Solvent: 7 parts by weight of dimethylformamide
[0896] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0897] 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.
[0898] 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 diamond
back moth (Plutella xylostella) while the leaves are still
moist.
[0899] 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.
[0900] In this test, for example, the following compounds of the
Preparation Examples show an activity of 100% at a concentration of
1000 ppm: Ex. I-2-a-2, Ex. I-2-b-2, Ex. I-1-a-2.
Example E
Spodoptera frugiperda Test (7:1)
[0901] Solvent: 7 parts by weight of dimethylformamide
[0902] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0903] 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.
[0904] 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.
[0905] 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.
[0906] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.85% at a
concentration of 1000 ppm: Ex. I-2-a-2, Ex. I-2-b-2, Ex. I-1-a-2,
Ex. I-1-a-3, Ex. I-1-c-3.
Example F
Nephotettix Test (7:1)
[0907] Solvent: 7 parts by weight of dimethylformamide
[0908] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0909] 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.
[0910] Rice seedlings (Oryza sativa) are treated by being dipped
into the preparation of active compound of the desired
concentration and are populated with the green rice leaf hopper
(Nephotettix cincticeps) while the leaves are still moist.
[0911] After the desired period of time, the kill in % is
determined. 100% means that all leaf hoppers have been killed; 0%
means that none of the leaf hoppers have been killed.
[0912] In this test, for example, the following compounds of the
Preparation Examples show an activity of 100% at a concentration of
1000 ppm: Ex. I-2-a-2, Ex. I-2-b-2, Ex. I-1-a-2.
Example G
Tetranychus Test (7:1) (OP Resistant/Dip Treatment)
[0913] Solvent: 7 parts by weight of dimethylformamide
[0914] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0915] 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.
[0916] Bean plants (Phaseolus vulgaris) which are heavily infested
by all stages of the greenhouse red spider mite (Tetranychus
urticae) are treated by being dipped into a preparation of active
compound of the desired concentration.
[0917] After the desired period of time, the activity in % is
determined. 100% means that all spider mites have been killed; 0%
means that none of the spider mites have been killed.
[0918] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.98% at a
concentration of 100 ppm: Ex. I-1-a-1, Ex. I-1-a-3, Ex. I-1-a-4,
Ex. I-1-c-4.
Example H
Meloidogyne Test (7:1)
[0919] Solvent: 7 parts by weight of dimethylformamide
[0920] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0921] 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.
[0922] Vessels 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.
[0923] After the desired period of time, the nematicidal activity
is determined in % by the formation of galls. 100% means that no
galls have been found; 0% means that the number of galls on the
treated plants corresponds to that of the untreated control.
[0924] In this test, for example, the following compound of the
Preparation Examples shows an activity of 95% at a concentration of
20 ppm: Ex. I-1-a-4.
Example I
Myzus persicae Test
[0925] Solvent: 7 parts by weight of dimethylformamide
[0926] Emulsifier: 2 parts by weight of alkylaryl polyglycol
ether
[0927] 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.
[0928] Cabbage leaves (Brassica oleracea) which are heavily
infested by the green peach aphid (Myzus persicae) are treated by
being dipped into the preparation of active compound of the desired
concentration.
[0929] 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.
[0930] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.80% at a
concentration of 100 ppm: Ex. Ex. I-1-a-11, Ex. I-1-a-14, Ex.
I-1-a-12, Ex. I-1-a-13.
Example J
Tetranychus Test (OP Resistant/Dip Treatment)
[0931] Solvent: 7 parts by weight of dimethylformamide
[0932] Emulsifier: 2 parts by weight of alkylaryl polyglycol
ether
[0933] 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.
[0934] Bean plants (Phaseolus vulgaris) which are heavily infested
by all stages of the greenhouse red spider mite (Tetranychus
urticae) are treated by being dipped into a preparation of active
compound of the desired concentration.
[0935] After the desired period of time, the activity in % is
determined. 100% means that all spider mites have been killed; 0%
means that none of the spider mites have been killed.
[0936] In this test, for example, the following compounds of the
Preparation Examples show an activity .gtoreq.90% at a
concentration of 100 ppm: Ex. I-1-a-11, Ex. I-1-a-14, Ex. I-1-a-12,
Ex. I-1-a-21, Ex. I-1-a-22, Ex. I-1-a-9, Ex. I-1-a-43, Ex.
I-1-a-46, Ex. I-1-a-53, Ex. I-1-a-70, Ex. I-1-c-16, Ex.
I-1-c-20.
Example K
Meloidogyne Test
[0937] Solvent: 7 parts by weight of dimethylformamide
[0938] Emulsifier: 2 parts by weight of alkylaryl polyglycol
ether
[0939] 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.
[0940] Vessels 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.
[0941] After the desired period of time, the nematicidal activity
is determined in % by the formation of galls. 100% means that no
galls have been found; 0% means that the number of galls on the
treated plants corresponds to that of the untreated control.
[0942] In this test, for example, the following compound of the
Preparation Examples shows an activity of 80% at a concentration of
20 ppm: Ex. I-1-a-12.
Example L
Aphis gossypii Test
[0943] Solvent: 7 parts by weight of dimethylformamide
[0944] Emulsifier: 2 parts by weight of alkylaryl polyglycol
ether
[0945] 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.
[0946] Cotton leaves (Gossypium hirsutum) which are heavily
infested by the cotton aphid (Aphis gossypii) are treated by being
dipped into the preparation of active compound of the desired
concentration.
[0947] 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.
[0948] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.80% at a
concentration of 100 ppm: Ex. I-1-a-19, Ex. I-1-a-7, Ex. I-1-a-14,
Ex. I-1-a-30, Ex. I-1-a-31, Ex. I-1-a-38, Ex. I-1-a-48, Ex.
I-1-a-50, Ex. I-1-a-53, Ex. I-1-a-56, Ex. I-1-a-58, Ex.
I-1-a-63,
[0949] Ex. I-1-b-4, Ex. I-1-c-15, Bsp.I-1-c-19, Bsp.I-1-c-20,
Bsp.I-1-c-32, Bsp.I-2-a-5.
Example M
Phaedon cochleariae Larvae Test
[0950] Solvent: 7 parts by weight of dimethylformamide
[0951] Emulsifier: 2 parts by weight of alkylaryl polyglycol
ether
[0952] 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.
[0953] 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.
[0954] 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.
[0955] In this test, for example, the following compound of the
Preparation Examples shows an activity of 100% at a concentration
of 100 ppm: Ex. I-1-a-23.
Example N
Phaedon Test (Spray Treatment)
[0956] Solvents: 78 parts by weight of acetone [0957] 1.5 parts by
weight of dimethylformamide
[0958] Emulsifier: 0.5 part by weight of alkylaryl polyglycol
ether
[0959] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvents and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[0960] Discs of Chinese cabbage (Brassica pekinensis) are sprayed
with a preparation of active compound of the desired concentration
and, after drying, populated with larvae of the mustard beetle
(Phaedon cochleariae).
[0961] After the desired period of time, the activity in % is
determined. 100% means that all beetle larvae have been killed; 0%
means that none of the beetle larvae have been killed.
[0962] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.80% at an
application rate of 100 g/ha: Ex. I-1-a-15, Ex. I-1-c-9, Ex.
I-1-a-21 and an activity of 100% at an application rate 500 g/ha:
Ex. I-1-a-18, Ex. I-1-a-20, Ex. I-1-a-22, Ex. I-1-a-8, Ex.
I-1-a-10, Ex. I-1-a-7, Ex. I-1-a-9, Ex. I-1-c-6, Ex. I-1-a-16, Ex.
I-1-a-24, Ex. I-1-a-27, Ex. I-1-a-30, Ex. I-1-a-31, Ex. I-1-a-32,
Ex. I-1-a-33, Ex. I-1-a-34, Ex. I-1-a-38, Ex. I-1-a-39, Ex.
I-1-a-43, Ex. I-1-a-45, Ex. I-1-a-46, Ex. I-1-a-47, Ex. I-1-a-49,
Ex. I-1-a-51, Ex. I-1-a-52, Ex. I-1-a-53, Ex. I-1-a-54, Ex.
I-1-a-56, Ex. I-1-a-61, Ex. I-1-a-63, Ex. I-1-a-64, Ex. I-1-a-65,
Ex. I-1-a-66, Ex. I-1-a-67, Ex. I-1-a-68, Ex. I-1-a-71, Ex.
I-1-c-19, Ex. I-1-c-31, Ex. I-1-c-34.
Example 0
Tetranychus Test (OP Resistant/Spray Treatment)
[0963] Solvents: 78 parts by weight of acetone [0964] 1.5 parts by
weight of dimethylformamide
[0965] Emulsifier: 0.5 part by weight of alkylaryl polyglycol
ether
[0966] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvents and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[0967] Bean plants (Phaseolus vulgaris) which are heavily infested
by all stages of the greenhouse red spider mite (Tetranychus
urticae) are treated by being dipped into a preparation of active
compound of the desired concentration.
[0968] After the desired period of time, the activity in % is
determined. 100% means that all spider mites have been killed; 0%
means that none of the spider mites have been killed.
[0969] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.80% at an
application rate of 100 g/ha: Ex. I-2-b-1, Ex. I-1-a-16, Ex.
I-1-a-15, Ex. I-1-c-9, Ex. I-1-c-11, Ex. I-1-a-23, Ex. I-1-c-6, Ex.
I-1-a-24, Ex. I-1-a-27 and Ex. I-1-a-38, Ex. I-1-a-50, Ex.
I-1-a-58, Ex. I-1-c-24, Ex. I-1-c-43.
Example P
Meloidogyne Test (Spray Treatment)
[0970] Solvent: 80 parts by weight of acetone
[0971] 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 concentrate is diluted with water to the desired
concentration.
[0972] Vessels 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.
[0973] After the desired period of time, the nematicidal activity
is determined in % by the formation of galls. 100% means that no
galls have been found; 0% means that the number of galls on the
treated plants corresponds to that of the untreated control.
[0974] In this test, for example, the following compound of the
Preparation Examples shows an activity of 100% at a concentration
of 20 ppm: Ex. I-1-a-15.
Example Q
Myzus Test (Spray Treatment)
[0975] Solvents: 78 parts by weight of acetone [0976] 1.5 parts by
weight of dimethylformamide
[0977] Emulsifier: 0.5 part by weight of alkylaryl polyglycol
ether
[0978] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvents and emulsifier, and the concentrate is diluted with
emulsifying-containing water to the desired concentration.
[0979] Discs of Chinese cabbage (Brassica pekinensis) which are
infested by all stages of the green peach aphid (Myzus persicae)
are sprayed with a preparation of active compound of the desired
concentration.
[0980] After the desired period of time, the activity in % is
determined. 100% means that all aphids have been killed; 0% means
that none of the aphids have been killed.
[0981] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.90% at an
application rate of 500 g/ha: Ex. I-1-a-18, Ex. I-1-a-19, Ex.
I-1-c-10, Ex. I-1-a-20, Ex. I-1-c-11, Ex. I-1-a-23, Ex. I-1-a-21,
Ex. I-1-a-22, Ex. I-1-a-8, Ex. I-1-a-10, Ex. I-1-a-7, Ex. I-1-a-9,
Ex. I-1-c-6, Ex. I-2-a-1, Ex. I-2-a-3, Ex. I-2-a-4, Ex. I-2-a-7,
Ex. I-2-b-1, Ex. I-2-b-3, Ex. I-2-b-4, Ex. I-2-a-5, Ex. I-1-a-16,
Ex. I-1-a-24, Ex. I-1-a-26, Ex. I-1-a-28, Ex. I-1-a-29, Ex.
I-1-a-30, Ex. I-1-a-31, Ex. I-1-a-32, Ex. I-1-a-33, Ex. I-1-a-34,
Ex. I-1-a-35, Ex. I-1-a-36, Ex. I-1-a-37, Ex. I-1-a-38, Ex.
I-1-a-39, Ex. I-1-a-40, Ex. I-1-a-41, Ex. I-1-a-42, Ex. I-1-a-43,
Ex. I-1-a-44, Ex. I-1-a-45, Ex. I-1-a-46, Ex. I-1-a-47, Ex.
I-1-a-48, Ex. I-1-a-49, Ex. I-1-a-50, Ex. I-1-a-51, Ex. I-1-a-52,
Ex. I-1-a-53, Ex. I-1-a-54, Ex. I-1-a-56, Ex. I-1-a-57, Ex.
I-1-a-58, Ex. I-1-a-59, Ex. I-1-a-60, Ex. I-1-a-61, Ex. I-1-a-62,
Ex. I-1-a-63, Ex. I-1-a-64, Ex. I-1-a-65, Ex. I-1-a-66, Ex.
I-1-a-67, Ex. I-1-a-69, Ex. I-1-a-70, Ex. I-1-a-71, Ex. I-1-b-4,
Ex. I-1-b-6, Ex. I-1-b-7, Ex. I-1-b-8, Ex. I-1-b-10, Ex. I-1-b-11,
Ex. I-1-c-14, Ex. I-1-c-15, Ex. I-1-c-16, Ex. I-1-c-17, Ex.
I-1-c-18, Ex. I-1-c-19, Ex. I-1-c-20, Ex. I-1-c-21, Ex. I-1-c-22,
Ex. I-1-c-23, Ex. I-1-c-24, Ex. I-1-c-25, Ex. I-1-c-26, Ex.
I-1-c-30, Ex. I-1-c-31, Ex. I-1-c-32, Ex. I-1-c-33, Ex. I-1-c-34,
Ex. I-1-c-35, Ex. I-1-c-36, Ex. I-1-c-40, Ex. I-1-c-41, Ex.
I-1-c-42, Ex. I-1-c-43.
Example R
Spodoptera frugiperda Test (Spray Treatment)
[0982] Solvents: 78 parts by weight of acetone [0983] 1.5 parts by
weight of dimethylformamide
[0984] Emulsifier: 0.5 part by weight of alkylaryl polyglycol
ether
[0985] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvents and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[0986] Discs of maize leaves (Zea mays) are sprayed with a
preparation of active compound of the desired concentration and,
after drying, populated with caterpillars of the army worm
(Spodoptera frugiperda).
[0987] After the desired period of time, the activity in % is
determined. 100% means that all caterpillars have been killed; 0%
means that none of the caterpillars have been killed.
[0988] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.80% at an
application rate of 500 g/ha: Ex. I-2-a-7, Ex. I-1-a-16, Ex.
I-1-a-21, Ex. I-1-a-22, Ex. I-1-a-8, Ex. I-1-a-10, Ex. I-1-a-27,
Ex. I-1-a-31, Ex. I-1-a-49, Ex. I-1-a-51, Ex. I-1-a-52, Ex.
I-1-a-54, Ex. I-1-a-64, Ex. I-1-a-65, Ex. I-1-a-66, Ex. I-1-a-67,
Ex. I-1-c-16, Ex. I-1-c-19, Ex. I-1-c-31, Ex. I-1-c-36, Ex.
I-1-c-40.
Example S
Myzus persicae Test (Hydroponic Treatment)
[0989] Solvent: 7 parts by weight of dimethylformamide
[0990] Emulsifier: 2 parts by weight of alkylaryl polyglycol
ether
[0991] 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.
[0992] The preparation of active compound is mixed with water. The
stated concentration relates to the amount of active compound per
volume unit of water (mg/l=ppm). The treated water is filled into
vessels containing a pea plant (Pisum sativum). After the desired
period of time, the plant is infected with the green peach aphid
(Myzus persicae).
[0993] 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.
[0994] In this test, for example, the following compounds of the
Preparation Examples show an activity of .gtoreq.95% at a
concentration of 20 ppm: Ex. I-1-a-23, Ex. I-1-a-21, Ex. I-1-a-7,
Ex. I-1-a-24, Ex. I-1-a-26, Ex. I-1-a-30, Ex. I-1-a-32, Ex.
I-1-a-34, Ex. I-1-a-35, Ex. I-1-a-36, Ex. I-1-a-38, Ex. I-1-a-39,
Ex. I-1-a-40, Ex. I-1-a-42, Ex. I-1-a-43, Ex. I-1-a-44, Ex.
I-1-a-45, Ex. I-1-a-46, Ex. I-1-a-47, Ex. I-1-a-48, Ex. I-1-a-50,
Ex. I-1-a-53, Ex. I-1-a-56, Ex. I-1-a-57, Ex. I-1-a-58, Ex.
I-1-a-59, Ex. I-1-a-69, Ex. I-1-a-70, Ex. I-1-a-71, Ex. I-1-b-4,
Ex. I-1-b-8, Ex. I-1-b-10, Ex. I-1-b-11, Ex. I-1-c-15, Ex.
I-1-c-17, Ex. I-1-c-19, Ex. I-1-c-20, Ex. I-1-c-23, Ex. I-1-c-24,
Ex. I-1-c-25, Ex. I-1-c-32, Ex. I-1-c-43.
Example T
Post-Emergence Test
[0995] Solvent: 5 parts by weight of acetone
[0996] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[0997] 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.
[0998] Test plants of a height of 5-15 cm are sprayed with the
preparation of active compounds 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.
[0999] After three weeks, the degree of damage to the plants is
rated in % damage in comparison to the development of the untreated
control.
[1000] The figures denote [1001] 0%=no effect (like untreated
control) [1002] 100%=total destruction
Example U
Pre-Emergence Test (Examination of Active Compounds Herbicides
Monheim)
[1003] Solvent: 5 parts by weight of acetone
[1004] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[1005] 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.
[1006] 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.
[1007] After three weeks, the degree of damage to the plants is
rated in % damage in comparison to the development of the untreated
control.
[1008] The figures denote: [1009] 0%=no effect (like untreated
control) [1010] 100%=total destruction
TABLE-US-00022 [1010] Concentration of active Greenhouse compound g
of a.i./ha Echinochloa Setaria Amaranthus Galium Sinapis Ex.
I-1-a-4 250 100 100 95 70 70 Concentration of active Greenhouse
compound g of a.i./ha Alopecurus Avena fatua Echinochloa Setaria
Sinapis Ex. I-1-c-4 250 80 -- 90 99 80 Ex. I-1-b-1 250 70 70 80 95
70 Ex. I-1-a-11 250 90 70 80 90 -- Concentration of active
Greenhouse compound g of a.i./ha Sugar beet Alopecurus Avena fatua
Echinochloa Setaria Ex. I-1-a-14 250 0 95 80 80 90 Ex. I-1-a-15 250
0 95 80 99 70 Concentration of active Greenhouse compound g of
a.i./ha Alopecurus Echinochloa Setaria Ex. I-1-a-11 250 80 80
100
Example V
1. Herbicidal Pre-Emergence Action
[1011] Seeds of monocotyledonous and dicotyledonous weed and crop
plants are placed in sandy loam in wood fibre pots and covered with
soil. The test compounds, formulated in the form of wettable
powders (WP), are then, as an aqueous suspension 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 in various
dosages.
[1012] 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 control plants).
[1013] In addition to the compounds mentioned above, the following
compounds, applied by the pre-emergence method at 320 g of a.i./ha,
show an activity of .gtoreq.80% against Solium multiflorum and
Setaria viridis: Ex. I-1-a-24, Ex. I-1-a-39, Ex. I-1-a-40, Ex.
I-1-a-42, Ex. I-1-a-43, Ex. I-1-a-44, Ex. I-1-a-45, Ex. I-1-a-48,
Ex. I-1-a-69, Ex. I-1-a-71, Ex. I-1-b-4, Ex. I-1-b-5, Ex. I-1-b-8,
Ex. I-1-b-9, Ex. I-1-b-10, Ex. I-1-c-14, Ex. I-1-c-15, Ex.
I-1-c-23, Ex. I-1-c-25, Ex. I-1-c-42 and Ex. I-1-c-43.
2. Herbicidal Post-Emergence Action
[1014] 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), are
then, 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 have been kept in
the 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 control plants).
TABLE-US-00023 Concentration of active Greenhouse compound g of
a.i./ha Lolium Setaria Sinapis Echinochloa Ex. I-1-a-18 320 80 100
-- 90 Ex. I-1-a-19 320 90 90 70 90 Ex. I-2-a-6 320 80 80 60 60 Ex.
I-2-b-3 320 100 90 -- 80 Ex. I-1-a-2 320 70 90 60 80 Ex. I-1-a-7
320 80 80 60 60 Ex. I-1-a-21 320 80 90 70 80 Ex. I-1-a-22 320 70 80
70 100 Ex. I-1-c-6 320 90 90 60 80 Concentration of active compound
Greenhouse g of a.i./ha Lolium Setaria Amaranthus Sinapis
Echinochloa Ex. I-2-a-2 320 90 100 60 70 80 Concentration of active
Greenhouse compound g of a.i./ha Lolium Setaria Amaranthus
Stellaria Ex. I-2-a-5 320 100 70 70 60
[1015] In addition to the compounds mentioned above, the following
compounds, applied by the post-emergence method at 320 g of
a.i./ha, show an activity of .gtoreq.80% against Echinocloa
crus-galli, Lolium multiflorum and Setaria viridis: Ex. I-1-a-10,
Ex. I-1-a-18, Ex. I-1-a-19, Ex. I-1-a-21, Ex. I-1-a-24, Ex.
I-1-a-25, Ex. I-1-a-27, Ex. I-1-a-39, Ex. I-1-a-40, Ex. I-1-a-42,
Ex. I-1-a-45, Ex. I-1-a-48, Ex. I-1-a-71, Ex. I-1-b-8, Ex. I-1-b-9,
Ex. I-1-b-10, Ex. I-1-b-11, Ex. I-1-c-6, Ex. I-1-c-15, Ex.
I-1-c-23, Ex. I-1-c-25, Ex. I-1-c-26, Ex. I-1-c-42, Ex. I-1-c-43,
Ex. I-2-a-2, and Ex. I-2-b-3.
Test Description for Profiling Tests
2. Herbicidal Post-Emergence Action
[1016] 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, during the
vegetation period also outdoors outside of the greenhouse, under
good growth conditions. 2-3 weeks after sowing, the test plants are
treated at the one- to three-leaf stage. The test compounds,
formulated as wettable powders (WP) or emulsifiable concentrates
(EC) are, in various dosages with a water application rate of 300
l/ha (converted), with wetting agent (0.2 to 0.3%) added, sprayed
onto the plants and the surface of the soil. 3-4 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 control plants).
Use of Safeners:
[1017] If it is additionally to be tested as to whether safeners
can improve the plant compatibility of test substances in the case
of crop plants, the following options are used for applying the
safener: [1018] seeds of the crop plants are, before sowing,
dressed with the safener substance (the amount of safener stated in
percent, based on the weight of the seed) [1019] before the
application of the test substances, the crop plants are sprayed
with the safener at a certain application rate per hectar (usually
1 day before the application of the test substances) [1020] the
safener is applied together with the test substance as a tank mix
(the amount of safener is stated in g/ha or as a ratio, based on
the herbicide).
[1021] By comparing the effect of the test substances on crop
plants without or with safener treatment, it is possible to assess
the effect of the safener substance.
Container Trials with Cereal in a Greenhouse
[1022] Mefenpyr 1 day prior to herbicide application
TABLE-US-00024 TABLE 1 10 days after application Application rate
Summer barley Summer wheat g of a.i./ha observed (%) observed (%)
I-1-a-25 25 50 40 12.5 30 20 I-1-a-25 + 25 + 100 15 10 mefenpyr
12.5 + 100 10 5
TABLE-US-00025 TABLE 2 28 days after application Application rate
Summer wheat g of a.i./ha observed (%) I-1-a-25 50 60 25 20 12.5 10
I-1-a-25 + 50 + 100 10 mefenpyr 25 + 100 5 12.5 + 100 0
TABLE-US-00026 TABLE 3 28 days after application Application rate
Summer barley Summer wheat g of a.i./ha observed (%) observed (%)
I-1-c-25 23.8 50 70 11.9 20 I-1-c-25 + 23.8 20 20 mefenpyr 11.9
10
Example W
Critical Concentration Test/Soil Insects--Treatment of Transgenic
Plants
[1023] Test insect: Diabrotica balteata-larvae in the soil
[1024] Solvent: 7 parts by weight of acetone
[1025] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[1026] 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.
[1027] 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 into 0.25 l pots, and these are allowed to stand
at 20.degree. C.
[1028] Immediately after the preparation, 5 pregerminated maize
corns of the cultivar YIELD GUARD (trademark, of Monsanto Comp.,
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 have emerged (1 plant=20% activity).
Example X
Heliothis virescens Test--Treatment of Transgenic Plants
[1029] Solvent: 7 parts by weight of acetone
[1030] Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
[1031] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[1032] Soybean shoots (Glycine max) of the cultivar Roundup Ready
(trademark 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 bud worm Heliothis virescens while
the leaves are still moist.
[1033] After the desired period of time, the kill of the insects is
determined.
* * * * *