U.S. patent application number 10/192361 was filed with the patent office on 2003-05-22 for arylphenyl-substituted cyclic ketoenols.
Invention is credited to Andersch, Wolfram, Bretschneider, Thomas, Dollinger, Markus, Drewes, Mark Wilhelm, Erdelen, Christoph, Feucht, Dieter, Fischer, Reiner, Graff, Alan, Lieb, Folker, Myers, Randy Allen, Pontzen, Rolf, Schneider, Udo, Wetcholowsky, Ingo.
Application Number | 20030096806 10/192361 |
Document ID | / |
Family ID | 7865908 |
Filed Date | 2003-05-22 |
United States Patent
Application |
20030096806 |
Kind Code |
A1 |
Lieb, Folker ; et
al. |
May 22, 2003 |
Arylphenyl-substituted cyclic ketoenols
Abstract
The present invention relates to novel arylphenyl-substituted
cyclic ketoenols of the formula (I) 1 in which X represents
halogen, alkyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl,
alkylsulphonyl, halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy,
nitro, cyano or in each case optionally substituted phenyl,
phenoxy, phenylthio, phenylalkoxy or phenylalkylthio, Y represents
in each case optionally substituted cycloalkyl, aryl or hetaryl, W
represents hydrogen, halogen, alkyl, alkoxy, alkenyloxy,
halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy, nitro or cyano,
Z represents halogen, alkyl, alkoxy, alkenyloxy, halogenoalkyl,
halogenoalkoxy, halogenoalkenyloxy, nitro or cyano, CKE represents
one of the groups 2 in which A, B, D, G and Q.sup.1, S, Q.sup.6 are
each as defined in the description, to a plurality of processes for
their preparation and to their use as pesticides and
herbicides.
Inventors: |
Lieb, Folker; (Leverkusen,
DE) ; Fischer, Reiner; (Monheim, DE) ; Graff,
Alan; (Koln, DE) ; Schneider, Udo;
(Leverkusen, DE) ; Bretschneider, Thomas; (Lohmar,
DE) ; Erdelen, Christoph; (Leichlingen, DE) ;
Andersch, Wolfram; (Bergisch Gladbach, DE) ; Drewes,
Mark Wilhelm; (Langenfeld, DE) ; Dollinger,
Markus; (Overland Park, KS) ; Wetcholowsky, Ingo;
(Estancia Marambaia, BR) ; Feucht, Dieter;
(Monheim, DE) ; Pontzen, Rolf; (Leichlingen,
DE) ; Myers, Randy Allen; (Overland Park,
KS) |
Correspondence
Address: |
BAYER CORPORATION
PATENT DEPARTMENT
100 BAYER ROAD
PITTSBURGH
PA
15205
US
|
Family ID: |
7865908 |
Appl. No.: |
10/192361 |
Filed: |
July 10, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10192361 |
Jul 10, 2002 |
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09673907 |
Jan 2, 2001 |
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6451843 |
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09673907 |
Jan 2, 2001 |
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PCT/EP99/02488 |
Apr 14, 1999 |
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Current U.S.
Class: |
514/212.01 ;
514/210.02; 514/317; 514/424; 540/200; 540/485; 546/216;
548/543 |
Current CPC
Class: |
C07D 309/14 20130101;
C07C 69/013 20130101; C07D 209/96 20130101; C07D 307/94 20130101;
C07C 49/88 20130101; C07D 513/04 20130101; C07D 211/60 20130101;
C07C 69/96 20130101; C07D 333/50 20130101; C07D 471/04 20130101;
C07D 279/06 20130101; C07D 491/10 20130101; C07C 49/733 20130101;
C07C 49/747 20130101 |
Class at
Publication: |
514/212.01 ;
514/317; 514/424; 514/210.02; 540/200; 540/485; 546/216;
548/543 |
International
Class: |
A61K 031/55; A61K
031/397; A61K 031/4015; A61K 031/445; C07D 207/24; C07D 223/10 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 27, 1998 |
DE |
198 18 732.7 |
Claims
1. Compounds of the formula (I) 198in which X represents halogen,
alkyl, alkoxy, alkenyloxy, alkylthio, alkyl-sulphinyl,
alkylsulphonyl, halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy,
nitro, cyano or in each case optionally substituted phenyl,
phenoxy, phenylthio, phenylalkoxy or phenylalkylthio, Y represents
in each case optionally substituted cycloalkyl, aryl or hetaryl, W
represents hydrogen, halogen, alkyl, alkoxy, alkenyloxy,
halo-genoalkyl, halogenoalkoxy, halogenoalkenyloxy, nitro or cyano,
Z represents halogen, alkyl, alkoxy, alkenyloxy, halogenoalkyl,
halogenoalkoxy, halogenoalkenyloxy, nitro or cyano, CKE represents
one of the groups 199 in which A represents hydrogen, in each case
optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,
polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated,
optionally substituted cycloalkyl in which optionally at least one
ring atom is replaced by a heteroatom, or in each case optionally
halogen-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, cyano-
or nitro-substituted aryl, arylalkyl or hetaryl, B represents
hydrogen, alkyl or alkoxyalkyl, or A and B together with the carbon
atom to which they are attached represent a saturated or
unsaturated unsubstituted or substituted cycle which optionally
contains at least one heteroatom, D represents hydrogen or an
optionally substituted radical selected from the series consisting
of alkyl, alkenyl, alkinyl, alkoxyalkyl, polyalkoxyalkyl,
alkylthioalkyl, saturated or unsaturated cycloalkyl in which one or
more ring members are optionally replaced by heteroatoms,
arylalkyl, aryl, hetarylalkyl or hetaryl or A and D together with
the atoms to which they are attached represent a saturated or
unsaturated cycle which is unsubstituted or substituted in the A,D
moiety and which optionally contains at least one (in the case
where CKE=(4) further) heteroatom, or A and Q.sup.1 together
represent alkanediyl or alkenediyl, each of which is optionally
substituted by in each case optionally substituted alkyl, hydroxyl,
alkoxy, alkylthio, cycloalkyl, benzyloxy or aryl, or Q.sup.1
represents hydrogen or alkyl, Q.sup.2, Q.sup.4, Q.sup.5 and Q.sup.6
independently of one another each represent hydrogen or alkyl,
Q.sup.3 represents hydrogen, alkyl, alkoxyalkyl, alkylthioalkyl,
optionally substituted cycloalkyl (in which optionally one
methylene group is replaced by oxygen or sulphur) or optionally
substituted phenyl, or Q.sup.3 and Q.sup.4 together with the carbon
atom to which they are attached represent a saturated or
unsaturated unsubstituted or substituted cycle which optionally
contains a heteroatom, G represents hydrogen (a) or represents one
of the groups 200 in which E represents a metal ion equivalent or
an ammonium ion, L represents oxygen or sulphur, M represents
oxygen or sulphur, R.sup.1 represents in each case optionally
halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl,
polyalkoxy-alkyl or optionally halogen-, alkyl- or
alkoxy-substituted cycloalkyl which may be interrupted by at least
one heteroatom, in each case optionally substituted phenyl,
phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, R.sup.2
represents in each case optionally halogen-substituted alkyl,
alkenyl, alkoxyalkyl, 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 each represent in
each case optionally halogen-substituted alky, alkoxy, alkylamino,
dialkylamino, alkylthio, alkenylthio, cycloalkylthio and represent
in each case optionally subsituted phenyl, benzyl, phenoxy or
phenylthio, R.sup.6 and R.sup.7 independently of one another each
represent hydrogen, in each case optionally halogen-substituted
alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent
optionally substituted phenyl, represent optionally substituted
benzyl, or together with the nitrogen atom to which they are
attached represent a cycle which is optionally interrupted by
oxygen or sulphur.
2. Compounds of the formula (I) according to claim 1 in which X
represents halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-halogenoalkyl, 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-halogenoalkoxy, C.sub.3-C.sub.6-halogenoalkenyloxy,
nitro, cyano 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-halogenoalkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
nitro- or cyano-substituted phenyl, phenoxy, phenylthio, benzyloxy
or benzylthio, Y represents one of the radicals 201V.sup.1
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-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
nitro, cyano or 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-halogenoal- kyl,
C.sub.1-C.sub.4-halogenoalkoxy, nitro or cyano. V.sup.2 and V.sup.3
independently of one another each represent hydrogen, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoal- kyl or C.sub.1-C.sub.4-halogenoalkoxy.
W represents hydrogen, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-halogenoalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-halogenoalkoxy, nitro or cyano. Z represents
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenoalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-halogenoalkoxy, nitro or
cyano. CKE represents one of the groups 202A represents hydrogen or
in each case optionally halogen-substituted C.sub.1-C.sub.12-alkyl,
C.sub.3-C.sub.8-alkenyl,
C.sub.1-C.sub.10-alkoxy-C.sub.1-C.sub.8-alkyl,
poly-C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.10-alkylthio-C.sub.1-C.sub.6-alkyl, 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 ring members are
replaced by oxygen and/or sulphur or represents in each case
optionally halogen-, C.sub.1-C.sub.6-alkyl-,
C.sub.1-C.sub.6-halogenoalkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.6-halogenoalkoxy-, cyano- or nitro-substituted
C.sub.6- or C.sub.10-aryl (phenyl or naphthyl), hetaryl having 5 to
6 ring atoms (for example, furanyl, pyridyl, imidazolyl, triazolyl,
pyrazolyl, pyrimidyl, thiazolyl or thienyl) or C.sub.6- or
C.sub.10-aryl-C.sub.1-C.sub.6-alkyl (phenyl-C.sub.1-C.sub.6-alkyl
or naphthyl-C.sub.1-C.sub.6-alkyi). B represents hydrogen,
C.sub.1-C.sub.12-alkyl or C.sub.1-C.sub.8-alkoxy-C.s-
ub.1-C.sub.6-alkyl or A, B and the carbon atom to which they are
attached represent saturated C.sub.3-C.sub.10-cycloalkyl or
unsaturated C.sub.5-C.sub.10-cycloalkyl in which in each case
optionally one ring member is replaced by oxygen or sulphur and
which are optionally mono- or disubstituted by
C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.10-cycloalkyl,
C.sub.1-C.sub.8-halogenoalkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.1-C.sub.8-alkylthio, halogen or phenyl or A, B and the carbon
atom to which they are attached represent
C.sub.3-C.sub.6-cycloalkyl which is substituted by an alkylenedilyl
group which optionally contains one or two not directly adjacent
oxygen and/or sulphur atoms, or by an alkylenedioxyl group or by an
alkylenedithioyl group which, together with, the carbon atom to
which it is attached, forms a further five- to eight-membered ring,
or A, B and the carbon atom to which they are attached represent
C.sub.3-C.sub.8-cycloalkyl or C.sub.5-C.sub.8-cycloalk- enyl, in
which two substituents together with the carbon atoms to which they
are attached represent in each case optionally
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy- or
halogen-substituted C.sub.2-C.sub.6-alkanediyl,
C.sub.2-C.sub.6-alkenediyl or C.sub.4-C.sub.6-alkanedienediyl in
which optionally one methylene group is replaced by oxygen or
sulphur, D represents hydrogen, in each case optionally
halogen-substituted C.sub.1-C<.sub.2-alkyl,
C.sub.3-C.sub.8-alkenyl, C.sub.3-C.sub.8-alkinyl,
C.sub.1-C.sub.10-alkoxy- -C.sub.2-C.sub.8-alkyl,
poly-C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl,
C.sub.1-C.sub.10-alkylthio-C.sub.2-C.sub.8-alkyl, optionally
halogen-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-halogenoalkyl-substituted
C.sub.3-C.sub.8-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur or in each case optionally halogen-,
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-halogenoalkyl-,
C.sub.1-C.sub.6-alkoxy-, C.sub.1-C.sub.6-halogenoalkoxy-, cyano- or
nitro-substituted phenyl, hetaryl having 5 or 6 ring atoms (for
example furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl,
pyrimidyl, pyrrolyl, thienyl or triazolyl),
phenyl-C.sub.1-C.sub.6-alkyl or hetaryl-C.sub.1-C.sub.6-alkyl
having 5 or 6 ring atoms (for example furanyl, imidazolyl, pyridyl,
thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl or triazolyl),
or A and D together represent in each case optionally substituted
C.sub.3-C.sub.6-alkane-diyl or C.sub.3-C.sub.6-alkenediyl in which
optionally one methylene group is replaced by oxygen or sulphur,
possible substituents in each case being: halogen, hydroxyl,
mercapto or in each case optionally halogen-substituted
C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.3-C.sub.7-cycloalkyl, phenyl or
benzyloxy, or a further C.sub.3-C.sub.6-alkanediyl grouping,
C.sub.3-C.sub.6-alkenediyl grouping or a butadienyl grouping which
is optionally substituted by C.sub.1-C.sub.6-alkyl or in which
optionally two adjacent substituents together with the carbon atoms
to which they are attached form a further saturated or unsaturated
cycle having 5 or 6 ring atoms (in the case of the compound of the
formula (I-1), A and D, together with the atoms to which they are
attached, then represent, for example, the groups AD-1 to AD-10
mentioned further below) which cycle may contain oxygen or sulphur,
or which may optionally contain one of the groups below 203A and
Q.sup.1 together represent C.sub.3-C.sub.6-alkanediyl or
C.sub.4-C.sub.6-alkenedi- yl, each of which is optionally mono- or
disubstituted by identical or different substituents selected from
the group consisting of halogen, hydroxyl; C.sub.1-C.sub.10-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6alkylthio,
C.sub.3-C.sub.7-cycloalkyl, each of which is optionally mono- to
trisubstituted by identical or different halogens; and benzyloxy
and phenyl, each of which is optionally mono- to trisubstituted by
identical or different substituents selected from the group
consisting of halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy, and which furthermore optionally contains
one of the groups below 204 or is bridged by a
C.sub.1-C.sub.2-alkanediyl group or by an oxygen atom, or Q.sup.1
represents hydrogen or C.sub.1-C.sub.4-alkyl, Q.sup.2, Q.sup.4,
Q.sup.5 and Q.sup.6 independently of one another each represent
hydrogen or C.sub.1-C.sub.4-alkyl. Q.sup.3 represents hydrogen,
C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.2-alkyl, optionally
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.3-C.sub.8-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulphur or optionally halogen-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.2-halogeno- alkyl-, C.sub.1-C.sub.2-halogenoalkoxy-,
cyano- or nitro-substituted phenyl, or Q.sup.3 and Q.sup.4 together
with the carbon atom to which they are attached represent an
optionally C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.2-halogenoalkyl-substituted
C.sub.3-C.sub.7 ring in which optionally one ring member is
replaced by oxygen or sulphur. G represents hydrogen (a) or
represents one of the groups 205 in which E represents a metal ion
or an ammonium ion, L represents oxygen or sulphur and M represents
oxygen or sulphur. R.sup.1 represents in each case optionally
halogen-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,
poly-C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl or optionally
halogen-, C.sub.1-C.sub.6-alkyl- or C.sub.1-C.sub.6-alkoxy-sub-
stituted C.sub.3-C.sub.8-cycloalkyl in which optionally one or.more
not directly adjacent ring members are replaced by oxygen and/or,
sulphur, 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-halogenoalkyl-, C.sub.1-C.sub.6-halogenoalkoxy-,
C.sub.1-C.sub.6-alkylthio- or
C.sub.1-C.sub.6-alkylsulphonyl-substituted phenyl, 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-halogenoalkyl- or
C.sub.1-C.sub.6-halogenoalkoxy-substit- uted
phenyl-C.sub.1-C.sub.6-alkyl, represents optionally halogen- or
C.sub.1-C.sub.6-alkyl-substituted 5- or 6-membered hetaryl (for
example pyrazolyl, thiazolyl, pyridyl, pyrimidyl, fiuranyl or
thienyl), represents optionally halogen- or
C.sub.1-C.sub.6-alkyl-substituted phenoxy-C.sub.1-C.sub.6-alkyl or
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 (for example
pyridyloxy-C.sub.1-C.sub.6-alkyl,
pyrimidyloxy-C.sub.1-C.sub.6-alkyl or
thiazolyloxy-C.sub.1-C.sub.6-alkyl)- . R.sup.2 represents in each
case optionally halogen-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,
poly-C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, 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
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-halogeno- alkyl- or
C.sub.1-C.sub.6-halogenoalkoxy-substituted phenyl or benzyl,
R.sup.3 represents optionally halogen-substituted
C.sub.1-C.sub.8-alkyl or represents 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-halogenoalkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
cyano- or nitro-substituted phenyl or benzyl. R.sup.4 and R.sup.5
independently of one another each 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, C.sub.2-C.sub.8-alkenylthio,
C.sub.3-C.sub.7-cycloalkylthio or represent in each case optionally
halogen-, nitro-, cyano-, C.sub.1-C.sub.4-alkoxy-- ,
C.sub.1-C.sub.4-halogenoalkoxy-, C.sub.1-C.sub.4-alkylthio-,
C.sub.1-C.sub.4-halogenoalkylthio-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-halogenoalkyl-substituted phenyl, phenoxy or
phenylthio, R.sup.6 and R.sup.7 independently of one another each
represent hydrogen, represent in each case optionally
halogen-substituted C.sub.1-CS-alkyl, C.sub.3-C.sub.8-cycloalkyl,
C.sub.1-C.sub.8-alkoxy, C.sub.3-C.sub.8-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl, represent optionally
halogen-, C.sub.1-CS-halogenoalkyl-, C.sub.1-C.sub.8-alkyl- or
C.sub.1-C.sub.8-alkoxy-substituted phenyl, optionally halogen-,
C.sub.1-C.sub.8-alkyl-, C.sub.1-C.sub.8-halogenoalky- l- or
C.sub.1-C.sub.8-alkoxy-substituted benzyl 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 carbon
atom is replaced by oxygen or sulphur. R.sup.13 represents
hydrogen, represents in each case optionally halogen-substituted
C.sub.1-C.sub.8-alkyl or C.sub.1-C.sub.8-alkoxy, represents
optionally halogen-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.3-C.sub.8-cycloalkyl in
which optionally one methylene group is replaced by oxygen or
sulphur, or represents 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-halogenoalkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
nitro- or cyano-substituted phenyl, phenyl-C.sub.1-C.sub.4-alkyl or
phenyl-C.sub.1-C.sub.4-alkoxy. R.sup.14 represents hydrogen or
C.sub.1-C.sub.8-alkyl, or R.sup.13 and R.sup.14 together represent
C.sub.4-C.sub.6-alkanediyl. R.sup.15 and R.sup.16 are identical or
different and each represent C.sub.1-C.sub.6-alkyl, or R.sup.15 and
R.sup.16 together represent a C.sub.2-C.sub.4-alkanediyl radical
which is optionally substituted by C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-halogenoalkyl or by optionally halogen-,
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.4-halogenoalkyl-,
C.sub.1-C.sub.6-alkoxy-, C.sub.1-C.sub.4-halogenoalkoxy-, nitro- or
cyano-substituted phenyl. R.sup.17 and R.sup.18 independently of
one another each represent hydrogen, represent optionally
halogen-substituted C.sub.1-C.sub.8-alkyl or represent optionally
halogen-, C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.4-halogeno- alkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
nitro- or cyano-substituted phenyl, or R.sup.17 and R.sup.18
together with the carbon atom to which they are attached represent
a carbonyl group or represent optionally halogen-,
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.5-C.sub.7-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulphur. R.sup.19 and R.sup.20
independently of one another each represent C.sub.1-C.sub.10-alkyl,
C.sub.2-C.sub.10-alkenyl, C.sub.1-C.sub.10-alkoxy,
C.sub.1-C.sub.10-alkylamino, C.sub.3-C.sub.10-alkenylamino,
di-(C.sub.1-C.sub.10-alkyl)amino or
di-(C.sub.3-C.sub.10-alkenyl)amino.
3. Compounds of the formula (I) according to claim 1 in which X
represents fluorine, chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.4-alkenyloxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
C.sub.3-C.sub.4-halogenoalkenyloxy, nitro or cyano, Y represents
one of the radicals 206V.sup.1 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-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
nitro, cyano or phenyl, phenoxy, phenoxy-C.sub.1-C.sub.2-alkyl,
phenyl-C.sub.1-C.sub.2-alkoxy, phenylthio-C.sub.1-C.sub.2-alkyl or
phenyl-C.sub.1-C.sub.2-alkylthio, 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-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
nitro or cyano. V.sup.2 and V.sup.3 independently of one another
each 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-halogenoalkyl or C.sub.1-C.sub.2-halogenoalkoxy, W
represents hydrogen, fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-halogenoalkoxy. Z
represents fluorine, chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-halogenoalkoxy, CKE represents one of the groups
207A represents hydrogen, in each case optionally fluorine- or
chlorine-substituted C.sub.1-C.sub.10-alkyl,
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.6-alkyl, optionally fluorine-,
chlorine-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.3-C.sub.7-cycloalkyl in
which optionally one ring member is replaced by oxygen or sulphur
or (but not in the case of the compounds of the formulae (I-5),
(I-7) and (I-8)) in each case optionally fluorine-, chlorine-,
bromine-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-halogenoalky- l-,
C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-halogenoalkoxy-substituted phenyl, furanyl,
pyridyl, imidazolyl, triazolyl, pyrazolyl, pyrimidyl, thiazolyl,
thienyl or phenyl-C.sub.1-C.sub.4-alkyl. B represents hydrogen or
C.sub.1-C.sub.6-alkyl, or A, B and the carbon atom to which they
are attached represent saturated or unsaturated
C.sub.5-C.sub.7-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur and which is optionally
monosubstituted by C.sub.1-C.sub.6-alkyl,
C.sub.5-C.sub.8-cycloalkyl, C.sub.1-C.sub.3-halogenoalkyl,
C.sub.1-C.sub.6-alkoxy, fluorine, chlorine or phenyl, or A, B and
the carbon atom to which they are attached represent
C.sub.5-C.sub.6-cycloalk- yl which is substituted by an
alkylenediyl group which optionally contains one or two not
directly adjacent oxygen or sulphur atoms or by an alkylenedioxyl
group or by an alkylenedithiol group which, together with the
carbon atom to which it is attached, forms a further five- or
six-membered ring, or A, B and the carbon atom to which they are
attached represents C.sub.3-C.sub.6-cycloalkyl or
C.sub.5-C.sub.6-cycloalkenyl in which two substituents together
with the carbon atoms to which they are attached represent in each
case optionally C.sub.1-C.sub.5-alkyl-, C.sub.1-C.sub.5-alkoxy-,
fluorine-, chlorine- or bromine-substituted
C.sub.2-C.sub.4-alkanediyl, C.sub.2-C.sub.4-alkenediyl, in which
optionally one methylene group is replaced by oxygen or sulphur, or
butadienediyl. D represents hydrogen, represents in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.6-alkyl or
C.sub.1-C.sub.8-alkylthio-C.sub.2-C.sub.6-alkyl, represents
optionally fluorine-, chlorine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.2-halogenoalkyl-substituted
C.sub.3-C.sub.7-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulphur or (but not in the case of the
compounds of the formulae (I-1) and (I-4)) represents in each case
optionally fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-halogenoalkyl-, C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-halogenoalkoxy-substituted phenyl, furanyt,
imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl,
thienyl, triazolyl or phenyl-C.sub.1-C.sub.4-alkyl, or A and D
together represent optionally substituted
C.sub.3-C.sub.5-alkanediyl in which one methylene group may be
replaced by a carbonyl group, oxygen or sulphur, possible
substituents being hydroxyl, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.4-alkoxy, or A and D (in the case of the compounds of
the formula (I-1)) together with the atoms to which they are
attached represent one of the groups AD-1 to AD-10: 208A and
Q.sup.1 together represent C.sub.3-C.sub.4-alkanediyl or
C.sub.3-C.sub.4-alkenediyl, each of which is optionally mono- or
disubstituted by identical or different substituents selected from
the group consisting of fluorine, chlorine, hydroxyl, and
C.sub.1-C.sub.8-alkyl and C.sub.1-C.sub.4-alkoxy, each of which is
optionally mono- to trisubstituted by fluorine, or Q.sup.1
represents hydrogen. Q.sup.2 represents hydrogen. Q.sup.4, Q.sup.5
and Q.sup.6 independently of one another each represent hydrogen or
C.sub.1-C.sub.3-alkyl. Q.sup.3 represents hydrogen,
C.sub.1-C.sub.4-alkyl,
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 or optionally
methyl- or methoxy-substituted C.sub.3-C.sub.6-cycloalkyl in which
optionally one methylene group is replaced by oxygen or sulphur, or
Q.sup.3 and Q.sup.4 together with the carbon atom to which they are
attached represent an optionally C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-substituted saturated C.sub.5-C.sub.6 ring
in which optionally one ring member is replaced by oxygen or
sulphur. G represents hydrogen (a) or represents one of the groups
209 in which E represents a metal ion or an ammonium ion, L
represents oxygen or sulphur and M represents oxygen or sulphur.
R.sup.1 represents in each case optionally fluorine- or
chlorine-substituted C.sub.1-C.sub.16-alkyl,
C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C- .sub.1-C.sub.6-alkyl,
poly-C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl or optionally
fluorine-, chlorine-, C.sub.1-C.sub.5-alkyl- or
C.sub.1-C.sub.5-alkoxy-substituted C.sub.3-C.sub.7-cycloalkyl in
which optionally one or two not directly adjacent ring members are
replaced by oxygen and/or sulphur, i represents optionally
fluorine-, chlorine-, bromine-, cyano-, nitro-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-- ,
C.sub.1-C.sub.3-halogenoalkyl-, C.sub.1-C.sub.3-halogenoalkoxy-,
C.sub.1-C.sub.4-alkylthio- or
C.sub.1-C.sub.4-alkylsulphonyl-substituted phenyl, represents
optionally fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.3-halogeno- alkyl- or
C.sub.1-C.sub.3-halogenoalkoxy-substituted
phenyl-C.sub.1-C.sub.4-alkyl, represents in each case optionally
fluorine-, chlorine-, bromine- or C.sub.1-C.sub.4-alkyl-substituted
pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl,
represents optionally fluorine-, chlorine-, bromine- or
C.sub.1-C.sub.4-alkyl-substi- tuted phenoxy-C.sub.1-C.sub.3-alkyl
or represents in each case optionally fluorine-, chlorine-,
bromine-, amino- or C.sub.1-C.sub.4-alkyl-substitut- ed
pyridyloxy-C.sub.1-C.sub.3-alkyl,
pyrimidyloxy-C.sub.1-C.sub.3-alkyl or
thiazolyloxy-C.sub.1-C.sub.3-alkyl. R.sup.2 represents in each case
optionally fluorine-substituted 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, represents
optionally fluorine-, chlorine-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-su- bstituted C.sub.3-C.sub.7-cycloalkyl or
represents in each case optionally 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-halogenoalkyl- or
C.sub.1-C.sub.3-halogenoalkoxy-substituted phenyl or benzyl;.
R.sup.3 represents optionally fluorine-substituted
C.sub.1-C.sub.6-alkyl or represents in each case optionally
fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.3-halogeno- alkyl-,
C.sub.1-C.sub.3-halogenoalkoxy-, cyano- or nitro-substituted phenyl
or benzyl, R.sup.4 and R.sup.5 independently of one another each
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, C.sub.3-C.sub.4-alkenylthio,
C.sub.3-C.sub.6-cycloalkylthio or represent in each case optionally
fluorine-, chlorine-, bromine-, nitro-, cyano-,
C.sub.1-C.sub.3-alkoxy-, C.sub.1-C.sub.3-halogenoalkoxy-,
C.sub.1-C.sub.3-alkylthio-, C.sub.1-C.sub.3-halogenoalkylthio-,
C.sub.1-C.sub.3-alkyl- or C.sub.1-C.sub.3-halogenoalkyl-substituted
phenyl, phenoxy or phenylthio., R.sup.6 and R.sup.7 independently
of one another each represent hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.6-alkenyl, C.sub.1-C.sub.6-alkoxy-C-
.sub.1-C.sub.6-alkyl, represent optionally fluorine-, chlorine-,
bromine-, C.sub.1-C.sub.3-halogenoalkyl-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-substituted phenyl, represent optionally
fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.3-halogenoalkyl- or
C.sub.1-C.sub.4-alkoxy-substituted benzyl, or together represent an
optionally methyl- or ethyl-substituted C.sub.4-C.sub.5-alkylene
radical in which optionally one methylene group is replaced by
oxygen or sulphur.
4. Compounds of the formula (I) according to claim 1 in which X
represents fluorine, chlorine, methyl, ethyl, propyl, iso-propyl,
methoxy, etboxy, propoxy, iso-propoxy, allyloxy, methallyloxy,
trifluoromethyl, difluoromethoxy, trifluoromethoxy, nitro or cyano.
Y represents one of the radicals 210V.sup.1 represents hydrogen,
fluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl,
n-butyl, iso-butyl, tert-butyl, methoxy, ethoxy, n-propoxy,
iso-propoxy, trifluoromethyl, trifluoromethoxy, nitro, cyano or
phenyl which is optionally monosubstituted by fluorine, chlorine,
methyl, methoxy, trifluoromethyl or trifluoromethoxy. V.sup.2 and
V.sup.3 independently of one another each represent hydrogen,
fluorine, chlorine, methyl, ethyl, n-propyl, iso-propyl, methoxy,
ethoxy, trifluoromethyl or trifluoromethoxy. W represents hydrogen,
fluorine, chlorine, methyl, ethyl, n-propyl, methoxy, ethoxy or
n-propoxy, Z represents fluorine, chlorine, methyl, ethyl,
n-propyl, methoxy, ethoxy or propoxy. CKE represents one of the
groups 211A represents hydrogen, in each case optionally
fluorine-substituted C.sub.1-C.sub.8-alkyl or
C.sub.1-C.sub.6-alkoxy-C.su- b.1-C.sub.4-alkyl, optionally
fluorine-, methyl-, ethyl- or methoxy-substituted
C.sub.3-C.sub.6-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur or (but not in the case of the
compounds of the formulae (I-5), (I-7) and (I-8)) represents in
each case optionally fluorine-, chlorine-, bromine-, methyl-,
ethyl-, n-propyl-, iso-propyl-, methoxy-, ethoxy-,
trifluoromethyl-, trifluoromethoxy-, cyano- or nitro-substituted
phenyl or benzyl, B represents hydrogen or C.sub.1-C.sub.4-alkyl,
or A, B and the carbon atom to which they are attached represent
saturated C.sub.5-C.sub.6-cycloalkyl or
C.sub.5-C.sub.6-cycloalkenyl in which optionally one ring member is
replaced by oxygen or sulphur and which is optionally
monosubstituted by methyl, ethyl, propyl, isopropyl, butyl,
iso-butyl, sec-butyl, tert-butyl, trifluoromethyl, methoxy, ethoxy,
n-propoxy, iso-propoxy, butoxy, iso-butoxy, sec-butoxy,
tert-butoxy, fluorine or chlorine, or A, B and the carbon atom to
which they are attached represent C.sub.5-C.sub.6-cycloalkyl or
C.sub.5-C.sub.6-cycloalkenyl in which two substituents together
with the carbon atoms to which they are attached represent
C.sub.2-C.sub.4-alkanediyl or C.sub.2-C.sub.4-alkenediyl in which
in each case optionally one methylene group is replaced by oxygen
or sulphur, or, butadienediyt. D represents hydrogen, represents in
each case optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.4-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.2-C.sub.4-alkyl or
C.sub.3-C.sub.6-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulphur or (but not in the case of the
compounds of the formulae (I-1) and (I-4)) represents in each case
optionally fluorine-, chlorine-, methyl-, ethyl-, n-propyl-,
iso-propyl-, methoxy-, ethoxy-, trifluoromethyl- or
trifluoromethoxy-substituted phenyl, furanyl, pyridyl, thienyl or
benzyl, or A and D together represent optionally substituted
C.sub.3-C.sub.4-alkanediyl in which optionally one carbon atom is
replaced by sulphur and which is optionally substituted by
hydroxyl, methyl, ethyl, methoxy or ethoxy, or A and D (in the case
of the compounds of the formula (I-1)) together with the atoms to
which they are attached represent one of the following groups AD:
212A and Q.sup.1 together represent C.sub.3-C.sub.4-alkanediyl or
butenediyl, each of which is optionally mono- or disubstituted by
fluorine, hydroxyl, methyl or methoxy, or Q.sup.1 represents
hydrogen, Q.sup.2 represents hydrogen. Q.sup.4, Q.sup.5 and Q.sup.6
independently of one another each represent hydrogen, methyl or
ethyl, Q.sup.3 represents hydrogen, methyl, ethyl or
C.sub.3-C.sub.6-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulphur, or Q.sup.3 and Q.sup.4 together
with the carbon atom to which they are attached represent an
optionally methyl- or methoxy-substituted saturated C.sub.5-C.sub.6
ring in which optionally one ring member is replaced by oxygen or
sulphur. G represents hydrogen (a) or represents one of the groups
213 in which E represents a metal ion or an ammonium ion, L
represents oxygen or sulphur and M represents oxygen or sulphur.
R.sup.1 represents in each case optionally fluorine- or
chlorine-substituted C.sub.1-C.sub.14-alkyl,
C.sub.2-C.sub.14-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-alkylthio-C- .sub.1-C.sub.6-alkyl,
poly-C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl or optionally
fluorine-, chlorine-, methyl-, ethyl-, propyl-, i-propyl-, butyl-,
i-butyl-, tert-butyl-, methoxy-, ethoxy-, n-propoxy- or
iso-propoxy-substituted C.sub.3-C.sub.6-cycloalkyl in which
optionally one or two not directly adjacent ring members are
replaced by oxygen and/or sulphur, represents optionally fluorine-,
chlorine-, bromine-, cyano-, nitro-, methyl-, ethyl-, n-propyl-,
i-propyl-, methoxy-, etboxy-, trifluoromethyl-, trifluoromethoxy-,
methylthio-, ethylthio-, methylsulphonyl- or
ethylsulphonyl-substituted phenyl, represents optionally fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n-propyl-, i-propyl-,
methoxy-, ethoxy-, trifluoromethyl- or trifluoro-methoxy-subst-
ituted benzyl, represents in each case optionally fluorine-,
chlorine-, bromine-, methyl- or ethyl-substituted fuiranyl,
thienyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl, represents
optionally fluorine-, chlorine, methyl- or ethyl-substituted
phenoxy-C.sub.1-C.sub.2-alkyl or represents in each case optionally
fluorine-, chlorine-, amino-, methyl- or ethyl-substituted
pyridyloxy-C.sub.1-C.sub.2-alkyl,
pyrimidyloxy-C.sub.1-C.sub.2-alkyl or
thiazolyloxy-C.sub.1-C.sub.2-alkyl. R.sup.2 represents in each case
optionally fluorine-substituted C.sub.1-C.sub.14-alkyl,
C.sub.2-C.sub.14-alkenyl, C.sub.1-C.sub.4-alkoxy--
C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.6-alkyl- , represents
optionally fluorine-, chlorine-, methyl-, ethyl-, n-propyl-,
iso-propyl- or methoxy-substituted C.sub.3-C.sub.6-cycloalkyl, or
represents in each case optionally fluorine-, chlorine-, cyano-,
nitro-, methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-, ethoxy-,
trifluoromethyl- or trifluoromethoxy-substituted phenyl or benzyl.
R.sup.3 represents in each case optionally fluorine-substituted
methyl, ethyl, n-propyl, isopropyl or in each case optionally
fluorine-, chlorine-, bromine-, methyl-, tert-butyl-, methoxy-,
trifluoromethyl-, trifluoromethoxy-, cyano- or nitro-substitued
phenyl or benzyl, R.sup.4 and R.sup.5 independently of one another
each represent C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-alkylamino- , di-(C.sub.1-C.sub.4-alkyl)amino,
C.sub.1-C.sub.4-alkylthio or represent in each case optionally
fluorine-, chlorine-, bromine-, nitro-, cyano-,
C.sub.1-C.sub.2-alkoxy-, C.sub.1-C.sub.2-fluoroalkoxy-,
C.sub.1-C.sub.2-alkylthio-, C.sub.1-C.sub.2-fluoroalkylthio- or
C.sub.1-C.sub.3-alkyl-substituted phenyl, phenoxy or phenylthiQ.
R.sup.6 and R.sup.7 independently of one another each 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, C.sub.1-C.sub.4-alkoxy-C-
.sub.1-C.sub.4-alkyl, represent optionally fluorine-, chlorine-,
bromine-, trifluoromethyl-, methyl- or methoxy-substituted phenyl,
represent optionally fluorine-, chlorine-, bromine-, methyl-,
trifluoromethyl- or methoxy-substituted benzyl, or together
represent a C.sub.5-C.sub.6-alkylene radical in which optionally
one methylene group is replaced by oxygen or sulphur.
5. Process for preparing compounds of the formula (I) according to
claim 1, characterized in that (A) Compounds of the formula (I-1-a)
214 in which A, B, D, WI X, Y and Z are each as defined in claim 1
are obtained by the intramolecular condensation of N-acylamino acid
esters of the formula (II) 215 in which A, B, D, W, X, Y and Z are
each as defined above, and R.sup.8 represents alkyl, in the
presence of a diluent and in the presence of a base, (B) Compounds
of the formula (I-2-a) 216 in which A, B, W, X, Y and Z are each as
defined above, are obtained by the intramolecular condensation of
carboxylic esters of the formula (1E) 217 in which A, B, X, Y, Z
and R.sup.8 are each as defined above, in the presence of a diluent
and in the presence of a base, (C) Compounds of the formula (I-3-a)
218 in which A, B, W, X, Y and Z are each as defined above, are
obtained by the intramolecular cyclization of .beta.-ketocarboxylic
esters of the formula (IV) 219 in which A, B, X, Y, Z and R.sup.8
are each as defined above and W represents hydrogen, halogen, alkyl
or alkoxy, if appropriate in the presence of a diluent and in the
presence of an acid, (D) Compounds of the formula (I-4-a) 220 in
which A, D, W, X, Y and Z are each as defined above, are obtained
by reacting (.alpha.) halogenocarbonyl ketenes of the formula (V)
221 in which W, X, Y and Z are each as defined above and Hal
represents halogen, or by reacting (.beta.) malonic acid
derivatives of the formula (VI) 222 in which R.sup.8, W, X, Y and Z
are each as defined above, with hydrazines of the formula (VII)
A--NH--NH-D (VII) in which A and D are each as defined above, if
appropriate in the presence of a diluent and if appropriate in the
presence of a base, (E) Compounds of the formula (I-5-a) 223 in
which A, D, W, X, Y and Z are each as defined above, are obtained
by reacting carbonyl compounds of the formula (VIII) 224 in which A
and D are each as defined above, or their silyl enol ethers of the
formula (VIlla) 225 in which A, D and R.sup.8 are each as defined
above, with ketene acid halides of the formula (V) 226 in which W,
X, Y and Z are each as defined above and Hal represents halogen, if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid acceptor, (F) Compounds of the formula (I-6-a)
227 in which A, W, X, Y and Z are each as defined above, are
obtained by reacting thioamides of the formula (IX) 228 in which A
is as defined above, with ketene acid halides of the formula (V)
229 in which Hal, W, X, Y and Z are each as defined above, if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid acceptor, (G) Compounds of the formula (I-7-a)
230 in which A, B, Q.sup.1, Q.sup.2, W. X, Y and Z are each as
defined in claim 1 are obtained by intramolecular cyclization of
ketocarboxylic esters of the formula (X) 231 in which A, B,
Q.sup.1, Q.sup.2, W, X, Y and Z are each as defined above and
R.sup.8 represents alkyl, if appropriate in the presence of a
diluent and in the presence of a base, (H) Compounds of the formula
(I-8-a) 232 in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W,
X, Y and Z are each as defined in claim 1 are obtained by
intramolecular condensation of 6-aryl-5-keto-hexanoic esters of the
formula (XI) 233 in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6,
W, X, Y and Z are each as defined above and R.sup.8 represents
alkyl, in the presence of a diluent and in the presence of a base,
(I) Compounds of the formulae (I-8-a) shown above in which A, B, D,
Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, X, Y and Z
are each as defined above are obtained by reacting compounds of the
formulae (I-1'-a) to (I-8'-a), 234 in which A, B, D, Q.sup.1,
Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X and Z are each as
defined above and Y' represents chlorine, bromine or iodine with
boronic acids of the formula (XII) 235 in which Y is as defined
above, in the presence of a solvent, a base and a catalyst and
subsequently reacting the resulting compounds of the formulae
(I-1-a) to (I-8-a) in each case (J.alpha.) with acyl halides of the
formula (Xffl) 236 in which R.sup.1 is as defined in claim 1 and
Hal represents halogen or (.beta.) with carboxylic anhydrides of
the formula (XIV) R.sup.1-CO--O--CO--R.sup.1 (XIV) in which R.sup.1
is as defined above, if appropriate in the presence of a diluent
and if appropriate in the presence of an acid binder, or in each
case (K) with chloroformic esters or chloroformic thioesters of the
formula (XV) R.sup.2--M--CO--Cl (XV) in which R.sup.2 and M are
each as defined in claim 1, if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder, or in
each case (L) with chloromonothioformic esters or
chloroditbiofoimic esters of the formula (XVI) 237 in which M and
R.sup.2 are each as defined above, if appropriate in the presence
of a diluent and if appropriate in the presence of an acid binder,
or in each case (M) with sulphonyl chlorides of the formula (XVII)
R.sup.3--SO.sub.2--Cl (XVH) in which R.sup.3 is as defined in claim
1, if appropriate in the presence of a diluent and if appropriate
in the presence of an acid binder, or in each case (N) with
phosphorus compounds of the formula (XVIII) 238 in which L, R.sup.4
and R.sup.5 are each as defined in claim 1 and Hal represents
halogen, if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder, or in each case (L)
with metal compounds or amines of the formulae (XIX) or (XX)
Me(OR.sup.10).sub.t (XIX) 239 in which Me represents a mono- or
divalent metal, t represents the number 1 or 2 and R.sup.10,
R.sup.11, R.sup.12 independently of one another each represent
hydrogen or alkyl, if appropriate in the presence of a diluent, or
in each case (P.alpha.) with isocyanates or isothiocyanates of the
formula (XXI) R.sup.6--N.dbd.C=L (XXI) in which R.sup.6 and L are
each as defined in claim 1, if appropriate in the presence of a
diluent and if appropriate in the presence of a catalyst, or in
each case (.beta.) with carbamoyl chlorides or thiocarbamoyl
chlorides of the formula (XXII) 240 in which L, R.sup.6 and R.sup.7
are each as defined in claim 1, if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder.
6. Compounds of the formula (II) 241in which A, B, D, W, X, Y and Z
are each as defined in claim 1 and R.sup.8 represents alkyl.
7. Compounds of the formula (XXIV) 242in which W, X, Y and Z are
each as defined in claim 1 and Hal represents chlorine or
bromine.
8. Compounds of the formula (XXV) 243in which A, B, D, W, X, Y and
Z are each as defined in claim 1.
9. Compounds of the formula (XXIX) 244in which A, B, D, W, X, Y and
Z are each as defined in claim 1.
10. Compounds of the formula (m) 245in which A, B, W, X, Y and Z
are each as defined above and R.sup.8 represents lkyl.
11. Compounds of the formula (XXVI) 246in which W, X, Y and Z are
each as defined in claim 1.
12. Compounds of the formula (XXXII) 247in which W, X, Y and Z are
each as defined in claim 1 and R.sup.8 represents alkyl.
13. Compounds of the formula (XXVII-b) 248in which W, X and Z are
each as defined in claim 1.
14. Compounds of the formula (IV) 249in which A, B, W, W.sup.1, X,
Y and Z are each as defined in claim 1 and R.sup.8 represents
alkyl.
15. Compounds of the formula (V) 250in which W, X, Y and Z are each
as defined in claim 1 and Hal represents chlorine or bromine.
16. Compounds of the formula (XXXVII) 251in which W, X, Y and Z are
each as defined in claim 1.
17. Compounds of the formula (VI) 252in which W, X, Y and Z are
each as defined in claim 1 and R.sup.8 represents alkyl.
18. Compounds of the formula (X) 253in which A, B, Q.sup.1,
Q.sup.2, W, X, Y and Z are each as defined in claim 1 and R.sup.8
represents alkyl.
19. Compounds of the formula (XXXVIII) 254in which W, X, Y, Z, A,
B, Q.sup.1 and Q.sup.2 are each as defined in claim 1.
20. Compounds of the formula (XXXIX) 255in which A, B, D.sup.1,
D.sup.2, W, X, Y and Z are each as defined in claim 1 and R.sup.8
and R.sup.8' each represent alkyl.
21. Compounds of the formula (XI) 256in which A, B, Q.sup.3,
Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are each as defined in
claim 1 and R.sup.8 represents alkyl.
22. Compounds of the formula (XLII) 257in which A, B, Q.sup.3,
Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are each as defined in
claim 1.
23. Compounds of the formula (XLIII) 258in which A, B, Q.sup.3,
Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are each as defined in
claim 1 and R.sup.8 and R.sup.8 each represent alky.
24. Pesticides and/or herbicides, characterized in that they
contain at least one compound of the formula (If according to claim
1.
25. The use of compounds of the formula (I) according to claim 1
for controlling pests in crop protection, in the domestic sector,
in the hygiene sector and in the protection of stored products.
26. Method for controlling pests in crop protection, in the
domestic sector, in the hygiene sector and in the protection of
stored products, characterized in that compounds of the formula (I)
according to claim 1 are allowed to act on the pests and/or their
habitat.
27. Method for preparing pesticides and/or herbicides)
characterized in that compounds of the formula (I) according to
claim 1 are mixed with extenders and/or surfactants.
Description
[0001] The present invention relates to novel
arylphenyl-substituted cyclic ketoenols, to a plurality of
processes for their preparation and to their use as pesticides and
herbicides.
[0002] Pharmaceutical properties of 3-acyl-pyrrolidine-2,4-diones
have already been described (S. Suzuki et al. Chem. Pharm. Bull. 15
1120 (1967)). Furthermore, N-phenylpyrrolidine-2,4-diones have been
synthesized by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem.
1985, 1095). A biological activity of these compounds has not been
described.
[0003] EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a
similar structure (3-aryl-pyrrolidine-2,4-diones) of which,
however, no herbicidal, insecticidal or acaricidal activity has
become known. Unsubstituted bicyclic 3-aryl-pyrrolidine-2,4-dione
derivatives (EP-A-355 599 and EP-415 211) and substituted
monocyclic 3-aryl-pyrrolidine-2,4-dio- ne derivatives (EP-A-377 893
and EP-442 077) having herbicidal, insecticidal or acaricidal
activity are known.
[0004] Also known are polycyclic 3-arylpyrrolidine-2,4-dione
derivatives (EP-442 073) and 1H-arylpyrrolidine-dione derivatives
(EP-456 063, EP-521 334, EP-596 298, EP-613 884, EP-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 and WO 97/36 868, DE
19 716 591).
[0005] It is known that certain substituted
.DELTA..sup.3-dihydrofuran-2-o- ne derivatives have herbicidal
properties (cf. DE-A-4 014 420). The synthesis of the tetronic acid
derivatives used as starting materials (such as, for example,
3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-.-
DELTA..sup.3-dihydrofuran-2-one) is likewise described in DE-A-4
014 420. Compounds of a similar structure are known from the
publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985,
(8) 1567-76, without any insecticidal and/or acaricidal activity
being mentioned. 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 and WO 97/36 868, DE 19 716 591.
3-Aryl-.DELTA..sup.3-dihydrothiophene-one derivatives are likewise
known (WO 95/26 345, 96/25 395, WO 97/01 535, WO 97/02 243, WO
97/36 868, DE 19 716 591).
[0006] Also known from the literature are certain 3H-pyrazol-3-one
derivatives, such as, for example,
1,2-diethyl-1,2-dihydro-5-hydroxy-4-ph- enyl-3H-pyrazol-3-one or
[5-oxo-1,2-diphenyl-4-(p-sulphophenyl)-3-pyrazoli- n-3-yl]-oxy,
disodium salt, or p-(3-hydroxy-5-oxo-1,2-diphenyl-3-pyrazolin-
-4-yl)-benzenesulphonic acid (cf. J. Heterocycl. Chem., 25(5),
1301-1305, 1988 or J. Heterocycl. Chem., 25(5), 1307-1310, 1988 or
Zh. Obshch. Khim., 34(7), 2397-2402, 1964). However, a biological
activity of these compounds is not described.
[0007] Furthermore, it is known that the trisodium salt of
4,4',4"-(5-hydroxy-3-oxo-1H-pyrazol-1,2,4
(3H)-triyl)-tris-benzenesulphon- ic acid has pharmacological
properties (cf. Farmnakol. Toksikol. (Moscow), 38(2), 180-186,
1976). However, it is not known to be used in crop protection.
[0008] Moreover, EP-508 126 and WO 92/16 510, WO 96/21 652 describe
4-arylpyrazolidin-3,5-dione derivatives having herbicidal,
acaricidal and insecticidal properties. Additionally,
4-arylpyrazolidines have become known of which fungicidal
properties have been described (WO 96/36 229, WO 96/36 615, WO
96/36 616, WO 96/36 633).
[0009] Certain phenyl-pyrone derivatives which are unsubstituted in
the phenyl ring have already become known (cf. A. M. Chirazi, T.
Kappe and E. Ziegler, Arch. Pharm. 309, 558 (1976) and K. -H.
Boltze and K. Heidenbluth, Chem. Ber. 91, 2849), a possible use of
these compounds as pesticides not being mentioned. Phenyl-pyrone
derivatives which are substituted in the phenyl ring and have
herbicidal, acaricidal and insecticidal properties are described in
EP-A-588 137, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02
243, WO 97/16 436, WO 97/19 941 and WO 97/36 868, DE 19 716
591.
[0010] Certain 5-phenyl-1,3-thiazine derivatives which are
unsubstituted in the phenyl ring have already become known (cf. E.
Ziegler and E. Steiner, Monatsh. 95, 147 (1964), R. Ketcham, T.
Kappe and E. Ziegler, J. Heterocycl. Chem. 10, 223 (1973)), a
possible use of these compounds as pesticides not being mentioned.
5-Phenyl-1,3-thiazine derivatives which are substituted in the
phenyl ring and have herbicidal, acaricidal and insecticidal
activity are described in WO 94/14 785, WO 96/02 539, WO 96/35 664,
WO 97/01 535, WO 97/02 243, WO 97/02 243, WO 97/36 868.
[0011] It is known that certain substituted
2-arylcyclopentanediones have herbicidal and acaricidal properties
(cf., for example, U.S. Pat. Nos. 4,283,348; 4,338,122; 4,436,666;
4,526,723; 4,551,547; 4,632,698; WO 96/01 798; WO 96/03 366 and
also WO 97/14 667). Moreover, compounds of a similar structure are
known: 3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-e- ne-1-one from
the publication Micklefield et al., Tetrahedron, (1992), 7519-26
and the natural product involutine (-)-cis-5-(3,4-dihydroxyphenyl-
)-3,4-dihydroxy-2-(4-hydroxyphenyl)-cyclopent-2-ene-one from the
publication Edwards et al., J. Chem. Soc. S, (1967), 405-9. An
insecticidal or acaricidal activity is not described. Moreover,
2-(2,4,6-trimethylphenyl)-1,3-indanedione is known from the
publication J. Economic Entomology, 66, (1973), 584 and the
Offenlegungsschrift DE-2 361 084, with herbicidal and acaricidal
activities being mentioned.
[0012] It is known that certain substituted 2-arylcyclohexanediones
have herbicidal and acaricidal properties (cf., for example, U.S.
Pat. Nos. 4,175,135, 4,209,432, 4,256,657, 4,256,658, 4,256,659,
4,257,858, 4,283,348, 4,303,669, 4,351,666, 4,409,153, 4,436,666,
4,526,723, 4,613,617, 4,659,372, DE-2 813 341, and also Wheeler, T.
N., J. Org. Chem. 44, 4906 (1979)).
[0013] However, the activity and the activity spectrum of these
compounds are, in particular at low application rates and
concentrations, not always entirely satisfactory. Furthermore, the
compatibility of these compounds with plants is not always
satisfactory.
[0014] This invention, accordingly, provides novel compounds of the
formula (I) 3
[0015] in which
[0016] X represents halogen, alkyl, alkoxy, alkenyloxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, halogenoalkyl, halogenoalkoxy,
halogenoalkenyloxy, nitro, cyano or in each case optionally
substituted phenyl, phenoxy, phenylthio, phenylalkoxy or
phenylalkylthio,
[0017] Y represents in each case optionally substituted cycloalkyl,
aryl or hetaryl,
[0018] W represents hydrogen, halogen, alkyl, alkoxy, alkenyloxy,
halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy, nitro or
cyano,
[0019] Z represents halogen, alkyl, alkoxy, alkenyloxy,
halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy, nitro or
cyano,
[0020] CKE represents one of the groups 4
[0021] in which
[0022] A represents hydrogen, in each case optionally
halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl,
alkylthioalkyl, saturated or unsaturated, optionally substituted
cycloalkyl in which optionally at least one ring atom is replaced
by a heteroatom, or in each case optionally halogen-, alkyl-,
halogenoalkyl-, alkoxy, halogenoalkoxy-, cyano- or
nitro-substituted aryl, arylalkyl or hetaryl,
[0023] B represents hydrogen, alkyl or alkoxyalkyl, or
[0024] A and B together with the carbon atom to which they are
attached represent a saturated or unsaturated unsubstituted or
substituted ring which optionally contains at least one
heteroatom,
[0025] D represents hydrogen or an optionally substituted radical
selected from the series consisting of alkyl, alkenyl, alkinyl,
alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or
unsaturated cycloalkyl in which one or more ring members are
optionally replaced by heteroatoms, arylalkyl, aryl, hetarylalkyl
or hetaryl or
[0026] A and D together with the atoms to which they are attached
represent a saturated or unsaturated ring which is unsubstituted or
substituted in the A,D moiety and which optionally contains at
least one (in the case where CKE=(4) further) heteroatom, or
[0027] A and Q.sup.1 together represent alkanediyl or alkenediyl,
each of which is optionally substituted by in each case optionally
substituted alkyl, hydroxyl, alkoxy, alkylthio, cycloalkyl,
benzyloxy or aryl, or
[0028] Q.sup.1 represents hydrogen or alkyl,
[0029] Q.sup.2, Q.sup.4, Q.sup.5 and Q.sup.6 independently of one
another each represent hydrogen or alkyl,
[0030] Q.sup.3 represents hydrogen, alkyl, alkoxyalkyl,
alkylthioalkyl, optionally substituted cycloalkyl (in which
optionally one methylene group is replaced by oxygen or sulphur) or
optionally substituted phenyl, or
[0031] Q.sup.3 and Q.sup.4 together with the carbon atom to which
they are attached represent a saturated or unsaturated
unsubstituted or substituted ring which optionally contains a
heteroatom,
[0032] G represents hydrogen (a) or represents one of the groups
5
[0033] in which
[0034] E represents a metal ion or an ammonium ion,
[0035] L represents oxygen or sulphur,
[0036] M represents oxygen or sulphur,
[0037] R.sup.1 represents in each case optionally
halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl,
polyalkoxyalkyl or optionally halogen-, alkyl- or
alkoxy-substituted cycloalkyl, which may be interrupted by at least
one heteroatom, in each case optionally substituted phenyl,
phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
[0038] R.sup.2 represents in each case optionally
halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or
represents in each case optionally substituted cycloalkyl, phenyl
or benzyl,
[0039] R.sup.3, R.sup.4 and R.sup.5 independently of one another
each represent in each case optionally halogen-substituted alkyl
alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio,
cycloalkylthio and represent in each case optionally substituted
phenyl, benzyl, phenoxy or phenylthio,
[0040] R.sup.6 and R.sup.7 independently of one another each
represent hydrogen, in each case optionally halogen-substituted
alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent
optionally substituted phenyl, represent optionally substituted
benzyl, or together with the nitrogen atom to which they are
attached represent a cycle which is optionally interrupted by
oxygen or sulphur.
[0041] Depending, inter alia, on the nature of the substituents,
the compounds of the formula (I) can be present as geometrical
and/or optical isomers or mixtures of isomers in varying
compositions, which can be separated, if desired, in a customary
manner. The present invention provides both the pure isomers and
the isomer mixtures, their preparation and use and also
compositions comprising them. In the following, for simplicity,
however, compounds of the formula (I) are always referred to,
although both pure compounds and, if appropriate, mixtures having
different proportions of isomeric compounds are intended.
[0042] Including the meanings (1) to (8) of the group CKE, the
following principal structures (I-1) to (I-8) result: 6
[0043] in which
[0044] A, B, D, G, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5,
Q.sup.6, W, X, Y and Z are each as defined above.
[0045] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-1-a)
to (I-1-g), result if CKE represents the group (1), 7
[0046] in which
[0047] A, B, D, E, L, M, W, X, Y, Z, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each as defined
above.
[0048] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-2-a)
to (I-2-g), result if CKE represents the group (2), 8
[0049] in which
[0050] A, B, E, L, M, W, X, Y, Z, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each as defined
above.
[0051] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-3-a)
to (I-3-g), result if CKE represents the group (3), 9
[0052] in which
[0053] A, B, E, L, M, W, X, Y, Z, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each as defined
above.
[0054] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-4-a)
to (I-4-g), result if CKE represents the group (4), 10
[0055] in which
[0056] A, D, E, L, M, W, X, Y, Z, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each as defined
above.
[0057] Depending on the position of the substituent G, the
compounds of the formula (I-5) can be present in the two isomeric
forms of the formulae (I-5-A) and (I-5-B), 11
[0058] which is meant to be indicated by the dashed line in the
formula (I-5).
[0059] The compounds of the formulae (I-5-A) and (I-5-B) can be
present both as mixtures and in the form of their pure isomers.
Mixtures of the compounds of the formulae (I-5-A) and (I-5-B) can
be separated, if desired, in a manner known per se by physical
methods, for example by chromatographic methods.
[0060] For reasons of clarity, hereinbelow in each case only one of
the possible isomers is given. This does not exclude that the
compounds may, if appropriate, be present in the form of the isomer
mixtures or in the respective other isomeric form.
[0061] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-5-a)
to (I-5-g) result if CKE represents the group (5), 12
[0062] in which
[0063] A, D, E, L, M, W, X, Y, Z, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each as defined
above.
[0064] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-6-a)
to (I-6-g), result if CKE represents the group (6), 13
[0065] in which
[0066] A, E, L, M, W, X, Y, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 are each as defined above.
[0067] Depending on the position of the substituent G, the
compounds of the formula (I-7) can be present in the two isomeric
forms of the formulae (I-7-A) and (I-7-B): 14
[0068] which is meant to be indicated by the dashed line in the
formula (I).
[0069] The compounds of the formulae (I-7-A) and (I-7-B) can be
present both as mixtures and in the form of their pure isomers.
Mixtures of the compounds of the formulae (I-7-A) and (I-7-B) can
be separated, if desired, by physical methods, for example by
chromatographic methods.
[0070] For reasons of clarity, hereinbelow in each case only one of
the possible isomers is given. This does not exclude that the
compounds may, if appropriate, be present in the form of the isomer
mixtures or in the respective other isomeric form.
[0071] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-7-a)
to (I-7-g) result: 15
[0072] in which
[0073] A, B, Q.sup.1, Q.sup.2, E, L, M, W, X, Y, Z, R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each as
defined above.
[0074] Depending on the position of the substituent G, the
compounds of the formula (I-8) can be present in the two isomeric
forms of the formulae (I-8-A) and (I-8-B) 16
[0075] which is meant to be indicated by the dashed line in the
formula (I).
[0076] The compounds of the formulae (I-8-A) and (I-8-B) can be
present both as mixtures and in the form of their pure isomers.
Mixtures of the compounds of the formulae (I-8-A) and (I-8-B) can
be separated, if desired, by physical methods, for example by
chromatographic methods.
[0077] For reasons of clarity, hereinbelow in each case only one of
the possible isomers is given. This takes into account that the
relevant compound may, if appropriate, be present as an isomer
mixture or in the respective other isomeric form.
[0078] Including the various meanings (a), (b), (c), (d), (e), (f)
and (g) of the group G, the following principal structures (I-8-a)
to (I-8-g) result: 17
[0079] in which
[0080] A, B, E, L, M, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y,
Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7
are each as defined above.
[0081] Furthermore, it has been found that the novel compounds of
the formula (I) are obtained by the processes described below:
[0082] (A) Substituted 3-phenylpyrrolidine-2,4-diones or their
enols of the formula (I-1-a) 18
[0083] in which
[0084] A, B, D, W, X, Y and Z are each as defined above
[0085] are obtained when
[0086] N-acylamino acid esters of the formula (II) 19
[0087] in which
[0088] A, B, D, W, X, Y and Z are each as defined above
[0089] and
[0090] R.sup.8 represents alkyl (preferably
C.sub.1-C.sub.6-alkyl)
[0091] are condensed intramolecularly in the presence of a diluent
and in the presence of a base.
[0092] (B) Moreover, it has been found that substituted
3-phenyl-4-hydroxy-.DELTA..sup.3-dihydrofuranone derivatives of the
formula (I-2-a) 20
[0093] in which
[0094] A, B, W, X, Y and Z are each as defined above
[0095] are obtained when
[0096] carboxylic esters of the formula (III) 21
[0097] in which
[0098] A, B, W, X, Y, Z and R.sup.8 are each as defined above
[0099] are condensed intramolecularly in the presence of a diluent
and in the presence of a base.
[0100] (C) Furthermore, it has been found that substituted
3-phenyl-4-hydroxy-.DELTA..sup.3-dihydrothiophenone derivatives of
the formula (I-3-a) 22
[0101] in which
[0102] A, B, W, X, Y and Z are each as defined above
[0103] are obtained when
[0104] .beta.-ketocarboxylic esters of the formula (IV) 23
[0105] in which
[0106] A, B, W, X, Y, Z and R.sup.8 are each as defined above
and
[0107] W.sup.1 represents hydrogen, halogen, alkyl (preferably
C.sub.1-C.sub.6-alkyl) or alkoxy (preferably
C.sub.1-C.sub.8-alkoxy)
[0108] are cyclized intramolecularly, if appropriate in the
presence of a diluent and in the presence of an acid.
[0109] (D) Furtherrnore, substituted
3-hydroxyl-4-phenyl-5-oxo-pyrazolines of the formula (I-4-a) 24
[0110] in which
[0111] A, D, W, X, Y and Z are each as defined above
[0112] are obtained when
[0113] (a) halogenocarbonyl ketenes of the formula (V) 25
[0114] in which
[0115] W, X, Y and Z are each as defined above
[0116] and
[0117] Hal represents halogen (in particular chlorine or
bromine)
[0118] or
[0119] (.beta.) malonic acid derivatives of the formula (VI) 26
[0120] in which
[0121] R.sup.8, W, X, Y and Z are each as defined above
[0122] are reacted with hydrazines of the formula (VII)
A--NH--NH-D (VII)
[0123] in which
[0124] A and D are each as defined above
[0125] if appropriate in the presence of a diluent and if
appropriate in the presence of a base.
[0126] (E) Furthermore, it has been found that the novel
substituted 3-phenylpyrone derivatives of the formula (I-5-a)
27
[0127] in which
[0128] A, D, W, X, Y and Z are each as defined above
[0129] are obtained when
[0130] carbonyl compounds of the formula (VIII) 28
[0131] in which
[0132] A and D are each as defined above
[0133] or their silyl enol ethers of the formula (Vila) 29
[0134] in which
[0135] A, D and R.sup.8 are each as defined above
[0136] are reacted with ketene acid halides of the formula (V)
30
[0137] in which
[0138] W, X, Y and Z are each as defined above and
[0139] Hal represents halogen (preferably represents chlorine or
bromine),
[0140] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid acceptor.
[0141] Furthermore, it has been found
[0142] (F) that the novel substituted phenyl-1,3-thiazine
derivatives of the formula (I-6-a) 31
[0143] in which
[0144] A, W, X, Y and Z are each as defined above
[0145] are obtained when thioamides of the formula (IX) 32
[0146] in which
[0147] A is as defined above
[0148] are reacted with ketene acid halides of the formula (V)
33
[0149] in which
[0150] Hal, W, X, Y and Z are each as defined above,
[0151] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid acceptor.
[0152] Furthermore, it has been found
[0153] (G) that compounds of the formula (I-7-a) 34
[0154] in which
[0155] A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are each as defined
above
[0156] are obtained when
[0157] ketocarboxylic esters of the formula (X) 35
[0158] in which
[0159] A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are each as defined
above and
[0160] R.sup.8 represents alkyl (in particular
C.sub.1-C.sub.8-alkyl)
[0161] are cyclized intramolecularly, if appropriate in the
presence of a diluent and in the presence of a base.
[0162] Moreover, it has been found
[0163] (H) that compounds of the formula (I-8-a) 36
[0164] in which
[0165] A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are
each as defined above
[0166] are obtained when
[0167] 6-aryl-5-keto-hexanoic esters of the formula (XI) 37
[0168] in which
[0169] A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are
each as defined above
[0170] and
[0171] R.sup.8 represents alkyl (preferably
C.sub.1-C.sub.6-alkyl)
[0172] are condensed intramolecularly in the presence of a diluent
and in the presence of a base;
[0173] or
[0174] (I) that compounds of the formulae (I-1-a) to (I-8-a) shown
above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, W, X, Y and Z are each as defined above are
obtained when compounds of the formula (I-1'-a) to (I-8'-a), 38
[0175] in which
[0176] A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5,
Q.sup.6, W, X and Z are each as defined above and
[0177] Y' represents chlorine, bromine or iodine, preferably
represents bromine,
[0178] are reacted with boronic acids of the formula (XII) 39
[0179] in which
[0180] Y is as defined above
[0181] in the presence of a solvent, a base and a catalyst,
suitable catalysts being, in particular, palladium complexes.
[0182] Moreover, it has been found
[0183] (J) that the compounds of the formulae (I-1-b) to (I-8-b)
shown above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.1, W, X, Y and Z are each as defined above
are obtained when compounds of the formulae (I-1-a) to (I-8-a)
shown above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, X, Y and Z are each as defined above are in each
case
[0184] (a) reacted with acyl halides of the formula (XIII) 40
[0185] in which
[0186] R.sup.1 is as defined above and
[0187] Hal represents halogen (in particular chlorine or
bromine)
[0188] or
[0189] (.beta.) reacted with carboxylic anhydrides of the formula
(XIV)
R.sup.1--CO--O--CO--R.sup.1 (XIV)
[0190] in which
[0191] R.sup.1 is as defined above,
[0192] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder;
[0193] (K) that the compounds of the formulae (I-1-c) to (I-8-c)
shown above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.2, M, W, X, Y and Z are each as defined
above and L represents oxygen are obtained when compounds of the
formulae (I-1-a) to (I-8-a) shown above in which A, B, D, Q.sup.1,
Q.sup.2, Q.sup.3, Q.sup.4, QS, Q.sup.6, W, X, Y and Z are each as
defined above are in each case reacted with chloroformic esters or
chloroformic thioesters of the formula (XV)
R.sup.2--M--CO--Cl (XV)
[0194] in which
[0195] R.sup.2 and M are each as defined above,
[0196] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder;
[0197] (L) that compounds of the formulae (I-1-c) to (I-8-c) shown
above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.2, M, W, X, Y and Z are each as defined
above and L represents sulphur are obtained when compounds of the
formulae (I-1-a) to (I-8-a) shown above in which A, B, D, Q.sup.1,
Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, y and Z are each
as defined above are in each case
[0198] reacted with chloromonothioformic esters or
chlorodithioformic esters of the formula (XVI) 41
[0199] in which
[0200] M and R.sup.2 are each as defined above
[0201] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder
[0202] and
[0203] (M) that compounds of the formulae (I-1-d) to (I-8-d) shown
above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.3, W, X, Y and Z are each as defined above
are obtained when compounds of the formulae (I-1-a) to (I-8-a)
shown above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, W, X, Y and Z are each as defined above are in
each case
[0204] reacted with sulphonyl chlorides of the formula (XVII)
R.sup.3--SO.sub.2--Cl (XVII)
[0205] in which
[0206] R.sup.3 is as defined above,
[0207] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder,
[0208] (N) that compounds of the formulae (I-1-e) to (I-8-e) shown
above in which A, B, D, L, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.4, R.sup.5, W, X, Y and Z are each as
defined above are obtained when compounds of the formulae (I-1-a)
to (I-8-a) shown above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3,
Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are each as defined above
are in each case
[0209] reacted with phosphorus compounds of the formula (XVIII)
42
[0210] in which
[0211] L, R.sup.4 and R.sup.5 are each as defined above and
[0212] Hal represents halogen (in particular chlorine or
bromine),
[0213] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder,
[0214] (L) that compounds of the formulae (I-1-f) to (I-8-f) shown
above in which A, B, D, E, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, W, X, Y and Z are each as defined above are
obtained when compounds of the formulae (I-1-a) to (I-8-a) in which
A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W,
X, Y and Z are each as defined above are in each case
[0215] reacted with metal compounds or amines of the formulae (XIX)
or (XX)
Me(OR.sup.10).sub.t (XIX) 43
[0216] in which
[0217] Me represents a mono- or divalent metal (preferably an
alkali metal or alkaline earth metal, such as lithium, sodium,
potassium, magnesium or calcium),
[0218] t represents the number 1 or 2 and
[0219] R.sup.11, R.sup.11, R.sup.1 .sup.2 independently of one
another each represent hydrogen or alkyl (preferably
C.sub.1-C.sub.8-alkyl),
[0220] if appropriate in the presence of a diluent,
[0221] (P) that compounds of the formulae (I-1-g) to (I-8-g) shown
above in which A, B, D, L, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4,
Q.sup.5, Q.sup.6, R.sup.6, R.sup.7, W, X, Y and Z are each as
defined above are obtained when compounds of the formulae (I-1-a)
to (I-8-a) shown above in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3,
Q.sup.4, Q.sup.5, Q.sup.6, X, Y and Z are each as defined above are
in each case
[0222] (.alpha.) reacted with isocyanates or isothiocyanates of the
formula (XXI)
R.sup.6--N.dbd.C.dbd.L (XXI)
[0223] in which
[0224] R.sup.6 and L are each as defined above
[0225] if appropriate in the presence of a diluent and if
appropriate in the presence of a catalyst, or
[0226] (.beta.) reacted with carbamoyl chlorides or thiocarbamoyl
chlorides of the formula (XXII) 44
[0227] in which
[0228] L, R.sup.6 and R.sup.7 are each as defined above
[0229] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0230] Furthermore, it has been found that the novel compounds of
the formula (I) have very good activity as pesticides, preferably
as insecticides, acaricides and herbicides.
[0231] 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 mentioned hereinabove
and hereinbelow are illustrated below:
[0232] X preferably represents halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-halogenoalkyl, 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-halogenoalkoxy, C.sub.3-C.sub.6-halogenoalkenyloxy,
nitro, cyano 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-halogenoalkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
nitro- or cyano-substituted phenyl, phenoxy, phenylthio, benzyloxy
or benzylthio.
[0233] Y preferably represents one of the radicals 45
[0234] 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-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, nitro, cyano or 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-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, nitro or cyano.
[0235] V.sup.2 and V.sup.3 independently of one another each
preferably represent hydrogen, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoalkyl or
C.sub.1-C.sub.4-halo-genoalkoxy.
[0236] W preferably represents hydrogen, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenoalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-halogenoalkoxy, nitro or
cyano.
[0237] Z preferably represents halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-halogenoalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-halogenoalkoxy, nitro or cyano.
[0238] CKE preferably represents one of the groups 46
[0239] A preferably represents hydrogen or in each case optionally
halogen-substituted C.sub.1-C.sub.12-alkyl,
C.sub.3-C.sub.8-alkenyl,
C.sub.1-C.sub.10-alkoxy-C.sub.1-C.sub.8-alkyl,
poly-C.sub.1-C.sub.8-alkox- y-C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.10-alkylthio-C.sub.1-C.sub.6-alkyl, optionally
halogen-, C.sub.1-C.sub.6-alkyl- or C.sub.1-C.sub.6-alkoxy-sub-
stituted C.sub.3-C.sub.8-cycloalkyl in which optionally one or two
not directly adjacent ring members are replaced by oxygen and/or
sulphur or represents in each case optionally halogen-,
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-halogenoalkyl-,
C.sub.1-C.sub.6-alkoxy-, C.sub.1-C.sub.6-halogenoalkoxy-, cyano- or
nitro-substituted C.sub.6- or C.sub.10-aryl (phenyl or naphthyl),
hetaryl having 5 to 6 ring atoms (for example furanyl, pyridyl,
imidazolyl, triazolyl, pyrazolyl, pyrimidyl, thiazolyl or thienyl)
or C.sub.6- or C.sub.10-aryl-C.sub.1-C.sub.6-alkyl
(phenyl-C.sub.1-C.sub.6-alkyl or
naphthyl-C.sub.1-C.sub.6-alkyl).
[0240] B preferably represents hydrogen, C.sub.1-C.sub.16alkyl or
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.6-alkyl or
[0241] A, B and the carbon atom to which they are attached
preferably represent saturated C.sub.3-C.sub.10-cycloalkyl or
unsaturated C.sub.5-C.sub.10-cycloalkyl in which in each case
optionally one ring member is replaced by oxygen or sulphur and
which are optionally mono- or disubstituted by
C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.10-cycloalkyl,
C.sub.1-C.sub.8-halogenoalkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.1-C.sub.8-alkylthio, halogen or phenyl or
[0242] A, B and the carbon atom to which they are attached
preferably represent C.sub.3-C.sub.6-cycloalkyl which is
substituted by an alkylenedilyl group which optionally contains one
or two not directly adjacent oxygen and/or sulphur atoms, or by an
alkylenedioxyl group or by an alkylenedithioyl group which,
together with the carbon atom to which it is attached, forms a
further five- to eight-membered ring, or
[0243] A, B and the carbon atom to which they are attached
preferably represent C.sub.3-C.sub.8-cycloalkyl or
C.sub.5-C.sub.8-cycloalkenyl, in which two substituents together
with the carbon atoms to which they are attached represent in each
case optionally C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy- or
halogen-substituted C.sub.2-C.sub.6-alkanediyl- ,
C.sub.2-C.sub.6-alkenediyl or C.sub.4-C.sub.6-alkanedienediyl in
which optionally one methylene group is replaced by oxygen or
sulphur.
[0244] D preferably represents hydrogen, in each case optionally
halogen-substituted C.sub.1-C.sub.12-alkyl,
C.sub.3-C.sub.8-alkenyl, C.sub.3-C.sub.8-alkinyl,
C.sub.1-C.sub.10-alkoxy-C.sub.2-C.sub.8-alkyl,
poly-C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl,
C.sub.1-C.sub.10-alkylthio-C.sub.2-C.sub.8-alkyl, optionally
halogen-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-halogenoalkyl-substituted
C.sub.3-C.sub.8-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur or in each case optionally halogen-,
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-halogenoalkyl-,
C.sub.1-C.sub.6-alkoxy-, C.sub.1-C.sub.6-halogenoalkoxy-, cyano- or
nitro-substituted phenyl, hetaryl having 5 or 6 ring atoms (for
example furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl,
pyrimidyl, pyrrolyl, thienyl or triazolyl),
phenyl-C.sub.1-C.sub.6-alkyl or hetaryl-C.sub.1-C.sub.6-alkyl
having 5 or 6 ring atoms (for example furanyl, imidazolyl, pyridyl,
thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl or triazolyl),
or
[0245] A and D together preferably represent in each case
optionally substituted C.sub.3-C.sub.6-alkanediyl or
C.sub.3-C.sub.6-alkenediyl in which optionally one methylene group
is replaced by oxygen or sulphur,
[0246] possible substituents in each case being:
[0247] halogen, hydroxyl, mercapto or in each case optionally
halogen-substituted C.sub.1-C.sub.1 o-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio,
C.sub.3-C.sub.7-cycloalkyl, phenyl or benzyloxy, or a further
C.sub.3-C.sub.6-alkanediyl grouping, C.sub.3-C.sub.6-alkenediyl
grouping or a butadienyl grouping which is optionally substituted
by C.sub.1-C.sub.6-alkyl or in which optionally two adjacent
substituents together with the carbon atoms to which they are
attached form a further saturated or unsaturated cycle having 5 or
6 ring atoms (in the case of the compound of the formula (I-1), A
and D, together with the atoms to which they are attached, then
represent, for example, the groups AD-1 to AD-10 mentioned further
below) which cycle may contain oxygen or sulphur, or which may
optionally contain one of the groups below 47
[0248] A and Q.sup.1 together preferably represent
C.sub.3-C.sub.6-alkaned- iyl or C.sub.4-C.sub.6-alkenediyl, each of
which is optionally mono- or disubstituted by identical or
different substituents selected from the group consisting of
halogen, hydroxyl; C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.3-C.sub.7-cycloalkyl, each of
which is optionally mono- to trisubstituted by identical or
different halogens; and benzyloxy and phenyl, each of which is
optionally mono- to trisubstituted by identical or different
substituents selected from the group consisting of halogen,
C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy, and which
furthermore optionally contains one of the groups below 48
[0249] or is bridged by a C.sub.1-C.sub.2-alkanediyl group or by an
oxygen atom, or
[0250] Q.sup.1 preferably represents hydrogen or
C.sub.1-C.sub.4-alkyl.
[0251] Q.sup.2, Q.sup.4, Q.sup.5 and Q.sup.6 independently of one
another each preferably represent hydrogen or
C.sub.1-C.sub.4-alkyl,
[0252] Q.sup.3 preferably represents hydrogen,
C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.6-alkylthio-C- .sub.1-C.sub.2-alkyl, optionally
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.3-C.sub.8-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulphur or optionally halogen-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.2-halogenoalkyl-, C.sub.1-C.sub.2-halogenoalkoxy-,
cyano- or nitro-substituted phenyl, or
[0253] Q.sup.3 and Q.sup.4 together with the carbon atom to which
they are attached represent an optionally C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy- or C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.2-halogenoalkyl-substituted C.sub.3-C.sub.7-ring, in
which optionally one ring member is replaced by oxygen or
sulphur.
[0254] G preferably represents hydrogen (a) or represents one of
the groups 49
[0255] (g), in particular represents (a), (b) or (c),
[0256] in which
[0257] E represents a metal ion or an ammonium ion,
[0258] L represents oxygen or sulphur and
[0259] M represents oxygen or sulphur.
[0260] R.sup.1 preferably represents in each case optionally
halogen-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,
poly-C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl or optionally
halogen-, C.sub.1-C.sub.6-alkyl- or C.sub.1-C.sub.6-alkoxy-sub-
stituted C.sub.3-C.sub.8-cycloalkyl in which optionally one or more
(preferably not more than two) not directly adjacent ring members
are replaced by oxygen and/or sulphur,
[0261] 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-halogeno- alkyl-, C.sub.1-C.sub.6-halogenoalkoxy-,
C.sub.1-C.sub.6-alkylthio- or
C.sub.1-C.sub.6-alkylsulphonyl-substituted phenyl,
[0262] 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-halogeno- alkyl- or
C.sub.1-C.sub.6-halogenoalkoxy-substituted
phenyl-C.sub.1-C.sub.6-alkyl,
[0263] represents optionally halogen- or
C.sub.1-C.sub.6-alkyl-substituted 5- or 6-membered hetaryl (for
example pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or
thienyl),
[0264] represents optionally halogen- or
C.sub.1-C.sub.6-alkyl-substituted phenoxy-C.sub.1-C.sub.6-alkyl
or
[0265] represents optionally halogen-, amino- or
C.sub.1-C.sub.6-alkyl-sub- stituted 5- or 6-membered
hetaryloxy-C.sub.1-C.sub.6-alkyl (for example
pyridyloxy-C.sub.1-C.sub.6-alkyl,
pyrimidyloxy-C.sub.1-C.sub.6-alkyl or
thiazolyloxy-C.sub.1-C.sub.6-alkyl).
[0266] R.sup.2 preferably represents in each case optionally
halogen-substituted C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.2O-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl,
poly-C.sub.1-C.sub.8-alkoxy- -C.sub.2-C.sub.8-alkyl,
[0267] 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
[0268] 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-halogeno- alkyl- or
C.sub.1-C.sub.6-halogenoalkoxy-substituted phenyl or benzyl.
[0269] R.sup.3 preferably represents optionally halogen-substituted
C.sub.1-C.sub.8-alkyl or represents 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-halogeno- alkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
cyano- or nitro-substituted phenyl or benzyl.
[0270] R.sup.4 and R.sup.5 independently of one another each
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-CS-alkylthio, C.sub.2-C.sub.8-alkenylthio,
C.sub.3-C.sub.7-cycloalkylthio or represent in each case optionally
halogen-, nitro-, cyano-, C.sub.1-C.sub.4-alkoxy-- ,
C.sub.1-C.sub.4-halogenoalkoxy-, C.sub.1-C.sub.4-alkylthio-,
C.sub.1-C.sub.4-halogenoalkylthio-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-halogenoalkyl-substituted phenyl, phenoxy or
phenylthio.
[0271] R.sup.6 and R.sup.7 independently of one another each
preferably represent hydrogen, represent in each case optionally
halogen-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, C.sub.1-C.sub.8-alkoxy-C-
.sub.1-C.sub.8-alkyl, represent optionally halogen-,
C.sub.1-C.sub.8-halogenoalkyl-, C.sub.1-C.sub.8-alkyl- or
C.sub.1-C.sub.8-alkoxy-substituted phenyl, optionally halogen-,
C.sub.1-C.sub.8-alkyl-, C.sub.1-C.sub.8-halogenoalkyl- or
C.sub.1-C.sub.8-alkoxy-substituted benzyl 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 carbon
atom is replaced by oxygen or sulphur.
[0272] R.sup.13 preferably represents hydrogen, represents in each
case optionally halogen-substituted C.sub.1-C.sub.8-alkyl or
C.sub.1-C.sub.8-alkoxy, represents optionally halogen-,
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.3-C.sub.8-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulphur, or represents 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-halogenoalkyl-,
C.sub.1-C.sub.4-halogenoalkoxy-, nitro- or cyano-substituted
phenyl, phenyl-C.sub.1-C.sub.4-alkyl or
phenyl-C.sub.1-C.sub.4-alkoxy.
[0273] R.sup.14 preferably represents hydrogen or
C.sub.1-C.sub.8-alkyl, or
[0274] R.sup.13 and R.sup.14 together preferably represent
C.sub.4-C.sub.6-alkanediyl.
[0275] R.sup.15 and R.sup.16 are identical or different and each
preferably represent C.sub.1-C.sub.6-alkyl, or
[0276] R.sup.15 and R.sup.16 together preferably represent a
C.sub.2-C.sub.4-alkanediyl radical which is optionally substituted
by C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenoalkyl or by
optionally halogen-, C.sub.1-C.sub.6-alkyl-,
C.sub.1-C.sub.4-halogenoalkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.4-halogenoalkoxy-, nitro- or cyano-substituted
phenyl.
[0277] R.sup.17 and R.sup.18 independently of one another each
preferably represent hydrogen, represent optionally
halogen-substituted C.sub.1-C.sub.8-alkyl or represent optionally
halogen-, C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-,
C.sub.1-C.sub.4-halogeno- alkyl-, C.sub.1-C.sub.4-halogenoalkoxy-,
nitro- or cyano-substituted phenyl, or
[0278] R.sup.17 and R.sup.18 together with the carbon atom to which
they are attached preferably represent a carbonyl group or
represent optionally halogen-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-sub- stituted C.sub.5-C.sub.7-cycloalkyl in
which optionally one methylene group is replaced by oxygen or
sulphur.
[0279] R.sup.19 and R.sup.20 independently of one another each
preferably represent C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.1
o-alkenyl, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.1 o-alkylamino,
C.sub.3-C.sub.10-alkenylamino, di-(C.sub.1-C.sub.10-alkyl)amino or
di-(C.sub.3-C.sub.10-alkenyl)amino.
[0280] In the preferred radical definitions, halogen represents
fluorine, chlorine, bromine and iodine and in particular represents
fluorine, chlorine and bromine.
[0281] X particularly preferably represents fluorine, chlorine,
bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenyloxy- , C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, C.sub.3-C.sub.4-halogenoalkenyloxy,
nitro or cyano.
[0282] Y particularly preferably represents one of the radicals
50
[0283] 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-halogenoalkyl,
C.sub.1-C.sub.2-halogenoalkoxy, nitro, cyano or phenyl, phenoxy,
phenoxy-C.sub.1-C.sub.2-alkyl, phenyl-C.sub.1-C.sub.2-alkoxy,
phenylthio-C.sub.1-C.sub.2-alkyl or
phenyl-C.sub.1-C.sub.2-alkylthio, 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-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
nitro or cyano.
[0284] V.sup.2 and V.sup.3 independently of one another each
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-halogenoal- kyl or
C.sub.1-C.sub.2-halogenoalkoxy.
[0285] W particularly preferably represents hydrogen, fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-halogenoalkoxy.
[0286] Z particularly preferably represents fluorine, chlorine,
bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-halogenoalkoxy.
[0287] CKE particularly preferably represents one of the groups
51
[0288] A particularly preferably represents hydrogen, in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.10-alkyl,
C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.6-alkyl, optionally fluorine-,
chlorine-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.3-C.sub.7-cycloalkyl in
which optionally one ring member is replaced by oxygen or sulphur
or (but not in the case of the compounds of the formulae (I-5),
(I-7) and (I-8)) in each case optionally fluorine-, chlorine-,
bromine-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-halogenoalky- l-,
C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-halogenoalkoxy-substituted phenyl, furanyl,
pyridyl, imidazolyl, triazolyl, pyrazolyl, pyrimidyl, thiazolyl,
thienyl or phenyl-C.sub.1-C.sub.4-alkyl.
[0289] B particularly preferably represents hydrogen or
C.sub.1-C.sub.6-alkyl, or
[0290] A, B and the carbon atom to which they are attached
particularly preferably represent saturated or unsaturated
C.sub.5-C.sub.7-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur and which is optionally
monosubstituted by C.sub.1-C.sub.6-alkyl,
C.sub.5-C.sub.8-cycloalkyl, C.sub.1-C.sub.3-halogenoalkyl,
C.sub.1-C.sub.6-alkoxy, fluorine, chlorine or phenyl, or
[0291] A, B and the carbon atom to which they are attached
particularly preferably represent C.sub.5-C.sub.6-cycloalkyl which
is substituted by an alkylenediyl group which optionally contains
one or two not directly adjacent oxygen or sulphur atoms or by an
alkylenedioxyl group or by an alkylenedithiol group which, together
with the carbon atom to which it is attached, forms a further five-
or six-membered ring, or
[0292] A, B and the carbon atom to which they are attached
particularly preferably represent C.sub.3-C.sub.6-cycloalkyl or
C.sub.5-C.sub.6-cycloalkenyl in which two substituents together
with the carbon atoms to which they are attached represent in each
case optionally C.sub.1-C.sub.5-alkyl-, C.sub.1-C.sub.5-alkoxy-,
fluorine-, chlorine- or bromine-substituted
C.sub.2-C.sub.4-alkanediyl, C.sub.2-C.sub.4-alkenediy- l, in which
optionally one methylene group is replaced by oxygen or sulphur, or
butadienediyl.
[0293] D particularly preferably represents hydrogen, represents in
each case optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.6-alkyl or
C.sub.1-C.sub.8-alkylthio-C.sub.2-C.sub.6-alkyl, represents
optionally fluorine-, chlorine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.2-halogenoalkyl-substituted
C.sub.3-C.sub.7-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulphur or (but not in the case of the
compounds of the formulae (I-1) and (I-4)) represents in each case
optionally fluorine-, chlorine-, bromine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-halogenoalkyl-, C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-halogenoalkoxy-substituted phenyl, furanyl,
imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl,
thienyl, triazolyl or phenyl-C.sub.1-C.sub.4-alkyl, or
[0294] A and D together particularly preferably represent
optionally substituted C.sub.3-C.sub.5-alkanediyl in which one
methylene group may be replaced by a carbonyl group, oxygen or
sulphur, possible substituents being hydroxyl,
C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.4-alkoxy, or
[0295] A and D (in the case of the compounds of the formula (I-1))
together with the atoms to which they are attached represent one of
the groups AD-I to AD-10: 52
[0296] A and Q.sup.1 together particularly preferably represent
C.sub.3-C.sub.4-alkanediyl or C.sub.3-C.sub.4-alkenediyl, each of
which is optionally mono- or disubstituted by identical or
different substituents selected from the group consisting of
fluorine, chlorine, hydroxyl, and C.sub.1-C.sub.8-alkyl and
C.sub.1-C.sub.4-alkoxy, each of which is optionally mono- to
trisubstituted by fluorine, or
[0297] Q.sup.1 particularly preferably represents hydrogen.
[0298] Q.sup.2 particularly preferably represents hydrogen.
[0299] Q.sup.4, Q.sup.5 and Q.sup.6 independently of one another
each particularly preferably represent hydrogen or
C.sub.1-C.sub.3-alkyl.
[0300] Q.sup.3 particularly preferably represents hydrogen,
C.sub.1-C.sub.4-alkyl,
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 or optionally
methyl- or methoxy-substituted C.sub.3-C.sub.6-cycloalkyl in which
optionally one methylene group is replaced by oxygen or sulphur,
or
[0301] Q.sup.3 and Q.sup.4 together with the carbon atom to which
they are attached particularly preferably represent an optionally
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted
saturated C.sub.5-C.sub.6 ring in which optionally one ring member
is replaced by oxygen or sulphur.
[0302] G particularly preferably represents hydrogen (a) or
particularly preferably represents one of the groups 53
[0303] (g), in particular represents (a), (b) or (c),
[0304] in which
[0305] E represents a metal ion or an ammonium ion,
[0306] L represents oxygen or sulphur and
[0307] M represents oxygen or sulphur.
[0308] R.sup.1 particularly preferably represents in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.16-alkyl, C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl,
poly-C.sub.1-C.sub.6-alk- oxy-C.sub.1-C.sub.6-alkyl or optionally
fluorine-, chlorine-, C.sub.1-C.sub.5-alkyl- or
C.sub.1-C.sub.5-alkoxy-substituted C.sub.3-C.sub.7-cycloalkyl in
which optionally one or two not directly adjacent ring members are
replaced by oxygen and/or sulphur,
[0309] represents optionally fluorine-, chlorine-, bromine-,
cyano-, nitro-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.3-halogenoalkyl-, C.sub.1-C.sub.3-halogenoalkoxy-,
C.sub.1-C.sub.4-alkylthio- or
C.sub.1-C.sub.4-alkylsulphonyl-substituted phenyl,
[0310] represents optionally fluorine-, chlorine-, bromine-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.3-halogeno- alkyl- or
C.sub.1-C.sub.3-halogenoalkoxy-substituted
phenyl-C.sub.1-C.sub.4-alkyl,
[0311] represents in each case optionally fluorine-, chlorine-,
bromine- or C.sub.1-C.sub.4-alkyl-substituted pyrazolyl, thiazolyl,
pyridyl, pyrimidyl, furanyl or thienyl,
[0312] represents optionally fluorine-, chlorine-, bromine- or
C.sub.1-C.sub.4-alkyl-substituted phenoxy-C.sub.1-C.sub.3-alkyl or
represents in each case optionally fluorine-, chlorine-, bromine-,
amino- or C.sub.1-C.sub.4-alkyl-substituted
pyridyloxy-C.sub.1-C.sub.3-alkyl,
pyrimidyloxy-C.sub.1-C.sub.3-alkyl or
thiazolyloxy-C.sub.1-C.sub.3-alkyl.
[0313] R.sup.2 particularly preferably represents in each case
optionally fluorine-substituted 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-alko- xy-C.sub.2-C.sub.6-alkyl,
[0314] represents optionally fluorine-, chlorine-,
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.3-C.sub.7-cycloalkyl or
[0315] represents in each case optionally 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-halogenoalkyl- or
C.sub.1-C.sub.3-halo-genoalkoxy-substit- uted phenyl or benzyl,
[0316] R.sup.3 particularly preferably represents optionally
fluorine-substituted C.sub.1-C.sub.6-alkyl or particularly
preferably represents in each case optionally fluorine-, chlorine-,
bromine-, C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.3-halogeno- alkyl-, C.sub.1-C.sub.3-halogenoalkoxy-,
cyano- or nitro-substituted phenyl or benzyl,
[0317] R.sup.4 and R.sup.5 independently of one another each
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,
C.sub.3-C.sub.4-alkenylthio, C.sub.3-C.sub.6-cycloalkylthio or
represent in each case optionally fluorine-, chlorine-, bromine-,
nitro-, cyano-, C.sub.1-C.sub.3-alkoxy-,
C.sub.1-C.sub.3-halogenoalkoxy-, C.sub.1-C.sub.3-alkylthio-,
C.sub.1-C.sub.3-halogenoalkylthio-, C.sub.1-C.sub.3-alkyl- or
C.sub.1-C.sub.3-halogenoalkyl-substituted phenyl, phenoxy or
phenylthio, and
[0318] R.sup.6 and R.sup.7 independently of one another each
particularly preferably represent hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.6-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, represent optionally
fluorine-, chlorine-, bromine-, C.sub.1-C.sub.3-halogenoalkyl-,
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted
phenyl, represent optionally fluorine-, chlorine-, bromine-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.3-halogenoalkyl- or
C.sub.1-C.sub.4-alkoxy-substituted benzyl, or together represent an
optionally methyl- or ethyl-substituted C.sub.4-C.sub.5-alkylene
radical in which optionally one methylene group is replaced by
oxygen or sulphur.
[0319] In the particularly preferred radical definitions, halogen,
if not stated otherwise, represents fluorine, chlorine, bromine and
iodine, in particular represents fluorine, chlorine and
bromine.
[0320] X very particularly preferably represents fluorine,
chlorine, methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy,
propoxy, iso-propoxy, allyloxy, methallyloxy, trifluoromethyl,
difluoromethoxy, trifluoromethoxy, nitro or cyano.
[0321] Y very particularly preferably represents one of the
radicals 54
[0322] in particular represents
[0323] V.sup.1 very particularly preferably represents hydrogen,
fluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl,
n-butyl, iso-butyl, tert-butyl, methoxy, ethoxy, n-propoxy,
iso-propoxy, trifluoromethyl, trifluoromethoxy, nitro, cyano or
phenyl which is optionally monosubstituted by fluorine, chlorine,
methyl, methoxy, trifluoromethyl or trifluoromethoxy.
[0324] V.sup.2 and V.sup.3 independently of one another each very
particularly preferably represent hydrogen, fluorine, chlorine,
methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy,
trifluoromethyl or trifluoromethoxy.
[0325] W very particularly preferably represents hydrogen,
fluorine, chlorine, methyl, ethyl, n-propyl, methoxy, ethoxy or
propoxy.
[0326] Z very particularly preferably represents fluorine,
chlorine, methyl, ethyl, n-propyl, methoxy, ethoxy or propoxy.
[0327] CKE very particularly preferably represents one of the
groups 55
[0328] A very particularly preferably represents hydrogen, in each
case optionally fluorine-substituted C.sub.1-C.sub.8-alkyl or
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, optionally fluorine-,
methyl-, ethyl- or methoxy-substituted C.sub.3-C.sub.6-cycloalkyl
in which optionally one ring member is replaced by oxygen or
sulphur or (but not in the case of the compounds of the formulae
(I-5), (I-7) and (I-8)) represents in each case optionally
fluorine-, chlorine-, bromine-, methyl-, ethyl-, n-propyl-,
iso-propyl-, methoxy-, ethoxy-, trifluoromethyl-,
trifluoromethoxy-, cyano- or nitro-substituted phenyl or
benzyl.
[0329] B very particularly preferably represents hydrogen or
C.sub.1-C.sub.4-alkyl, or
[0330] A, B and the carbon atom to which they are attached very
particularly preferably represent saturated
C.sub.5-C.sub.6-cycloalkyl or C.sub.5-C.sub.6-cycloalkenyl in which
optionally one ring member is replaced by oxygen or sulphur and
which is optionally monosubstituted by methyl, ethyl, propyl,
isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl,
trifluoromethyl, methoxy, ethoxy, propoxy, iso-propoxy, butoxy,
iso-butoxy, sec-butoxy, tert-butoxy, fluorine or chlorine, or
[0331] A, B and the carbon atom to which they are attached very
particularly preferably represent C.sub.5-C.sub.6-cycloalkyl or
C.sub.5-C.sub.6-cycloalkenyl in which two substituents together
with the carbon atoms to which they are attached represent
C.sub.2-C.sub.4-alkaned- iyl or C.sub.2-C.sub.4-alkenediyl in which
in each case optionally one methylene group is replaced by oxygen
or sulphur, or butadienediyl.
[0332] D very particularly preferably represents hydrogen,
represents in each case optionally fluorine- or
chlorine-substituted C.sub.1-C.sub.8-alkyl,
C.sub.3-C.sub.4-alkenyl, C.sub.1-C.sub.6-alkoxy-C.-
sub.2-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.2-C.sub.4-alkyl or
C.sub.3-C.sub.6-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulphur or (but not in the case of the
compounds of the formulae (I-1) and (I-4)) represents in each case
optionally fluorine-, chlorine-, methyl-, ethyl-, n-propyl-,
iso-propyl-, methoxy-, ethoxy-, trifluoromethyl- or
trifluoro-methoxy-substituted phenyl, furanyl, pyridyl, thienyl or
benzyl,
[0333] or
[0334] A and D together very particularly preferably represent
optionally substituted C.sub.3-C.sub.4-alkanediyl in which
optionally one carbon atom is replaced by sulphur and which is
optionally substituted by hydroxyl, methyl, ethyl, methoxy or
ethoxy,
[0335] or
[0336] A and D (in the case of the compounds of the formula (I-1))
together with the atoms to which they are attached represent one of
the following groups AD: 56
[0337] A and Q.sup.1 together very particularly preferably
represent C.sub.3-C.sub.4-alkanediyl or butenediyl, each of which
is optionally mono- or disubstituted by fluorine, hydroxyl, methyl
or methoxy, or
[0338] Q.sup.1 very particularly preferably represents
hydrogen.
[0339] Q.sup.2 very particularly preferably represents
hydrogen.
[0340] Q.sup.4, Q.sup.5 and Q.sup.6 independently of one another
each very particularly preferably represent hydrogen, methyl or
ethyl.
[0341] Q.sup.3 very particularly preferably represents hydrogen,
methyl, ethyl or C.sub.3-C.sub.6-cycloalkyl in which optionally one
methylene group is replaced by oxygen or sulphur, or
[0342] Q.sup.3 and Q.sup.4 together with the carbon to which they
are attached very particularly preferably represent an optionally
methyl- or methoxy-substituted saturated C.sub.5-C.sub.6 ring in
which optionally one ring member is replaced by oxygen or
sulphur.
[0343] G very particularly preferably represents hydrogen (a) or
represents one of the groups 57
[0344] in particular represents (a), (b) or (c),
[0345] in which
[0346] E represents a metal ion or an ammonium ion,
[0347] L represents oxygen or sulphur and
[0348] M represents oxygen or sulphur.
[0349] R.sup.1 very particularly preferably represents in each case
optionally fluorine- or chlorine-substituted
C.sub.1-C.sub.14-alkyl, C.sub.2-C.sub.14-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.6-alkyl,
poly-C.sub.1-C.sub.4-alk- oxy-C.sub.1-C.sub.4-alkyl or optionally
fluorine-, chlorine-, methyl-, ethyl-, propyl-, i-propyl-, butyl-,
i-butyl-, tert-butyl-, methoxy-, ethoxy-, n-propoxy- or
iso-propoxy-substituted C.sub.3-C.sub.6-cycloalkyl in which
optionally one or two not directly adjacent ring members are
replaced by oxygen and/or sulphur,
[0350] represents optionally fluorine-, chlorine-, bromine-,
cyano-, nitro-, methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-,
ethoxy-, trifluoromethyl-, trifluoro-methoxy-, methylthio-,
ethylthio-, methylsulphonyl- or ethylsulphonyl-substituted
phenyl,
[0351] represents optionally fluorine-, chlorine-, bromine-,
methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-, ethoxy-,
trifluoromethyl- or trifluoromethoxy-substituted benzyl,
[0352] represents in each case optionally fluorine-, chlorine-,
bromine-, methyl- or ethyl-substituted furanyl, thienyl, pyridyl,
pyrimidyl, thiazolyl or pyrazolyl,
[0353] represents optionally fluorine-, chlorine-, methyl- or
ethyl-substituted phenoxy-C.sub.1-C.sub.2-alkyl or
[0354] represents in each case optionally fluorine-, chlorine-,
amino-, methyl- or ethyl-substituted
pyridyloxy-C.sub.1-C.sub.2-alkyl,
pyrimidyloxy-C.sub.1-C.sub.2-alkyl or
thiazolyloxy-C.sub.1-C.sub.2-alkyl.
[0355] R.sup.2 very particularly preferably represents in each case
optionally fluorine-substituted C.sub.1-C.sub.16-alkyl,
C.sub.2-C.sub.16-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.6-alkyl,
[0356] represents optionally fluorine-, chlorine-, methyl-, ethyl-,
n-propyl-, iso-propyl- or methoxy-substituted
C.sub.3-C.sub.6-cycloalkyl,
[0357] or represents in each case optionally fluorine-, chlorine-,
cyano-, nitro-, methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-,
ethoxy-, trifluoromethyl- or trifluoromethoxy-substituted phenyl or
benzyl.
[0358] R.sup.3 very particularly preferably represents in each case
optionally fluorine-substituted methyl, ethyl, n-propyl, isopropyl
or in each case optionally fluorine-, chlorine-, bromine-, methyl-,
tert-butyl-, methoxy-, trifluoromethyl-, trifluoromethoxy-, cyano-
or nitro-substituted phenyl or benzyl,
[0359] R.sup.4 and R.sup.5 independently of one another each very
particularly preferably represent C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylamino,
di-(C.sub.1-C.sub.4-alkyl)amino, C.sub.1-C.sub.4-alkylthio or
represent in each case optionally fluorine-, chlorine-, bromine-,
nitro-, cyano-, C.sub.1-C.sub.2-alkoxy-,
C.sub.1-C.sub.2-fluoroalkoxy-, C.sub.1-C.sub.2-alkylthio-,
C.sub.1-C.sub.2-fluoroalkylthio- or
C.sub.1-C.sub.3-alkyl-substituted phenyl, phenoxy or
phenylthio.
[0360] R.sup.6 and R.sup.7 independently of one another each 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,
C.sub.1-C.sub.4-alkoxy-C- .sub.1-C.sub.4-alkyl, represent
optionally fluorine-, chlorine-, bromine-, trifluoromethyl-,
methyl- or methoxy-substituted phenyl, represent optionally
fluorine-, chlorine-, bromine-, methyl-, trifluoromethyl- or
methoxy-substituted benzyl, or together represent a
C.sub.5-C.sub.6-alkylene radical in which optionally one methylene
group is replaced by oxygen or sulphur.
[0361] The abovementioned general or preferred radical definitions
or illustrations can be combined with each other as desired, i.e.
including combinations between the respective ranges and preferred
ranges. They apply both to the end products and, correspondingly,
to the precursors and intermediates.
[0362] Preference according to the invention is given to the
compounds of the formula (I) which contain a combination of the
meanings listed above as being preferred (preferable).
[0363] Particular preference according to the invention is given to
the compounds of the formula (I) which contain a combination of the
meanings listed above as being particularly preferred.
[0364] Very particular preference according to the invention is
given to the compounds of the formula (I) which contain a
combination of the meanings listed above as being very particularly
preferred.
[0365] Saturated or unsaturated hydrocarbon radicals such as alkyl
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.
[0366] Unless stated otherwise, optionally substituted radicals may
be mono- or polysubstituted, and in the case of polysubstitutions
the substituents may be identical or different.
[0367] Besides the compounds mentioned in the Preparation Examples,
the following compounds of the formula (I-1-a) may be specifically
mentioned:
1TABLE 1 58 W = H, X = CH.sub.3, Z = CH.sub.3, V.sup.1 = H, V.sup.2
= H. A B D CH.sub.3 H H C.sub.2H.sub.5 H H C.sub.3H.sub.7 H H
i-C.sub.3H.sub.7 H H C.sub.4H.sub.9 H H i-C.sub.4H.sub.9 H H
s-C.sub.4H.sub.9 H H t-C.sub.4H.sub.9 H H CH.sub.3 CH.sub.3 H
C.sub.2H.sub.5 CH.sub.3 H C.sub.3H.sub.7 CH.sub.3 H
i-C.sub.3H.sub.7 CH.sub.3 H C.sub.4H.sub.9 CH.sub.3 H
i-C.sub.4H.sub.9 CH.sub.3 H s-C.sub.4H.sub.9 CH.sub.3 H
t-C.sub.4H.sub.9 CH.sub.3 H C.sub.2H.sub.5 C.sub.2H.sub.5 H
C.sub.3H.sub.7 C.sub.3H.sub.7 H 59 CH.sub.3 H 60 CH.sub.3 H 61
CH.sub.3 H --(CH.sub.2).sub.2-- H --(CH.sub.2).sub.4-- H
--(CH.sub.2).sub.5-- H --(CH.sub.2).sub.6-- H --(CH.sub.2).sub.7--
H --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H
--CH.sub.2--O--(CH.sub.2).sub.3-- H
--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2-- H
--CH.sub.2--CHCH.sub.3--(CH.sub.2).sub.3-- H
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHC.sub.2H.sub.5--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHC.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHi-C.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHOC.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CHi-C.sub.3H.sub.7--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--C(CH.sub.3).sub.2--(CH.sub.2).sub.2-- H
--CH.sub.2--(CHCH.sub.3).sub.2--(CH.sub.2).sub.2-- H 62 H 63 H 64 H
65 H 66 H A D B --(CH.sub.2).sub.3-- H --(CH.sub.2).sub.4-- H
--CH.sub.2--CHCH.sub.3--CH.sub.2-- H --CH.sub.2--CH.sub.2--CHCH.s-
ub.3 H --CH.sub.2--CHCH.sub.3--CHCH.sub.3-- H
--CH.sub.2--S--CH.sub.2-- H --CH.sub.2--S--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--S--CH.sub.2-- H 67 H H CH.sub.3 H H
C.sub.2H.sub.5 H H C.sub.3H.sub.7 H H i-C.sub.3H.sub.7 H H 68 H H
69 H H 70 H CH.sub.3 CH.sub.3 H CH.sub.3 C.sub.2H.sub.5 H CH.sub.3
C.sub.3H.sub.7 H CH.sub.3 i-C.sub.3H.sub.7 H CH.sub.3 71 H CH.sub.3
72 H CH.sub.3 73 H C.sub.2H.sub.5 CH.sub.3 H C.sub.2H.sub.5
C.sub.2H.sub.5 H
[0368] Table 2: A, B and D are each as given in Table 1
[0369] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1.dbd.H; V.sup.2.dbd.H.
[0370] Table 3: A, B and D are each as given in Table 1
[0371] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1.dbd.H; V.sup.2.dbd.H.
[0372] Table 4: A, B and D are each as given in Table 1
[0373] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=4-Cl;
V.sup.2.dbd.H.
[0374] Table 5: A, B and D are each as given in Table 1
[0375] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1=4-Cl; V.sup.2.dbd.H.
[0376] Table 6: A, B and D are each as given in Table 1
[0377] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=4-Cl; V.sup.2.dbd.H.
[0378] Table 7: A, B and D are each as given in Table 1
[0379] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=3-Cl;
V.sup.2.dbd.H.
[0380] Table 8: A, B and D are each as given in Table 1
[0381] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1=3-Cl; V.sup.2.dbd.H.
[0382] Table 9: A, B and D are each as given in Table 1
[0383] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=3-Cl; V.sup.2.dbd.H.
[0384] Table 10: A, B and D are each as given in Table 1
[0385] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=2-Cl;
V.sup.2=4-Cl.
[0386] Table 11: A, B and D are each as given in Table 1
[0387] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1=2-Cl; V.sup.2=4-Cl.
[0388] Table 12: A, B and D are each as given in Table 1
[0389] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=2-Cl; V.sup.2 4-Cl.
[0390] Table 13: A, B and D are each as given in Table 1
[0391] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=4-CF.sub.3;
V.sup.2.dbd.H.
[0392] Table 14: A, B and D are each as given in Table 1
[0393] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1=4-CF.sub.3; V.sup.2H.
[0394] Table 15: A, B and D are each as given in Table 1
[0395] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=4-CF.sub.3; V.sup.2H.
[0396] Table 16: A, B and D are each as given in Table 1
[0397] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; Vi=4-CH.sub.3;
V.sup.2.dbd.H.
[0398] Table 17: A, B and D are each as given in Table 1
[0399] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1=4-CH.sub.3;
V.sup.2.dbd.H.
[0400] Table 18: A, B and D are each as given in Table 1
[0401] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=4-CH.sub.3;
V.sup.2.dbd.H.
[0402] Table 19: A, B and D are each as given in Table 1
[0403] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=4-OCH.sub.3;
V.sup.2.dbd.H.
[0404] Table 20: A, B and D are each as given in Table 1
[0405] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1=4-OCH.sub.3;
V.sup.2.dbd.H.
[0406] Table 21: A, B and D are each as given in Table 1
[0407] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=4-OCH.sub.3;
V.sup.2.dbd.H.
[0408] Besides the compounds mentioned in the Preparation Examples,
the following compounds of the formula (I-2-a) may be specifically
mentioned:
2TABLE 22 74 W = H, X = CH.sub.3, Z = CH.sub.3, V.sup.1 = H,
V.sup.2 = H. A B CH.sub.3 H C.sub.2H.sub.5 H C.sub.3H.sub.7 H
i-C.sub.3H.sub.7 H C.sub.4H.sub.9 H i-C.sub.4H.sub.9 H
s-C.sub.4H.sub.9 H t-C.sub.4H.sub.9 H CH.sub.3 CH.sub.3
C.sub.2H.sub.5 CH.sub.3 C.sub.3H.sub.7 CH.sub.3 i-C.sub.3H.sub.7
CH.sub.3 C.sub.4H.sub.9 CH.sub.3 i-C.sub.4H.sub.9 CH.sub.3
s-C.sub.4H.sub.9 CH.sub.3 t-C.sub.4H.sub.9 CH.sub.3 C.sub.2H.sub.5
C.sub.2H.sub.5 C.sub.3H.sub.7 C.sub.3H.sub.7 75 CH.sub.3 76
CH.sub.3 77 CH.sub.3 --(CH.sub.2).sub.2-- --(CH.sub.2).sub.4--
--(CH.sub.2).sub.5-- --(CH.sub.2).sub.6-- --(CH.sub.2).sub.7--
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
--CH.sub.2--O--(CH.sub.2).sub.3-- --(CH.sub.2).sub.2--S--(CH.su-
b.2).sub.2-- --CH.sub.2--CHCH.sub.3--(CH.sub.2).sub.3--
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2--
(CH.sub.2).sub.2--CHC.sub.2H.sub.5--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHC.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHi-C.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHOC.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CHi-C.sub.3H.sub.7--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--C(CH.sub.3).sub.2--(CH.sub.2).sub.2--
--CH.sub.2--(CHCH.sub.3).sub.2--(CH.sub.2).sub.2-- 78 79 80 81
82
[0409] Table 23: A and B are each as given in Table 22
[0410] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1.dbd.H; V.sup.2.dbd.H.
[0411] Table 24: A and B are each as given in Table 22
[0412] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1.dbd.H; V.sup.2.dbd.H.
[0413] Table 25: A and B are each as given in Table 22
[0414] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=4-Cl; V.sup.2H.
[0415] Table 26: A and B are each as given in Table 22
[0416] W.dbd.H, X CH.sub.3; Z=Cl; V.sup.1=4-Cl; V.sup.2.dbd.H.
[0417] Table 27: A and B are each as given in Table 22
[0418] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=4-Cl; V.sup.2.dbd.H.
[0419] Table 28: A and B are each as given in Table 22
[0420] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=3-Cl;
V.sup.2.dbd.H.
[0421] Table 29: A and B are each as given in Table 22
[0422] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1=3-Cl; V.sup.2.dbd.H.
[0423] Table 30: A and B are each as given in Table 22
[0424] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=3-Cl; V.sup.2.dbd.H.
[0425] Table 31: A and B are each as given in Table 22
[0426] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=4-CF.sub.3;
V.sup.2.dbd.H.
[0427] Table 32: A and B are each as given in Table 22
[0428] W.dbd.H. X=CH.sub.3; Z=Cl; V.sup.1=4-CF.sub.3;
V.sup.2.dbd.H.
[0429] Table 33: A and B are each as given in Table 22
[0430] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=4-CF.sub.3;
V.sup.2.dbd.H.
[0431] Table 34: A and B are each as given in Table 22
[0432] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=2-Cl; V2=4-Cl.
[0433] Table 35: A and B are each as given in Table 22
[0434] W.dbd.H, X=CH.sub.3; Z=Cl; Vi=2-Cl; V.sup.2=4-Cl.
[0435] Table 36: A and B are each as given in Table 22
[0436] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=2-Cl; V.sup.1=4-Cl.
[0437] Table 37: A and B are each as given in Table 22
[0438] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=4-CH.sub.3;
V.sup.2.dbd.H.
[0439] Table 38: A and B are each as given in Table 22
[0440] W.dbd.H, X=CH.sub.3; Z.dbd.C; V=4-CH.sub.3; V.sup.2H.
[0441] Table 39: A and B are each as given in Table 22
[0442] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=4-CH.sub.3;
V.sup.2.dbd.H.
[0443] Table 40: A and B are each as given in Table 22
[0444] W.dbd.H, X=CH.sub.3; Z=CH.sub.3; V.sup.1=4-OCH.sub.3;
V.sup.2.dbd.H.
[0445] Table 41: A and B are each as given in Table 22
[0446] W.dbd.H, X=CH.sub.3; Z=Cl; V.sup.1=4-OCH.sub.3;
V.sup.2H.
[0447] Table 42: A and B are each as given in Table 22
[0448] W.dbd.H, X=Cl; Z=CH.sub.3; V.sup.1=4-OCH.sub.3;
V.sup.2.dbd.H.
[0449] Using, in accordance with process (A), ethyl
N-[(2,5-dimethyl-4-phenyl)-phenyl-acetyl]-1-amino-cyclohexane-carboxylate
as starting material, the course of the process according to the
invention can be represented by the following equation: 83
[0450] Using, in accordance with process (B), ethyl (B)
O-[(2-chloro-5-methoxy-4-(4-chloro)-phenyl)-phenylacetyl]-2-hydroxyisobut-
yrate, the course of the process according to the invention can be
represented by the following equation: 84
[0451] Using, in accordance with process (C), ethyl
2-[(2,5-dimethyl-4-phenyl)-phenyl]4-(4-methoxy)-benzylmercapto-4-methyl-3-
-oxo-valerate, the course of the process according to the invention
can be represented by the following equation: 85
[0452] Using, for example in accordance with process (D-ax),
chlorocarbonyl 3-[(3-chloro-6-methyl-4-(4-methyl)-phenyl)-phenyl]
ketene and 1,2-diazacyclopentane as starting materials, the course
of the process according to the invention can be represented by the
following equation: 86
[0453] Using, for example in accordance with process (D-.beta.),
diethyl 3-[2,5-dimethyl-4-(3-chloro-phenyl)]-phenylmalonate and
1,2-diazacyclopentane as starting materials, the course of the
process according to the invention can be represented by the
following equation: 87
[0454] Using, for example in accordance with process (E),
chlorocarbonyl
2-[(2-ethyl-6-methyl-(4-trifluoromethoxy-phenyl))-phenyl] ketene
and acetone as starting materials, the course of the process
according to the invention can be represented by the following
equation: 88
[0455] Using, for example in accordance with process (F),
chlorocarbonyl 2-[(2-chloro-5-methyl-4-phenyl)-phenyl] ketene and
thiobenzamide as starting materials, the course of the process
according to the invention can be represented by the following
equation: 89
[0456] Using, in accordance with process (G), ethyl
5-[(2-chloro-5-methyl-4-phenyl)-phenyl]-2,3-tetramethylene-4-oxo-valerate-
, the course of the process according to the invention can be
represented by the following equation; 90
[0457] Using, in accordance with process (H), ethyl
5-[(2,5-dichloro-4-phenyl)-phenyl]-2,2-dimethyl-5-oxo-hexanoate,
the course of the process according to the invention can be
represented by the following equation: 91
[0458] Using, in accordance with process (I),
3-[(2,5-dimethyl-4-bromo)-ph-
enyl]-4,4-(penta-methylene)-pyrrolidine-2,4-dione and
4-chlorophenylboronic acid as starting materials, the course of the
reaction can be represented by the following scheme: 92
[0459] Using, in accordance with process (Ja),
3-[(2-chloro-5-methyl-4-(3--
chloro-phenyl))-phenyl]-5,5-dimethylpyrrolidine-2,4-dione and
pivaloyl chloride as starting materials, the course of the process
according to the invention can be represented by the following
equation: 93
[0460] Using, in accordance with process (J), (variant B),
3-[(2,5-dichloro-4-(4-methoxy-phenyl))-phenyl]-4-hydroxy-5-phenyl-.DELTA.-
.sup.3-dihydrofuran-2-one and acetic anhydride as starting
materials, the course of the process according to the invention can
be represented by the following equation: 94
[0461] Using, in accordance with process (K),
8-[(2-chloro-5-methyl-4-phen-
yl)-phenyl]-1,6-diaza-bicyclo-(4.3.0.sup.1..sup.6)-nonane-7,9-dione
and ethoxyethyl chloroformate as starting materials, the course of
the process according to the invention can be represented by the
following equation: 95
[0462] Using, in accordance with process (L),
3-[(2-chloro-5-methyl-4-(4-f-
luoro-phenyl))-phenyl]-4-hydroxy-5-methyl-6-(3-pyridyl)-pyrone and
methyl chloromonothio-formate as starting materials, the course of
the reaction can be represented as follows: 96
[0463] Using, in accordance with process (M),
2-[(2,5-dimethyl-4-(4-methyl-
-phenyl))-phenyl]-5,5-pentamethylene-pyrrolidine-2,4-dione and
methanesulphonyl chloride as starting materials, the course of the
reaction can be represented by the following equation: 97
[0464] Using, in accordance with process (N),
2-[(3-chloro-6-methyl-4-phen-
yl)-phenyl]-4-hydroxy-5,5-dimethyl-.DELTA..sup.3-dihydrofuran-2-one
and 2,2,2-trifluoroethyl methanethio-phosphonyl chloride as
starting materials, the course of the reaction can be represented
by the following equation: 98
[0465] Using, in accordance with process (O),
3-[(2,5-dimethyl-4-(4-triflu-
oromethyl-phenyl))-phenyl]-5-cyclopropyl-5-methyl-pyrrolidine-2,4-dione
and NaOH as components, the course of the process according to the
invention can be represented by the following equation: 99
[0466] Using, in accordance with process (P), variant cx,
3-[(3-chloro-6-methyl-4-(3-trifluoromethyl-phenyl))-phenyl]-4-hydroxy-5-t-
etramethylene-.DELTA..sup.3-dihydro-fiuran-2-one and ethyl
isocyanate as starting materials, the course of the reaction can be
represented by the following equation: 100
[0467] Using, in accordance with process (P), variant .beta.,
3-[(2-chloro-5-methyl-4-phenyl)-phenyl]-5-methyl-pyrrolidine-2,4-dione
and dimethylcarbamoyl chloride as starting materials, the course of
the reaction can be represented by the following scheme: 101
[0468] The compounds of the formula (11) 102
[0469] in which
[0470] A, B, D, W, X, Y, Z and R.sup.8 are each as defined
above
[0471] which are required as starting materials in the process (a)
according to the invention are novel.
[0472] The acylamino acid esters of the formula (II) are obtained,
for example, when amino acid derivatives of the formula (XXIII)
103
[0473] in which
[0474] A, B, R.sup.8 and D are each as defined above
[0475] are acylated with substituted phenylacetyl halides of the
formula (XXIV) 104
[0476] in which
[0477] W, X, Y and Z are each as defined above and
[0478] Hal represents chlorine or bromine
[0479] (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J.
Chem. 6, 341-5, 1968)
[0480] or when acylamino acids of the formula (XXV) 105
[0481] in which
[0482] A, B, D, W, X, Y and Z are each as defined above
[0483] are esterified (Chem. Ind. (London) 1568 (1968)).
[0484] The compounds of the formula (XXV) 106
[0485] in which
[0486] A, B, D, W, X, Y and Z are each as defined above
[0487] are novel.
[0488] The compounds of the formula (XXV) are obtained when amino
acids of the formula (XXVI) 107
[0489] in which
[0490] A, B and D are each as defined above
[0491] are acylated with substituted phenylacetyl halides of the
formula (XXIV) 108
[0492] in which
[0493] W, X, Y and Z are each as defined above and
[0494] Hal represents chlorine or bromine,
[0495] for example according to Schotten-Baumann (Organikum, VEB
Deutscher Verlag der Wissenschaften, Berlin 1977, p. 505).
[0496] The compounds of the formula (XXIV) are novel. They can be
prepared by processses which are known in principle (see, for
example, H. Henecka, Houben-Weyl, Methoden der Organischen Chemie,
Vol. 8, p. 467-469 (1952)).
[0497] The compounds of the formula (XXIV) are obtained, for
example, by reacting substituted phenylacetic acids of the formula
(XXVII) 109
[0498] in which
[0499] W, X, Y and Z are each as defined above
[0500] with halogenating agents (for example thionyl chloride,
thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride,
phosphorus tribromide or phosphorus pentachloride), if appropriate
in the presence of a diluent (for example optionally chlorinated
aliphatic or aromatic hydrocarbons such as toluene or methylene
chloride), at temperatures from -20.degree. C. to 150.degree. C.,
preferably from -10.degree. C. to 100.degree. C.
[0501] Some of the compounds of the formulae (XXIII) and (XXVI) are
known, and/or they can be prepared by known processes (see, for
example, Compagnon, Miocque Ann. Chim. (Paris) [14] 5, p.
11.sup.-22, 23-27 (1970)).
[0502] The substituted cyclic aminocarboxylic acids of the formula
(XXVIa) in which A and B form a ring are generally obtainable by
the Bucherer-Bergs synthesis or by the Strecker synthesis and are
in each case obtained in different isomer forms. Thus, under the
conditions of the Bucherer-Bergs synthesis, the isomers (for
simplicity called .beta. below), in which the radicals R and the
carboxyl group are equatorial are predominantly obtained, while
under the conditions of the Strecker synthesis the isomers (for
simplicity called a below) in which the amino group and the
radicals R are equatorial are predominantly obtained. 110
[0503] (L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C.
Jitrangeri, Can. J. Chem. 53, 3339 (1975).
[0504] Furthermore, the starting materials of the formula (U)
111
[0505] in which
[0506] A, B, D, W, X, Y, Z and R.sup.8 are each as defined
above
[0507] used in the above process (A) can be prepared when
aminonitriles of the formula (XXVIII) 112
[0508] in which
[0509] A, B and D are each as defined above
[0510] are reacted with substituted phenylacetyl halides of the
formula (XXIV) 113
[0511] in which
[0512] W, X, Y, Z and Hal are each as defined above
[0513] to give compounds of the formula (XXIX) 114
[0514] in which
[0515] A, B, D, W, X, Y and Z are each as defined above
[0516] and these are subsequently subjected to acidic
alcoholysis.
[0517] The compounds of the formula (XXIX) are likewise novel
[0518] The compounds of the formula (III) 115
[0519] in which
[0520] A, B, W, X, Y, Z and R.sup.8 are each as defined above
[0521] required as starting materials in the process (B) according
to the invention are novel.
[0522] They can be prepared by methods known in principle.
[0523] Thus, the compounds of the formula (1E), for example, are
obtained when
[0524] 2-hydroxycarboxylic esters of the formula (XXX) 116
[0525] in which
[0526] A, B and R.sup.8 are each as defined above
[0527] are acylated with substituted phenylacetyl halides of the
formula (XXIV) 117
[0528] in which
[0529] W, X, Y, Z and Hal are each as defined above
[0530] (Chem. Reviews 52, 237-416 (1953)) and applications cited in
the introduction.
[0531] Furthermore, compounds of the formula (III) are obtained
when substituted phenylacetic acids of the formula (XXVII) 118
[0532] in which
[0533] W, X, Y and Z are each as defined above
[0534] are alkylated with a-halogenocarboxylic esters of the
formula (XXXI) 119
[0535] in which
[0536] A, B and R.sup.8 are each as defined above and
[0537] Hal represents chlorine or bromine.
[0538] The compounds of the formula (XXVII) are novel.
[0539] The compounds of the formula (XXXI) are commercially
available.
[0540] The compounds of the formula (XXVII) 120
[0541] in which
[0542] W, X, Y and Z are each as defined above
[0543] are obtained, for example,
[0544] .alpha.) when compounds of the formula (XXVII-a) 121
[0545] in which
[0546] W, X and Z are each as defined above
[0547] Y' represents chlorine or bromine, preferably represents
bromine,
[0548] are reacted with boronic acids of the formula (XII) 122
[0549] in which
[0550] Y is as defined above
[0551] in the presence of a solvent, a base and a catalyst
(preferably a palladium complex, such as, for example, tetrakis
(triphenylphosphine)-pa- lladium or
[0552] .beta.) when phenylacetic esters of the formula (XXXII)
123
[0553] in which
[0554] W, X, Y, Z and R.sup.8 are each as defined above
[0555] are hydrolysed under generally known standard conditions in
the presence of acids or bases, in the presence of a solvent,
or
[0556] .gamma.) when phenylacetic acids of the formula (XXVII-b)
124
[0557] in which
[0558] W, X and Z are each as defined above
[0559] are reacted with halogen compounds of the formula
(XXXIII),
Y-Hal (XXXIII)
[0560] in which
[0561] Y is as defined above and
[0562] Hal represents chlorine, bromine or iodine, preferably
bromine or iodine,
[0563] in the presence of a solvent, a base and a catalyst
(preferably one of the abovementioned palladium complexes).
[0564] Some of the compounds of the formulae (XII) and (XXXIII) are
known, some of them are commercially available, or they can be
prepared by processes known in principle. Some of the phenylacetic
acids of the formula (XXVII-a) are known from WO 96/35 664 and WO
97/02 243, or they can be prepared by the processes described
therein.
[0565] The compounds of the formula (XXVII-b) and (XXXII) are
novel.
[0566] The compounds of the formula (XXVII-b) 125
[0567] in which
[0568] W, X and Z are each as defined above
[0569] are obtained, for example, when phenylacetic acids of the
formula (XXVII-a) 126
[0570] in which
[0571] W, X, Y' and Z are each as defined above
[0572] are reacted with lithium compounds of the formula
(XXXIV)
Li--R.sup.21 (XXXIV)
[0573] in which
[0574] R.sup.21 represents C.sub.1-C.sub.8-alkyl or phenyl,
preferably represents n-C.sub.4H.sub.9,
[0575] and boronic esters of the formula (XXXV)
B(OR.sup.8).sub.3 (XXXV)
[0576] in which
[0577] R.sup.8 is as defined above
[0578] in the presence of a diluent.
[0579] The compounds of the formulae (XXXIV) and (XXXV) are
commercially available compounds.
[0580] The compounds of the formula (XXXII) 127
[0581] in which
[0582] W, X, Y, Z and R.sup.8 are each as defined above
[0583] are obtained, for example,
[0584] when phenylacetic esters of the formula (XXX-a) 128
[0585] in which
[0586] R.sup.8, W, X, Y' and Z are each as defined above
[0587] are reacted with boronic acids of the formula (XII) 129
[0588] in which
[0589] Y is as defined above
[0590] in the presence of a solvent, a base and a catalyst
(preferably one of the abovementioned palladium complexes).
[0591] Some of the phenylacetic esters of the formula (XXXII-a) are
known from the applications WO 96/35 664 and WO 97/02 243, or they
can be prepared by the processes described therein.
[0592] The compounds of the formula (IV) 130
[0593] in which
[0594] A, B, W, X, Y, Z and R.sup.8 are each as defined above
[0595] required as starting materials in the above process (C) are
novel.
[0596] They can be prepared by methods known in principle.
[0597] The compounds of the formula (IV) are obtained, for example,
when
[0598] substituted phenylacetic esters of the formula (XXXI)
131
[0599] in which
[0600] W, X, Y, R.sup.8 and Z are each as defined above
[0601] are acylated with 2-benzylthio-carbonyl halides of the
formula (XXXVI) 132
[0602] in which
[0603] A, B and W are each as defined above and
[0604] Hal represents halogen (in particular chlorine or
bromine)
[0605] in the presence of strong bases (see, for example, M. S.
Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem.
Commun., (1987), 1228).
[0606] The compounds of the formula (XXXII) are novel. Compounds of
the formula (XXXII) are obtained, for example, when compounds of
the formula (XXVII) 133
[0607] in which
[0608] W, X, Y and Z are each as defined above
[0609] are esterified in the presence of alcohols and dehydrating
agents (for example conc. sulphuric acid),
[0610] or when alcohols are acylated with compounds of the formula
(XXIV) 134
[0611] in which
[0612] W, X, Y, Z and Hal are each as defined above
[0613] (Chem. Reviews 52, 237-416 (1953)).
[0614] Some of the benzylthio-carbonyl halides of the formula
(XXXVI) are known, and/or they can be prepared by known processes
(J. Antibiotics (1983), 26, 1589).
[0615] The halogenocarbonyl ketenes of the formula (V) required as
starting materials in the above processes (D), (E) and (F) are
novel. They can be prepared simply by methods which are known in
principle (cf., for example, Org. Prep. Proced. Int., 7, (4),
155-158, 1975 and DE 1 945 703). Thus, for example, the compounds
of the formula (V) 135
[0616] in which
[0617] W, X, Y and Z are each as defined above and
[0618] Hal represents chlorine or bromine
[0619] are obtained when
[0620] substituted phenylmalonic acids of the formula (XXXVII)
136
[0621] in which
[0622] W, X, Y and Z are each as defined above
[0623] are reacted with acyl halides, such as, for example, thionyl
chloride, phosphorus(V) chloride, phosphorus(mII) chloride, oxalyl
chloride, phosgene or thionyl bromide, if appropriate in the
presence of catalysts, such as, for example, dimethylformamide,
methyl-steryl-formamide or triphenylphosphine and if appropriate in
the presence of bases such as, for example, pyridine or
triethylamine.
[0624] The substituted phenylmalonic acids of the formula (XXXVII)
are novel. They can be prepared simply by known processes (cf., for
example, Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin
1977, p. 517 ff, EP-A-528 156, WO 96/35 664, WO 97/02 243).
[0625] Thus, phenylmalonic acids of the formula (XXXVII) 137
[0626] in which
[0627] W, X, Y and Z are each as defined above
[0628] are obtained when phenylmalonic esters of the formula (VI)
138
[0629] in which
[0630] W, X, Y, Z and R.sup.8 are each as defined above
[0631] are initially hydrolysed in the presence of a base and in a
solvent and subsequently carefully acidified (EP-528 156, WO 96/35
664, WO 97/02 243).
[0632] The malonic esters of the formula (VI) 139
[0633] in which
[0634] W, X, Y, Z and R.sup.8 are each as defined above
[0635] are novel.
[0636] They can be prepared by generally known methods of organic
chemistry (cf., for example, Tetrahedron Lett. 27, 2763 (1986) and
Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p.
587 ff.).
[0637] Some of the hydrazines of the formula (VII)
A--NH--NH-D (VII),
[0638] in which
[0639] A and D are each as defined above
[0640] required as starting materials for the process (D) according
to the invention are known, and/or they can be prepared by methods
known from the literature (cf., for example, Liebigs Ann. Chem.
585, 6 (1954); Reaktionen der organischen Synthese, C. Ferri, p.
212, 513; Georg Thieme Verlag Stuttgart, 1978; Liebigs Ann. Chem.
443, 242 (1925); Chem. Ber. 98, 2551 (1965), EP-508 126).
[0641] The carbonyl compounds of the formula (VIII) (VIII) 140
[0642] in which
[0643] A and D are each as defined above
[0644] or their silyl enol ethers of the formula (Vila) 141
[0645] in which
[0646] A, D and R.sup.8 are each as defined above
[0647] required as starting materials for the process (E) according
to the invention are commercially available, generally known
compounds or compounds which are obtainable by known processes.
[0648] The preparation of the ketene acid chlorides of the formula
(V), required as starting materials for carrying out the process
(F) according to the invention has already been described above.
The thioamides of the formula (IX) 142
[0649] in which
[0650] A is as defined above
[0651] required for carrying out the process (F) according to the
invention are compounds which are generally known in organic
chemistry.
[0652] The compounds of the formula (X) 143
[0653] in which
[0654] A, B, Q.sup.1, Q.sup.2, W, X, Y, Z and R.sup.8 are each as
defined above
[0655] required as starting materials in the above process (G) are
novel.
[0656] They can be prepared by methods known in principle.
[0657] The 5-aryl-4-ketocarboxylic esters of the formula (X) are
obtained, for example, when 5-aryl-4-ketocarboxylic acids of the
formula (XXXVIII) 144
[0658] in which
[0659] W, X, Y, Z, A, B, Q.sup.1 and Q.sup.2 are each as defined
above
[0660] are esterified (cf., for example, Organikum, 15th edition,
Berlin, 1977, page 499) or alkylated (see Preparation Example).
[0661] The 5-aryl-4-ketocarboxylic acids of the formula (XXXVIII)
145
[0662] in which
[0663] A, B, Q.sup.1, Q.sup.2, W, X, Y and Z are each as defined
above
[0664] are novel but can be prepared by methods known in principle
(see Preparation Example).
[0665] The 5-aryl-4-ketocarboxylic acids of the formula (XXXVffl)
are obtained, for example, when 2-phenyl-3-oxo-adipic esters of the
formula (XXXIX) 146
[0666] in which
[0667] A, B, D.sup.1, D.sup.2, W, X, Y and Z are each as defined
above and
[0668] R.sup.8 and R.sup.8' each represent alkyl (in particular
C.sub.1-C.sub.8-alkyl)
[0669] are decarboxylated, if appropriate in the presence of a
diluent and if appropriate in the presence of a base or acid (cf.,
for example, Organikum, 15th edition, Berlin, 1977, pages 519 to
521).
[0670] The compounds of the formula (XXXIX) 147
[0671] in which
[0672] A, B, Q.sup.1, Q.sup.2, W, X, Y, Z, R.sup.8, R.sup.8 are
each as defined above
[0673] are novel.
[0674] The compounds of the formula (XXXIX) are obtained, for
example,
[0675] when dicarboxylic monoester chlorides of the formula (XL),
148
[0676] in which
[0677] A, B, Q.sup.1, Q.sup.2 and R.sup.8 are each as defined above
and
[0678] Hal represents chlorine or bromine
[0679] or carboxylic anhydrides of the formula (XLI) 149
[0680] in which
[0681] A, B, Q.sup.1 and Q.sup.2 are each as defined above are
acylated with a phenyl acetic ester of the formula (XXXII) 150
[0682] in which
[0683] W, X, Y, Z and R.sup.8' are each as defined above in the
presence of a diluent and in the presence of a base (cf., for
example, M. S. Chambers, E. J. Thomas, D. J. Williams, J. Chem.
Soc. Chem. Commun., (1987), 1228, cf. also the Preparation
Examples).
[0684] Some of the compounds of the formulae (XL) and (XLI) are
known compounds of organic chemistry or are commercially available,
and/or they can be prepared in a simple manner by methods known in
principle.
[0685] The compounds of the formula (XI) 151
[0686] in which
[0687] A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y, Z and
R.sup.8 are each as defined above
[0688] required as starting materials in the above process (H) are
novel.
[0689] They can be prepared by methods known in principle.
[0690] The 6-aryl-5-ketocarboxylic esters of the formula (XI) are
obtained, for example, when 6-aryl-5-ketocarboxylic acids of the
formula (XLII) 152
[0691] in which
[0692] A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are
each as defined above
[0693] are esterified (cf., for example, Organikum, 15th edition,
Berlin, 1977, page 499).
[0694] The 6-aryl-5-ketocarboxylic acids of the formula (XLII)
153
[0695] in which
[0696] A, B, Q.sup.3, Q.sup.4, QS, Q.sup.6, W, X, Y and Z are each
as defined above
[0697] are novel. They can be prepared by methods known in
principle, for example by hydrolysing and decarboxylating
[0698] substituted 2-phenyl-3-oxo-heptanedioic esters of the
formula (XL1H) 154
[0699] in which
[0700] A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y and Z are
each as defined above and
[0701] R.sup.8 and R.sup.8 are each alkyl (preferably
C.sub.1-C.sub.6-alkyl),
[0702] if appropriate in the presence of a diluent and if
appropriate in the presence of a base or acid (cf., for example,
Organikum, 15th edition, Berlin, 1977, page 519 to 521).
[0703] The compounds of the formula (XLII) 155
[0704] in which
[0705] A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W, X, Y, Z,
R.sup.8 and R.sup.8 are each as defined above
[0706] are novel. They can be obtained
[0707] when dicarboxylic anhydrides of the formula (XLIV), 156
[0708] in which
[0709] A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6 and R.sup.8 are
each as defined above
[0710] are condensed with a substituted phenylacetic ester of the
formula (XXXII) 157
[0711] in which
[0712] W, X, Y, Z and R.sup.8' are each as defined above
[0713] in the presence of a diluent and in the presence of a
base.
[0714] Some of the compounds of the formula (XLIV) are known,
and/or they can be prepared by known processes.
[0715] The compounds of the formula (XXXII) have already been
described under the precursors for the process (B). Furthermore,
compounds of the formula (XXXII) are obtained by reacting
substituted 1,1,1-trichloro-2-phenylethanes of the formula (XLV)
158
[0716] in which
[0717] W, X, Y and Z are each as defined above
[0718] initially with alkoxides (for example alkali metal alkoxides
such as sodium methoxide or sodium ethoxide) in the presence of a
diluent (for example the alcohol derived from the alkoxide) at
temperatures between 0.degree. C. and 150.degree. C., preferably
between 20.degree. C. and 120.degree. C., and subsequently with an
acid (preferably an inorganic acid such as, for example, sulphuric
acid) at temperatures between -20.degree. C. and 150.degree. C.,
preferably between 0.degree. C. and 100.degree. C. (cf. DE 3 314
249).
[0719] Some of the compounds of the formula (XLV) are novel, they
can be prepared by processes known in principle.
[0720] The compounds of the formula (XLV) are obtained, for
example, when anilines of the formula (XLVI) 159
[0721] in which
[0722] W, X, Y and Z are each as defined above
[0723] are reacted with vinylidene chloride
(CH.sub.2.dbd.CCl.sub.2) in the presence of an alkyl nitrite of the
formula (XLVII)
R.sup.21--ONO (XLVII)
[0724] in which
[0725] R.sup.21 represents alkyl, preferably
C.sub.1-C.sub.6-alkyl,
[0726] in the presence of copper(II) chloride and, if appropriate,
in the presence of a diluent (for example an aliphatic nitrile such
as acetonitrile), at a temperature of from -20.degree. C. to
80.degree. C., preferably from 0.degree. C. to 60.degree. C.
[0727] The compounds of the formula (XLVII) are known compounds of
organic chemistry. Copper(II) chloride and vinylidene chloride have
been known for a long time and are commercially available.
[0728] Some of the anilines of the formula (XLVI) are novel. The
anilines of the formula (XLVI) 160
[0729] in which
[0730] W, X, Y and Z are each as defined above, for example, are
obtained when anilines of the formula (XLVI-a) 161
[0731] in which
[0732] W, X and Z are each as defined above
[0733] Y' represents chlorine or bromine, preferably represents
bromine,
[0734] are reacted with boronic acids of the formula (XII) 162
[0735] in which
[0736] Y is as defined above
[0737] in the presence of a solvent, a base and a catalyst
(preferably a palladium complex, such as, for example, tetrakis
(triphenylphosphine)pal- ladium.
[0738] The anilines of the formula (XLVI-a) are known compounds or
can be prepared by generally known processes.
[0739] Some of the compounds of the formulae (I-1'-a) to (I-8'-a)
in which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5,
Q.sup.6, X and Z are each as defined above and Y' represents
chlorine and bromine, preferably represents bromine, and which are
required as starting materials in the above process (I) are known
(WO 96/35 664, WO 97/02 243) or they can be prepared by the
processes described therein or by processes (A) to (H).
[0740] Some of the boronic acids of the formula (XII) 163
[0741] in which
[0742] Y is as defined above
[0743] are commercially available, or they can be prepared in a
simple manner by generally known processes.
[0744] The acyl halides of the formula (XIII), carboxylic
anhydrides of the formula (XIV), chloroformic esters or
chloroformic thioesters of the formula (XV), chloromonothioformic
esters or chlorodithioformic esters of the formula (XVI), sulphonyl
chlorides of the formula (XVII), phosphorus compounds of the
formula (XVIIU) and metal hydroxides, metal alkoxides or amines of
the formulae (XIX) and (XX) and isocyanates of the formula (XXI)
and carbamoyl chlorides of the formula (XXII) furthermore required
as starting materials for carrying out the processes (J), (K), (L),
(M), (N), (O) and (P) according to the invention are generally
known compounds of organic or inorganic chemistry.
[0745] Moreover, the compounds of the formulae (VII), (VUI), (IX),
(XIII) to (XXIII), (XXVI), (XXVM), (XXX), (XXXVI), (XL), (XLI) and
(XLIV) are known from the patent applications cited at the outset,
and/or they can be prepared by the methods given therein.
[0746] The process (A) is characterized in that compounds of the
formula (II) in which A, B, D, W, X, Y, Z and R.sup.8 are each as
defined above are subjected to an intramolecular condensation in
the presence of a base.
[0747] Suitable diluents for the process (A) according to the
invention are all inert organic solvents. Preference is given to
using hydrocarbons, such as toluene and xylene, furthermore ethers,
such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl
ether and diglycol dimethyl ether, moreover polar solvents, such as
dimethyl sulphoxide, sulpholane, dimethylformamide and
N-methyl-pyrrolidone, and also alcohols, such as methanol, ethanol,
propanol, iso-propanol, butanol, iso-butanol and tert-butanol.
[0748] 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 employed in the presence of phase-transfer catalysts,
such as, for example, triethylbenzylammonium chloride,
tetrabutylammonium bromide, Adogen 464
(=methyltrialkyl(C.sub.8-C.sub.10)amnmonium chloride) or TDA 1
(=tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium
and potassium can also be used. Furthermore, alkali metal and
alkaline earth metal amides and hydrides, such as sodium amide,
sodium hydride and calcium hydride, and additionally also alkali
metal alkoxides, such as sodium methoxide, sodium ethoxide and
potassium tert-butoxide can be employed.
[0749] When carrying out the process (A) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the reaction is carred out at
temperatures between 0.degree. C. and 250.degree. C., preferably
between 50.degree. C. and 150.degree. C.
[0750] The process (A) according to the invention is generally
carried out under atmospheric pressure.
[0751] When carrying out process (A) according to the invention,
the reaction components of the formula (II) and the deprotonating
bases are generally employed in approximately double-equimolar
amounts. However, it is also possible to use a larger excess (up to
3 mol) of one component or the other.
[0752] The process (B) is characterized in that compounds of the
formula (III) in which A, B, W, X, Y, Z and R.sup.8 are each as
defined above are subjected to an intramolecular condensation in
the presence of a diluent and in the presence of a base.
[0753] Suitable diluents for the process (B) according to the
invention are all inert organic solvents. Preference is given to
using hydrocarbons, such as toluene and xylene, furthermore ethers,
such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl
ether and diglycol dimethyl ether, moreover polar solvents, such as
dimethyl sulphoxide, sulpholane, dimethylformamide and
N-methyl-pyrrolidone, and also alcohols, such as methanol, ethanol,
propanol, iso-propanol, butanol, iso-butanol and tert-butanol.
[0754] 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 employed in the presence of phase-transfer catalysts,
such as, for example, triethylbenzylammonium chloride,
tetrabutylammonium bromide, Adogen 464
(=methyltrialkyl(C.sub.8-C.sub.10)ammonium chloride) or TDA 1
(=tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium
and potassium can also be used. Furthermore, alkali metal and
alkaline earth metal amides and hydrides, such as sodium amide,
sodium hydride and calcium hydride, and additionally also alkali
metal alkoxides, such as sodium methoxide, sodium ethoxide and
potassium tert-butoxide can be employed.
[0755] When carrying out the process (B) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between 0.degree. C. and 250.degree. C., preferably
between 50.degree. C. and 150.degree. C.
[0756] The process (B) according to the invention is generally
carried out under atmospheric pressure.
[0757] When carrying out the process (B) according to the
invention, the reaction components of the formula (II) and the
deprotonating bases are generally employed in approximately
equimolar amounts. However, it is also possible to use a relatively
large excess (up to 3 mol) of one component or the other.
[0758] The process (C) is characterized in that compounds of the
formula (IV) in which A, B, W, X, Y, Z and R.sup.8 are each as
defined above are cyclized intramolecularly in the presence of an
acid and, if appropriate, in the presence of a diluent.
[0759] Suitable diluents for the process (C) according to the
invention are all inert organic solvents. Preference is given to
using hydrocarbons, such as toluene and xylene, furthermore
halogenated hydrocarbons such as dichloromethane, chloroform,
ethylene chloride, chlorobenzene, dichlorobenzene, moreover polar
solvents, such as dimethyl sulphoxide, sulpholane, dimethyl
formamide and N-methyl-pyrrolidone. Furthermore, it is possible to
employ alcohols such as methanol, ethanol, propanol, iso-propanol,
butanol, isobutanol, tert-butanol.
[0760] If appropriate, the acid used can also serve as diluent.
[0761] Suitable acids for the process (C) according to the
invention arc all customary inorganic and organic acids, such as,
for example, hydrohalic acids, sulphuric acid, alkyl, aryl and
haloalkylsulphonic acids, in particular halogenated alkylcarboxylic
acids, such as, for example, trifluoroacetic acid.
[0762] When carrying out the process (C) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between 0.degree. C. and 250.degree. C., preferably
between 50.degree. C. and 150.degree. C.
[0763] The process (C) according to the invention is generally
carried out under atmospheric pressure.
[0764] When carrying out the process (C) according to the
invention, the reaction components of the formula (IV) and the acid
are employed, for example, in equimolar amounts. However, it is
also possible, if appropriate, to use the acid as solvent or as
catalyst.
[0765] The processes (D-.alpha.) and (D-.beta.) are characterized
in that compounds of the formula (V) or (VI) in which W, X, Y, Z,
R.sup.8 and Hal are each as defined above are reacted with
compounds of the formula (VII) in which A and D are each as defined
above, if appropriate in the presence of a base and if appropriate
in the presence of a diluent.
[0766] Suitable diluents for the processes (D-.alpha.) and
(D-.beta.) according to the invention are all inert organic
solvents. Preference is given to using hydrocarbons, such as
toluene and xylene, furthermore ethers, such as dibutyl ether,
tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol
dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone,
and also, only in the case where compounds of the formula (VI) are
employed, alcohols such as methanol, ethanol, propanol,
iso-propanol, butanol, iso-butanol and tert-butanol.
[0767] When compounds of the formula (V) are employed, suitable
bases are inorganic bases, in particular alkali metal or alkaline
earth metal carbonates such as sodium carbonate, potassium
carbonate or calcium carbonate, and also organic bases, such as,
for example, pyridine or triethylamine, and when compounds of the
formula (VI) are employed, alkali metal and alkaline earth metal
oxides, hydroxides and carbonates, such as sodium hydroxide,
potassium hydroxide, magnesium hydroxide, calcium oxide, sodium
carbonate, potassium carbonate and calcium carbonate, which can
also be employed in the presence of phase-transfer catalysts, such
as, for example, triethylbenzylammonium chloride,
tetrabutylammonium bromide, Adogen 464
(=methyltrialkyl(C.sub.8-C.sub.10)- -ammonium chloride) or TDA 1
(=tris-(methoxyethoxyethyl)-amine), furthermore alkali metals, such
as sodium or potassium, alkali metal amides and hydnrdes and
alkaline earth metal amides and hydrides, such as sodium amide,
sodium hydride and calcium hydride, and additionally alkali metal
alkoxides, such as sodium methoxide and potassium
tert-butoxide.
[0768] When carrying out the processes (D-.alpha.) and (D-.beta.)
according to the invention, the reaction temperatures can be varied
within a relatively wide range. In general, the reaction is carried
out at temperatures between -20.degree. C. and 250.degree. C.,
preferably between 0.degree. C. and 150.degree. C.
[0769] The processes (D-.alpha.) and (D-.beta.) according to the
invention are generally carried out under atmospheric pressure.
[0770] When carrying out the processes (D-.alpha.) and (D-.beta.)
according to the invention, the reaction components of the formulae
(V) and (VII) or (VI) and (VII) and the deprotonating bases which
are employed if appropriate are generally employed in approximately
equimolar amounts. However, it is also possible to use a relatively
large excess (up to 3 mol) of one component or the other.
[0771] The process (E) according to the invention is characterized
in that carbonyl compounds of the formula (VIII) or enol ethers
thereof of the formula (VIII-a) are reacted with ketene acid
halides of the formula (V) in the presence of a diluent and, if
appropriate, in the presence of an acid acceptor.
[0772] Suitable diluents for the process (E) according to the
invention are all inert organic solvents. Preference is given to
using hydrocarbons, such as toluene and xylene, furthermore ethers,
such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl
ether, moreover polar solvents, such as dimethyl sulphoxide,
sulpholane, dimethylformamide or N-methyl-pyrrolidone.
[0773] Suitable acid acceptors for carrying out the process variant
E) according to the invention are all customary acid acceptors.
[0774] Preference is given to using tertiary amines, such as
triethylamine, pyridine, diazabicyclooctane (DABCO),
diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethyl-aniline.
[0775] When carrying out the process variant E) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. Advantageously, the reaction is carried out
at temperatures between 0.degree. C. and 250.degree. C., preferably
between 50.degree. C. and 220.degree. C.
[0776] The process (E) according to the invention is advantageously
carried out under atmospheric pressure.
[0777] When carrying out the process (E) according to the
invention, the reaction components of the formulae (VHI) and (V) in
which A, D, W, X, Y and Z are each as defined above and Hal
represents halogen, and, if appropriate, the acid acceptors, are
generally employed in approximately equimolar amounts. However, it
is also possible to use a relatively large excess (up to 5 mol) of
one component or the other.
[0778] The process (F) according to the invention is characterized
in that thioamides of the formula (IX) are reacted with ketene acid
halides of the formula (V) in the presence of a diluent and, if
appropriate, in the presence of an acid acceptor.
[0779] Suitable diluents for the process variant F) according to
the invention are all inert organic solvents. Preference is given
to using hydrocarbons, such as toluene and xylene, furthermore
ethers, such as dibutyl ether, glycol dimethyl ether and diglycol
dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide and
N-methyl-pyrrolidone.
[0780] Suitable acid acceptors for carrying out the process (F)
according to the invention are all customary acid acceptors.
[0781] Preference is given to using tertiary amines, such as
triethylamine, pyridine, diazabicyclooctane (DABCO),
diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethyl-aniline.
[0782] When carrying out the process (F) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. Advantageously, the reaction is carried out
at temperatures between 0.degree. C. and 250.degree. C., preferably
between 20.degree. C. and 22.sup.0.degree. C.
[0783] The process (F) according to the invention is advantageously
carried out under atmospheric pressure.
[0784] When carrying out the process (F) according to the
invention, the reaction components of the formulae (IX) and (V) in
which A, W, X, Y and Z are each as defined above and Hal represents
halogen, and, if appropriate, the acid acceptors, are generally
employed in approximately equimolar amounts. However, it is also
possible to use a relatively large excess (up to 5 mol) of one
component or the other. The process (G) is characterized in that
compounds of the formula (X) in which A, B, Q.sup.1, Q.sup.2, W, X,
Y, Z and R.sup.8 are each as defined above are subjected to an
intramolecular condensation in the presence of a base.
[0785] Suitable diluents for the process (G) 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, dimethylfomiamide and N-methyl-pyrrolidone.
It is furthermore possible to use alcohols, such as methanol,
ethanol, propanol, iso-propanol, butanol, isobutanol,
tert-butanol.
[0786] Suitable bases (deprotonating agents) for carrying out the
process (G) 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 employed in the presence of phase-transfer catalysts,
such as, for example, triethylbenzylammonium chloride,
tetrabutylammonium bromide, Adogen 464
(methyltrialkyl(C.sub.8-C.sub.10)ammonium chloride) or TDA 1
(tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium or
potassium can also be used. Furthermore, alkali metal and alkaline
earth metal amides and hydrides, such as sodium amide, sodium
hydride and calcium hydride, and additionally also alkali metal
alkoxides, such as sodium methoxide, sodium ethoxide and potassium
tert-butoxide can be employed.
[0787] When carrying out the process (G) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between -75.degree. C. and 250.degree. C., preferably
between -50.degree. C. and 150.degree. C.
[0788] The process (G) according to the invention is generally
carried out under atmospheric pressure.
[0789] When carrying out the process (G) according to the
invention, the reaction components of the formula (X) and the
deprotonating bases are generally employed in approximately
equimolar amounts. However, it is also possible to use a relatively
large excess (up to 3 mol) of one component or the other.
[0790] The process (H) is characterized in that compounds of the
formula (XI) in which A, B, Q.sup.3, Q.sup.4, Q.sup.5, Q.sup.6, W,
X, Y, Z and R.sup.8 are each as defined above are subjected to an
intramolecular condensation in the presence of bases.
[0791] Suitable diluents for the process (H) 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-methyl-pyrrolidone.
Alcohols, such as methanol, ethanol, propanol, iso-propanol,
butanol, isobutanol and tert-butanol can also be used.
[0792] Suitable bases (deprotonating agents) for carrying out the
process (H) 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 employed in the presence of phase-transfer catalysts,
such as, for example, triethylbenzyl-ammonium chloride,
tetrabutylammonium bromide, Adogen 464
(methyltrialkyl(C.sub.8-C.sub.10)ammonium chloride) or TDA 1
(tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium and
potassium can also be used. Furthermore, alkali metal and alkaline
earth metal amides and hydrides, such as sodium amide, sodium
hydride and calcium hydride, and additionally also alkali metal
alkoxides, such as sodium methoxide, sodium ethoxide and potassium
tert-butoxide can be employed.
[0793] When carrying out the process (H) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between 0.degree. C. and 250.degree. C., preferably
between 50.degree. C. and 150.degree. C.
[0794] The process (H) according to the invention is generally
carried out under atmospheric pressure.
[0795] When carrying out the process (H) according to the
invention, the reaction components of the formula (XII) and the
deprotonating bases are generally employed in approximately
equimolar amounts. However, it is also possible to use a relatively
large excess (up to 3 mol) of one component or the other.
[0796] For carrying out the process (I) according to the invention,
palladium(0) complexes are suitable as catalysts. Preference is
given, for example, to tetrakis-(triphenyl-phosphine)palladium.
[0797] Suitable acid acceptors for carrying out the process (I)
according to the invention are inorganic or organic bases. These
preferably include alkaline earth metal or alkali metal hydroxides,
acetates, carbonates or bicarbonates, such as, for example, sodium
hydroxide, potassium hydroxide, barium hydroxide or amrnmonium
hydroxide, sodium acetate, potassium acetate, calcium acetate or
ammonium acetate, sodium carbonate, potassium carbonate or ammonium
carbonate, sodium bicarbonate or potassium bicarbonate, alkali
metal fluorides, such as, for example, caesium fluoride, and also
tertiary amines, such as trimethylamine, triethylamine,
tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine,
pyridine, N-methylpiperidine, N-methylmorpholine,
N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),
diazabicyclononene (DBN) or diazabicycloundecene (DBU). Suitable
diluents for carrying out the process (I) according to the
invention are water, organic solvents and any mixtures thereof.
Examples include: aliphatic, alicyclic or aromatic hydrocarbons,
such as, for example, petroleum ether, hexane, heptane,
cyclohexane, methylcyclohexane, benzene, toluene, xylene or
decalin; halogenated hydrocarbons, such as, for example,
chlorobenzene, dichlorobeiizene, methylene chloride, chloroform,
carbon tetrachloride, dichloroethane, trichloroethane or
tetrachloroethylene; ethers, such as diethyl ether, diisopropyl
ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,
tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane,
diethylene glycol dimethyl ether or anisole; alcohols, such as
methanol, ethanol, n- or i-propanol, n-, iso-, sec- or
tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol,
methoxyethanol, diethylene glycol monomethyl ether, diethylene
glycol monoethyl ether; water.
[0798] The reaction temperature in the process (I) according to the
invention can be varied within a relatively wide range. In general,
the reaction is carried out at temperatures between 0.degree. C.
and +140.degree. C., preferably between 50.degree. C. and
+100.degree. C.
[0799] When carrying out the process (I) according to the
invention, boronic acid of the formula (XII), in which Y is as
defined above, and compounds of the formulae (I-1-a) to (I-8-a), in
which A, B, D, Q.sup.1, Q.sup.2, Q.sup.3, Q.sup.4, Q.sup.5,
Q.sup.6, W, X, Y, and Z are as defined above, are employed in a
molar ratio of from 1:1 to 3:1, preferably from 1:1 to 2:1. In
general, 0.005 to 0.5 mol, preferably 0.01 mol to 0.1 mol of
catalyst is employed per mole of the compounds of the formulae
(I-1-a) to (I-8-a). The base is usually employed in excess.
[0800] The process (J-.alpha.) is characterized in that compounds
of the formulae (I-1-a) to (I-8-a) are in each case reacted with
carbonyl halides of the formula (XIII), if appropriate in the
presence of a diluent and if appropriate in the prescence of an
acid binder.
[0801] Suitable diluents for the process (J-.alpha.) according to
the invention are all solvents which are inert towards the acyl
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 methyl isopropyl ketone, furthermore
ethers, such as diethyl ether, tetrahydrofuran and dioxane,
additionally carboxylic esters, such as ethyl acetate, and also
strongly polar solvents, such as dimethyl sulphoxide and
sulpholane. The hydrolytic stability of the acyl halide permitting,
the reaction can also be carried out in the presence of water.
[0802] Suitable acid binders for the reaction according to the
process (J-.alpha.) according to the invention are all customary
acid acceptors. Preference is given to using tertiary amines, such
as triethylamine, pyridine, diazabicyclooctane (DABCO),
diazabicyclo-undecene (DBU), diazabicyclononene (DBN), Htinig base
and N,N-dimethyl-aniline, 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.
[0803] The reaction temperatures in the process (J-a) according to
the invention can be varied within a relatively wide range. In
general, the reaction is carried out at temperatures between
-20.degree. C. and +1 50.degree. C., preferably between 0.degree.
C. and 100.degree. C.
[0804] When carrying out the process (J-.alpha.) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-8-a) and the carbonyl halide of the formula (XIU) are generally
in each case employed 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.
[0805] The process (J-.beta.) is characterized in that compounds of
the formulae (I-1-a) to (I-8-a) are reacted with carboxylic
anhydrides of the formula (XIV), if appropriate in the presence of
a diluent and if appropriate in the presence of an acid binder.
[0806] Preferred diluents for the process (J-.beta.) according to
the invention are those diluents which are also preferred when acyl
halides are used. Otherwise, it is also possible for a carboxylic
anhydride employed in excess to act simultaneously as a
diluent.
[0807] In the process (J-13), acid binders which are added, if
appropriate, are preferably those acid binders which are also
preferred when acyl halides are used.
[0808] In the process (J-.beta.) according to the invention, the
reaction temperatures can be varied within a relatively wide range.
In general, the reaction is carried out at temperatures between
-20.degree. C. and +150.degree. C., preferably between 0.degree. C.
and 100.degree. C.
[0809] When carrying out the process (J-.beta.) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-8-a) and the carboxylic anhydride of the formula (XIV) are
generally each employed in approximately equivalent amounts.
However, it is also possible to use a relatively large excess (up
to 5 mol) of the carboxylic anhydride. Work-up is carried out by
customary methods.
[0810] In general, the adopted procedure is to remove diluent and
excess carboxylic anhydride and also the carboxylic acid formed by
distillation or by washing with an organic solvent or with
water.
[0811] The process (K) is characterized in that compounds of the
formulae (I-1-a) to (I-8-a) are in each case reacted with
chloroformic esters or chloroformic thiol esters of the formula
(XV), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0812] Suitable diluents for the reaction according to the process
(K) according to the invention are all customary acid acceptors.
Preference is given to using tertiary amines, such as
triethylamine, pyridine, DABCO, DBU, DBA, Hunig base and
N,N-dimethyl-aniline, furthermore alkaline earth metal oxides, such
as magnesium oxide and calcium oxide, moreover alkali metal
carbonates and alkaline earth metal carbonates, such as sodium
carbonate, potassium carbonate and calcium carbonate, and also
alkali metal hydroxides such as sodium hydroxide and potassium
hydroxide.
[0813] Suitable diluents for the process (K) according to the
invention are all solvents which are inert towards the chloroformic
esters or chloroformic thiol esters. 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, and also strongly polar solvents, such as
dimethyl sulphoxide and sulpholane.
[0814] When carrying out the process (K) according to the invention
the reaction temperatures can be varied within a relatively wide
range. If the reaction is carried out in the presence of a diluent
and an acid binder, the reaction temperatures are generally between
-20.degree. C. and +100.degree. C., preferably between 0.degree. C.
and 50.degree. C.
[0815] The process (K) according to the invention is generally
carried out under atmospheric pressure.
[0816] When carrying out the process (K) according to the
invention, the starting materials of the formulae (I-1-a) to
(I-8-a) and the appropriate chloroformic ester or chloroformic
thiol ester of the formula (XV) are generally in each case employed
in approximately equivalent amounts. However, it is also possible
to employ 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 stripping the diluent.
[0817] The process (L) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-8-a) are in each
case reacted with compounds of the formula (XVI) in the presence of
a diluent and, if appropriate, in the presence of an acid
binder.
[0818] In the preparation process (L), approximately 1 mol of
chloromonothioformic ester or chlorodithioformic ester of the
formula (XVI) is reacted per mole of starting material of the
formulae (I-1-a) to (I-8-a), at from 0 to 120.degree. C.,
preferably from 20 to 60.degree. C.
[0819] Suitable diluents which are added if appropriate are all
inert polar organic solvents, such as ethers, amides, sulphones,
sulphoxides, but also halogenoalkanes.
[0820] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide or methylene chloride.
[0821] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-8-a) is prepared by addition of strong
deprotonating agents, such as, for example, sodium hydride or
potassium tert-butoxide, it is not necessary to add further acid
binders.
[0822] If acid binders are employed, these are customary inorganic
or organic bases, for example sodium hydroxide, sodium carbonate,
potassium carbonate, pyridine, triethylamine.
[0823] 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.
[0824] The process (M) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-8-a) are in each
case reacted with sulphonyl chlorides of the formula (XVII), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0825] In the preparation process (M), approximately 1 mol of
sulphonyl chloride of the formula (XVII) is reacted per mole of
starting material of the formula (I-1-a) to (I-8-a), at from -20 to
150.degree. C., preferably at from 20 to 70.degree. C. um.
[0826] Suitable diluents which are added if appropriate are all
inert polar organic solvents, such as ethers, amides, nitrites,
sulphones, sulphoxides or halogenated hydrocarbons, such as
methylene chloride.
[0827] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide, methylene chloride.
[0828] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-8-a) is prepared by addition of strong
deprotonating agents (such as, for example, sodium hydride or
potassium tert-butoxide), it is not necessary to add further acid
binders.
[0829] If acid binders are employed, these are customary inorganic
or organic bases, for example sodium hydroxide, sodium carbonate,
potassium carbonate, pyridine, triethylamine.
[0830] 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.
[0831] The process (N) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-8-a) are in each
case reacted with phosphorus compounds of the formula (XVIII), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0832] In the preparation process (N), 1 to 2, preferably 1 to 1.3,
mol of the phosphorus compound of the formula (XVIII) are reacted
per mole of the compounds (I-1-a) to (I-8-a) at temperatures
between 40.degree. C. and 150.degree. C., preferably between -10
and 110.degree. C., to give compounds of the formulae (I-1-e) to
(I-8-e).
[0833] Suitable solvents which are added if appropriate are all
inert polar organic solvents, such as ethers, amides, nitriles,
alcohols, sulphides, sulphones, sulphoxides, etc.
[0834] Preference is given to using acetonitrile, dimethyl
sulphoxide, tetrahydrofuran, dimethylformamide, methylene
chloride.
[0835] Suitable acid binders which are added if appropriate are
customary inorganic or organic bases such as hydroxides, carbonates
or amines. Examples include sodium hydroxide, sodium carbonate,
potassium carbonate, pyridine, triethylamine.
[0836] The reaction can be carried out at atmospheric pressure or
under elevated pressure and is preferably carried out under
atmospheric pressure. Work-up is carried out by customary methods
of organic chemistry. The resulting end products are preferably
purified by crystallization, chromatographic purification or by
so-called "incipient distillation", i.e. removal of the volatile
components under reduced pressure.
[0837] The process (O) is characterized in that compounds of the
formulae (I-1-a) to (I-8-a) are reacted with metal hydroxides or
metal alkoxides of the formula (XIX) or amines of the formula (XX),
if appropriate in the presence of a diluent.
[0838] Preferred diluents for the process (O) according to the
invention are ethers, such as tetrahydrofuran, dioxane, diethyl
ether, or else alcohols, such as methanol, ethanol, isopropanol,
but also water.
[0839] The process (O) according to the invention is generally
carried out under atmospheric pressure.
[0840] The reaction temperatures are generally between -20.degree.
C. and 100.degree. C., preferably between 0.degree. C. and
50.degree. C.
[0841] The process (P) according to the invention is characterized
in that compounds of the formulae (I-1-a) to (I-8-a) are in each
case reacted with (P-.alpha.) compounds of the formula (XXI), if
appropriate in the presence of a diluent and if appropriate in the
presence of a catalyst, or (P-.beta.) with compounds of the formula
(XXII), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0842] In the preparation process (P-.alpha.), approximately one
mol of isocyanate of the formula (XXI) is reacted per mole of
starting material of the formulae (I-1-a) to (I-8-a), at from 0 to
100.degree. C., preferably at from 20 to 50.degree. C.
[0843] Suitable diluents which are added if appropriate are all
inert organic solvents, such as ethers, amides, nitrites,
sulphones, sulphoxides.
[0844] If appropriate, catalysts may be added to accelerate the
reaction. Very advantageously, the catalysts which are employed are
organotin compounds, such as, for example, dibutyltin dilaurate.
The reaction is preferably carried out at atmospheric pressure.
[0845] In the preparation process (P-.beta.), approximately 1 mol
of carbamoyl chloride of the formula (XXII) is reacted per mole of
starting material of the formulae (I-1-a) to (I-8-a), at from -20
to 150.degree. C., preferably from 0 to 70.degree. C. um.
[0846] Suitable diluents which are added if appropriate are all
inert polar organic solvents, such as ethers, amides, sulphones,
sulphoxides or halogenated hydrocarbons.
[0847] Preference is given to using dimethyl sulphoxide,
tetrahydrofuran, dimethylformamide or methylene chloride.
[0848] If, in a preferred embodiment, the enolate salt of the
compounds (I-1-a) to (I-8-a) is prepared by addition of strong
deprotonating agents (such as, for example, sodium hydride or
potassium tert-butoxide), it is not necessary to add further acid
binders.
[0849] If acid binders are employed, these are customary inorganic
or organic bases, for example sodium hydroxide, sodium carbonate,
potassium carbonate, triethylamine or pyridine.
[0850] 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.
[0851] The active compounds are suitable for controlling animal
pests, preferably arthropods and nematodes, in particular insects
and arachnids, which are encountered in agriculture, in forestry,
in the protection of stored products and of materials, and in the
hygiene sector. They are active against normally sensitive and
resistant species and against all or some stages of development.
The abovementioned pests include:
[0852] From the order of the Isopoda, for example, Oniscus asellus,
Armadillidium vulgare and Porcellio scaber.
[0853] From the order of the Diplopoda, for example, Blaniulus
guttulatus.
[0854] From the order of the Chilopoda, for example, Geophilus
carpophagus and Scutigera spp.
[0855] From the order of the Symphyla, for example, Scutigerella
immaculata.
[0856] From the order of the Thysanura, for example, Lepisma
saccharina.
[0857] From the order of the Collembola, for example, Onychiurus
armatus.
[0858] From the order of the Orthoptera, for example, Blatta
orientalis, Periplaneta americana, Leucophaea maderae, Blattella
germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria
migratorioides, Melanoplus differentialis and Schistocerca
gregaria.
[0859] From the order of the Dermaptera, for example, Forficula
auricularia.
[0860] From the order of the Isoptera, for example, Reticuliternes
spp.
[0861] From the order of the Anoplura, for example, Phylloxera
vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus
spp., Linognathus spp.,
[0862] From the order of the Mallophaga, for example, Trichodectes
spp. and Damalinia spp.
[0863] From the order of the Thysanoptera, for example,
Frankliniella occidentalis, Hercinothrips femoralis, Thrips palmi
and Thrips tabaci.
[0864] From the order of the Heteroptera, for example, Eurygaster
spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius,
Rhodnius prolixus and Triatoma spp.
[0865] From the order of the Homoptera, for example, Aleurodes
brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis
gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae,
Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum
padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps,
Lecanium cormi, Saissetia oleae, Laodelphax striatellus,
Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,
Pseudococcus spp. and Psylla spp.
[0866] From the order of the Lepidoptera, for example, Pectinophora
gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis
blancardella, Hyponomeuta padella, Plutella maculipennis,
Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.,
Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp.,
Euxoa spp., Feltia spp., Earias insulana, Heliothis spp.,
Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia
litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella,
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella,
Galleria mellonella, Tineola bisselliella, Tinea pellionella,
Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana,
Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and
Tortrix viridana.
[0867] From the order of the Coleoptera, for example, Anobium
punctatum, Rhizopertha dominica, Acanthoscelides obtectus,
Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata,
Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala,
Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis,
Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus,
Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,
Dermnestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp.,
Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus,
Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes
spp., Conoderus spp., Melolontha melolontha, Amphimallon
solstitialis and Costelytra zealandica.
[0868] From the order of the Hymenoptera, for example, Diprion
spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa
spp.
[0869] From the order of the Diptera, for example, Aedes spp.,
Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp.,
Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia
spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Liriomyza
spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp.,
Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp.,
Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula
paludosa.
[0870] From the order of the Siphonaptera, for example, Xenopsylla
cheopis and Ceratophyllus spp.
[0871] From the order of the Arachnida, for example, Scorpio
maurus, Latrodectus mactans.
[0872] From the order of the Acarina for example, Acarus siro,
Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes
ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp.,
Amblyonrma spp., Hyalonmma spp., Ixodes spp., Psoroptes spp.,
Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia
praetiosa, Panonychus spp. and Tetranychus spp.
[0873] The active compounds according to the invention have high
insecticidal and acaridical activity after foliar and soil
application.
[0874] They can be employed particularly successfully for
controlling plant-damaging insects, such as, for example, against
the larvae of the mustard beetle (Phaedon cochleariae), against the
larvae of the green rice leafhopper (Nephotettix cincticeps) and
against the larvae of the green peach aphid (Myzus persicae).
[0875] The active compounds according to the invention can further
be used as defoliants, desiccants, haulm killers and, especially,
as weed killers. By weeds in the broadest sense there are to be
understood all plants which grow in locations where they are
undesired. Whether the substances according to the invention act as
total or selective herbicides depends essentially on the amount
used.
[0876] The dosages of the active compounds according to the
invention required for controlling weeds are between 0.001 and 10
kg/ha, preferably between 0.005 and 5 kg/ha.
[0877] The active compounds according to the invention can be used,
for example, in connection with the following plants:
[0878] Dicotyledonous Weeds of the Genera:
[0879] Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis,
Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca,
Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia,
Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotola, Lindernia,
Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,
Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
[0880] Dicotyledonous Crops of the Genera:
[0881] Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum,
Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica,
Lactuca, Cucumis, Cucurbita.
[0882] Monocotyledonous Weeds of the Genera:
[0883] Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa,
Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sorghum, Agropyron, Cycnodon, Monochoria, Fimbristylis, Sagittaria,
Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,
Dactyloctenium, Agrostis, Alopecurus, Apera.
[0884] Monocotyledonous Crops of the Genera:
[0885] Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum,
Panicum, Sachharum, Ananas, Asparagus, Allium.
[0886] However, the use of the active compounds according to the
invention is in no way restricted to these genera, but also extends
in the same manner to other plants.
[0887] Depending on the concentration, the compounds are suitable
for total weed control, for example on industrial terrain and rail
tracks and on paths and areas with or without tree growth. Equally,
the compounds can be employed for controlling weeds in perennial
crops, for example forests, ornamental tree plantings, orchards,
vineyards, citrus groves, nut orchards, banana plantations, coffee
plantations, tea plantations, rubber plantations, oil palm
plantations, cocoa plantations, soft fruit plantings and hop
fields, on lawns and turf and pastures and for selective weed
control in annual crops.
[0888] The active compounds according to the invention are highly
suitable for selective control of monocotyledonous weeds in
dicotyledonous crops, by the pre-emergence and by the
post-emergence method. In cotton or sugar beet, for example, they
can be employed with very good results for controlling harmful
grass.
[0889] The active compounds can be converted to the customary
formulations, such as solutions, emulsions, wettable powders,
suspensions, powders, dusts, pastes, soluble powders, granules,
suspension-emulsion concentrates, natural and synthetic materials
impregnated with active compound and microencapsulations in
polymeric substances.
[0890] 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.
[0891] 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, 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.
[0892] As solid carriers there are suitable:
[0893] for example ammomnum salts and ground natural minerals such
as kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, and ground synthetic
minerals, such as highly disperse silica, alumina and silicates; as
solid carriers for granules there are suitable: for example crushed
and fractionated natural rocks such as calcite, marble, pumice,
sepiolite and dolomite, and also synthetic granules of inorganic
and organic meals, and granules of organic material such as
sawdust, coconut shells, maize cobs and tobacco stalks; as
emulsifiers and/or foam-formers there are suitable: 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 also protein hydrolysates; as dispersants there
are suitable: for example lignin-sulphite waste liquors and
methylcellulose.
[0894] 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, as
well as natural phospholipids such as cephalins and lecithins, and
synthetic phospholipids, can be used in the formulations. Other
additives can be mineral and vegetable oils.
[0895] It is possible to use colorants such as inorganic pigments,
for example iron oxide, titanium oxide and Prussian Blue, and
organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and
metal phthalocyanine dyestuffs, and trace nutrients such as salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[0896] The formulations generally comprise between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90% and, in
addition, preferably extenders and/or surfactants.
[0897] The active compound according to the invention can be
present in its commercially available formulations and in the use
forms, prepared from these formulations, as a mixture with other
active compounds, such as insecticides, attractants, sterilizing
agents, acaricides, nematicides, flugicides, growth-regulating
substances or herbicides. The insecticides include, for example,
phosphoric acid esters, carbarnates, carboxylates, chlorinated
hydrocarbons, phenylureas and substances produced by
microorganisms, inter alia.
[0898] Particularly favourable examples of co-components in
mixtures are the following compounds:
[0899] Fungicides:
[0900] 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;
2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazol-
e-5-carboxanilide;
2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;
(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;
8-hydroxyquinoline sulphate; methyl
(E)-2-{2-[6-(2-cyano-phenoxy)-pyrimid-
in-4-yloxy]-phenyl}-3-methoxyacrylate; methyl
(E)-methoximino-[alpha-(o-to- lyloxy)-o-tolyllacetate;
2-phenylphenol (OPP),
[0901] aldimorph, ampropylfos, anilazine, azaconazole,
[0902] benalaxyl, benodanil, benomyl, binapacryl, biphenyl,
bitertanol, blasticidin-S, bromuconazole, bupirimate,
buthiobate,
[0903] calcium polysulphide, captafol, captan, carbendazim,
carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil,
chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
[0904] dichlorophen, diclobutrazole, diclofluanid, diclomezine,
dicloran, diethofencarb, difenoconazole, dimethirimol,
dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione,
ditalimfos, dithianon, dodine, drazoxolon,
[0905] edifenphos, epoxiconazole, ethirimol, etridiazole,
[0906] fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,
fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide,
ferbam, ferimzone, fluazinam, fluoromide, fluquinconazole,
flusilazole, flusulfamide, flutolanil, flutriafol, folpet,
fosetyl-aluminium, fthalide, fuberidazole, furalaxyl,
furmecyclox,
[0907] guazatine,
[0908] hexachlorobenzene, hexaconazole, hymexazole,
[0909] imazalil, imibenconazole, iminoctadine, iprobenfos (1BP),
iprodione, irurnamycin, isoprothiolane,
[0910] kasugamycin, copper preparations, such as: copper hydroxide,
copper naphthenate, copper oxychloride, copper sulphate, copper
oxide, oxine-copper and Bordeaux mixture,
[0911] mancopper, mancozeb, maneb, mepanipyrim, mepronil,
metalaxyl, metconazole, methasulfocarb, methfuroxam, metirarn,
metsulfovax, myclobutanil,
[0912] nickel dimethyldithiocarbamate, nitrothal-isopropyl,
nuarimol,
[0913] ofurace, oxadixyl, oxamocarb, oxycarboxim,
[0914] pefurazoate, penconazole, pencycuron, phosdiphen, phthalide,
pimaricin, piperalin, polycarbamate, polyoxin, probenazole,
prochloraz, procymidone, propamocarb, propiconazole, propineb,
pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
[0915] quintozene (PCNB),
[0916] sulphur and sulphur preparations,
[0917] tebuconazole, tecloftalam, tecnazene, tetraconazole,
thiabendazole, thicyofen, thiophanate-methyl, thiram,
tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,
triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,
triforine, triticonazole,
[0918] validamycin A, vinclozolin,
[0919] zineb, ziram.
[0920] Bactericides:
[0921] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, fuirancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
[0922] Insecticides/Acaricides/Nematicides:
[0923] abamectin, AC.sub.303 630, acephate, acrinathrin, alanycarb,
aldicarb, alphamethrin, amitraz, avermectin, AZ 60541,
azadirachtin, azinphos A, azinphos M, azocyclotin,
[0924] Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,
betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A,
bufencarb, buprofezin, butocarboxim, butylpyridaben,
[0925] cadusafos, carbaryl, carbofuran, carbophenothion,
carbosulfan, cartap, CGA 157 419, CGA 184699, chloethocarb,
chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlorrnephos,
chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin,
clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin,
cyhexatin, cypermethrin, cyromazine,
[0926] deltamethrin, demeton M, demeton S, demeton-S-methyl,
diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,
dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos,
dioxathion, disulfoton,
[0927] edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,
ethofenprox, ethoprophos, etrimfos,
[0928] fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,
fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,
fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,
flucycloxuron, flucythrinate, flufenoxuron, flufenprox,
fluvalinate, fonophos, formothion, fosthiazate, fubfenprox,
furathiocarb,
[0929] HCH, heptenophos, hexaflumuron, hexythiazox,
[0930] imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,
isoxathion, ivermectin,
[0931] lambda-cyhalothrin, lufenuron,
[0932] malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde,
methacrifos, methamidophos, methidathion, methiocarb, methomyl,
metolcarb, milbemectin, monocrotophos, moxidectin,
[0933] naled, NC.sub.184, NI 25, nitenpyram,
[0934] omethoate, oxamyl, oxydemethon M, oxydeprofos,
[0935] parathion A, parathion M, permethrin, phenthoate, phorate,
phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,
pirimiphos A, profenofos, promecarb, propaphos, propoxur,
prothiofos, prothoate, pymetrozine, pyrachlophos, pyridaphenthion,
pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxyfen,
[0936] quinalphos,
[0937] RH 5992,
[0938] salithion, sebufos, silafluofen, sulfotep, sulprofos,
[0939] tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,
tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos,
thiafenox, thiodicarb, thiofanox, thiomethon, thionazine,
thuringiensin, thionazine, tralomethrin, triarathene, triazophos,
triazuron, trichlorfon, triflumuron, trimethacarb,
[0940] vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.
[0941] Herbicides:
[0942] for example anilides such as, for example, diflufenican and
propanil; arylcarboxylic acids such as, for example,
dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids
such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP
and triclopyr; aryloxy-phenoxy-alkanoic esters such as, for
example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl,
haloxyfop-methyl and quizalofop-ethyl; azinones such as, for
example, chloridazon and norflurazon; carbamates such as, for
example, chlorpropham, desmedipham, phenmedipham and propham;
chloroacetanilides such as, for example, alachlor, acetochlor,
butachlor, metazachlor, metolachlor, pretilachlor and propachlor;
dinitroanilines such as, for example, oryzalin, pendimethalin and
trifluralin; diphenyl ethers such as, for example, acifluorfen,
bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and
oxyfluorfen; ureas such as, for example, chlortoluron, diuron,
fluometuron, isoproturon, linuron and methabenzthiazuron;
hydroxylamines such as, for example, alloxydim, clethodim,
cycloxydim, sethoxydim and tralkoxydim; imidazolinones such as, for
example, imazethapyr, imazamethabenz, imazapyr and imazaquin;
nitriles such as, for example, bromoxynil, dichlobenil and ioxynil;
oxyacetamides such as, for example, mefenacet; sulphonylureas such
as, for example, amidosulphuron, bensulphuron-methyl,
chlorimuron-ethyl, chlorsulphuron, cinosulphuron,
metsulphuron-methyl, nicosulphuron, primisulphuron,
pyrazosulphuron-ethyl, thifensulphuron-methyl, triasulphuron and
tribenuron-methyl; thiolcarbamates such as, for example, butylate,
cycloate, diallate, EPTC, esprocarb, molinates, prosulphocarb,
thiobencarb and triallates; triazines such as, for example,
atrazine, cyanazine, simazine, simetryne, terbutryne and
terbutylazine; triazinones such as, for example, hexazinone,
metamitron and metribuzin; others such as, for example,
aminotriazole, benfuresate, bentazone, cinmethylin, clomazone,
clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone,
glufosinate, glyphosate, isoxaben, pyridate, quinchlorac,
quinmerac, sulphosate and tridiphane.
[0943] The active compound according to the invention can
furthermore be present in its commercially available formulations
and in the use forms, prepared from these formulations, as a
mixture with synergistic agents. Synergistic agents are compounds
which increase the action of the active compounds, without it being
necessary for the synergistic agent added to be active itself.
[0944] The active compound content of the use forms prepared from
the commercially available formulations can vary within wide
limits. The active compound concentration of the use forms can be
from 0.0000001 to 95% by weight of active compound, preferably
between 0.0001 and 1% by weight.
[0945] The compounds are employed in a customary manner appropriate
for the use forms.
[0946] When used against hygiene pests and pests of stored
products, the active compound is distinguished by an excellent
residual action on wood and clay as well as a good stability to
alkali on limed substrates.
[0947] The active compounds according to the invention act not only
against plant, hygiene and stored product pests, but also in the
veterinary medicine sector against animal parasites
(ectoparasites), such as hard ticks, soft ticks, mange mites, leaf
mites, flies (biting and licking), parasitic fly larvae, lice, hair
lice, feather lice and fleas. These parasites include:
[0948] From the order of the Anoplurida, for example, Haematopinus
spp., Linognathus spp., Pediculus spp., Phtirus spp. and
Solenopotes spp.
[0949] From the order of the Mallophagida and the suborders
Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon
spp., Trinoton spp., Bovicola spp., Wemeckiella spp., Lepikentron
spp., Damalina spp., Trichodectes spp. and Felicola spp.
[0950] From the order of the Diptera and the suborders 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.
[0951] From the order of the Siphonapterida, for example Pulex
spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus
spp.
[0952] From the order of the Heteropterida, for example, Cimex
spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
[0953] From the order of the Blattarida, for example Blatta
orientalis, Periplaneta americana, Blattela gernanica and Supella
spp.
[0954] From the subclass of the Acaria (Acarida) and the orders of
the Meta- and Mesostigmata, for example, Argas spp., Omithodorus
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.
[0955] From the order of the Actinedida (Prostigmata) und 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.
[0956] The active compounds of the formula (I) according to the
invention are also suitable for controlling arthropods which infest
agricultural productive livestock, such as, for example, cattle,
sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits,
chickens, turkeys, ducks, geese and bees, other pets, such as, for
example, dogs, cats, caged birds and aquarium fish, and also
so-called test animals, such as, for example, hamsters, guinea
pigs, rats and mice. By controlling these arthropods, cases of
death and reduction in productivity (for meat, milk, wool, hides,
eggs, honey etc.) should be diminished, so that more economic and
easier animal husbandry is possible by use of the active compounds
according to the invention.
[0957] The active compounds according to the invention are used in
the veterinary sector in a known manner by enteral administration
in the form of, for example, tablets, capsules, potions, drenches,
granules, pastes, boluses, the feed-through process and
suppositories, by parenteral administration, such as, for example,
by injection (intramuscular, subcutaneous, intravenous,
intraperitoneal and the like), implants by nasal administration, by
dermal use in the form, for example, of dipping or bathing,
spraying, pouring on and spotting on, washing and powdering, and
also with the aid of molded articles containing the active
compound, such as collars, ear marks, tail marks, limb bands,
halters, marking devices and the like.
[0958] When used for cattle, poultry, pets and the like, the active
compounds of the formula (1) can be used as formulations (for
example powders, emulsions, free-flowing compositions), which
comprise the active compounds in an amount of 1 to 80% by weight,
directly or after 100 to 10 000-fold dilution, or they can be used
as a chemical bath.
[0959] It has furthermore been found that the compounds of the
formula (I) according to the invention also have a strong
insecticidal action against insects which destroy industrial
materials.
[0960] The following insects may be mentioned as examples and as
preferred--but without a limitation:
[0961] Beetles, such as
[0962] Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,
Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex,
Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus
africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,
Trogoxylon aequale, Minthes rugicollis, Xyleborus spec.
Tryptodendron spec. Apate monachus, Bostrychus capucins,
Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.
[0963] Hymenopterons, such as
[0964] Sirex juvencus, Urocerus gigas, Urocerus gigas taignus,
Urocerus augur.
[0965] Termites, such as
[0966] Kaloterrnes flavicollis, Cryptotermes brevis, Heterotermes
indicola, Reticulitermes flavipes, Reticulitermnes santonensis,
Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis
nevadensis, Coptoterrnes formosanus.
[0967] Bristletails, such as
[0968] Lepisma saccarina.
[0969] Industrial materials in the present connection are to be
understood as meaning non-living materials, such as, preferably,
plastics, adhesives, sizes, papers and cards, leather, wood and
processed wood products and coating compositions.
[0970] Wood and processed wood products are materials to be
protected, especially preferably, from insect infestation.
[0971] Wood and wood processed wood products which can be protected
by the agents according to the invention or mixtures comprising
these are to be understood as meaning, for example: building
timber, wooden beams, railway sleepers, bridge components, boat
jetties, wooden vehicles, boxes, pallets, containers, telegraph
poles, wood panelling, wooden windows and doors, plywood,
chipboard, joinery or wooden products which are used quite
generally in house-building or in building joinery.
[0972] The active compounds can be used as such, in the form of
concentrates or in generally customary formulations, such as
powders, granules, solutions, suspensions, emulsions or pastes.
[0973] 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, dispersing agent and/or binder
or fixing agent, a water repellent, if appropriate siccatives and
UV stabilizers and if appropriate dyestuffs and pigrnents, and also
other processing auxiliaries.
[0974] The insecticidal compositions or concentrates used for the
preservation of wood and wood-derived timber products comprise the
active compound according to the invention in a concentration of
0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
[0975] The amount of the compositions or concentrates employed
depends on the nature and occurrence of the insects and on the
medium. The optimum amount employed can be determined for the use
in each case by a series of tests. In general, however, it is
sufficient 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
preserved.
[0976] Solvents and/or diluents which are used are an organic
chemical solvent or solvent mixture and/or an oily or oil-like
organic chemical solvent or solvent mixture of low volatility
and/or a polar organic chemical solvent or solvent mixture and/or
water, and if appropriate an emulsifier and/or wetting agent.
[0977] Organic chemical solvents which are preferably used are oily
or oil-like solvents having an evaporation number above 35 and a
flashpoint above 30.degree. C., preferably above 45.degree. C.
Substances which are used as such oily or oil-like water-insoluble
solvents of low volatility are appropriate mineral oils or aromatic
fractions thereof, or solvent mixtures containing mineral oils,
preferably white spirit, petroleum and/or alkylbenzene.
[0978] Mineral oils having a boiling range from 170 to 220.degree.
C., white spirit having a boiling range from 170 to 220.degree. C.,
spindle oil having a boiling range from 250 to 350.degree. C.,
petroleum and aromatics having a boiling range from 160 to
280.degree. C., terpentine oil and the like, are advantageously
employed.
[0979] In a preferred embodiment, liquid aliphatic hydrocarbons
having a boiling range from 180 to 210.degree. C. or high-boiling
mixtures of aromatic and aliphatic hydrocarbons having a boiling
range from 180 to 220.degree. C. and/or spindle oil and/or
monochloronaphthalene, preferably .alpha.-monochloronaphthalene,
are used.
[0980] The organic oily or oil-like solvents of low volatility
which have an evaporation number above 35 and a flashpoint above
30.degree. C., preferably above 45.degree. C., can be replaced in
part by organic chemical solvents of high or medium volatility,
providing that the solvent mixture likewise has an evaporation
number above 35 and a flashpoint above 30.degree. C., preferably
above 45.degree. C., and that the insecticide/fungicide mixture is
soluble or emulsifiable in this solvent mixture.
[0981] According to a preferred embodiment, some of the organic
chemical solvent or solvent mixture is replaced by an aliphatic
polar organic chemical solvent or solvent mixture. Aliphatic
organic chemical solvents containing hydroxyl and/or ester and/or
ether groups, such as, for example, glycol ethers, esters or the
like, are preferably used.
[0982] Organic chemical binders which are used in the context of
the present invention are the synthetic resins and/or binding
drying oils which are known per se, are water-dilutable and/or are
soluble or dispersible or emulsifiable in the organic chemical
solvents employed, in particular binders consisting 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, phenolic
resin, hydrocarbon resin, such as indene-cumarone resin, silicone
resin, drying vegetable oils and/or drying oils and/or physically
drying binders based on a natural and/or synthetic resin.
[0983] The synthetic resin used as the binder can be employed in
the form of an emulsion, dispersion or solution. Bitumen or
bituminous substances can also be used as binders in an amount of
up to 10% by weight. Dyestuffs, pigments, water-repelling agents,
odour correctants and inhibitors or anticorrosive agents and the
like which are known per se can additionally be employed.
[0984] It is preferred according to the invention for the
composition or concentrate to comprise, as the organic chemical
binder, at least one alkyd resin or modified alkyd resin and/or one
drying vegetable oil. Alkyd resins having an oil content of more
than 45% by weight, preferably 50 to 68% by weight, are preferably
used according to the invention.
[0985] All or some of the binder mentioned can be replaced by a
fixing agent (mixture) or a plasticizer (mixture). These additives
are intended to prevent evaporation of the active compounds and
crystallization or precipitation. They preferably replace 0.01 to
30% of the binder (based on 100% of the binder employed).
[0986] The plasticizers originate from the chemical classes of
phthalic acid esters, such as dibutyl, dioctyl or benzyl butyl
phthalate, phosphoric acid esters, such as tributyl phosphate,
adipic acid esters, such as di-(2-ethylhexyl) adipate, stearates,
such as butyl stearate or amyl stearate, oleates, such as butyl
oleate, glycerol ethers or higher molecular weight glycol ethers,
glycerol esters and p-toluenesulphonic acid esters.
[0987] Fixing agents are based chemically on polyvinyl alkyl
ethers, such as, for example, polyvinyl methyl ether or ketones,
such as benzophenone or ethylenebenzophenone.
[0988] Possible solvents or diluents are, in particular, also
water, if appropriate as a mixture with one or more of the
abovementioned organic chemical solvents or diluents, emulsifiers
and dispersing agents.
[0989] Particularly effective preservation of wood is achieved by
impregnation processes on a large industrial scale, for example
vacuum, double vacuum or pressure processes.
[0990] The ready-to-use compositions can also comprise other
insecticides, if appropriate, and also one or more fungicides, if
appropriate.
[0991] Possible additional mixing partners are, preferably, the
insecticides and fungicides mentioned in WO 94/29 268. The
compounds mentioned in this document are an explicit constituent of
the present application.
[0992] Especially preferred mixing partners which may be mentioned
are insecticides, such as chlorpyriphos, phoxim, silafluofin,
alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permetlrin,
imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron,
and also fungicides, such as epoxyconazole, hexaconazole,
azaconazole, propiconazole, tebuconazole, cyproconazole,
metconazole, imazalil, dichlorfluanid, tolylfluanid,
3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and
4,5-dichloro-N-octylisothiazolin-3-one.
[0993] The preparation and the use of the active compounds
according to the invention is illustrated by the examples
below.
EXAMPLE I-1-a-1
[0994] 164
[0995] At room temperature and under argon, 1.7 g of the bromine
compound shown above (Example I-1-a-6 known from WO 97/01535) in 40
ml of 1,2-dimethoxyethane are admixed with 1 g of
4-chlorophenylboronic acid and 150 mg of
tetrakis-(triphenylphosphine)-palladium, and the mixture is stirred
for 15 minutes. 25 ml of 20% strength aqueous sodium carbonate
solution are then added, and the mixture is stirred at about
80.degree. C. for 1 day. The mixture is concentrated and the
residue is taken up in water and acidified with hydrochloric acid.
The mixture is extracted with methylene chloride and the extract is
dried and concentrated. The residue is clromatographed over silica
gel (mobile phase: methylene chloride/ethyl acetate 3/1).
[0996] Yield: 0.2 g (11% of theory); m.p.: 276.degree. C.,
EXAMPLE I-1-a-11
[0997] 165
[0998] At 60.degree. C., 9.5 g of the compound of Example II-1 in
15 ml of dimethylformamide are added dropwise to a solution of 5.8
g of potassium tert-butoxide in 30 ml of dimethylformamide, and the
mixture is stirred at 80.degree. C. for 4 h. The mixture is
concentrated and the residue is taken up in 120 ml of water and, at
0-10.degree. C., acidified with concentrated hydrochloric acid
until a pH of 2 is reached. The precipitate is filtered off with
suction and purified over silica gel.
[0999] Yield: 1.85 g (22% of theory); m.p.: >245.degree. C.
[1000] The following compounds of the formula (1-II-a) are obtained
analogously and/or in accordance with the general preparation
procedures:
3 (I-1-a) 166 Ex. No. B A D W X Y Z isomer m.p. I-1-a-2
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5-- -(CH.sub.2).sub.2-- H H Cl
4-Cl--Ph* CH.sub.3 .beta. >240.degree. C. I-1-a-3
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H H Cl 4-Cl--Ph*
CH.sub.3 .beta. 248 I-1-a-4 --(CH.sub.2).sub.2--CHOC.sub-
.2H.sub.5--(CH.sub.2).sub.2-- H H CH.sub.3 4-Cl--Ph* Cl .beta. 183
I-1-a-5 --(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H H Cl
3-Cl--Ph* CH.sub.3 .beta. 141 I-1-a-6 --(CH.sub.2).sub.2--CHOC.sub-
.2H.sub.5--(CH.sub.2).sub.2-- H H Cl Ph* CH.sub.3 .beta. 158
I-1-a-7 --(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2-- H
H Cl 4-Cl--Ph* CH.sub.3 .alpha. 185 I-1-a-8
--(CH.sub.2).sub.2--O--(CH.- sub.2).sub.2-- H H CH.sub.3 4-Cl--Ph*
CH.sub.3 -- >250 I-1-a-9
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2-- H H
CH.sub.3 4-Cl--Ph* CH.sub.3 .beta. >240 I-1-a-10
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H H CH.sub.3
4-Cl--Ph* CH.sub.3 .beta. 185 I-1-a-11 --CH.sub.2--CHCH.sub.3--(C-
H.sub.2).sub.3-- H H CH.sub.3 4-Cl--Ph* CH.sub.3 .beta. >245
I-1-a-12 --(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- H H
CH.sub.3 4-Cl--Ph* CH.sub.3 .beta. >250 I-1-a-13 H
--CH.sub.2--S--(CH.sub.2).sub.2-- H CH.sub.3 4-Cl--Ph* CH.sub.3 --
>250 I-1-a-14 H --(CH.sub.2).sub.4-- H CH.sub.3 4-Cl--Ph*
CH.sub.3 -- >250 I-1-a-15 --CH.sub.2--O--(CH.sub.2).sub.3-- H H
CH.sub.3 4-Cl--Ph* CH.sub.3 -- >235 *Ph = phenyl
EXAMPLE I-1-b-1
[1001] 167
[1002] At about 80.degree. C., 0.25 g of ethoxyacetyl chloride in 5
ml of ethyl acetate is added to a mixture of 1.6 g of the compound
of Example I-1-a-2, 30 ml of ethyl acetate and 0.3 ml of
triethylamine, and the mixture is stirred at this temperature for 1
day. The mixture is concentrated and the residue is taken up in
methylene chloride and extracted with 0.5 N aqueous sodium
hydroxide solution. The mixture is dried and concentrated and the
residue is chromatographed over silica gel (mobile phase: methylene
chloride/ethyl acetate 5/3).
[1003] Yield: 0.9 g (48% of theory); m.p.: 115.degree. C.
[1004] The following compounds of the formula (I-1-b) are obtained
analogously and/or in accordance with the general preparation
procedures:
4 168 (I-1-b) Ex. No. B A D W X Y Z R.sup.1 m.p. I-1-b-2
--(CH.sub.2).sub.2--CHOC.sub.2H.sub- .5--(CH.sub.2).sub.2-- H H Cl
4-Cl--Ph CH.sub.3 Ph 148.degree. C. I-1-b-3
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.3--(CH.sub.2).sub.2-- H H Cl
4-Cl--Ph CH.sub.3 --CH(CH.sub.3).sub.2 165.degree. C.
EXAMPLE I-1-c-1
[1005] 169
[1006] At about 0.degree. C., 0.22 g of ethyl chloroformate in 5 ml
of methylene chloride is added to a mixture of 1.6 g of the
compound of Example I-1-a-2, 30 ml of methylene chloride and 0.35
ml of triethylamine, and the mixture is stirred at room temperature
for 1 day. Work-up and chromatography are carried out as described
in Example I-1-b-1.
[1007] Yield: 0.9 g (50% of theory); m.p.: 129.degree. C.
EXAMPLE I-1-c-2
[1008] 170
[1009] At about 0.degree. C., 0.13 g of ethyl chloroformate in 1 ml
of methylene chloride is added to a mixture of 0.55 g of the
compound of Example I-1-a-3, 30 ml of methylene chloride and 0.2 ml
of triethylamine, and the mixture is stirred at room temperature
for 1 day. Work-up and chromatography are carried out as described
in Example I-1-b-1.
[1010] Yield: 0.25 g (63% of theory); m.p.: 213.degree. C.
EXAMPLE I-2-a-1
[1011] 171
[1012] Under protective gas, 1.6 g of 4-chloro-phenylboronic acid
and 0.6 g of tetrakis-(triphenylphosphine)-palladium are added to a
mixture of 3.5 g of the bromine compound shown above (Ex. I-2-a-7
known from WO 97/01535) in 40 ml of dimethoxyethane, and the
mixture is stirred at room temperature for 15 min. 44 ml of a 20%
strength sodium carbonate solution are added, and the mixture is
stirred at 80.degree. C. for 8 h. The reaction mixture is acidified
using citric acid and extracted with methylene chloride, dried and
concentrated.
[1013] Yield: 3.52 g; m.p.: 244-246.degree. C.
[1014] The following compounds are obtained analogously to Example
I-2-a-1 and/or in accordance with the general procedures for
preparing compounds of the formula (I-2-a)
5 172 (I-2-a) Ex. No. A B W X Y Z m.p. .degree. C. I-2-a-2
--(CH.sub.2).sub.2--CHOCH.sub.3--- (CH.sub.2).sub.2-- H Cl
4-Cl--Ph* CH.sub.3 210-212 *Phenyl
EXAMPLE I-2-b-1
[1015] 173
[1016] At room temperature, 0.33 g of isobutyryl chloride is added
to a mixture of 1.3 g of the compound of Example I-2-a-2, 20 ml of
methylene chloride and 0.32 g of triethylamine, and the mixture is
stirred at room temperature for 1 day.
[1017] The organic phase is initially washed with dilute citric
acid and then with 1N sodium hydroxide solution, dried and
concentrated, and the residue is purified over a silica gel
column.
[1018] Yield: 0.92 g
[1019] .sup.1H-NMR (300 MHz; CDCl.sub.3): .delta.=1.20 (d, 6H),
1.50-2.40 (m, 9H), 2.25 (s, 3H), 2.70 (2m, 1H), 3.40 (2s, 3H),
3.25/3.60 (2m, 1H), 7.15-7.70 (m, 6H) ppm.
EXAMPLE I-2-c-1
[1020] 174
[1021] At room temperature, 0.38 g of isopropyl chlorofomiate in
3.1 ml of toluene (1 M sol.) is added to a mixture of 1.3 g of the
compound of Example I-2-a-1, 20 ml of methylene chloride and 0.32 g
of triethylamine, and the mixture is stirred at room temperature
for 1 day.
[1022] Work-up and chromatography are carried out as described in
Example I-2-b-1.
[1023] Yield: 1.42 g.
[1024] .sup.1H-NMR (300 MHz; CDCl.sub.3): .delta.=1.15 (d, 6H),
1.50-2.40 (m, 8H), 2.35 (2s, 3H), 3.25/3.60 (2m, 1H), 3.40 (2s,
3H), 4.70 (m, 1H), 7.10-7.50 (m, 6H) ppm.
EXAMPLE I-3-a-1
[1025] 175
[1026] A mixture of 42.1 g of the compound of Example IV-1 in 86 ml
of trifluoroacetic acid and 200 ml of toluene is heated under
reflux for 8 h.
[1027] The mixture is concentrated, the residue is taken up in 600
ml of water and 200 ml of methyl tert-butyl ether (MTBE), sodium
hydroxide is added until a pH of 14 has been reached, the mixture
is extracted twice with MTBE and the aqueous phase is acidified
with hydrochloric acid and stirred for 1 h. The precipitate is
separated off and dried.
[1028] Yield: 15 g (49% of theory); m.p.: 225.degree. C.
EXAMPLE I-3-c-1
[1029] 176
[1030] At 0.degree. C., 0.71 g of ethyl chloroformate in 3 ml of
methylene chloride is added to a mixture of 2.0 g of the compound
of Example I-3-a-1, 20 ml of methylene chloride and 0.76 g of
triethylamine, and the mixture is stirred at room temperature for 2
h.
[1031] Work-up and chromatography are carried out as described in
Example I-2-b-1.
[1032] Yield: 1.9 g (81% of theory).
[1033] .sup.1H-NMR (400 MHz; CDCl.sub.3): =1.2 (t, 3H,
CH.sub.2CH.sub.3 ), 1.3-2.0 (m, 10H, CH.sub.2), 2.05, 2.15 (2s,
2.times.3H, Ar--CH.sub.3), 4.3 (q, 2H, CH.sub.2CH.sub.3), 7.0-7.5
(m, 6H, ArH) ppm.
EXAMPLE I-7-a-1
[1034] 177
[1035] 8.24 g of potassium tert-butoxide are added to a mixture of
20 g of the compound of Example X-1 in 50 ml of absolute
dimethylformamide, and the mixture is stirred at 80.degree. C. for
1 h.
[1036] The mixture is added dropwise with ice-cooling to about 2.01
of 1N hydrochloric acid, and the precipitate is then filtered and
dried.
[1037] Yield: 22 g (100% of theory); m.p.: 197-199.degree. C.
EXAMPLE I-7-b-1
[1038] 178
[1039] At about 0.degree. C., 0.82 g of isovaleryl chloride in 3 ml
of methylene chloride is added to a mixture of 2.0 g of the
compound of Example I-7-a-1, 20 ml of methylene chloride and 0.8 g
of triethylamine, and the mixture is stirred at room temperature
for 2 h. Work-up and chromatography are carried out as described in
Example I-2-b-1.
[1040] Yield: 2.1 g (86% of theory).
[1041] .sup.1H-NMR (400 MHz; CDCl.sub.3): .delta.=0.8 (d,
2.times.3H, CH--CH.sub.3), 1.2-1.8 (m, 10H, cyclohexyl-H); 1.95 (m,
1H, CH), 2.05, 2.15 (s, 2.times.3H, Ar--CH.sub.3), 2.3-2.4 (dd, 2H,
CH.sub.2CH); 6.9-7.5 (m, 6H, ArH) ppm.
EXAMPLE I-7-c-1
[1042] 179
[1043] At 0.degree. C., 0.74 g of ethyl chloroformate in 3 ml of
methylene chloride is added to a mixture of 2.0 g of the compound
of Example I-7-a-1, 20 ml of methylene chloride and 0.8 g of
triethylamine, and the mixture is stirred at room temperature for 2
h. Work-up and chromatography are carried out as described in
Example I-2-b-1.
[1044] Yield: 1.75 g (74% of theory).
[1045] .sup.1H-NMR (400 MHz; CDCl.sub.3): .delta.=1.2 (t, 3H,
CH.sub.2--CH.sub.3), 1.3-1.8 (m, 10H, cyclohexyl-H); 2.05, 2.15 (s,
2.times.3H, Ar--CH.sub.3), 4.25 (q, 2H, CH2CH.sub.3); 6.9-7.5 (m,
6H, ArH) ppm.
EXAMPLE I-8-a-1
[1046] 180
[1047] 1.44 g of potassium tert-butoxide are added to a mixture of
3.3 g of the compound of Example XI-1 in 15 ml of absolute
dimethylformamide, and the mixture is stirred at 80.degree. C. for
1 h.
[1048] Work-up is carried out according to Example I-7-a-1.
[1049] Yield: 2.7 g (89.5% of theory); m.p.: 172-175.degree. C.
EXAMPLE I-8-a-2
[1050] 181
[1051] 3.9 g of potassium tert-butoxide are added to a mixture of
8.9 g of methyl
6-(4-(4-chlorophenyl)-2,5-dimethyl-phenyl)-3,3-dimethyl-5-oxo-hexa-
necarboxylate in 30 ml of absolute dimethylformamide, and the
mixture is stirred at 80.degree. C. for 1 h.
[1052] Work-up is carried out according to Example I-7-a-1.
[1053] Yield: 7.5 g (92% of theory); m.p.: 183-185.degree. C.
EXAMPLE I-8-b-1
[1054] 182
[1055] At 0.degree. C., 0.66 g of isovaleryl chloride in 2 ml of
methylene chloride is added to a mixture of 1.5 g of the compound
of Example I-8-a-2, 10 ml of methylene chloride and 0.64 g of
triethylamine, and the mixture is stirred at room temperature for 2
h. Work-up and chromatography are carried out as described in
Example I-2-b-1.
[1056] Yield: 1.7 g (92% of theory).
[1057] .sup.1H-NMR (400 MHz; CDCl.sub.3): .delta.=0.6 (d,
2.times.3H, CH--(CH.sub.3).sub.2); 1.15 (s, 2.times.3H,
C--(CH.sub.3).sub.2); 1.65 (m, 1H, CH--(CH.sub.3).sub.2); 2.05,
2.15 (s, 2.times.3H, Ar--CH.sub.3), 2.6-2.7 (m, 3.times.2H,
CH.sub.2); 6.8-7.5 (m, 6H, ArH) ppm.
EXAMPLE I-8-c-1
[1058] 183
[1059] At 0.degree. C., 0.60 g of ethyl chloroformate in 2 ml of
methylene chloride is added to a mixture of 1.5 g of the compound
of Example I-8-a-2, 20 ml of methylene chloride and 0.64 g of
triethylamine, and the mixture is stirred at room temperature for 2
h. Work-up and chromatography are carried out as described in
Example I-2-b-1.
[1060] Yield: 1.55 g (86% of theory).
[1061] .sup.1H-NMR (400 MHz; CDCl.sub.3): .delta.=1.1 (t, 3H,
CH.sub.2--CH.sub.3); 1.15 (s, 2.times.3H, C--(CH.sub.3).sub.2;
2.05, 2.15 (s, 2.times.3H, Ar--CH.sub.3), 2.45/2.7 (s, 2.times.2H,
cyclohexyl-CH.sub.2); 4.1 (q, 2H, CH2CH.sub.3); 6.8-7.5 (m, 6H,
ArH) ppm.
EXAMPLE II-1
[1062] 184
[1063] At about 5.degree. C., 10 g of ground potassium carbonate
are added to a mixture of 4.57 g of methyl
3-methyl-1-amino-cyclohexane-carboxylate- .times.HCl in 20 ml of
acetonitrile. Over a period of about 15 min, 5.86 g of
2,5-dimethyl-4-(4-chloro-phenyl)-phenylacetyl chloride in 10 ml of
acetonitrile are added dropwise, and the mixture is stirred at room
temperature for 3 hours. The reaction mixture is added to 200 ml of
ice-water and seeded.
[1064] The precipitate is filtered off with suction, washed with
water and taken up in methylene chloride, dried and concentrated.
The residue is recrystallized from MTB ether/n-hexane.
[1065] Yield: 10.3 g (99% of theory), m.p. 112.degree. C.
EXAMPLE II-2
[1066] 185
[1067] At about 30-40.degree. C., 8.1 g [lacuna] of Example XXIX-1
in 100 ml of methylene chloride are added to 12 g of concentrated
sulphuric acid, and the mixture is stirred at 30-40.degree. C. for
2 hours. 15 ml of absolute methanol are then added dropwise such
that an internal temperature of 40.degree. C. results. Stirring is
continued at 40-70.degree. C. for a further 6 hours.
[1068] The solution is poured onto 200 g of ice and extracted with
methylene chloride, and the extract is washed with a sodium
bicarbonate solution. The extract is dried and concentrated. The
residue is recrystallized from MTB ether/n-hexane.
[1069] Yield: 5 g (57% of theory); m.p.: 126.degree. C.
[1070] The following compounds are obtained analogously to Example
II-1 and II-2 and/or in accordance with the general procedures for
preparing compounds of the formula II
6 (II) 186 Ex. No. W X Y Z B A D R.sup.8 m.p. .degree. C. Isomer
II-3 H CH.sub.3 4-Cl--Ph* CH.sub.3
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2-- H CH.sub.3 169 -- II-4 H
CH.sub.3 4-Cl--Ph* CH.sub.3 --(CH.sub.2).sub.3--O--CH.sub.2-- H
CH.sub.3 108 -- II-5 H CH.sub.3 4-Cl--Ph* CH.sub.3
--CH.sub.2--CHCH.sub.3--O--(CH.sub.2).sub.2-- H CH.sub.3 139 .beta.
II-6 H CH.sub.3 4-Cl--Ph* Cl
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2)- .sub.2-- H CH.sub.3
114 .beta. II-7 H CH.sub.3 4-Cl--Ph* CH.sub.3
--(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2-- H
CH.sub.3 118 .beta. II-8 H CH.sub.3 4-Cl--Ph* CH.sub.3 H
--(CH.sub.2).sub.4-- C.sub.2H.sub.5 oil -- II-9 H CH.sub.3
4-Cl--Ph* CH.sub.3
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- H CH.sub.3 142
.beta. II-10 H CH.sub.3 4-Cl--Ph* CH.sub.3
--(CH.sub.2).sub.2--CHCH.sub.- 3--(CH.sub.2).sub.2-- H CH.sub.3 76
.beta. II-11 H CH.sub.3 4-Cl--Ph* CH.sub.3 H
--(CH.sub.2).sub.2--S--CH.sub.2-- C.sub.2H.sub.5 oil -- Ph* =
phenyl
EXAMPLE IV-1
[1071] 187
[1072] A: 9.63 g of thionyl chloride are added to a mixture of 15 g
of 1-(4-methoxy-benzyl)-mercapto-cyclohexanecarboxylic acid in 100
ml of toluene and 1 drop of dimethylformamide, and the mixture is
stirred at room temperature for 5 min. The mixture is then stirred
at 100.degree. C. until the evolution of gas has ceased. The
mixture is concentrated.
[1073] B: At 0.degree. C., 26.4 g of methyl
2,5-dimethyl-4(4-chlorophenyl)- -phenylacetate in 30 ml of
tetrahydrofuran are added to a mixture of 45.8 ml of lithium
diisopropylamide (LDA) solution in 100 ml of tetrahydrofuran, and
the mixture is stirred at 0.degree. C. for 30 min. The acyl
chloride A in 30 ml of tetrahydrofuran is then added dropwise at
0.degree. C., and the mixture is stirred at room temperature for 1
h. 300 ml of MTB ether and a few drops of water are added. The
mixture is washed twice with 10% ammonium chloride solution, dried
and concentrated.
[1074] Yield: 42.1 g (100% of theory).
[1075] .sup.1H-NMR (400 MHz; CDCl.sub.3): .delta.=3.2 (dd, 2H,
SCH.sub.2); 3.6 (s, 2.times.3H, 2.times.OCH.sub.3); 6.7-7.5 (m,
10H, ArH) ppm.
EXAMPLE X-1
[1076] 188
[1077] 23.2 g of potassium carbonate and 71.7 g of methyl iodide
are added to a mixture of 67.3 g of the compound of Example XXXVM-1
in 400 ml of acetone, and the mixture is stirred under reflux for
16 h. The reaction mixture is filtered and concentrated. The
residue is purified by silica gel chromatography (mobile phase
methylene chloride/petroleum ether 2:1, towards the end mobile
phase 100% methylene chloride).
[1078] Yield: 20 g (40% of theory).
[1079] .sup.1H-NMR (400 MHz; CDCl.sub.3): .delta.=2.1/2.15 (s,
2.times.3H, 2.times.Ar--CH.sub.3); 3.55 (s, 3H, OCH.sub.3);
7.35/7.5 (d, 2.times.2H, p-Cl-aromatic) ppm.
EXAMPLE XI-1
[1080] 189
[1081] 43.7 g of methyl iodide are added to a mixture of 38 g of
the compound of Example XLII-1 in 250 ml of acetone and 14.1 g of
potassium carbonate, and the mixture is stirred under reflux for 16
h. Work-up is carried out according to Example X-1.
[1082] Yield: 3.5 g (8.4% of theory).
[1083] .sup.1H-NMR (400 MHz; CDCl.sub.3): .delta.=1.1 (s, 6H,
2.times.C--CH.sub.3); 2.15/2.20 (s, 2.times.3H,
2.times.ArCH.sub.3); 3.6 (s, 3H, OCH.sub.3); 7.35/7.5 (d,
2.times.2H, p-Cl aromatic) ppm.
EXAMPLE XXIX-1
[1084] 190
[1085] Over a period of 15 min, 8.79 g of
2,5-dimethyl-4-(chloro-phenyl)-p- henylacetyl chloride in 15 ml of
acetonitrile are added at 5-10.degree. C. to a mixture of 3.7 g of
2-amino-2,3-dimethylbutyronitrile in 30 ml of acetonitrile and 13.8
g of ground potassium carbonate, and the mixture is stirred at room
temperature for 3 h.
[1086] Work-up is carried out according to Example II-1.
[1087] Yield: 8.9 g (81% of theory); m.p.: 99.degree. C.
EXAMPLE XXXII-1
[1088] 191
[1089] 98 ml of a 1M sodium carbonate solution are added to a
mixture of 11.97 g of methyl 4-bromo-2,5-dimethyl-phenylacetate in
130 ml of dimethoxyethane. Furthermore, 9.15 g of
4-chlorophenylboranic acid and 0.275 g of
bis-(triphenylphosphine)-palladium(II) chloride are added, and the
mixture is stirred under reflux for 8 h.
[1090] The mixture is taken up in water and extracted with ethyl
acetate, and the extract is washed with ammonium chloride, water
and sodium chloride solution. The extract is dried and
concentrated. The residue is purified by silica gel chromatography
(mobile phase: petroleum ether/ethyl acetate 15/1).
[1091] Yield: 9 g (70% of rheory); m.p.: 38.degree. C.
EXAMPLE XXXII-2
[1092] 192
[1093] 64 g of 88% pure potassium hydroxide in 1000 ml of methanol
are added to 81 g of the compound of Example XLV-1.
[1094] The mixture is stirred under reflux for 8 h, then acidified
at room temperature with 50 ml of concentrated sulphuric acid and
stirred under reflux for 1 h. The solid is filtered off and washed
with methanol. Purification is carried out by silica gel
chromatography (mobile phase: petroleum ether/ethyl acetate
20/1).
[1095] Yield: 2 g (8% of theory).
EXAMPLE XXXVIII-1
[1096] 193
[1097] At -15.degree. C., a solution of 54.06 g of methyl
2,5-dimethyl-4-(4-chlorophenyl)-phenylacetate in 80 ml of
tetrahydrofuran is added dropwise to a solution of 100 ml of LDA in
200 ml of tetrahydrofaran, and the mixture is stirred at 0.degree.
C. for 1 h.
[1098] At -15.degree. C., a solution of 17.04 g of
2,2-pentamethylenesucci- nic anhydride in 30 ml of tetrahydrofuran
is then added dropwise, and the mixture is stirred at room
temperature for 2 h. 300 ml of water and 80 g of ammonium chloride
are then added, and the mixture is acidified with hydrochloric
acid. The mixture is extracted with diethyl ether and the extract
is concentrated. The residue is heated under reflux with 200 g of
potassium hydroxide in 660 ml of water for 2 days.
[1099] The mixture is cooled, acidified with concentrated
hydrochloric acid and extracted with diethyl ether. The crude
product is directly reacted further.
[1100] Yield: 67.3 g (100% of theory).
EXAMPLE XLII-1
[1101] 194
[1102] At -15.degree. C., a solution of 32.4 g of methyl
2,5-dimethyl-4-(4-chlorophenyl)-phenylacetate in 40 ml of
tetrahydrofuran is added dropwise to a solution of 60 ml of LDA in
120 ml of tetrahydrofuran, and the mixture is stirred at 0.degree.
C. for 1 h.
[1103] At -15.degree. C., a solution of 10.3 g of
2,2-dimethylglutaric anhydride in 30 ml of tetrahydrofuran is then
added dropwise, and the mixture is stirred at room temperature for
2 h. 180 ml of water and 48 g of ammonium chloride are then added,
and the mixture is acidified with hydrochloric acid. The mixture is
extracted with diethyl ether and the extract is concentrated. The
residue is heated under reflux with 120 g of potassium hydroxide in
400 ml of water for 2 days.
[1104] The mixture is cooled, acidified with concentrated
hydrochloric acid and extracted with diethyl ether. The crude
product is directly reacted further.
[1105] Yield: 38.5 g (96% of theory).
EXAMPLE XXVII-1
[1106] 195
[1107] A solution of 0.54 g of 98% lithium hydroxide in 100 ml of
water is added dropwise to a mixture of 6 g of the compound of
Example XXXII-1 in 100 ml of tetra-hydrofuran. 25 ml of ethanol are
added, and the mixture is stirred for 8 h. The mixture is
concentrated, taken up in water and extracted with MTBE.
[1108] The mixture is then acidified using concentrated
hydrochloric acid, and the precipitate is filtered off with suction
and dried.
[1109] Yield: 5 g (96% of theory); m.p.: 153.degree. C.
EXAMPLE XLV-1
[1110] 196
[1111] 20.5 g of isopentylnitrite in 60 ml of acetonitrile and 18 g
of anhydrous copper(ll) chloride in 139 ml of dichloroethene
are.
[1112] Added dropwise at about 30.degree. C. to a mixture of 31 g
of the compound of Example XLVI-I in acetonitrile, and the mixture
is stirred at room temperature for 8 h. The mixture is taken up in
800 ml of ice-cooled 20% strength hydrochloric acid and extracted
with MTBE, and the extract is dried and concentrated.
[1113] The crude product is reacted without any further
purification.
[1114] Yield: 40 g (91% of theory)
EXAMPLE XLVI-1
[1115] 197
[1116] At room temperature, 48.8 ml of a 1N sodium carbonate
solution are added to a mixture of 5 g of the amine compound shown
above in 65 ml of dimethoxyethane. Furthermore, 4.57 g of
4-chlorophenylboronic acid and 0.11 g of
bis-(triphenyl-phosphine)-palladium-(II) chloride are added, and
the mixture is stirred under reflux for 8 h. The mixture is taken
up in water and extracted with ethyl acetate, and the extract is
washed with ammonium chloride solution, water and sodium chloride
solution, dried and concentrated. The residue is purified by silica
gel chromatography (mobile phase petroleum ether/ethyl acetate
3/1).
[1117] Yield: 4 g (82% of theory).
USE EXAMPLES
EXAMPLE A
[1118] Phaedon Larvae Test
7 Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1
part by weight of alkylaryl polyglycol ether
[1119] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentration.
[1120] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are populated with mustard beetle larvae (Phaedon
cochleariae) whilst the leaves are still moist.
[1121] After the desired period of time, the plants are populated
with mustard beetle larvae (Phaedon cochleariae). In each case
after 3 days, 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.
[1122] In this test, for example, the compound of Preparation
Example (I-1-a-2) effected, at an exemplary active compound
concentration of 1%, a kill of 90% after 7 days.
EXAMPLE B
[1123] Tetranychus Test (OP-Resistant/Dip Treatment)
8 Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1
part by weight of alkylaryl polyglycol ether
[1124] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent and the stated amount of emulsifier, and the concentrate is
diluted with water to the desired concentrations. Bean plants
(Phaseolus vulgaris) which are heavily infested by all development
stages of the greenhouse red spider mite or bean spider mite
(Tetranychus urticae) are dipped into a preparation of active
compound of the desired concentration.
[1125] After the desired period of time, the kill in % is
determined. 100% means that all spider mites have been killed; 0%
means that none of the spider mites have been killed.
[1126] In this test, for example, the compound of Preparation
Example (I-1-a-2) had, at an exemplary active compound
concentration of 0.1%, an effect of 95% after 13 days.
* * * * *